JPH01216348A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance whiteness and sensitivity and to prevent static mark by incorporating a diaminostilbene type fluorescent whitening agent in at least one layer and an ultraviolet absorber in layer located farther than a blue sensitive silver halide emulsion layer from a support. CONSTITUTION:At least one of the layers formed on the support contains the diaminostilbene type fluorescent whitening agent and the layer located farther than the blue sensitive emulsion layer from the support contains the ultraviolet absorber, and said blue sensitive layer is regulated so as to have a ratio of sensitivity S400 at 400nm wavelength to sensitivity S460 at 460nm wavelength of <=0.7, thus permitting the obtained silver halide photographic sensitive material to be improved in whiteness, high in sensitivity, and high in static mark preventing effect.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, particularly a silver halide photographic material suitable for direct viewing, and more specifically, to a silver halide photographic material suitable for direct viewing. This invention relates to a silver halide photographic material which is highly sensitive and prevents the generation of static marks.

[Conventional technology]

In photographic materials intended for direct viewing, the whiteness of the background has an important effect on the image. Improving the whiteness of the background increases contrast, improves color purity (coloring), and improves aesthetics. Therefore, various methods have been devised to improve whiteness.

Fluorescent brighteners are known as one of the effective means for improving the whiteness of silver halide photographic materials.

One method of using this fluorescent whitening agent is to include it in the color development process, for example,
It is described in Japanese Patent Publications No. 46-35240, No. 49-20975, and No. 50-25336. However, these methods have drawbacks such as insufficient fluorescent whitening effects and poor developer stability, and they are not suitable for the increasing speed and diversification of processing that has been in high demand in recent years. This is a difficult method to deal with.

Another method of using a fluorescent whitening agent is to incorporate the fluorescent brightening agent into a light-sensitive material.
-21189, 48-27692, 49-10
No. 696, No. 51-28225 and No. 52-322
It is described in each publication No. 54. According to these methods, more preferable results can be obtained since the fluorescence intensity is increased and the whiteness of unexposed areas is improved compared to the above-mentioned method in which a fluorescent whitening agent is included in the developer. However, in the conventional method of incorporating a fluorescent brightener into a light-sensitive material, the fluorescent brightener is added alone to one of the constituent layers of the light-sensitive material such as a support coating layer, an emulsion layer, or a non-emulsion layer. In the past, the whitening agent contained a fluorescent whitening agent and a compound that captured the fluorescent whitening agent and enhanced the whitening effect.
According to such conventional methods, although the above-mentioned effect of improving the whiteness of the unexposed areas can be sufficiently obtained, when each constituent layer of the photosensitive material is coated on the support at high speed, there is a problem in the color printer during printing. There is a serious drawback in that static failures such as static marks occur during manufacturing or processing of the photosensitive material, such as when transporting it or peeling off the tape attached to the surface of the photosensitive material.

Moreover, in the conventional method, the higher the fluorescence intensity, the more likely stack marks are to occur, and the conventional method 4 does not provide an equivalent solution for both purposes of improving the white background and preventing stuck marks. It had become undetectable. Furthermore, in photosensitive materials using a hydrophobic support in which a paper support is coated with a polyolefin, static marks tend to occur frequently, and there has been an urgent need to find a solution to this problem.

Therefore, as a method for incorporating a fluorescent brightener into a silver halide photographic material without producing stack marks, JP-A-59
No. 71049 has a layer structure in which the layers are arranged in order from the layer closest to the support, including a layer containing a fluorescent brightener, an ultraviolet absorber, and a layer containing a fluorescent brightener-trapping compound, and the fluorescent brightener is diffused by high pH development. A method of transferring is disclosed.

By this method, it was possible to add the optical brightener to the photosensitive material without producing static marks.

However, depending on the above method, when a highly sensitive silver halide emulsion is used, the prevention of stitch marks is insufficient, and therefore it is necessary to lower the sensitivity or reduce the amount of optical brightener added. As a result, the improvement of the white background was insufficient.

Therefore, it has a large white background improvement effect and high sensitivity.
In addition, a silver halide photographic material in which the generation of static marks is sufficiently prevented has been desired.

[Problem that the invention seeks to solve]

In order to solve the above-mentioned problems, the first object of the present invention is to provide a silver halide photographic material which has improved whiteness, high sensitivity, and is highly effective in preventing the occurrence of stack marks.

A second object of the present invention is to provide a silver halide photographic material which does not undergo yellowing in white areas even after continuous processing in an automatic processor and is prevented from producing static marks. A third object of the present invention is to provide a silver halide photographic material with good color reproducibility.

[Means for solving problems]

The above object of the present invention is to provide a silver rhodanide photographic light-sensitive material having at least one blue-sensitive silver decagenide emulsion layer on a support, at least one layer containing a diaminostilbene fluorescent brightener. and the sensitivity of the blue-sensitive silver halide emulsion at a wavelength of 400 nm (S4°);
A relationship such as the sensitivity (S, .) at a wavelength of 460 nm is established, and the ultraviolet absorber is contained in a layer provided at a position farther from the support than the blue-sensitive silver-no-rodanide emulsion layer. This is achieved by a silver halide photographic material characterized by:

The present invention will be explained in more detail below.

A diaminostilbene type optical brightener is used as the optical brightener of the present invention. A preferred optical brightener is 6.0
An organic acid group with a pKa of 7.5 or less, or 9
It is a water-soluble optical brightener having at least one organic base exhibiting Kb in its molecule. More preferably, an organic acid group exhibiting a pKa of 5.0 or less, or a pKa of 4.0 or more and 7.
A water-soluble optical brightener having in its molecule at least one organic base exhibiting a pKb of 5 or more, more preferably 5.0.
at least one organic acid group having a pKa of 4
．． A water-soluble optical brightener having at least one organic base having a pKb of 0 or more and 7.5 or less in the same molecule. The pkb of the organic base is 4.0 or more and 7.
Most preferably, it is 0 or less.

In the present invention, pKa is a so-called acid dissociation constant, which is an ionization equilibrium constant of an acid, and is one of the measures showing the strength of an acid. For example, Chemistry Handbook (Basic Edition ■) (Nippon Kagaku Kinsen) P4
Defined in O10.

The dissociation of acid HA is represented by HA−H”+A−, and the dissociation constant Ka at this time is Ka=[H”l[A−]/[HA],
pKa is expressed as pKa=-QogKa. Similarly, pKb is also a so-called base dissociation constant, and when the dissociation of base B is represented by B + H, 0-B H"+ OH-, the dissociation constant Kb is Kb-[BH"l [OH-] / [B ] and
pKb is designated pKb--QogKb.

The fluorescent whitening agent used in the present invention is preferably represented by the following general formula.

- Formula I In the formula, R, %R3, R3 and R4 are each a hydrogen atom, a halogen atom, a sulfonic acid or a salt thereof, a carboxylic acid or a salt thereof, an alkylamino group, an ali, -ruamino group, a hydroxyl group, an amino group , alkoxyl group,
Represents an aryloxy group or a morpholino group. Xl
represents a sulfonic acid or a carboxylic acid, or a negative acid thereof. Specific examples of the 4.4'-diaminostilbendisulfonic acid derivatives include the following. “ [1-11 [1-2) [1-3] l-41 [1-51 [1-61 [1-7'] [1-Fl] [)-1111 [l-111 T-121 [1 -131 [)-14] 1Jella
OL! b[1-151 l-161 [l-171 [)-1sl OCII@0GIa l-191 CI-23) DC1 plate-0CII Eng(]-231 N11CIt・
NIICIIaCl-24] [! -25'1 (1-2(il Nllllfffl・
8Nshi ■ Lu ([-3jJ [I-: (2] (1-33] [I -34] Nll'l1m [11mff1
Nil Kol5GIsO! 1(I-
35) The 4,4'-diaminostilbendisulfonic acid derivative used in the present invention can be prepared by the usual method described in, for example, Kasei Kogyo Kinen Line, "Fluorescent Whitening Agent" (Published in August 1975), page 8. It can be synthesized with

The layer containing the optical brightener used in the present invention may be any layer, and may be the same layer as the silver halide emulsion layer. The optical brightener-containing layer is preferably a non-emulsion layer closer to the support than the ultraviolet absorber-containing layer furthest from the support.

For example, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the hydrophobic support side. When a layer containing an ultraviolet absorber is provided between the protective layer and the protective layer, the optical brightener is added to the layer between the blue-sensitive emulsion layer and the green-sensitive silver halide emulsion layer and/or the green-sensitive silver halide emulsion layer. It is preferably contained in a layer between a red-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer.

When the optical brightener-containing layer is coated, the coating amount of the optical brightener is usually 0.1" 1.0 mg/dm2.

Many conventionally known hydrophilic powders can be used in the layer containing the optical brightener.

The hydrophilic binder preferably has an organic acid group with a pKa of 6.0 or less or an organic base with a pKb of 7.5 or less.

It is preferable to use a compound (hereinafter referred to as a scavenger) that captures the optical brightener and enhances the whitening effect.

Particularly useful as scavengers are hydrophilic polymers (
For example, polyvinylpyrrolidone, a polymer containing vinylpyrrolidone as a repeating unit (monomers that form a repeating unit together with vinylpyrrolidone include acrylic acid, methacrylic acid, amides of acrylic acid and methacrylic acid)
For example, acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide, diacetone acrylamide, N-( 1,1-dimethyl-3-hydroxybutyl)acrylamide, N-(β-morpholino)
Ethylacrylamide, N-benzylacrylamide,
N-acryloylmorpholine, N-methacryloylmorpholine, N-methyl-N'-acryloylpiperazine, N
-acryloylpiperidine, N-acryloylpyrrolidine, N-acryloylhexamethyleneimine, etc.), alkyl ester acids of acrylic and methacrylic acids (e.g. methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2- ethylhexyl acrylate, decyl acrylate, β-cyanoethyl acrylate, β-chloroethyl acrylate, 2-ethoxyethyl acrylate, sulfopropyl methacrylate, etc.), vinyl esters (such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl lactate, etc.) , vinyl ethers (e.g. methyl vinyl ether, butyl vinyl ether, oleyl vinyl ether, etc.), vinyl ketones (e.g. methyl vinyl ketone, ethyl vinyl ketone, etc.), styrenes (e.g. styrene, methylstyrene, dimethylstyrene, 2.4.6-1- Dimethylstyrene, ethylstyrene, laurylstyrene, chlorostyrene, dichlorostyrene, methoxystyrene, cyanostyrene, dimethylaminostyrene, chloromethylstyrene, vinyl'Rzoic acid, styrene sulfone a, a-methylstyrene, etc.), vinyl heterostyrene Ring compounds (e.g. vinylpyridine, vinylpyrrolidone, vinylisoxazoline, vinylimidasol, etc.), acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, isoprene, chlorobrene, maleic anhydride, itaconic anhydride, citraconic anhydride , vinyl sulfonic acid and the like. ), and 1 other special public official 1977-
Poly-N-vinyl- described in Publication No. 31842
5-Methyl-2-oxazolidinone, -Formula 〇 〇 2
” A polymer of N-vinylamide compound represented by CHN Rr COR2, a wood-philic polymer containing a cationic nitrogen-containing active group described in JP-A-48-42723, a wood-philic polymer containing a cationic nitrogen-containing active group, as described in JP-A-44-2522 Polymers of N-morpholinoalkylalkenoylamides as described,
Copolymer of vinyl alcohol and vinyl pyrrolidone described in Japanese Patent Publication No. 47-20738, Japanese Patent Publication No. 47-20738
A polymer represented by the general formula % formula % described in Japanese Patent Publication No. 49028, a polymer represented by the formula -H1-CHs
, C2H6, -C,H,, -C,H,, R3 is -H, -
CH3, -C, H-C1 old, -C, H,,X /Y
-9515 to 20/80 is shown. ) Acrylic modified polymer of polyvinyl alcohol (degree of modification 17)
%). Particularly preferred scavengers are polyvinylpyrrolidone and copolymers thereof.

The molecular weight of the hydrophilic polymer used in the present invention is preferably 1.000 or more, more preferably 10.000 or more in terms of weight average molecular weight. Even more preferably 50.00
0 to 1.000.000. The layer containing these scavengers is a layer different from the layer containing the optical brightener, and the layer containing the ultraviolet absorber furthest from the support and/or the layer furthest from the support. This layer is provided at a position farther from the support than the far ultraviolet absorber-containing layer.

The scavenger is typically used at a coating weight of 0.05 to 3.0 mg/dm''.

The ultraviolet absorber-containing layer used in the present invention is a layer provided at a position farther from the support than the blue-sensitive silver halide emulsion layer.

Suitable ultraviolet absorbers used in the present invention include benzotriazole compounds represented by the following formula (2).

The biggest ■ 0 ■ K.

In the above formula H, R8, R1 and R1 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group,
Represents nitro or hydroxyl.

Typical specific examples of ultraviolet absorbers represented by the maximum symbol (1) are shown below.

V-1 H V-2 0 ■ V-3 0 ■ V-4 0 ■ V-5 0 ■ V-6 0 ■ C4H, (t) UV-7 0■ UV-a H UV-9 H u　v　-t.

H Uv-・11 0 ■ UV-12 H U V -13 H U V -14 H U V -15 H U V -16 H u v -17 0 ■ U V -18 H u v -19 These benzotriazole-based The compound is designated as
No. 0466, No. 42-26187, No. 48-5496
No. 48-41572 and U.S. Patent No. 3.754
．． It can be easily synthesized by the method described in No. 919, No. 4.220.711, etc.

These ultraviolet absorbers are contained in an amount of about 0.001 to 2 parts by weight per 1 part by weight of the hydrophilic binder contained in the layer.

The blue-sensitive silver halide emulsion according to the present invention has a wavelength of 400n.
The sensitivity at a wavelength of 460 nm (S406) is between that at a wavelength of 460 nm (S4..).

It is a blue-sensitive silver halide emulsion.

In the present invention, sensitivity S 4 at wavelength 460n+a
60 refers to a commercially available interference filter (with a wavelength of 480 nm that provides maximum spectral transmittance between a light source with a known spectral distribution and a silver halide color photographic light-sensitive material).
For example, a combination of Toshiba's interference filter KL-46 and colored glass filter Y-44) is inserted, and sensitometry is performed using a conventional method.

The wavelength that gives maximum spectral transmittance at 460n- is 46On+
If an interference filter that is ++ is not available,
It may also be determined by interpolating from the sensitivity values determined using two types of interference filters sandwiching this. S. . can also be determined by a similar method.

Such a change in sensitivity balance can be produced by variously changing the type and amount of the blue-sensitive sensitizing dye, the composition of the silver halide emulsion, and the shape of the grain size.

The silver halide grains of the present invention have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

The grain size of the silver halide grains of the present invention is not particularly limited, but in consideration of other photographic properties such as rapid processing and sensitivity, it is preferably 0.2 to 1.6 μm1, more preferably 0.
．． It is in the range of 25 to 1.2μ. Note that the particle size can be measured by various methods commonly used in the technical field.

A typical method is Loveland's [Particle Size Analysis Method J
(A', S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122) or Theory of the Photographic Process (co-authored by Mies and James, 3rd edition, published by Macmillan, 1966) ), Chapter 2).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is
It is a coefficient indicating the breadth of the particle size distribution, and is expressed by the following formula % Formula % Here, ri is the particle size on each side of the particle, and ni is the number thereof.

The grain size here means the diameter in the case of spherical /% silver Rorodide grains, or the diameter when the projected image is converted into a circular image of the circumferential area in the case of grains with shapes other than cubic or spherical. represents.

The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble rhodan salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but the method obtained by the simultaneous mixing method is preferable. Further, as a type of simultaneous mixing method, the PAg-chondral double jet method described in JP-A-54-48521 and the like can also be used.

Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, US Pat. No. 4,183,756 and US Pat. No. 4,225.
No. 666, JP-A-55-26589, JP-A-55-4
2737, The Journal on Photographic Science (J, Photogr, Sci,)
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared by the method described in literature such as , 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The /-silver rhodanide grains used in the emulsion of the present invention may be prepared from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, rhodium salts or complex salts, Metal ions can be added to the interior of the particles and/or on the surface of the particles by using iron salts or complex salts, and reduction sensitization can be achieved within the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can give a nucleus.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of /X silver halide grains, or unnecessary soluble salts may be left as they are contained. But that's fine. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The /10 silver oxide grains used in the emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or may be grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

The emulsion of the present invention is chemically sensitized by conventional methods.

In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

As the blue-sensitive sensitizing dye used in the present invention, a compound represented by the following formula (III) is preferably used.

General formula (III) In the formula, -2 and 21 are respectively an oxazole nucleus, a thiazole nucleus, a selenazonyl nucleus, a pyridine nucleus, a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a naphthoxazole nucleus, and a naphthothiazole nucleus. , represents the atomic group necessary to form a naphthoselenazole nucleus, a naphthoimidazole nucleus, or a quinoline nucleus.

R3 and Rm each represent an alkyl group, an alkenyl group, or an aryl group.

xe represents an anion, and Q represents 0 or l.

Next, specific examples of the blue-sensitive sensitizing dye represented by the general formula (III) will be shown, but the invention is not limited thereto.

(III-1) ([1-2) (III-3) (III-4) (III-6) (III =7) jm-8) (III-10) (III-12) (III-13) (m-14) [III-15) (m-17) (Illl-15) ([[-20) In the present invention, the blue-sensitive sensitizing dye represented by formula (1) is Added to particle formation process. Here, the particle forming step includes the period during particle formation and before desalting. It is preferably added during grain growth. Addition during grain growth means that it may be added at any time during nucleation or at any time during the growth of the nucleus, both of which are effective. If it is added at any time during grain growth, a remarkable effect will be brought about.More preferably, it is added after the generation of nuclei.

The blue-sensitive sensitizing dye of the general formula (III) of the present invention has a content of 5 X 10-' mole-2X 10-' mole per mole of silver halide.
It is preferably used in a range of 3 mols, more preferably in the range of 1X10-' mols to 7 X 10-' mols.

The blue-sensitive sensitizing dye of the general formula (III) of the present invention may be added in an additional form at any time after the formation of silver halide grains until coating.

These sensitizing dyes may be added after being dispersed in a water-miscible organic solvent without being dissolved, or they may be added by dispersing them in water or methanol,
It may be added after being dissolved in a water-miscible organic solvent or a mixture of water-miscible organic solvents such as ethanol, acetone, and dimethylformamide.

Furthermore, the blue-sensitive sensitizing dye of the present invention can be used in combination with other sensitizing dyes within a range that does not impair the effects of the present invention. In this case, the two sensitizing dyes may be dissolved separately and mixed before being added, or may be added as separate solutions. There are two addition times (7) Solution 1 may be added at the same time or at predetermined time intervals.

In the silver halide emulsion of the present invention, compounds called antifoggants and stabilizers are added in order to optimally apply chemical sensitization and to prevent a decrease in sensitivity and the occurrence of fog during storage or development of the light-sensitive material. be able to.

These compounds include many heterocyclic compounds and mercapto compounds, including 4-hydroxy-6-methyl-1°3.3a, 7-tetrazaindene, 3-methylbenzothiazole, and l-7enyl-5-mercaptotetrazole. Among these, a mercapto compound represented by formula (S) is particularly preferably used.

General Formula (S) Z, -5M In the formula, zo is a heterocyclic residue, and M is a hydrogen atom, an alkali metal atom, or ammonium.

More preferably, a mercapto compound represented by the following formula [S0] is used.

-Formula [S,],,0-,, In the formula, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings. , M represents a hydrogen atom or a cation.

The mercapto compound represented by the formula [S,] will be described below.

In the general formula [S,], Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings, but Q represents Examples of the heterocycle include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring,
Examples include a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, and a benzoxazole ring.

Examples of the cation represented by M include alkali metals (
Examples include sodium, potassium, etc.), ammonium groups, and the like.

The mercapto compound represented by the general formula [S,] can be further prepared by the following formulas (SA), (SB), (SC) and (SD
) are preferred.

General formula (SA) where RA represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group,
2 represents -NH-, -0- or -S-, and M has the same meaning as M in general formula (S).

General formula (S B) r ■ In the formula, Ar represents, and Rm represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group, or a sulfonamide. represents a group. n represents an integer of 0 to 2. M has the same meaning as M in general formula (S).

In general formulas (SA) and (SB), RA and R
Examples of the alkyl group represented by 11 include methyl group, ethyl group, butyl group, etc., examples of alkoxy groups include methoxy group, ethoxy group, etc., and examples of salts of carboxyl group or sulfo group include sodium salt,
Examples include ammonium salts.

In the general formula (SA), examples of the aryl group represented by RA include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom.

Examples of the acylamino group represented by R8 in the general formula (SB) include a methylcarbonylamino group and a benzoylamino group; examples of the carbamoyl group include an ethylcarbamoyl group and a phenylcarbamoyl group; Examples of the group include methylsulfonamide group and phenylsulfonamide group.

The above-mentioned alkyl groups, alkoxy groups, aryl groups, amino groups, acylamino groups, carbamoyl groups, sulfonamide groups, etc. further include those having substituents.

General formula [SC] Represents. RA is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -5RA.

or represents a heterocyclic group, RAl is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group,
CORA4. or -5OsRAs, RAI and RA3 represent a hydrogen atom, an alkyl group, or an aryl group, and RA4 and RAM represent an alkyl group or an aryl group. M has the same meaning as M in general formula (S).

R AI RAll R1eJ in general formula (SC)
Examples of the alkyl group represented by Rhs*RA4 and RAS include a methyl group, benzyl group, ethyl group, and propyl group, and examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkenyl group represented by RA and RAI include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group.

Examples of the heterocyclic group represented by RA include a 7lyl group and a pyridinyl group.

The above RA, RA1. RAz, RA3. RA4 and RA
The alkyl group and aryl group represented by I, the alkenyl group and cycloalkyl group represented by RA and RAI, and the heterocyclic group represented by RA further include those having a substituent.

General formula [SD] μ In the formula, RA and M each represent the same groups as RA and M in the general formula (SC). Also Rml and R
m2 represents a group synonymous with RAI and RA2 in formula (SC), respectively.

Specific examples of heterocyclic compounds and compounds represented by the formula [S0] are shown below;
The compound represented by
No. 96, JP-A No. 50-89034, Journal on Chemical Society (J, Ches, Soc,) 49
．． 1748 (1927), 4237 (1952), Journal on Organic Chemistry (J, Or
Chem,) 39°2469 (1965), U.S. Patent No. 2,824.001, Journal on Chemical Society, 1723 (1951), JP-A-1987-
No. 111846, British Patent No. 1,275.7 Old No., U.S. Pat. It can be synthesized by

In order to incorporate the compound represented by the general formula [S0] according to the present invention (hereinafter referred to as compound [S0]) into a silver halide emulsion layer containing silver halide grains according to the present invention, water or It may be added after dissolving it in an organic solvent (for example, methanol, ethanol, etc.) which is optionally miscible with the compound.

- The formula (S o) may be used alone, or - the formula [S o
Two or more of the compounds represented by formula (SO) may be used together, or may be combined with other stabilizers or fog suppressants other than the compound represented by the formula (SO).

Compound [S0] is generally added at the end of chemical sensitization of silver halide, but during the formation of silver halide grains, from after the formation of silver halide grains to before chemical sensitization. It is also possible to add it at any time selected from the start of chemical sensitization, during chemical sensitization, at the end of chemical sensitization, and after the end of chemical sensitization in the coating liquid preparation step.

There is no particular restriction on the amount added, but it is usually lXl0-' mol to lxlrho 1 mol per mol of silver halide, preferably lXl0-' mol to lxl0-
It is added in a range of 10-10 mol to I x 10-2 mol.

Although any surfactant may be used in the present invention, a surfactant represented by the following formula (rV) is preferably used.

General Formula (mV) In the formula, one of R21 and R2□ represents a hydrogen atom, and the other represents a group represented by the formula -5o3'M (M represents a monovalent cation). A is an oxygen atom or 2NRfS (
Rls represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ), preferably an oxygen atom.

RlS and R2 each represent an alkyl group having 4 to 16 carbon atoms.

However, the alkyl group represented by R13, R14 or R1s is not substituted with a fluorine atom.

Specific compounds of the anionic surfactant represented by the general formula (IV) include those shown below.
The surfactant represented by IV) is not limited to these.

(IV-1) (IV-2) (IV-3) (IV-4) (IV-5) CH2COOC+oH□ (IV-6) (IV-7) (IV-8) (rV-9) Silver halide photographic light-sensitive materials can be, for example, color negative and positive films, color photographic papers, etc., and may be monochrome or multicolor.

In the case of multicolor silver halide photographic light-sensitive materials, silver halide emulsion layers containing magenta, yellow, and cyan couplers and non-light-sensitive layers are usually formed on a support in an appropriate number and layer order. Although it has a layered structure, the number of layers and the order of the layers may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsions used in the silver halide photographic material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are commonly used in silver halide emulsions. Any silver chloride containing silver chloride of 90 mol % or more is preferably used.

The silver halide emulsion used in the present invention can be prepared by sulfur sensitization method,
Chemically sensitized by selenium sensitization, reduction sensitization, noble metal sensitization, etc.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids of synthetic hydrophilic polymeric sugars such as derivatives, cellulose derivatives, monopolymers or copolymers can also be used.

The silver halide photographic material of the present invention requires additives such as hardeners, color clouding prevention agents, image stabilizers, plasticizers, latex, surfactant matting agents, lubricants, and antistatic agents. It can be used accordingly.

An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.

Example The following examples illustrate the effects of the present invention.

Example 1 Each layer having the structure shown in Table 1 was coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side to form a multilayer paper support. A silver halide color photographic material was prepared. The coating solution was prepared as follows: ◎First layer coating solution Yellow coupler (Y-1) 26.7g, dye image stabilizer (ST-1) IO, Og, dye image stabilizer (S
T-2) 6.7g, stain inhibitor (HQ-1) 0.
Add and dissolve 67 g of ethyl acetate and 6.7 g of a high-boiling organic solvent (DNP), and dissolve this solution in 200 m of a 10% gelatin aqueous solution containing 10% sodium alkylnaphthalene sulfonate (10 m) using an ultrasonic homogenizer. A yellow coupler dispersion liquid was prepared by emulsifying and dispersing the yellow coupler.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution. Further, blue-sensitive silver halide emulsions, ultraviolet absorbers, and optical brighteners were prepared using the combinations shown in Table 2. The hardener is H-1 and H-2 below, and the coating aid is S-1 and S below.
-2 was used.

5-1C, II.

ClIC0OCIIICII Cals■ S-2CHCOOCIIt(CFsCFJa11C11
COOC11! (CF*CF*)all? SO, Na Ca II-2C (CIIaSO*Cl1- C11ri4 [
Preparation method of blue-sensitive silver halide emulsion] The following (liquid A) was added to 1000 m++2 of a 2% gelatin aqueous solution kept at 40°C.
and (Liquid B) were simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and then the following (Liquid C)
and (Solution D) were simultaneously added over 180 minutes while controlling the pH to -7.3 and pH -5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and DH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) NaCI2 3.42
gKBr O,0
Add 3g1120 2
00+5Q (Liquid B) AgN0. 10gH
,0 is added to 200■Q
(Liquid C) NaCQ 102.
Br 1 in 7g
．． Add OgH, O and terrorism 00 m Q (D liquid) 8gNO, 300g Add H, 0 and 600a+
4 After addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85.
μm, coefficient of variation (σ/r) -0.07, silver chloride content 9
A monodisperse cubic emulsion EMP-1 with a concentration of 9.5 mol % was obtained.

The above emulsion EMP-1 was chemically ripened at 50°C for 90 minutes using the following compound, and blue-sensitive silver halide emulsion (E
M-, A-1) were obtained.

Sodium thiosulfate 0.8 g 1 mol Ag
X Chloroauric acid 0.5 mg 1 mol 1
Mol A fixer 5R-56X to-"trultru A
gx sensitizing dye D-15x 10-'mol 1 mol Ag
X Next, blue-sensitive silver halide emulsions EM-A-2 and EM- were prepared in the same manner as EM-A-1, and the spectral sensitivity spectrum was changed by changing the amount and time of addition of sensitizing dye D-1.
A-3 and EM-A-4 were adjusted.

Silver chloride content IO% adjusted in the same way as EM-A-1
A silver chlorobromide silver halide emulsion EM-1 was prepared.

Furthermore, it was adjusted in the same manner as EM-1 to give an average particle diameter of 0.97/a1.
To prepare a highly sensitive silver chlorobromide/% silver halide emulsion EM-2 with a silver chloride content of 10% and a coefficient of variation (σ/γ) of 0.07.

[Preparation method of green-sensitive silver halide emulsion] (Liquid A) and (B
The average particle size was 0 in the same manner as EMP-1 except that the addition time of liquid) and the addition time of (liquid C) and (liquid D) were changed.
, 43 μm, a coefficient of variation (d/r) of 0.08, and a silver chloride content of 99.5 mol %, a monodisperse cubic emulsion EMP-2 was obtained.

For EMP-2, the following compound was used at 55 °C for 12
After 0 minute chemical ripening, green sensitivity/% silver halide emulsion (EM
-n) was obtained.

f: tm acid sodium jJ') 1.5eeg/l#
AgX chloroauric acid 1.0 g/mo #AgX stabilizer 5B-5 (3x IQ-'11 mol AgX sensitizing dye D-2'
4. OX IQ-'tl/l AgX [Preparation method of red-sensitive silver halide emulsion] Change the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D). Except for the same procedure as EMP-1, the average particle size was 0.50 μm,
Coefficient of variation (σ/F) -0.08, silver chloride content 99.5
A monodisperse cubic emulsion EMP-3 with mol % was obtained.

90°C at 60°C using the following compound for EMP-3.
A red-sensitive silver halide emulsion (EM-C
) was obtained.

Sodium thiosulfate 1.8 mg 1 mol 1 mol A-auric acid 2.0 mg 1 mol 1
Mol A fixer 5B-55x 10-'t/l A
gX sensitizing dye D-3a, ox 10-' mol 1 mol Ag DIDP (diisodecyl phthalate) pvp (
Polyvinylpyrrolidone) I-1 Al-2 The treatment was carried out according to the following treatment steps.

[Processing process] Temperature Time color development
35.0±0.3℃ 45 seconds bleach fixing
35.0±0.5℃ Stabilized for 45 seconds 30~
34°0 90 seconds dry 60
~80℃ 60 seconds [color developer 1 pure water
800mff triethanolamine
10g N,N-diethylhydroxylamine Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g1-t Floxene-1,1-diphosphonic acid
1.0g pre-processed diamine tetrah acid
1.0g Catechol-3,5-disulfonic acid disodium salt
1.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g optical brightener (4,4″
-diaminostilbendisulfonic acid derivative)
1.0g potassium carbonate
Add 27g water to make the total amount IQ, pH = 10.10
Adjust to.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 60g ethylenediamine vinegar M 3g ammonium thiosulfate (70% aqueous solution) 100ml ammonium sulfite (40% aqueous solution) 27.5mff Add water to make IQ, potassium carbonate or glacial acetic acid Adjust the pH to 5.7.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1. Ogl-hydroxyethylidene-1,1-diphosphonic acid
2.0g ethylenediaminetetraacetic acid
1'. 0g ammonium hydroxide (20% aqueous solution) 3.0g ammonium sulfite
3.0g optical brightener (4.4''-diTminostilbe7dunesfosnic acid derivative) 1.5g Add water to make 112, and add sulfuric acid or potassium hydroxide to p.
Adjust to H=7.0.

In addition, the sensitivity, whiteness, and stack mark resistance of each sample were evaluated as follows. The results are shown in Table-2.

〔sensitivity〕

Each sample was exposed to blue light, then developed.
Obtained I; Dye image was measured using a PDA-65 densitometer (manufactured by Konica)
Measure the sensitivity by passing it through a blue filter. The sensitivity was expressed as a relative sensitivity with sample 1 set as 100.

[Whiteness]

Each sample was processed unexposed in an automatic processor according to the processing steps described above. At this time, a four-stage countercurrent waterless washing system was used in the stabilizing bath section of the automatic developing machine.

The spectral reflection spectrum of the white portion of each of the obtained samples was measured using a color analyzer (model 607, manufactured by Hitachi).

Reflection density of 440n+s (A
l4. ) was read and used as a measure of whiteness. After running the same automatic developing machine continuously for two weeks, each sample was processed again and the whiteness was measured in the same manner to evaluate the whiteness after running.

[Static mark resistance evaluation]

Each sample was transported 50 times using an automatic printing machine (Printer Nu manufactured by Konica) at a transport speed of 800 sheets/hour under conditions of a temperature of 25° C. and a relative humidity of 20%. Separately, adhesive tape (trade name Nislon No. 360,
After pasting and peeling off the adhesive (manufactured by Building Blocks Chemical), these samples were treated in the treatment process described above.As is clear from Table 2, the samples of the present invention were highly sensitive and did not generate static marks. It is possible to obtain clear color images because of the high whiteness.

In particular, the whiteness after running is good, and such an effect cannot be obtained with comparative samples. Furthermore, it is clear from Sample 1, which was processed by adding a fluorescent brightener only to the processing solution, that this effect is not simply due to fluorescence.

Also, instead of the fluorescent whitening agent of sample 8 (I-363, Cl
Samples 14, 15, and 16, which are the same as sample 8 except that Cl-37) and Cl-38) were used, similarly prevented the generation of static marks, had high sensitivity, and had good whiteness even after the runnige treatment. Image obtained.

Example 2 Same as Sample 8 of Example 1, containing a blue-sensitive silver halide emulsion, an ultraviolet absorber, an optical brightener, a stabilizer for the blue-sensitive emulsion,
Surfactant and sixth layer polyvinylpyrrolidone (PV
Create each sample in which P) was changed in the combinations shown in Table 3,
As in Example 1, sensitivity, whiteness before and after running over time,
Static mark resistance was evaluated.

As is clear from Table 3, the sample of the present invention has high sensitivity,
It also has good whiteness and suppresses static marks. Furthermore, the whiteness after running treatment is also good.

Such an effect was large in Sample 8.17.18 in which a mercapto compound was used as a blue-sensitive emulsion stabilizer.

Moreover, the effect of the present invention was large in Samples 8, 17, 18, 19, 21, and 22 in which the compound represented by the general formula (II) was used as a surfactant.

Example 3 Samples 25 to 31 were prepared by changing the structure of sample 8 of Example 1 as shown in Table 4, and the same physical examination and tests as in Example 1 were conducted together with Sample 1 and Sample 8. .

[Preparation of silver halide emulsion]

Add 2% gelatin aqueous solution 1000+a12 at 70°C to sulfuric acid (
After adjusting the pH to -2.0 using halogen (silver halide solvent) CH.

Furthermore, while maintaining the temperature at 70°C, (Liquid E) and (Liquid F) shown below were simultaneously added over 15 minutes, and then (
Solution G) and solution H were simultaneously added over 70 minutes.

(Liquid E) NaCQ 1.72g
H! Add O and 150mQ (
F solution) Add AgNO3” H!O and 150mff
(G liquid) lr O・8gNa
Add CQ40.9g H,0 and 320m (2
(II liquid) AgNOs
Add 120g+120
5 minutes after the completion of addition of 320 m2, the temperature was lowered to 40°C over 30 minutes, and after desalting was performed in the same manner as EMP-1, the pH was adjusted to -6.0 and the average particle size was 0.
．． Monodisperse cubic silver chlorobromide emulsion EMP- with 9 μm, coefficient of variation (6/r) = 0.09, and silver chloride content of 99 mol%.
I got 4.

For EMP-4, sensitizing dye D-4 (addition amount 7.OX
10-' mol 1 mol AgX)
Chemical ripening was performed in the same manner as in A to obtain blue-sensitive silver halide emulsion EM-D.

EMP-5 and EMP-6 were prepared by adjusting the addition times of (Liquid H) and (Liquid H) and (Liquid G) and (Liquid H) in accordance with the preparation method of EMP-4. The results are shown in the table below.

For EMP-5, sensitizing dye D-5 (addition amount: 4,
OX 10-' mol 1 mol AgX)
- Same as B and i: Then, chemical ripening is performed to create a green-sensitive emulsion EM-
I got an E.

For EMP-6, sensitizing dye D-6 (addition fk: 1
, Ox 10-'truatlAgX)
Chemical ripening was carried out in the same manner as in -C, and the red-sensitive emulsion EM-F was
I got it.

M-2 is 0.18g/la” DBP (dibutyl phthalate) TOP (trioctyl phosphate) TCP (1-licresyl phosphate) TINP
(Triisononyl phosphate) PUA (Acrylic modified copolymer of polyvinyl alcohol) I-3 I-4 HQ-2 ST-5 ST-6 V-I V-2 V-3 V-4 V-5 C12 Shiμ I2 T-7 01st T-8 0■ UH3 to II3 T-9 C11.

α to T-10 A clear color image with good stability and stack mark resistance was obtained.

〔Effect of the invention〕

According to the present invention, it has been possible to provide a silver halide photographic material with improved whiteness, high sensitivity, a large effect of preventing the generation of static marks, and good color reproducibility.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer on a support, at least one layer containing a diaminostilbene-based optical brightener, and the blue There is S_4_0_0/ between the sensitivity at a wavelength of 400 nm (S_4_0_0) and the sensitivity at a wavelength of 460 nm (S_4_6_0) of the sensitive silver halide emulsion.
A halogenated compound characterized in that the following relationship holds: S_4_6_0≦0.7, and the ultraviolet absorber is contained in a layer provided at a position farther from the support than the blue-sensitive silver halide emulsion layer. Silver photosensitive material.