JPS6210648A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent tackiness trouble under high temperature and high humidity, and sweating resistance by incorporating a matting agent and a benzotriazole type compound being liquid at ordinary temperature in at least one of nonphotosensitive hydrophilic colloidal layers located farthest from the support. CONSTITUTION:The silver halide photographic sensitive material is obtained by laminating at least one silver halide emulsion layer and at least one nonphotosensitive hydrophilic colloidal layer on the support, and at least one of said nonphotosensitive hydrophilic colloidal layers located farthest apart from the support contains the matting agent and the 2-(2'-hydroxyphenyl)- benzotriazole type compound liquid at ordinary temperature. When the protective colloid layer comprises one layer, it has a film thickness of 0.1-5.0mum and contains a binder resin in an amount of 0.1-5.0g/m<2>, and when it comprises 2 layers, the upper layer has a film thickness of 0.1-3.0mum and contains a binder resin in an amount of 0.1-3.0g/m<2>, and the lower layer has a film thickness of 0.1-4.0mum and contains a binder resin in an amount of 0.1-4.0g/m<2>, thus permitting deterioration of sharpness under high temp. and high humidity to be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material with excellent sharpness and good storage stability.

[Conventional technology]

In general, photosensitive silver halide emulsions have the property of being sensitive not only to visible light but also to ultraviolet light, and this property has been a major obstacle depending on the purpose and use of the photosensitive material. For example, when photosensitive materials are manufactured or photographed, frictional electrification causes electrostatic discharge during transportation, and the ultraviolet light generated at this time causes static marks on the photosensitive materials. This is not desirable, especially in color photography. The presence of ultraviolet rays during photography sensitized the silver halide emulsion, resulting in a decrease in color reproducibility. In order to prevent troubles caused by such discharge phenomena, ultraviolet absorbing compounds have been added to silver halide photosensitive materials. However, the ultraviolet absorbing compounds used in photosensitive materials have not only physical properties such as absorption spectrum characteristics related to the essential action of absorbing ultraviolet rays and extinction coefficients in the necessary wavelength range, but also characteristics that are contained in the photosensitive materials. In such cases, chemical properties are required that do not adversely affect photographic properties such as sensitivity, or on photographic processing such as manufacturing or development.

Conventionally, many UV absorbers suitable for the above-mentioned photosensitive materials have been proposed. For example, 2-(2°-hydroxy'/-5'
-tert-butylphenyl)benzotriazole exhibits excellent UV absorption properties, but it has been found that when this compound is added to the protective layer of a light-sensitive material, the image quality, particularly the sharpness, in the emulsion layer is slightly deteriorated.

On the other hand, silver halide photographic light-sensitive materials may contain a so-called matting agent in the protective layer located farthest from the support. The purpose was to prevent the adhesion (sticking) phenomenon that occurs when the film is left in contact with the camera for a long period of time or exposed to high heat or high humidity, but from the perspective of image quality, it may deteriorate the sharpness. It turns out.

Further, for example, the above 2-(2'-hydroxy-5'-1c
It has been found that when rt-butylphenyl)penztriazole and a matting agent are included in the protective layer of a light-sensitive material, the sharpness is significantly deteriorated, especially when the material is placed under high temperature and high humidity.

This phenomenon is rarely observed with the ultraviolet absorber alone, nor is it observed with the matting agent alone, and is considered to be a unique phenomenon caused by the coexistence of the ultraviolet absorber and the matting agent.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic material that does not cause adhesion under high temperature and high humidity conditions and has improved perspiration properties. A second object of the present invention is to provide a silver halide photographic material whose sharpness does not deteriorate even under high temperature and high humidity conditions.

(Means for Solving the Problems) According to the present invention, as a result of various studies, the above-mentioned object of the present invention is to provide at least one photosensitive silver halide emulsion layer on a support and at least In a silver halide photographic light-sensitive material consisting of one non-photosensitive hydrophilic colloid layer and laminated together, the non-photosensitive hydrophilic colloid layer α located farthest from the support is in at least one layer. It has been found that this can be achieved by a silver halide photographic material containing a matting agent and a liquid α2-(2'-hydroxyphenyl)-benzotriazole compound at room temperature.

The silver halide photographic material of the present invention is formed by laminating at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on the above-mentioned support. Therefore, the silver halide photographic material of the present invention is formed by laminating only one light-sensitive silver halide emulsion layer and only one light-insensitive hydrophilic colloid layer on a support.
A structure in which a plurality of photosensitive silver halide emulsion layers and a plurality of non-photosensitive hydrophilic colloid layers are laminated on a support, for example, a total of 0 to 2 layers. This includes various layer configurations.

According to the present invention, the non-photosensitive hydrophilic colloid layer that is farthest from the support is generally located further away from the support than the light-sensitive silver halide emulsion layer that is furthest from the support. 1 protective colloid layer'.

Therefore, in the present invention, the term "one non-photosensitive hydrophilic colloid layer" includes all of the non-photosensitive hydrophilic colloid layers, for example, when the non-photosensitive hydrophilic colloid layer is composed of two or more layers.
In addition, when the non-photosensitive hydrophilic colloid layer consists of two layers,
These 2 m are collectively referred to as a non-photosensitive hydrophilic colloid layer unit, and when the above-mentioned two layers of non-photosensitive hydrophilic colloid thin layers are included in a protective colloid layer, they are particularly referred to as a protective colloid layer unit.

Photosensitive materials with a multilayer structure as described above are often found in color photosensitive materials, but in such color photosensitive materials, the non-photosensitive hydrophilic colloid layer furthest from the support is the protective colloid layer. It is preferable that The effects of the present invention, which will be described later, are remarkable in color photosensitive materials.

That is, although the effects of the present invention can be obtained even when the protective colloid layer consists of one layer, it is more preferable to use a protective colloid layer consisting of two layers.

In this way, when the protective colloid layer is composed of two layers,
It is preferable that the protective colloid layer farther from the support, that is, the upper protective colloid layer, contain a matting agent, and the lower protective colloid layer contain an ultraviolet absorber.

When the protective colloid layer is one layer, the film thickness is 6.1μ ~
50μ, preferably 0.3μ to 3.0μ, and the binder # is 0.19/ln' to 5.0? /lri',
Preferably 0.3 trn' to 3.0? /It's quiet.

On the other hand, when the protective colloid layer is composed of two layers, the upper layer has a thickness of 0.1μ to 3.0μ and a binder amount of 0.
1/m'~1 in 3,02 Preferably the film thickness is 0.2μ~
10μ, binder amount 0.2 Y/n? ~1.09
/rr? and the lower layer has a film thickness of 0.1μ to 4.0μ,
The amount of binder is 0.1 to 4.0? /rr? , preferably the film thickness is 04μ to 3.0μ, and the binder amount is 0.4μ.
Ri/ze ~ 3.0g, 6♂.

According to the present invention, a matting agent is contained in at least one layer of the non-photosensitive hydrophilic colloid layer at the position α farthest from the support. As this matting agent, an inorganic matting agent or an organic matting agent is used, and an organic matting agent is preferable.

Examples of the above-mentioned inorganic mantle agents include silica, magnesium oxide, titanium dioxide, and lithium carbonate. Examples of organic matting agents include matting agents insoluble in alkaline processing solutions such as polymethyl methacrylate and cellulose acetate propionate, or copolymers of methacrylic esters and/or acrylic esters and methacrylic acid and/or acrylic acid. A matting agent soluble in an alkaline processing solution such as . Among these, particularly preferred matting agents are polymethyl methacrylate or alkali-soluble matting agents. The average particle diameter of these matting agents is in the range of 0.1μ to 10μ, preferably 0.2μ to 5.0μ.

The amount of matting agent added depends on the type of manting agent, particle size, and protective coating.
．． Although it cannot be said unconditionally depending on the thickness of the id layer, if the amount used is too small, the adhesion resistance will deteriorate, and if the amount is too large, the sharpness will decrease, so the range of use is naturally limited. Therefore, in the case of an inorganic matting agent, 1 my/rr? ~100
'Wz tall, preferably 5 wry/rr? ~50m
y/rr? It is. In addition, in the case of organic matting agents, alkali-insoluble matting agents have a range of 5 m77m'' to 500 my
/rr? , preferably 10 my/m to 1001 nf/r
r? 10 to 1 for alkali-soluble matting agents.
10001 n/m', preferably 50 rq/lr?
~800 m9/m'.

According to the present invention, in at least one of the non-photosensitive hydrophilic colloid layers located farthest from the support, 2-(2'-hydroxyphenyl)-benzoyl, which is a liquid at room temperature, is added together with the above-mentioned matting agent. Contains a triazole compound.

In the present invention, liquid at room temperature means liquid at 15°C.

In this case, the effect of improving sharpness is not sufficient unless it is liquid, and even if it is liquid, UV absorbers other than 2-(2'-hydroxyphenyl)-benzotriazole compounds have no effect of improving sharpness. I can't get it.

By the way, 2-(2'-hydroxyphenyl)-benzotriazole is represented by the following general formula (1).

The liquid ultraviolet absorber used in the present invention has substituents at the 3' and 5' positions of such 2-(2'-hydroxyphenyl)-benzotriazole and, if necessary, at the 5-position. It has the following.

Examples of such substituents at the 3'-position and 5'-position include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, and alkoxycarbonylalkyl groups. Further, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, a hydroxyl group, etc. may be substituted at the 5-position.

Next, typical specific examples of the compound represented by the above general formula (1) will be listed, but the present invention is of course not limited to these.

(Compound example) C< HQ (Sec) 2.
6゜3・

74.8゜5.9゜C5Hn (S11゜C,)i, (Sec) 12゜13゜H C,Ho (iMesu15, Such liquid 2- (2'-hydroxyphenyl)
- The benzotriazole ultraviolet absorber (hereinafter referred to as a light-related ultraviolet absorber) can be added alone to the non-photosensitive aqueous colloid layer unit, or two or more types can be added in combination.

Furthermore, the ultraviolet absorber of the above-mentioned ultraviolet absorber according to the present invention can be added to the non-photosensitive hydrophilic colloid knit. UV absorbers that can be used in combination include:
For example, 2-(2'-hydroxyphenyl)-benztriazole ultraviolet absorbers which are solid at room temperature include those described below.

That is, U.S. Patent No. 2,882,150;
No. 739,971, No. 2,798,067, No. 2
No. 875, No. 053, No. 3,352,681, No. 2, 739.

888, Dowara No. 2,719,162, Dowara No. 2, 80
8, No. 330, thiazolidones as described in Pl. No. 3,365,295, JP-A-47-1053
No. 7, Special Publication No. 48-30492, No. 49-43888
Acrylonitrile compounds as described in Belgian Patent Nos. 833 and 511; British Patent No. 1, 321, 3;
No. 55, benzophenones such as those described in U.S. Pat. No. 3,215,530, as well as U.S. Pat.
No. 1,155, No. 2,748,021, No. 2,6
No. 85,512, No. 2, 763, 566, No. 2,632,701, West German Patent No. 1,023,859
It is also possible to use ultraviolet absorbers such as those described in No.

The added amount of the ultraviolet absorber according to the present invention is 1TtFj
rI? ~1? /m', preferably 〈5''If/rr
r' to 600 TQ/rrt'. Furthermore, when the ultraviolet absorber according to the present invention and other ultraviolet absorbers are used together, the total amount of ultraviolet absorbers is 1 m? /enemy~6oo
Add to correspond to my/i. The ratio of the ultraviolet absorber according to the present invention and other ultraviolet absorbers when used in combination is 1:1 to 1:1, preferably 1:0 to 1:5.
is within the range of

In order to incorporate the ultraviolet absorber according to the present invention into the non-photosensitive hydrophilic colloid layer, the ultraviolet absorber according to the present invention is mixed alone or with other additives, and if necessary, a low boiling point An organic solvent and/or a high boiling point organic solvent is added, and an aqueous solution containing a surfactant and a hydrophilic colloid such as gelatin is mixed with a high-speed rotating mixer.
Emulsification and dispersion is performed using a colloid mill or an ultrasonic dispersion device, and the resulting dispersion is added to a coating solution for a non-photosensitive hydrophilic colloid layer containing a hydrophilic colloid substance, and then applied to a support or onto a support. It is applied onto the coated photosensitive emulsion layer, etc.

The above low boiling point organic solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate,
Cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane, tetrahydrofuran, methyl alcohol,
Ethyl alcohol, fluorinated alcohol, acetonitrile, dimethylformamide,
Dioxane, acetone, methyl ethyl ketone, methyl inobutyl ketone, etc. can be mentioned.

In addition, the above-mentioned high boiling point organic solvent has a boiling point of 1 at normal pressure.
The temperature is preferably 80°C or higher, and specific examples thereof include diethyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexyl adipate,
Dioctyl adipate, dicyclohexyl azelate,
di-2-ethylhexyl azelate, dioctyl sebacate, diisooctyl sebacate, dibutyl succinate, octyl stearate, dibenzyl phthalate,)
IJ-0-cresyl phosphate, diphenyl-mono-o-tert-butylphenyl phosphate, mono-phenyl dilychlorophenyl phosphate, monobutyl-dioctyl phosphate, 2,4-di-n-
amylphenol, 2,4-di-tert-amylphenol, 4-n-nonylphenol, 2-methyl-4-
n-octylphenol, 2,4-di-tert-nonylphenol, N,N-diethylcaprylamide, N,
N-diethyl laurylamide, glycerol tripropionate, glycerol tributyrate, glycerol monolactate diacetate, tributyl citrate,
Acetyl triethyl citrate, di-2-ethylhexyl adipate), di-isooctyl azelate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethyl citrate, tri(2-ethylhexyl) citrate, acetyl tri-n-butyl citrate , di(isodecyl) 4.5-epoxytetrahydrophthalate, oligovinylethyl ether, dibutyl fumarate, polyethylene oxide (+1>
16), glycerol tributyrate, ethylene glycol diprobionate, di(2-ethylhexyl)
Inphthalate, butyl laurate, tri(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, silicone oil, dimethyl phthalate, diethyl phthalate, diethyl phthalate, cyamyl phthalate, di-n-octyl phthalate, Cyamylnaphthalene, triamylnaphthalene, monocaprin, monolaurin, monomyristin, monopalmitin, monostearin, monoolein, cicaprin, dilaurin, diminostin, cybalmitin, distearin, diolein, 1-ste, arrow 2-palmitin, 1,
<Lumito-3-stearin, l-palmito-2-stearin, triacetin, tricaprin, trilauri/, trimyristin, tripalmitin, tristearin, triolein, tripetroserin, trinirudine, trilycyruin, liluodistearin, lyluojirinin, oleogelsin , riluziercin, palmitooleolinoninin, paraffin, linseed oil, soybean oil, eno oil, tung oil, thistle oil, kaya oil, walnut oil, canola oil, poppy seed oil, sunflower oil, catalpa oil, mulberry oil, sugar Drying oils such as flower oil: cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil, lotus oil, kaboku oil, semi-drying oils such as dehydrated castor oil: peanut oil, olive oil, camellia oil, sasanquat oil, tea oil, castor oil, hydrogenated castor oil, almont oil, linseed oil, pen oil, daikon oil, etc.

Further, a compound represented by the formula %formula% or the formula CH2C0OR 中CHlCoo -C-C0OR CH,C0OR (wherein R represents an alkyl group having 1 to 8 carbon atoms) is also used as a high-boiling point organic solvent in the present invention. It can be used as

Among these, esters such as geltaric acid, adipic acid, phthalic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, mazelaic acid, isophthalic acid, terephthalic acid, phosphoric acid, esters of glycerin, paraffin, fluorinated paraffin, etc. It can be conveniently used because it has no adverse effect on photosensitive materials, is easily available, is chemically stable, and is easy to handle. -Octyl phthalate,')-2-
Ethylhexyl phthalate, glycerol tributyrate, glycerol tripropionate, dioctyl sebacate, paraffin, fluorinated halafine, silicone oil, 2.4-tert-amylphenol, 2
．． 4-di-tert-nonylphenol, N,N-diethyldodecanamide, and the like are particularly preferred high-boiling organic solvents.

As the surfactant, anionic surfactants such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate are preferably used.

In the present invention, oil droplets containing an ultraviolet absorber are present in the non-photosensitive hydrophilic colloid layer unit, and the oil droplet density is preferably in the range of 0.01 to 50. Here, the oil droplet density is defined as the ratio of the total volume of oil droplets in each layer in the non-photosensitive hydrophilic colloid layer unit to the total binder volume contained in the layer. (However, the amount of low-boiling organic solvent is excluded) The hydrophilic colloid used in the non-photosensitive hydrophilic colloid layer and the photosensitive silver halide emulsion layer according to the present invention is alkali-treated gelatin or acid-treated gelatin that is commonly used in the art. , enzyme-treated gelatin, etc. can be used, and derivative gelatin such as phthalated gelatin, malonated gelatin, etc. can also be used. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, colloidal albumin, agar, gum arabic dextran, alginic acid, such as acetyl content 19 to 26
Cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, casein, and vinyl alcohol/
Vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl cyanacetate copolymers, polyvinyl alcohol/bolyhinyl pyrrolidone copolymers, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins, and monomers containing vinyl groups. Polyvinylpyridine, a polymer obtained by the polymerization of
polyvinylamine, polyaminoethyl methacrylate,
Polyethyleneimine and the like can also be used.

Hydrophilic colloids preferably used in the present invention include:
Gelatin and various gelatin derivatives.

In the present invention, when the non-photosensitive hydrophilic colloid layer located farthest from the support is a protective colloid layer unit, the upper layer of the layer unit may contain colloidal silica. Specific examples include Rudonox (1J1d IX) AM, As, and LS from DuPont (USA).
, ro + T to 1, H8, etc., and from Nichiryo Kagaku■, Snowtexx 20, Snowtex C1
With product names such as Snowtex N and Snowtex O, Monsando (USA) sells Cyton (Sgt++).
n) (-30, 200, etc., and from Nalco Chemical Company (USA) as Nalcoag (Nnlcag)
Examples include those commercially available under trade names such as 1030 + 1060 and ID-21-64.

The protective colloid waste upper layer of the present invention may contain a slipping agent. Useful materials include higher alkyl sodium sulfate, higher fatty acid higher alcohol ester, carbowanox, higher alkyl phosphoric acid ester, and 7-licon compounds. In particular, U.S. Pat. No. 2.88'2,157, U.S. Pat.
The compounds described in JP-A-51-141623 and the like are particularly effective when used alone or in combination of two or more.

Hardening of the emulsion is carried out according to conventional methods.

The hardeners used are conventional photographic hardeners, such as aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, derivative compounds thereof such as acetals or sodium bisulfite adducts, methanesulfonic acid ester compounds, and mucochlor. Acid or mucohalogen acid compounds, ezexy compounds, aziridine compounds, active halogen compounds, maleic acid imide compounds, active vinyl compounds, carbonimide compounds,
Inoxazole compounds, N-methylol compounds,
Examples include isocyanate compounds, and inorganic hardeners such as chromium ammonium and zirconium sulfate. Among these, compounds that can be preferably used include aziridine compounds, active halogen compounds, and active vinyl compounds.

Silver halide used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material according to the present invention includes silver chloride,
Any of those used in ordinary silver halide photographic emulsions, such as silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be rice grains or fine grains, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111:] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art. This silver halide is generally dispersed in gelatin, but in addition to gelatin, polymers such as polyvinyl alcohol can also be used instead of gelatin or mixed with gelatin. Silver halide emulsions in which the silver halide is dispersed in a suitable binder can be chemically sensitized. They can be done by any conventional method. Namely, activated gelatin, water-soluble gold salt, water-soluble platinum salt, water-soluble palladium salt, water-soluble rhodium salt,
Noble metal sensitizers such as water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines.

Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin chloride alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, a trimethine dye, or a merocyanine dye alone or by using an optical sensitizer such as a merocyanine dye. They can be used in combination (for example, superchromatic sensitization) to optically sensitize.

However, known 2-equivalent and 4-equivalent couplers can be used in the silver halide color photographic light-sensitive material according to the present invention. As the yellow coupler, open-chain ketomethylene couplers can be used, among which benzoylacetanilide type and pivaloylacetanilide type yellow couplers are advantageous.

A specific example of a yellow coupler that can be used is U.S. Patent No. 2.8.
No. 75,057, No. 3,265,506, No. 3.
No. 277.155, No. 3,408,194, No. 3
．． No. 415,652, No. 3,447,928, No. 3,664,841, Japanese Patent Publication No. 13576/1976, Japanese Patent Publication No. 29432/1983, No. 48-66834, No. 4
No. 9-10736, No. 49-122335, No. 50-
No. 28834, No. 50-132926, Patent Application No. 1983-
It is described in No. 145024, etc.

As magenta couplers, compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indacylon, and cyanoacetyl are used. Specific examples of magenta couplers that can be used include U.S. Pat.
No. 600,788, No. 3.061,432, No. 3
, 062,653, 3.127,269, 3,311,476, 3.419,391, 3,519,429, 3.558,319 ,
British Patent No. 3,684,514, British Patent No. 3,888,680, British Patent No. 1,247,493, British Patent No. 1,534,
No. 349, West German Patent Application (OLS) 2.156,111
Belgian Patent No. 769,116, Belgian Patent No. 792,5
No. 25, Special Publication No. 46-60479, Japanese Patent Publication No. 49-29
No. 639, No. 49-111, 631, No. 49-129
No. 538, No. 50-13041, No. 5゜-12293
No. 5, No. 51-20826, No. 52-58533,
It is described in Japanese Patent Application No. 52-80027, Japanese Patent Application No. 52-98876, Japanese Patent Application No. 52-101247, Japanese Patent Application No. 52-104437, etc.

As a colored magenta coupler as a masking coupler, a compound in which an arylazo group is substituted at the active site of a colorless magenta coupler is generally used.
For example, U.S. Patent No. 2,801°171, U.S. Patent No. 2,98
No. 3,608, No. 3, 005.

No. 712, No. 3,684,514, British Patent No. 93
7.621, JP-A-123625, JP-A No. 49-1
Examples include compounds described in No. 31448 and the like.

Additionally, colored magenta couplers of the type described in U.S. Pat. No. 3,419,391, in which the dye is leached into the processing bath by reaction with the oxidation products of the color developing agent, may also be used.

Phenol or naphthol derivatives are generally used as cyan couplers. Specific examples include U.S. Pat. No. 2,423,730, U.S. Pat.
No. 2,801,171, No. 2, 895.

No. 826, No. 3,476.563, No. 3, 73
7.

No. 316, No. 3,758,308, No. 3, 83
9.

No. 044, No. 3,998,642, JP-A-47-3
No. 7425, No. 50-10135, No. 50-2522
No. 8, No. 50-112038, No. 50-117422
No. 50-130441, No. 51-21828,
No. 52-18315, No. 53-52423, No. 53
-105226, No. 53-109630, etc.

As a colorless cyan coupler as a masking coupler, a compound in which an arylazo group is substituted at the active site of a colorless cyan coupler is used, such as those disclosed in U.S. Pat. Nos. 2,521,908 and 3,034,892 No., British Patent No. 1,255,111, Japanese Unexamined Patent Publication No. 1983-22
Examples include compounds described in No. 028 and the like.

Furthermore, U.S. Patent No. 3,476.563 and Japanese Patent Application Laid-open No. 1987-1
Colored cyan couplers of the type in which the dye flows out into the processing bath by reaction with the oxidation product of a color developing agent, such as those described in No. 0135 and No. 50-123341, can also be used.

Further, in order to improve photographic properties, a so-called competing coupler, which forms a colorless dye, may be included.

Further, the silver halide color photographic light-sensitive material according to the present invention includes:
The photosensitive layer and/or other constituent layers (for example, intermediate layer, subbing layer, filter layer, protective layer, image-receiving layer, etc.) may contain various other photographic additives depending on the purpose.

, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salt polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinyl sulfone-based,
Hardening agents such as acryloyl, albodiimide, maleimide, methanesulfonic acid ester, and triazine;
Tone adjusters such as Group 8 metals (e.g. rhodium, ruthenium) or cadmium, thallium; Development accelerators such as benzyl alcohol, polyoxyethylene compounds; Chroman, Claman, bisphenol, phosphite esters image stabilizers; lubricants such as wax, chryselite of higher fatty acids, and higher alcohol esters of higher fatty acids;

It can also be used as a surfactant, as a coating aid, as an emulsifier, as a permeability improver for processing solutions, as an antifoaming agent, or as a leaf material for controlling various physical properties of photosensitive materials, such as anionic, cationic, and nonionic types. Alternatively, each species of both sexes can be used. The mordant is an N-guanylhydrazone compound.

Quaternary onium salt compounds and the like are effective. Antistatic agent L
, TeIri Diacetyl cellulose, styrene barfluoroalkyl phosphoram maleate copolymer.

An alkali salt of a reaction product of a styrene-maleic anhydride copolymer and p-aminebenzenesulfonic acid is effective.

Examples of the color turbidity inhibitor include polymers containing vinylpyrrolidone monomers, polymers containing vinylimidazole monomers, and the like.

Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers.

It is also possible to use colloidal silicon oxide. Acrylic ester is added as a latex to improve film properties.

Examples include copolymers of vinyl esters and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

The silver halide color photographic light-sensitive material according to the present invention contains various photographic additives as described above, if necessary.A silver halide emulsion layer and other constituent layers are coated on a support. Manufactured by Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc. The support is appropriately selected depending on the intended use of each silver halide photographic material.

These supports are subjected to undercoat processing if necessary.

After exposure, the silver halide color photographic material of the present invention can be developed by a commonly used known method.

(Effects of the Invention) According to the present invention, at least one of the non-photosensitive hydrophilic colloid layers located farthest from the support contains a mast agent and a 2-(2'-hydroxyphenyl )-By containing a benzotriazole compound,
It was possible to obtain a silver halide photographic material that does not deteriorate in sharpness even under high temperature and high humidity conditions.

This effect of the present invention is due to the solid 2-(2'-
This cannot be obtained by using a benzotriazole (hydroxyphenyl)-benzotriazole compound, and it is not yet foreseeable that the sharpness will be improved by using the above-mentioned compound according to the present invention in combination with a matting agent. Rarely. What is more, the effect of the present invention is surprising, in that even under high temperature and high humidity conditions, fresh brass does not deteriorate by 1 degree.

Example 1 Coated samples 1 to 15 were prepared by sequentially providing layers having the compositions shown below on a subbed cellulose acetate film support from the support side. In this example, the amounts of silver halide and colloidal silver are shown in terms of metallic silver.

(Sample-1) Layer 1: Antihalation layer black colloidal silver 0.297m2, gelatin 71.797m2
It has 2. Film thickness: 125 μm Layer 2: Intermediate layer: gelatin 1.0! /m”.

Film thickness: 0.75 μm Layer 3: Red-sensitive, low-g silver halide emulsion layer Core-shell type, red-sensitive, low-sensitivity with an average grain size of 0.5 μm, containing an average of 5 moles of silver iodide in a core of 10 moles and a shell of 2 moles. Silver iodobromide emulsion 1.6 f/m'', gelatin 1.79/m?, 0.075 mol of the following coupler C-1 per mol of silver, 0.005 mol per mol of coupler CC-1. , the following DI
The R compound D-1 is contained in an amount of 0.004 mol per mol of silver.

Film thickness: 2.75 μm Layer 4: Red-sensitive, high-sensitivity silver halide emulsion layer Red-sensitive, high-sensitivity silver iodobromide emulsion containing 5.5 mol of silver iodide and having an average grain size of 0.8 μm, 1.1 fhr? , gelatin 1. Of/rrr,
0.004 mol of coupler C-1 per mol of silver, 0.013 mol of coupler C-2 below per mol of silver, 0.003 mol of coupler CC-1 per mol of silver, Contains 0.002 mole of DIR compound D-1 per mole of silver. Film thickness 1.2 μm0 layer 5; middle layer containing gelatin 0.6 t/m”.

Layer 6 with a film thickness of 0.45 μm; green sensitivity, low sensitivity silver halide emulsion layer containing silver iodide in a core of 10 mol%, a shell of 2 mol%, and an average grain size of 0.5 μm, with an average grain size of 0.5 μm. Sensitivity Silver iodobromide emulsion 1.3'j/ni-, gelatin 1.6 f/rr?
, the following coupler M-1 in an amount of 0.055 mol per mol of silver, the coupler CM 1 in an amount of 0.014 mol per mol of silver, and the following DIR compound D-2 in an amount of 0.05 mol per mol of silver.
Contains 0.004 mol.

Film thickness: 2.7 μm Layer 7: Green-sensitive, high-sensitivity silver halide emulsion layer: 1.097 m2 of green-sensitive, high-sensitivity silver iodobromide emulsion with an average grain size of 0.8 μm, containing 5.5 mol of silver iodide, and 0 gelatin. .89/ni',
The following coupler M-1 is 0.016 mol per mol of silver, the coupler CM-1 is 0.005 mol per mol of silver,
Contains 0.002 mole of DIR compound D-2 per mole of silver. Film thickness 1.3μmN8; middle layer gelatin 0.6! /m'.

Film thickness: 0.45μm0 Layer 9: Yellow filter, yellow colloidal silver layer: 0.1K, gelatin: 0.72/I,
Anti-fouling agent HO-10,06ri/rr? , contains.

(HO-1 is added as an emulsified dispersion) Film thickness: 0.6 μm Layer 10: Blue-sensitive, low-sensitivity silver halide emulsion layer core: 10 mol%, shell: 2 mol%, average grain size, including silver oxide: 5 mol% 0.5μ? n core-shell type blue-sensitive low-sensitivity silver iodobromide emulsion 0.5't/rr? , gelatin 2.0 y/m”,
The following coupler Y-1 was contained in an amount of 0.34 mol per mol of silver. Film thickness: 3.1 μm0 Layer 11: Blue-sensitive, high-sensitivity silver halide emulsion layer Blue-sensitive, high-sensitivity silver iodobromide emulsion containing 7 mol of silver iodide and having an average grain size of 0.8 μm. /rr? , gelatin 1.2 t/rr? ,
The following Turnip 9-Y-1 was contained in an amount of 0.10 mol per mol of silver.

Film thickness 14μtn0 Layer 12; protective colloid layer Gelatin 2.0 f/rr? , contains.

Film thickness: 1.5μ7710 The materials used to prepare sample 1 are as follows.

Q-1 (rH SuH Coupler C-1 Coupler C-2 Coupler Y-1 In addition, during coating, G2-ethyl/l/
Sodium hexfursulfosuccinate was added, and 1,2-bis(vinylsulfonylethane) was added as a hardening agent to each layer.

In addition to the above Sample-1, the 1st to 11th layers had exactly the same composition as Sample-1, and the 12th layer, the protective colloid layer, had the composition listed in Table 1 below. The ultraviolet absorbers and high boiling point solvents listed in Table 1 are the following compounds.

V-1 V-2 V-3 H3 V-4 V-5 C,,H.

V-6 V-7 0P C2H.

Seika 2H5 NP H Test piece of specimen 1 to 15 (3.5mX 14α
) was stored unexposed in an atmosphere at 50°C and 80°C for 3 days, and then exposed to white light by placing it in close contact with a transparent rectangular wave chart, along with a sample that was not subjected to the same treatment, and subjected to the following treatments. The process yielded a sample with a dye image.

Development process (38℃) Processing time Color development・・・・・・・・・・・・・・・・・・・・・
・・・・・・3 minutes 15 seconds bleaching・・・・・・・・・・
・・・・・・・・・・・・・・・6 minutes 30 seconds water
Washing・・・・・・・・・・・・・・・・・・・・・
・・・3 minutes 15 seconds Fixed・・・・・・・・・・・・
・・・・・・・・・・・・・・・6 minutes 30 seconds washing・・
・・・・・・・・・・・・・・・・・・・・・・・・－
Stable bath for 3 minutes and 15 seconds...
・・・・・・・・・1 minute 30 seconds In each processing step,
The composition of the treatment liquid used was as follows.

Color developer composition: 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.757 anhydrous sodium sulfite 425f hydroxylamine sulfate 2. O7 Anhydrous potassium carbonate 37.5 9 Sodium bromide
1.3f Trisodium nitrilotriacetate (monohydrate) 2.5f
Potassium hydroxide 1.02 Add water to make 1i and adjust to PI (10.0).

Bleach solution composition: Ethylenediaminetetraacetate iron ammonium salt 10
0. Or ethylenediaminetetraacetic acid diammonium salt 10.0? ammonium bromide
150.02 Glacial acetic acid 10. (1 Add water to make 1ρ and adjust the pH to 5.Q.

Fixer composition: Ammonium thiosulfate 50% aqueous solution 162ml! anhydrous firi, e sodium 12
．． Add 4ml water to make IQ and adjust to p)(6,5).

Stable bath composition: Formalin 37T aqueous solution 5.0m/Konidagusu (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5 ml water to make one flood.

Table 2 shows the results of measuring the sharpness of the obtained color images.

The sharpness in the table below was measured using a microdensitometer and is expressed as the MTE value of magenta and cyan images at a frequency of 30 lines/.

In addition, the surfaces of the test pieces of Samples 1 to 15 were brought into close contact with a cellulose triacetate base, and a load of 5002 was applied, and the test pieces were left in an atmosphere of 50° C. and 80% pH for 2 days to evaluate their adhesion resistance. The evaluation result is expressed as the area ratio where "<sticking" occurs, so 0% is good and 10
0% indicates a defective state.

The results obtained are shown below.

In addition, the test pieces of samples 1 to 15 were tested at 23°C, 20°C, pH
The humidity was adjusted under the same conditions, and a static mark generation test was conducted under the same conditions. The results are shown in Table 2.

This static mark generation test involves fixing an unexposed test piece on a flat surface on a desk with the emulsion side facing up, pressing the rubber side of a weight with a rubber sheet pasted onto the emulsion side, and then The peeled test piece was treated in the same manner as the sharp sample, and the extent of static marks generated was determined.

The extent of the static occurrence was evaluated in the following five stages. (Create a reference sample for comparison and compare) A: No static marks occur B: A little bit of 〃 occurs C: 〃
1) : // occurs significantly E
As shown in the table above, the silver halide photographic material containing the matting agent and the ultraviolet absorber which is liquid at room temperature according to the present invention in the protective colloid layer has problems in preserving color images. It can be seen that the deterioration of sharpness after printing is very small and the adhesion resistance is also good.

Example 2 The 1st to 12th layers were prepared in exactly the same manner as Sample-1, and the 13th and 14th layers having the compositions shown below were coated thereon.

13th layer: Protective colloid layer lower layer Contains 15% gelatin.

Film thickness 1.1 μm 14th layer: Protective colloid layer upper layer gelatin 0.5 f/rr? Contains. Film thickness 0.4μ
m1 Next, Samples 17 to 28 were prepared in exactly the same manner as Sample 16 except that the 13th layer and the 14th layer were configured as shown in Table 3 below.

Each of the obtained samples was treated in exactly the same manner as in Example 1, and the results are shown in Table 4 below. It can be seen that the silver halide photographic material containing the ultraviolet absorber exhibits very little deterioration in the sharpness of color images after storage, and also has good adhesion resistance.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer layered on a support, the most It is characterized by containing a matting agent and a 2-(2'-hydroxyphenyl)-benzotriazole compound that is liquid at room temperature in at least one of the non-photosensitive hydrophilic colloid layers located apart from each other. Silver halide photographic material.