JPH0650375B2 - Photographic material - Google Patents

Description

The present invention relates to a photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material.

(Prior Art) Color photosensitive materials for printing, slides, photography, instant photography, etc. are exposed to various environmental conditions during the manufacturing process, during photographic processing after photography, and after photographic processing. The gelatin-based film forming the light-sensitive material may not be able to maintain an optically uniform film and may cause fine irregularities on the surface, resulting in a decrease in the light transmittance of the film.

When such a phenomenon occurs, after the completion of the photograph, the beauty of the image is significantly impaired, and the designed performance cannot be sufficiently exhibited.

In a color light-sensitive material in which at least one of the hydrophilic colloid layers contains a large amount of an oil component, and the hydrophilic colloid layer adjacent to this layer contains no oil component or contains a relatively small amount of oil component, each layer contains a surrounding oil layer. The above phenomenon is particularly likely to occur because the layer does not expand and contract uniformly with respect to changes in environmental conditions, that is, temperature, humidity, pH of the treatment liquid, salt concentration, etc.

Therefore, in a multi-layer color photosensitive material consisting of a gelatin film containing a large amount of oil component, a uniform film surface is maintained during all processes of manufacturing the photosensitive material, photographing, photo processing, and storing the photograph after processing. In order to obtain a high quality photograph, it was necessary to finely control the oil component / gelatin ratio of each layer so as not to largely change between layers.

However, in particular, including a large amount of the oil component in the outermost surface of the light-sensitive material causes a failure such as leaching during the manufacturing process of the oil component, and the outermost surface layer substantially suppresses the oil component to a low level, or Or, I was in a situation where I could not enter.

In order to solve this problem, the oil component in the light-sensitive material is reduced, the salt concentration in photographic processing is controlled, the temperature of the processing bath is controlled, the drying temperature after processing is controlled, or An attempt was made to cover the sensitive material afterwards with a special protective film so as not to directly expose it to the surrounding atmosphere.

It has also been attempted to add polyvinyl alcohol to the hydrophilic colloid layer to change the physical and mechanical film characteristics.

(Problems to be Solved by the Invention) Among the above-mentioned attempts, the former method is insufficient in that the quality of the photograph is kept high and other harmful effects are not caused, and it is complicated and economically good. It was not there.

In addition, in the latter method using polyvinyl alcohol, not only the balance between the layers is improved, but also the photographic density is lowered, and unevenness due to a non-uniform film is generated on the surface.

Therefore, an object of the present invention is to provide a photographic light-sensitive material which gives a beautiful image by greatly improving the above problems. Another object of the present invention is to improve the adhesion between layers in a photographic light-sensitive material to provide a photographic light-sensitive material having no interlayer peeling during the manufacturing process of the light-sensitive material, the treatment process, and after the treatment. Another object of the present invention is to provide a light-sensitive material which gives a photograph having a beautiful gloss under various environments that have undergone high-temperature rapid processing and subsequent high-temperature drying.

(Means for Solving Problems) As a result of intensive studies, the present inventors have found that the above-mentioned object is to provide a photographic light-sensitive material in which at least two hydrophilic colloid layers are coated on a support. At least one of the hydrophilic colloid layers contains an oil component, and this layer or a hydrophilic colloid layer adjacent to this layer is a protective layer, and the protective layer contains a polyvinyl alcohol polymer as one component. , A water-soluble or water-dispersible block copolymer containing a polymer having an ionic group as another component (hereinafter referred to as "block polymer used in the present invention"), gelatin constituting the protective layer and the block 0.5 of total polymer (solid content)
It has been found that a photographic light-sensitive material characterized by being contained in an amount of up to 40% by weight can effectively achieve this.

The photographic light-sensitive material of the present invention will be described in detail below.

A hydrophilic colloid containing an oil component of a photographic light-sensitive material obtained by coating at least two hydrophilic colloid layers on at least one side of a support, and a hydrophilic colloid containing a block copolymer used in the present invention. The inter-layer relationships with the layers are illustrated below, but the present invention is not limited to these.

An oil component is contained in the hydrophilic colloid layer above the photosensitive layer farthest from the support, and a protective layer (hydrophilic colloid layer) containing the block copolymer used in the present invention is further provided on this layer. .

Including an oil component in the photosensitive layer (hydrophilic colloid layer),
The block copolymer used in the present invention is contained in an intermediate layer, a protective layer, or another hydrophilic colloid layer adjacent to this layer.

The hydrophilic colloid layer containing the dye-donor compound contains an oil component, and the hydrophilic colloid layer adjacent to this layer contains the block copolymer used in the present invention.

Including an oil component in the intermediate layer (hydrophilic colloid layer),
In addition, the hydrophilic colloid layer adjacent to this layer contains the block copolymer used in the present invention.

Among them, the block copolymer used in the present invention is most effectively contained in the protective layer of the color light-sensitive material.

The block copolymer used in the present invention is used in an amount of 0.5 to 40% by weight based on the total (solid content) of gelatin and the block copolymer, which is the main binder constituting the hydrophilic colloid layer. Preferably, further 2 to 10% by weight
It is particularly preferable to use the ratio of If the content of the block copolymer is smaller or larger than this, the degree of improvement of the surface gloss is small.

Examples of gelatin that can be used in the present invention include lime-processed gelatin, acid-processed gelatin, and "Journal of Japan Society for Science and Photography" (Brll. So.
c.Sci.Phot.Japan) No. 16, page 30 (1966), enzyme-treated gelatin, or derivative gelatin such as phthalated gelatin and malonated gelatin can be mentioned. However, it is preferable to use acid-treated gelatin.

On the other hand, the amount of the oil component varies considerably depending on the type of oil, so that it can be used in a wide range of 10 to 200% by weight of gelatin constituting the hydrophilic colloid layer.

The block copolymer used in the present invention can be produced by any method, but is radical-polymerized in the presence of a polyvinyl alcohol-based polymer having a mercapto group at the terminal as described in JP-A-59-189113. It is preferably produced by radical polymerization of a monomer having a possible ionic group.

The method for producing a polyvinyl alcohol-based polymer having a mercapto group at the terminal is described in the above-mentioned publication,
Further details are described in JP-A-59-187003.

Further, as the monomer having a radically polymerizable ionic group, a carboxyl group, a sulfate group, or an ionic group,
A vinyl-based monomer having a group such as a sulfonic acid group or a phosphoric acid group that provides compatibility with gelatin, for example, acrylic acid,
Methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2
-Acryloyloxyethyl phosphoric acid, vinyl sulfuric acid, vinyl sulfonic acid, 2-acrylamido propane sulfonic acid, p-styrene sulfonic acid and their metal salts or ammonium salts can be mentioned.

By a homopolymer or copolymer of the above-mentioned monomer having an ionic group or a copolymer of these monomers and other radically copolymerizable nonionic monomers,
A polymer with ionic groups is formed.

Examples of the radical copolymerizable nonionic monomer include olefins (eg, ethylene, propylene, isobutylene, etc.), halogenated olefins (eg, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, etc.), vinyl esters ( For example, vinyl formate, vinyl acetate, vinyl propionate, etc.), acrylic acid or methacrylic acid ester [eg methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate) , Dodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc.], acrylamide-based monomers (eg, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, etc.), styrene-based Nomar (e.g. styrene, alpha-
(Methylstyrene etc.), N-vinylpyrrolidone and the like.

The polyvinyl alcohol-based polymer preferably contains a vinyl alcohol component in an amount of 50 mol% or more, more preferably 7%.
The content is 0 mol% or more, and the ionic monomer and nonionic monomer listed above may be included as other components.

The amount of the ionic group in the ionic polymer is preferably at least 0.5 mol%, more preferably 1 mol% or more, particularly preferably 2 mol in order to have water solubility or water dispersibility. % Of ionic groups.

The weight ratio (A / B) of the polyvinyl alcohol polymer component (A) to the polymer component (B) having an ionic group in the block copolymer used in the present invention is not particularly limited, When it is about 0.2 to 50, more preferably 0.3 to 40, and particularly preferably 2 to 10, compatibility with gelatin is excellent and the object of the present invention can be effectively achieved. The molecular weight of this block copolymer is preferably 10,000 to 100,000.

The oil component used in the present invention is one that can be dispersed as droplets in the hydrophilic colloid layer. Oil droplet particles that are liquid at room temperature and are substantially insoluble in water are preferable. The size of oil droplets is generally 0.01 to 20 μm, but the typical average particle size is 0.1 to 10 μm.

There are various photographic additives useful as such oil components, for example, ultraviolet absorbers, organic solvents for dispersion, color mixing inhibitors, color couplers, anti-fading agents, lubricants, surfactants and the like. I can name it.

Specific examples of the liquid ultraviolet absorber are disclosed in JP-A-57-11.
2- (2'-hydroxyphenyl) benzotriazole compounds described in No. 42975, JP-B-55-36984, U.S. Pat. Nos. 3,794,493, 4,518,686 and the like can be mentioned. .

The 2- (2′-hydroxyphenyl) benzotriazole compound preferably has a melting point of 15 ° C. or lower.

The 2- (2'-hydroxyphenyl) benzotriazole compound which is liquid at room temperature is preferably selected from those represented by the following general formula (I).

In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ₃ represents a hydrogen atom, a chlorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, Or represents a hydroxyl group.

The compound of the general formula (I) is more preferably selected from the compounds represented by the following general formulas (II) to (VI).

In the formula, R ₄ represents a methyl, ethyl or propyl group,
R ₅ represents a secondary alkyl group having 4 to 10 carbon atoms, and R ₆
Represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 8 carbon atoms.

In the formula, R ₇ , R ₈ and R ₉ each have 4 to 10 carbon atoms.
Represents an alkyl group. However, at least one of these groups represents a secondary alkyl group.

In the formula, R ₁₀ represents a secondary or tertiary alkyl group having 1 to 8 carbon atoms. X represents an alkylene group having 1 to 6 carbon atoms,
R ₁₁ represents an alkyl group having 1 to 12 carbon atoms, R ₁₂
Is synonymous with R ₆ .

In the formula, R ₁₃ and R ₁₄ each represent a secondary or tertiary alkyl group having 4 to 10 carbon atoms, and R ₁₅ has the same meaning as R ₆ .

In the formula, R ₁₆ represents a secondary alkyl group having 4 to 10 carbon atoms, R ₁₇ represents an alkyl group having 1 to 10 carbon atoms, and R _17
18 has the same meaning as R ₆ .

Specific examples of the compound included in the above general formula (I) are listed below.

These ultraviolet absorbers which are liquid at room temperature can be contained in the hydrophilic colloid layer alone or in combination of two or more kinds. Further, a UV absorber which is liquid at room temperature and a UV absorber which is solid at room temperature may be used in combination. Examples of UV absorbers that are solid at room temperature include US Pat. No. 4,518,68
Other 2- (2'-hydroxyphenyl) benzotriazole-based UV absorbers such as those disclosed in No. 6 can be mentioned.

The amount of the total ultraviolet absorber that can be used in the present invention is 0.1 to
Preferably 5 g / ^{m 2,} especially 0.5 to 2 g / ^{m 2} is preferred.

As the organic solvent for dispersion, those having a boiling point of about 175 ° C. or higher are preferable. Examples of such compounds include US Pat. Nos. 2,322,027, 2,533,514 and 2,882,157. 2,353,262, 3,676,142, 3,700,454, JP-B-46-23233, JP-A-50-82078, 51-27921, 51-141623. , British Patents 958441 and 1,222,753.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoates (2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.) ),
Aliphatic carboxylic acid esters (dioctyl azelate,
Glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc., aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) ) And the like.

As an example of the liquid color mixture, various hydroquinone derivatives (mixtures) can be selected. More specifically, two tertiary alkyl groups having 15 carbon atoms disclosed in British Patent No. 2,005,040B are 2,5 of a benzene ring.
Alternatively, a mixture of hydroquinone compounds substituted at the 2,6 position, a secondary dodecylhydroquinone isomer mixture described in US Pat. No. 3,700,453, and other 2 described in US Pat. No. 4,366,236. It can be chosen from among acylhydroquinone derivative mixtures.

Examples of the lubricant include higher alkylsulfate soda, esters of higher fatty acids and higher alcohols, high molecular weight polyethylene glycols, higher alkyl phosphates, and silicon compounds as described in JP-B-56-8346.

The liquid surfactant used as an antistatic agent or a coating aid can be selected from alkylene oxide derivatives such as polyethylene oxide and polypropylene oxide.

Specific examples of the alkylene oxide derivative include polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines, or Amides,
Examples thereof include polyethylene oxide adducts of silicone.

Liquid couplers and anti-fading agents can be obtained by selecting compounds that do not crystallize from compounds of a known type, or those that do not crystallize even if they crystallize.

Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxy. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Also,
A metal complex represented by (bissalicylaldoximato) nickel complex and (bisN, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
As described in US Pat. No. 4,268,593,
A compound having both partial structures of hindered amine and hindered phenol in the same molecule gives good results. Further, in order to prevent the deterioration of the image of the magenta dye, particularly the deterioration by light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether described in JP-A-55-89835. The chromans given give favorable results.

The block copolymer used in the present invention is preferably contained in the protective layer or the outermost layer. Although there are various embodiments of the light-sensitive material having such a layer structure, it is most preferable to incorporate a block copolymer in the protective layer or the outermost layer of the light-sensitive material having the following structure. That is, it has a silver halide emulsion layer containing a ketomethylene type yellow coupler and a silver halide emulsion layer containing a 5-pyrazolone type or pyrazoloazole type magenta coupler on a reflective support, A silver halide emulsion layer containing a phenol or naphthol type cyan coupler is provided on the far side, and the first non-photosensitive layer is provided adjacent to the silver halide emulsion layer containing the cyan coupler and on the side opposite to the support. Further, a second non-photosensitive layer is provided on the support side, and at least the first non-photosensitive layer is solid or liquid at room temperature.
It is a photosensitive material containing one or more kinds of (2'-hydroxyphenyl) benzotriazole type ultraviolet absorbers. The ultraviolet absorber contained in the second non-photosensitive layer is 2- (2 '
It may be a -hydroxyphenyl) benzotriazole compound or another ultraviolet absorber. 2-
If the (2'-hydroxyphenyl) benzotriazole compound is not an oil component, or even if it is an oil component, it can be dissolved in the above-mentioned high boiling point solvent and dispersed in the hydrophilic colloid. Further, a protective layer can be further provided on the first non-photosensitive layer.

Regarding the layer structure of such a light-sensitive material and the couplers and ultraviolet absorbers used therein, JP-A Nos. 58-208745, 58-209734, 58-211147, and 5-58 are disclosed.
8-209735, 58-214152 (U.S. Pat. No. 4,518,686), 58-221844 and the like.

In another embodiment, when a non-photosensitive hydrophilic colloid layer is applied as the outermost layer as described in JP-B-56-8346, a plurality of non-photosensitive hydrophilic colloid layers are applied. A plurality of layers, and at least one layer of the plurality of layers contains oil drops, and the density of the oil drops of the outermost layer of the plurality of layers is determined by the density of the individual oil drops of the plurality of layers. A light-sensitive material having a non-light-sensitive hydrophilic colloid layer adjusted so as not to be maximum can be applied to the present invention.

The term "oil drop density" as used herein is defined as the ratio of the total volume of oil drops added to the non-photosensitive hydrophilic colloid layer to the total binder volume contained in the non-photosensitive hydrophilic colloid layer, and is hereinafter expressed as oil / binder. The thickness of the outermost layer applied in this embodiment is generally 0.2 to 5 µ, preferably 0.5 to 3 µ.

The preferable density of the oil droplets in the outermost layer is the kind of the oil droplets,
Depending on the size and the kind and properties of the binder in the coated non-photosensitive hydrophilic colloid layer or the dry state of the photosensitive material containing the non-photosensitive hydrophilic colloid layer, oil / binder = 0.3 or less. Is preferable, and oil / binder = 0.15 or less is particularly preferable.

In another embodiment to which the present invention is applied, at least one silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer are formed on a support as described in JP-B-57-9053. In a silver halide photographic light-sensitive material having a protective layer, the protective layer is composed of a plurality of non-photosensitive hydrophilic colloid layers, at least one layer of which contains oil droplets, and a matting agent is added to the outermost layer of the protective layer. A silver halide photographic light-sensitive material containing the outermost layer, wherein the film thickness of the outermost layer is 1/4 or less of the average particle size of the matting agent.

Matting agents are silica, magnesium oxide, titanium dioxide,
Inorganic substances such as calcium carbonate, polymethylmethacrylate, cellulose acetate propionate or alkali-soluble porous polymer particles composed of acrylic acid and methyl acrylate as described in JP-A-51-135958 The organic substance can be used, and the particle size is preferably about 0.1 to 20 μm, and particularly preferably 0.5 to 10 μm. In a further preferred embodiment of the present invention, the matting agent is polymethylmethacrylate or silica having an average particle size of 1-8 .mu.m.

The thickness of the protective layer in this embodiment is usually in the range of 0.1 to 5 μ, but preferably 0.5 to 3 μ. The film thickness of the outermost layer of the protective layer in this embodiment varies depending on the kind of binder, the particle size of the matting agent and the intended degree of matting, but is generally 3 μm or less, particularly preferably 1 μm.
is μ.

It is preferable that the density of the oil droplets in the outermost layer of the plurality of layers constituting the protective layer does not exceed 0.2 with respect to the binder volume. It is preferable that the protective layers other than the outermost layer contain oil droplets having an oil droplet density of 0.1 or more, particularly 0.2 to 0.
A range of 8 is more preferable.

The density of oil droplets in this embodiment is defined as the ratio of the total volume of oil droplets added to the non-photosensitive hydrophilic colloid layer to the total binder volume of the layer.

Further, as another embodiment to which the present invention is applied, as described in JP-B-60-24456, at least one light-sensitive silver halide emulsion layer and an outermost layer are provided on the same side of a support. In a silver halide photographic light-sensitive material having a non-photosensitive hydrophilic colloid layer (protective layer) composed of two layers as a layer, in the non-photosensitive hydrophilic colloid layer, an oil is provided in a layer outside the support. The inner layer of the non-photosensitive hydrophilic colloid layer has a ratio of the film thickness of the inner layer to that of the non-photosensitive hydrophilic colloid layer of 1 It is a silver halide photographic light-sensitive material characterized by being 0.5 or more.

In this embodiment, the oil droplets contained in the upper layer of the non-photosensitive hydrophilic colloid layer (protective layer) preferably have an oil droplet density of 0.1 to 0.4 with respect to the binder volume.

The fine particle powder in the lower layer of the non-photosensitive hydrophilic colloid layer (protective layer) in this embodiment means that the average particle diameter of the organic or inorganic compound is 0.005 μ, and particularly preferably 0.0.
2 to 3.0 μ.

These fine particle powders are organic or inorganic matting agents and polymeric latex and colloidal silica and the like used in the art.

Specific examples of the organic compound include copolymers of esters of acrylic acid or methacrylic acid, cellulose acetate propionate, polystyrene and the like. As the inorganic compound, silver halide, strontium sulfate, barium sulfate, calcium carbonate, SiO ₂ (silica), Zn
Examples thereof include crystalline oxides such as O, TiO ₂ , Al ₂ O ₃ , MgO, and BaO, or composite oxides thereof. Examples of silver halides include silver bromide, silver chloride, silver iodobromide, and chlorobromide. Any of those commonly used in silver halide photographic emulsions such as silver and silver chloroiodobromide are included.

Particularly preferred as the fine particle powder in this embodiment is silicon dioxide (silica), which may contain alumina or sodium aluminate as a minor component. In addition, water is mainly used as a dispersion medium, and colloidal silica dispersed in water is also included. Furthermore, inorganic substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide are added to these colloidal silica as alkaline components. Also included are those containing salts or organic salts such as tetramethylene ammonium ion as a stabilizer.

The amount of the fine particle powder used in the present invention is not particularly limited, but is 3 to 50% based on the weight of gelatin in the lower layer of the non-photosensitive hydrophilic colloid layer (protective layer) containing the fine particle powder, and the coating amount is 0.02 to 0. 0.5 g / m ² is preferred.

The thickness of the non-photosensitive hydrophilic colloid layer (protective layer) composed of two layers in this embodiment is not particularly limited as to the total film thickness, and the thickness of the protective layer lower layer is the protective layer. The effect appears as it becomes thicker than the upper layer,
Particularly preferably, the ratio of the thickness of the lower layer of the protective layer to the thickness of the upper layer of the protective layer is 1.5 or more.

In this embodiment, the upper layer of the non-photosensitive hydrophilic colloid layer (protective layer) composed of two layers constitutes a substantial surface layer of the silver halide photographic light-sensitive material, and is composed of silica, titanium dioxide and magnesium oxide. A matting agent composed of such an inorganic substance or an organic substance such as polymethylmethacrylate or cellulose acetate propionate may be contained. In addition, it may contain dispersed colloidal silver and is also described, for example, in US Pat. No. 3,050,391.
No. 3,140,179, etc., may contain substantially undeveloped fine grain silver halide. Furthermore, in the lower layer of (protective layer), (protective layer)
It may include oil droplets added to the upper layer.

At least one layer of the non-photosensitive hydrophilic colloid layer of the above-mentioned embodiment can contain the block copolymer used in the present invention. Also, the previously mentioned Japanese Patent Publication Sho 56-83.
You may use together with the organic fluoro compound described in No. 46 and 57-9053.

In the present invention, various color couplers can be used as a dye-donor compound to obtain a color image. Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and closed or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are Research Disclosure (RD) 17643 (December 1978) Item VII-D and 18717 (1979 1).
(January).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The two-equivalent color coupler in which the coupling active position is substituted with a leaving group can reduce the coated silver amount, as compared with the four-equivalent color coupler in which the hydrogen atom is a hydrogen atom. It is also possible to use couplers in which the color forming dye has a suitable diffusivity, uncolored couplers or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082. Same number 2,
343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
No. etc. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,619
Nitrogen atom leaving group described in U.S. Pat.
The arylthio groups described in 51,897 are particularly preferred. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole coupler, US Pat.
No. 061,432 pyrazolobenzimidazoles, preferably the pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure. 24220 (1
And the pyrazolopyrazoles described in Research Disclosure 24230 (June 1984). The imidazo [1,2] described in European Patent 119,741 in view of the small yellow sub-absorption of the coloring dye and the light fastness.
-B] pyrazoles are preferred and are described in EP 119,8
No. 60 pyrazolo [1,5-b] [1,2,4]
Triazole is especially preferred.

Cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and No. 2,369,929.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenolic cyan coupler having an ethyl group or higher alkyl group at the meta-position of the phenol nucleus, U.S. Pat. Nos. 2,772,162 and 3,3.
758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729 and JP-A-58-.
2,5-diacylamino-substituted phenol couplers described in US Pat. No. 4,2671, and US Pat. No. 3,44.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, etc., and has a phenylureido group at the 2-position and 5-
Examples thereof include phenol couplers having an acylamino group at the position.

A coupler in which the color forming dye has an appropriate diffusibility can be used in combination. Such couplers are described in US Pat.
66,237 and British Patent 2,125,570, specific examples of magenta couplers, and European Patent 96,237.
No. 570 and West German Application No. 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer except for the coupler in which the color-forming dye has diffusibility. Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent 2,102,
173 and U.S. Pat. No. 4,367,282.

Various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the photosensitive layer in order to satisfy the properties required for the light-sensitive material, or two or more layers in which the same compound is different. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, the boiling point as exemplified above is 1
After being dissolved in a single liquid or a mixed liquid of either one of a high-boiling organic solvent having a boiling point of 75 ° C. or higher and a so-called auxiliary solvent having a low boiling point, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . When emulsifying and dispersing, the block polymer used in the present invention can be used in place of or together with gelatin.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.003 for the magenta coupler. In the cyan coupler, it is 0.002 to 0.3 mol.

The silver halide emulsion used in the photosensitive layer in the present invention is
Usually, a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide, sodium chloride, potassium iodide alone or a mixture thereof) solution are mixed in the presence of a water-soluble polymer solution such as gelatin. Manufactured.
In the production of silver halide emulsion, at least a part of gelatin can be replaced with the block copolymer used in the present invention. The silver halide preferably used in the present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide containing no silver iodide or containing 3 mol% or less. These silver halides are preferably chemically and spectrally sensitized by a conventional method.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper and cloth usually used for photographic light-sensitive materials or a rigid support such as glass, pottery and metal. It

The present invention can be applied to various light-sensitive materials. That is, typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention also provides
It can also be applied to a black-and-white light-sensitive material utilizing a mixture of three-color couplers described in Research Disclosure 17123 (July 1978).

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N, N.
-Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl- 4-amino-N-
Examples thereof include ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.

The color developer includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Etc. are generally included.

The color developer may be substantially free of benzyl alcohol. By "substantially free" is meant having a benzyl alcohol concentration of preferably 2 ml / or less, more preferably 0.5 ml / or less, and most preferably free of benzyl alcohol.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds. Typical bleaching agents are ferriciyanides; dichromates; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2.
-Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, malic acid; persulfates; manganates; nitrosphenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in a stand-alone bleaching solution as well as in a one-bath bleach-fixing solution.

After the desilvering step (bleach-fixing or fixing), a treatment such as washing with water and / or stabilization is performed. Various compounds can be used for various purposes in the washing and stabilizing steps. For example, it is known to add bactericides and antifungal agents in order to prevent the generation of various bacteria, molds and algae. For example, Journal of Antibacterial and Antifungal Agents (J.An.
tibact.Antifung.Agents) vol. 11, No.5, p207
No. 223 (1983) and Hiroshi Horiguchi, "Compounds of Antibacterial and Antifungal Chemistry") or JP-A-57-8543, JP-A-57-58143, and JP-A-5-58143.
7-97530, JP-A-58-105145, JP-A-5-105145
8-134636, JP-A-59-91440, JP-A-5-
9-126533, JP 59-184344, JP 59-185336, JP 60-239250, JP 60-239751, JP 60-247241, JP 60-260952, and JP 61. -2149, JP-A-61-28947, JP-A-61-28945, JP-A-59-158475 and Japanese Patent Application No. 60-105487, and the method of using the same can be applied.

In particular, isothiazolone derivatives (2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-
Isothiazolin-3-one and the like), sulfanilamide derivatives (such as sulfanilamide), and benzotriazole derivatives (such as benzotriazole, 5-methyl-benzotriazole, 5-chloro-benzothiazole) are useful.

It is known to add various chelating agents for the purpose of improving the image stability after processing. For example, inorganic phosphoric acid, organic carboxylic acid, aminopolycarboxylic acid and organic phosphonic acid are useful, and they are disclosed in JP-A-57-8543 and JP-A-5757.
-197540, JP-A-58-14834, JP-A-58-134636, JP-A-59-126533,
JP-A-59-184343, JP-A-59-18434
4, JP-A-59-184345 and JP-A-59-18.
5336, JP-A-60-135942, JP-A-60
-238832, JP-A-60-239748, JP-A-60-239749, and JP-A-60-239750.
No. 60-239751, JP-A 60-242
No. 458, JP-A-60-262161, and JP-A-61-162.
No. 4047, JP-A-61-4050, JP-A-61-4
051, JP-A-61-4052, JP-A-61-40
53, JP-A-61-4054, and JP-A-61-289.
42, JP-A-61-28945, and the compounds and methods of use described in the specification. In particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and ethylenediaminetetramethylphosphonic acid are useful.

A metal compound may be used in combination with these chelating agents. For example, a bismuth compound (JP-A-58-13)
4636), Ba, Ca, Ce, Co, In, La,
Mn, Ni, Pb, Ti, Sn, Zn, Zr compounds (JP-A-59-184344), Mg, Al, Sr compounds (JP-A-59-185336) and the like, particularly Bi,
Ca, Mg and Al are useful.

Further, in order to effectively promote washing with water, a surfactant is used (Japanese Patent Laid-Open No. 57-197540), or a method of contacting with an ion exchange resin for the purpose of removing a component having a bad influence (Japanese Patent Laid-Open No. 2007-187242). No. 60-220345), a method of reverse osmosis treatment (JP-A-60-241053), activated carbon, a clay substance, a polyamide-based polymer compound, a polyurethane-based polymer compound, a phenol resin, an epoxy resin, and a high hydrazide group-containing compound. Molecular compound, polymer compound containing polytetrafluoroethylene, method of contact with monohydric or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer (JP-A-60-263151), electricity A method such as dialysis treatment (Japanese Patent Laid-Open No. 61-28949) can be applied.

Further, it can be applied as a method for preventing the generation of bacteria and mold, such as a method of irradiating ultraviolet rays or passing a magnetic field. Further, when the treatment is continuously performed, JP-A-60-233651,
60-235133, 60-263941, 61-4048, 61-4049, 61-40.
The methods of No. 55, No. 61-4056, No. 61-4057, No. 61-4058, and No. 61-4060 can be applied.

In addition to the above-mentioned additives, a fluorescent whitening agent, a hardener, etc. may be added to the washing and stabilizing baths.

Further, ammonium chloride as a film pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve the image storability.

As the various additives, the same or different target compounds may be used in combination of two or more depending on the purpose. From the viewpoint of the physical properties (e.g., stickiness) of the emulsion film of the processed light-sensitive material, it is preferable to add the minimum amount necessary for achieving the purpose.

It is preferable that the washing or stabilizing step is performed in a multi-stage countercurrent flow of two or more tanks to reduce the amount of replenisher. The amount of replenisher is
For the carry-in amount of the pre-bath per unit area of the photosensitive material,
It is preferably 0.1 to 50 times, more preferably 3 to 30 times.
Double.

The washing or stabilization treatment time of the present invention depends on the type of sensitive material,
The time is 20 seconds to 2 minutes, and more preferably 20 seconds to 1 minute 30 seconds, although it varies depending on the processing conditions.

The washing or stabilization treatment temperature of the present invention is 20 to 45 ° C.
And preferably 25 to 40 ° C, and more preferably 30 to 35 ° C.

In order to enhance the effect of washing out components in the film in washing or stabilizing treatment, it is preferable to circulate and stir the liquid,
In particular, it is preferable to use a method in which the surface of the emulsion film of the light-sensitive material is exposed to a strong liquid flow (eg, gas stirring, liquid spraying, etc.).

The silver halide color photographic material of the present invention is particularly useful in a processing method in which the amount of washing water is remarkably reduced.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.

Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C. to 38 ° C. is standard, but it is possible to increase the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Example 1. A color photosensitive material was prepared by coating the following photosensitive layers consisting of the first to seventh layers on a paper support laminated on both sides with polyethylene. The polyethylene coated with the first layer contains titanium dioxide and a trace amount of ultramarine.

(Structure of Photosensitive Layer) The numbers corresponding to the respective components represent the coating amount expressed in units of g / m ² , and the silver halide coating amount represents the coating amount in terms of silver.

First layer (blue-sensitive layer) Silver chlorobromide emulsion (80 mol% silver bromide) ...... Silver 0.30 Yellow coupler (* 1) ...... 0.70 Same as above Solvent (TNP) ...... 0.15 Gelatin ...... ... 1.20 Second layer (intermediate layer) Gelatin ... 0.90 Di-t-octylhydroquinone ... 0.05 Same as above solvent (DBP) ... 0.10 Third layer (green-sensitive layer) Silver chlorobromide Emulsifier (70 mol% of brominating agent) ... Silver 0.4
5 Magenta coupler (* 2) ...... 0.35 Same as above solvent (TOP) ...... 0.44 Anti-fading agent (* 3 / * 4) ...... 0.05 / 0.10 Gelatin ...... 1.00 4th layer (Ultraviolet Absorbing Intermediate Layer) Ultraviolet absorber (* 5 / * 6 / * 7) ... 0.06 / 0.
25 / 0.25 Same as above Solvent (TNP) ...... 0.20 Gelatin ...... 1.5 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (silver bromide 50 mol%) ...... Silver 0.20 Cyan coupler (* 8 / * 9) ...... 0.2 / 0.2 Coupler solvent (TNP / DBP) ...... 0.10 / 0.2
0 Gelatin ...... 0.9 6th layer (UV absorbing intermediate layer) UV absorber (* 5 / * 6 / * 7) ...... 0.06 / 0.
25 / 0.25 Same as above Solvent (DBP) ...... 0.20 Gelatin ...... 1.5 7th layer (protective layer) Gelatin ...... 1.5 Hardener (H-1) ...... 0.4 Where: DBP represents dibutyl phthalate, TOP represents tri (n-octyl phosphate), TNP represents tri (n-nonyl phosphate), and (H-1) represents the following compound.

The following dyes were used as the spectral sensitizer for each emulsion layer.

Blue-sensitive emulsion layer; 4- {5-chloro-2- [5-chloro-3- (4-sulfonatobutyl) benzothiazoline-2-ylidenemethyl] -3-benzothiazolio} butanesulfonate triethylammonium salt (silver halide 1 mol) Per 2
X10 ^-4 mol) Green-sensitive emulsion layer; 3,3'-di- (γ-sulfopropyl) 5,5'-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 x per mol of silver halide) 10 ⁻⁴ mol) Red-sensitive emulsion layer; 3,3′-di- (γ-sulfopropyl) -9-methyl-
Thiadicarbocyanine sodium salt (2.5 × 10 ⁻⁴ mol per mol of silver halide) The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; This photosensitive material was used as Sample 101.

Next, as shown in Table 1, the light-sensitive materials of Samples 102 to 111 were prepared in the same manner except that the block copolymers A and B of the present invention were added to the seventh layer as shown in Table 1 to control the pH. It was created. After these samples were subjected to gradation exposure for sensitometry by a stretcher (Fuji Color Head 609 manufactured by Fuji Photo Film Co., Ltd.), the following five processing steps (A), (B), (C), ( The development processing was performed according to D) and (E), and hot air drying at 80 ° C. was performed.

Developer Nitrilotriacetic acid / 3Na 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Na ₂ SO ₃ 2.0 g KBr 0.5 g Hydroxylamine sulphate 3.0 g 4-Amino-3-methyl-N-ethyl-N- [β- (Methanesulfonamido) ethyl] -p-phenylenediamine / sulfate 5.0 g Na ₂ CO ₃ (monohydrate) 30 g Water to make 1 litter (pH 10.1) Bleach-fixer Ammonium thiosulfate (54 wt% ) 150 ml Na ₂ SO ₃ 15 g NH ₄ [Fe (EDTA)] 55 g EDTA · 2Na 4 g Add water to make 1 (pH 6.9) (B) Process standard treatment time The composition of the treatment liquid used is as follows.

<Color developer> <Bleaching fixer> <Rinse liquid> (C) Washing time reduction type treatment The composition of each treatment liquid used is as follows.

<Color developer> <Bleaching fixer> <Rinse liquid> (D) Rapid processing The composition of the treatment liquid used is as follows.

<Color developer> <Bleaching fixer> <Rinse liquid> (E) Rapid processing The composition of each treatment liquid used is as follows.

<Color developer> <Bleaching fixer> <Rinse Solution A> 0.5 g of ethylenediaminetetraacetic acid.2Na is added to water to make 1.

<Rinse Solution B> 1.0 g of sulfanil acid is added to water to make 1.

<Rinse Solution C> Water is added to 30 mg of 5-chloro-2-methyl-4-isothiazolin-3-one to make 1.

<Rinse liquid D> <Rinse solution E> Next, the dried sample was allowed to stand at room temperature under 55% RH for 2 days and then allowed to stand at 80% RH for 5 minutes to observe the surface irregularity.

As shown in the results in Table 1, by adding the block copolymers A and B ^* to the gelatin protective layer, the treatment (A) and the conventional surface and the treatments (B) and (C) which further deteriorate the glossiness,
Also in (D) and (E), a light-sensitive material having a high surface gloss was obtained.

* Block copolymer A: Acrylic acid-modified copolymer of polyvinyl alcohol (17% modification degree) Block copolymer B: Acrylic acid-modified copolymer of polyvinyl alcohol (23% modification degree) Example 2 A sample 201 was prepared by using the same sample as in Example 1 except that the amounts of the ultraviolet absorber and the solvent that were the oil component of the sixth layer were each ⅔.

Next, the block copolymer B of Example 1 was added to the 7th layer as shown in Table 2 to prepare samples 202 to 207, which were treated and evaluated in the same manner as in Example 1.

(Effects of the Present Invention) By the method of the present invention, a light-sensitive material having improved surface gloss during storage after processing can be obtained without substantially reducing the maximum color density. This effect was also achieved in a so-called anhydrous washing process and a process in which benzyl alcohol was substantially removed from the color developing solution.

Further, the photosensitive material of the present invention has good adhesion between hydrophilic colloid layers.

Continuation of the front page (56) Reference JP 59-215378 (JP, A) JP 57-152949 (JP, A) JP 59-193910 (JP, A) JP 58-49944 (JP , A) JP 58-121037 (JP, A) JP 54-121728 (JP, A) JP 59-41175 (JP, B2) JP 50-27375 (JP, B2) US Patent 3022169 (US, A)

Claims (1)

[Claims] 1. A photographic light-sensitive material comprising at least two hydrophilic colloid layers coated on a support, at least one of the hydrophilic colloid layers containing an oil component, and this layer or this layer. A hydrophilic colloid layer adjacent to the protective layer is a protective layer, and the protective layer contains a polyvinyl alcohol polymer as one component and a polymer having an ionic group as another component, which is a water-soluble or water-dispersible block copolymer. A photographic light-sensitive material containing a polymer in an amount of 0.5 to 40% by weight based on the total (solid content) of gelatin and the block copolymer constituting the protective layer.