JPH07111558B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material using a reflective support which is excellent in image sharpness and non-image area whiteness, and is particularly rapid. The present invention relates to a color photographic paper excellent in development processing.

(Prior Art) With the recent spread of silver halide light-sensitive materials, silver halide color light-sensitive materials with excellent finished quality that can be developed more rapidly and easily than other image forming systems can be developed. Strong demand. Regarding photosensitive materials for photography,
The gradation reproducibility and image graininess as well as the image sharpness have been improved. For example, silver halide emulsion with high sensitivity and fine grain, multi-layering and thinning of photosensitive layer, reduction of the amount of silver halide used, silver halide emulsion with less light scattering and dye for preventing halation and anti-irradiation, etc. There are many contrivances such as a mordant layer using. In the case of color photosensitive materials, DIR couplers and color mixing inhibitors are also used to improve the sharpness by the inter image effect.
In many cases, a light-sensitive material for photography uses a transparent plate or a film support, but the support itself is dyed to prevent halation, and a black back layer (AHB) or anti-halation layer (AHU) is provided. Can be used.

With regard to color print light-sensitive materials, improvements have been made in color reproducibility, tone reproducibility, speeding up of processing, and dyes for preventing irradiation. For example, Japanese Patent Laid-Open No. 50-145
No. 125, No. 52-20830, No. 50-147712, No. 59-111
641, Do 61-148448, Do 61-151538, Do 61-15
1649, 61-151650, 61-151651, 61-1
70742, 61-175638, 61-235837, 61-
No. 248044, No. 62-164043, No. 62-253145, No. 62
-253146, 62-253142, 62-275262, 6
2-283336 Specification and Research Disclosure RD-1
7643 (22 December 1978) and RD-18716 (64 November 1979)
See page 7) for details on dye improvements. Further, a method of providing an AHU on a color light-sensitive material is known. For example, U.S. Patent Nos. 2882156, 2326057, and 2839401.
No. 3706563, JP-A-55-33172, and JP-A-59-193447.
No. 62-32448, and the like.

Further, a method in which a dye insoluble in water is finely dispersed and used is disclosed in JP-A-55-155350, JP-A-55-155351, and JP-A-56-12639.
No. 63-197943 and European Patent No. 15,601.

Further, a method of using a dye adsorbed on the metal salt fine particles, U.S. Pat.Nos. 2,719,088, 2,496,841, and 2,
No. 496,843 and JP-A-60-45237.

Originally, baryta paper was used as a support for the color print photosensitive material. Recently, in order to speed up the development process, a water resistant support having polyethylene laminated on both sides is used. Titanium oxide or titanium oxide whose particle surface is treated with aluminum oxide or silicon oxide is used for the polyethylene layer in order to maintain whiteness on par with baryta paper, but the effect on image sharpness does not reach that of baryta paper. Regarding the improvement of the polyethylene layer containing titanium oxide, for example, JP-B-58-43734 and JP-A-58-17433.
No. 58-14830, No. 61-259246, and the like.

The water-resistant resin layer on the base paper is coated with a coating solution containing an unsaturated organic compound having one or more double bonds in one molecule capable of being polymerized by an electron beam and a white pigment, and then heated. The method of curing by electron beam irradiation is described in, for example, JP-A Nos. 57-27257, 57-49946, 61-262738 and 62-61049.

A silver halide light-sensitive material using a specularly reflective or type 2 diffusely reflective support is also known. For example, JP-A-62-2
It is described in Nos. 4251 to 24253 and No. 63-24255.

Japanese Patent Laid-Open No. 63-63036 discloses that the sharpness deterioration due to the transmission density of the support of direct positive color photographic printing paper or high-sensitivity reflective color printing paper, which is thinner than that of the conventional one, is less than 0.8. , It has been shown to suppress by providing an anti-halation layer using colloidal silver.
Further, Japanese Patent Laid-Open No. 63-63040 discloses that contact fog caused by colloidal silver generated by rapid development using a silver chloride-containing emulsion layer and a colloidal silver layer in a direct positive light-sensitive material or a negative-type light-sensitive material should be prevented from contacting. It describes that prevention is provided by providing an auxiliary layer.

(Problems to be Solved by the Invention) Silver halide light-sensitive material using a reflective support, especially the first
For color photographic paper using a diffuse support white substrate, it is a special device to improve the sharpness of images and the tone reproducibility of highlight details without deteriorating the whiteness. is necessary.

The use of conventional anti-irradiation dyes and conventional anti-halation agents using colloidal silver has not only problems such as fog generation, increased stain, residual color and decreased sensitivity, but also limited improvement in sharpness.

An object of the present invention is to solve these problems, and the first object thereof is to provide a photographic light-sensitive material using a white reflective support which is excellent in image sharpness while improving the whiteness of the non-image area. The second object is to provide a color photographic paper excellent in tone reproduction of highlight details. A third object is to provide a color photographic paper suitable for rapid development (color development time of 90 seconds or less), which improves photographic contamination due to dyeing of developing solution from the cutting side of the color photographic paper. is there. Other purposes will be apparent from the description of the specification.

(Means for Solving the Problems) The inventors have found that the above objects can be effectively achieved by improving the support used and the colloid layer provided thereon.

That is, the present invention is as follows.

(1) In a photographic light-sensitive material having at least one silver halide light-sensitive layer on a reflective support containing white pigment particles in the water-resistant resin layer, the white pigment particles are contained in the water-resistant resin layer in an amount of 10% by weight. % Of the content of the white pigment particles, and the dispersion coefficient of the white pigment particles is defined as the occupying area ratio (%) per unit area of the coefficient of variation s / (here, the average occupying area ratio per unit area, s is a standard deviation of the occupied area ratio per unit area) is 0.20 or less, and further, a colored layer which can be decolorized by photographic processing is provided between the support and the silver halide photosensitive layer. Silver halide photographic light-sensitive material.

(2) In a photographic light-sensitive material having at least one silver halide light-sensitive layer on a reflective support having a water-resistant resin layer coated on a support substrate, the silver halide light-sensitive layer is coated. 10% by weight of white pigment particles in the water-resistant resin layer on the side
It is contained at the above density, and the coefficient of variation of the occupied area ratio of the white pigment particles per 6 μm × 6 μm (unit area)
A silver halide photographic light-sensitive material having a s / of 0.20 or less and further having a colored layer capable of being decolorized by photographic processing between the support and the silver halide light-sensitive layer.

(3) The colored layer that can be decolorized by photographic processing contains a solid fine particle dispersion of a dye that is substantially insoluble in water having a pH of 7.0 and is soluble in water having a pH of more than 9.0. The silver halide photographic light-sensitive material according to item (1) or (2).

(4) A solid of a dye selected from the compounds represented by the following general formulas (II), (III), (IV), (V) and (VI) in the colored layer which can be decolorized by photographic processing. A fine particle dispersion is contained, Claims (1)-which are characterized by the above-mentioned.
The silver halide photographic light-sensitive material as described in any of (3).

General formula (II) General formula (III) General formula (IV) A ₂ = L ₁ − (L ₂ = L _{3 n} A ₂ General formula (V) General formula (VI) (In the formula, A ₂ is an acidic nucleus having at least one substituent selected from a carboxyphenyl group, a sulfamoylphenyl group, a sulfonamidephenyl group, a carboxyalkyl group and a hydroxyphenyl group (as a substituent, May have in addition to the above groups), the acidic nucleus, 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione,
It is selected from the group consisting of isoxazolidinone, barbituric acid, thiobarbituric acid, indandione and hydroxypyridone. B ₂ represents a basic nucleus having at least one substituent selected from a carboxyl group, a sulfamoyl group and a sulfonamide group (the substituent may have other than the above groups), and the basic nucleus is , Pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole and pyrrole. R ₄₀ represents a hydrogen atom or an alkyl group, R ₄₁ and R ₄₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group, and R ₄₁ and R ₄₂ are linked to each other. To form a 5- or 6-membered ring. R ₄₃ and R ₄₆ each represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a halogen atom, and R ₄₄ and R ₄₅ each represent a hydrogen atom or R _41.
And R ₄₄ or R ₄₂ and R ₄₅ are connected to each other to represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represent a substituted or unsubstituted methine group, X ₃ and Y ₃ each represent an electron-withdrawing group, and at least one carboxy group is present in either X ₃ or Y _3. It has an enyl group, a sulfamoylphenyl group, a sulfonamidephenyl group, a carboxyalkyl group or a hydroxyphenyl group. m represents 0 or 1, and n represents 0, 1 or 2. p represents 0 or 1, but when p is 0, R ₄₃ represents a hydroxy group or a carboxy group and R ₄₄ and R ₄₅ represent a hydrogen atom. ) Next, the present invention will be described in detail.

The white support used in the silver halide photographic light-sensitive material of the present invention can be provided by coating a water-resistant resin layer on a substrate. As the substrate, base paper obtained from natural pulp, synthetic pulp or a mixture thereof, polyester film such as polyethylene terephthalate and polybutylene terephthalate, plastic film such as cellulose triacetate film, polystyrene film, polypropylene film and polyolefin film are used. be able to.

The base paper used in the present invention is selected from materials generally used for photographic printing paper. That is, natural pulp selected from softwood, hardwood, etc. is used as a main raw material, and if necessary, clay, talc, calcium carbonate, salt agents such as urea resin fine particles, rosin, alkyl ketene dimer, higher fatty acid, paraffin wax, alkenyl succinic acid. A sizing agent such as the above, a paper strengthening agent such as polyacrylamide, a fixing agent such as a sulfuric acid band, a cationic polymer, and the like are used. In particular, a neutral paper using a reactive sizing agent such as an alkyl ketene dimer or alkenyl succinic acid (measured with a pH meter that uses Toa Denpa Kogyo Co., Ltd. flat GST-5313F as an electrode) The one used is preferred. Further, synthetic pulp may be used in place of the above natural pulp, or natural pulp and synthetic pulp may be mixed in an arbitrary ratio.

The surface of the pulp may be surface-sized with a film-forming polymer such as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol. Examples of the modified polyvinyl alcohol in this case include a modified carboxyl group, a modified silanol, and a copolymer with acrylamide. Further, the coating amount of the film-forming polymer when the surface size is treated with the film-forming polymer is adjusted to 0.1 to 5.0 g / m ² , preferably 0.5 to 2.0 g / m ² . Further, an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent and the like can be added to the film-forming polymer at this time, if necessary.

Further, the base paper is a pulp slurry containing the above-mentioned pulp and, if necessary, an additive such as a salting agent, a sizing agent, a paper-strengthening agent, and a fixing agent, and is dried with a paper machine such as a Fourdrinier paper machine. It is then rolled and manufactured. The surface size treatment is performed before or after the drying, and the calender treatment is performed between the drying and the winding. When the surface sizing treatment is performed after drying, this calendering treatment can be performed either before or after the surface sizing treatment.

Whether or not the base paper used as the support substrate of the present invention is a neutral paper can be determined by measuring the pH value using, for example, GST-5313F for flat surface manufactured by Toa Denpa Kogyo KK as an electrode. PH value of neutral paper is 5
Above, preferably 5 to 9 is shown.

Further, the water resistant resin layer according to the present invention may itself constitute a support, such as a vinyl chloride resin.

The water resistant resin used in the present invention means water absorption (% by weight)
Is 0.5 or less, preferably 0.1 or less, such as polyalkylene (polyethylene, polypropylene, or copolymer thereof), vinyl polymer or copolymer thereof (polystyrene, polyacrylate is copolymer thereof), polyester or copolymer thereof. Preferably, the polyalkylene resin is low density polyethylene, high density polyethylene, polypropylene or a blend thereof. If necessary, a brightening agent, an antioxidant, an antistatic agent, a release agent, etc. are added. In this case, the resin layer has a thickness of about 5 to 200 μm, particularly preferably 10 to 40 μm.
In general, a white pigment is kneaded by a melt mixing method or the like, and the pigment is passed through a melt extruder and melt-extruded for lamination.

Further, for example, JP-A-57-27257, 57-49946 and 61.
-262738, unsaturated organic compounds having one or more polymerizable carbon-carbon double bonds in one molecule, for example, methacrylic acid ester compounds, JP-A-61-61
In the specification of No. 262738, gintry or tetra-acrylic acid ester represented by the general formula can be used. In this case, after being applied on a substrate, it is cured by electron beam irradiation to form a waterproof resin layer. White pigments and the like are dispersed in this unsaturated organic compound. It is also possible to mix and disperse other resins.

The method for coating the water-resistant resin layer of the present invention is, for example, a lamination method described in “New Laminating Manual” edited by Processing Technology Research Group, for example, dry lamination, solventless dry lamination, etc., and coating. The gravure roll type, the wire bar type, the doctor blade type, the reverse roll type, the dip type, the air knife type, the calendar type, the kiss type, the squeezing type, the phantine type coating and the like are used.

White pigments are contained in the waterproof resin, for example, methyl type, titanium oxide, anatase type titanium oxide, barium sulfate, calcium sulfate, silicon oxide, zinc oxide, titanium phosphate, aluminum oxide, etc. are used. The surface of the fine particles of the pigment is combined with or separately from an inorganic oxide such as silica or aluminum oxide, or a divalent or tetravalent alcohol, for example, 2,4-dihydroxy-2-methyl described in JP-A-58-17151. It is preferable to use it after surface-treating it with pentane or trimethylolethane.

The surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, flame treatment or the like to provide a protective colloid layer group of the silver halide light-sensitive material.

The support has a total thickness of 30 to 350 g / m ² (about 30 to 400 g
μm) is preferred, more preferably about 50 to 200 g / m ²
The water resistant resin layer is about 5 to 200 μm.
Is preferable, and more preferably about 10 to 40 μm.

The feature of the support in the present invention is that the fine particles of a white pigment (particularly preferably titanium oxide) are more than 10% by weight, preferably 12% by weight or more, more preferably 15% by weight or more and 60% by weight or less. First, it is to be dispersed in the water resistant resin layer. In particular, the fine particles of the white pigment are preferably densely and uniformly dispersed (so that there is no rough portion) on the surface of the waterproof resin layer or at a thickness of about 10 μm from the surface.

The dispersibility of the white pigment fine particles in the resin layer is such that the resin on the surface of the resin or about 0.1 μm, preferably about 500 Å, is scattered by the ion sputtering method by glow discharge to expose the exposed fine particles of the pigment to the electron. It can be evaluated by the coefficient of variation of the occupied area ratio (%) by observing with a microscope, obtaining the occupied area for photographing. The ion sputtering method is described in detail in Yoichi Murayama, Kunihiro Kashiwagi “Surface Treatment Technology Using Plasma”, Machinery Research Vol. 33 No. 6 (1981), etc.

In order to control the coefficient of variation of the white pigment particles to 0.20 or less, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and the surface of the pigment particles should have a valence of 2 to 4 as described above. It is preferable to use the one treated with alcohol.

The occupying area ratio (%) of the white pigment fine particles per defined unit area is most typically projected by dividing the observed area into adjacent 6 μm × 6 μm unit areas. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio of the standard deviation s of R _{i to} the average value of R _i () s /
Can be obtained by The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s / is Can be obtained by

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.20 or less, more preferably 0.15 or less and particularly preferably 0.10 or less. When it is 0.08 or less, the dispersibility of the particles can be said to be "uniform".

In general, when such a white pigment is contained in the support of a silver halide light-sensitive material, it gives a white background (white background) and at the same time deteriorates the sharpness of an image when viewing a photograph. On the other hand, if the conditions of the density and dispersibility of the white pigment in the present invention are satisfied, the intensity of the first-class diffuse reflected light with respect to the incident light can be increased, and the spread of the diffused light can be reduced. This improvement effect of the support is remarkable not only in the incident light at the time of exposure but also in the incident light when viewing a photograph.

Another feature of the silver halide photographic light-sensitive material of the present invention is that it can be decolorized between the support and the silver halide light-sensitive layer after photographic processing (development, bleaching / fixing / washing or stabilization processing). It is to provide a layer.

By fixing the light absorber to the colored layer, the effect of preventing halation on the silver halide photosensitive layer can be effectively exhibited while avoiding the inhibition of spectral sensitivity and the occurrence of fog. Colloidal silver (black to yellow) or dye is used as the light absorber. By providing this colored layer, it is possible to more effectively prevent the deterioration of development sharpness due to the spread of diffused light from the support side.

It is preferable to use a colloidal silver emulsion as a light absorber in the colored layer of the present invention. As the colloidal silver emulsion, those used for color photographic materials for photographing can be used.

Colloidal silver is disclosed, for example, in U.S. Pat. Nos. 2,868,601 and 3,459,563.
It can be manufactured according to the method described in No. 622695 or the Belgian Patent No. 622695. The colloidal silver used in the present invention is preferably desalted to a conductivity of 1800 μscm ⁻¹ or less after preparation. The amount of the colloidal silver-containing layer used is 0.01 to 0.5 g per m ² as silver, preferably 0.05 to 0.
2g is preferred.

A dye can also be used together for other purposes such as prevention of irradiation, stabilization of sensitivity, improvement of safelight safety and improvement of spectral sensitivity distribution.

As another preferable embodiment, a dye and a cationic polymer for mordant thereof can be used in the colored layer of the present invention.

The cationic polymer that can be preferably used in the present invention is a cation-polymer that functions as an anion exchange polymer.
It is a non-color forming polymer having an ammonium base having at least one hydrogen atom at the site.

General formula (I) In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable monomer having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in a side chain. B
Represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer. R ₁ represents a hydrogen atom, a lower alkyl group or an aralkyl group. Q is a single bond or an alkylene group, an arylene group, an aralkylene group, Represents a group represented by. Here, L represents an alkylene group, an arylene group or an aralkylene group, and R represents an alkyl group.

Represents R₂, R₃, R_Four, R_Five, R₆, R₇, R₈, R₉Is hydrogen
Represents a child, an alkyl group, an aryl group, or an aralkyl group.
However, these may be the same as or different from each other. Well
In addition, all the above-mentioned groups include those which are substituted. X
Represents an anion.

Further, Q, R ₂ , R ₃ , R ₄ or any two or more groups of Q, R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are bonded to each other to form a ring structure together with a nitrogen atom. You may form.

However, In, at least one of R ₂ , R ₃ and R ₄ is a hydrogen atom.

x, y, and z represent mole percentages, and x is 0 to
Up to 60, y represents a value of 0 to 60 and z represents a value of 30 to 100.

Explaining the general formula (I) in more detail, examples of the monomer in A include divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Examples thereof include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, and tetramethylene dimethacrylate, among which divinylbenzene and ethylene glycol dimethacrylate are particularly preferable.

Examples of ethylenically unsaturated monomers in B are ethylene, propylene, 1-butene, isobutene, styrene,
α-methylstyrene, vinyl ketone, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, allyl acetate), ester of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (eg methyl methacrylate, ethyl methacrylate, n-butyl) Methacrylate, n-
Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (eg acrylonitrile) or dienes (eg butadiene, isoprene) and the like, of which styrene , N-butyl methacrylate, cyclohexyl methacrylate and the like are particularly preferable. B may contain two or more of the above monomer units.

R ₁ is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl,
An n-amyl, n-hexyl) aralkyl group (for example, benzyl) is preferable, and a hydrogen atom or a methyl group is particularly preferable.

Q is preferably a divalent optionally substituted alkylene group having 1 to 12 carbon atoms (for example, a methylene group or — (CH ₂ ) ₆ —).
A group represented by), an optionally substituted phenylene group, or an optionally substituted aralkylene group having 7 to 12 carbon atoms (for example, Is also preferable, and a group represented by the following formula is also preferable.

Here, L is preferably an optionally substituted alkylene group having 1 to 6 carbon atoms, an optionally substituted arylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms, and 1 to 6 carbon atoms. The optionally substituted alkylene group of is more preferable. R is preferably an alkyl group having 1 to 6 carbon atoms.

G is The _{stands, R 2, R 3, R} 4, R 5, R 6, R 7, R 8, R 9 is a hydrogen atom or 1
An alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms are preferable, and they may be the same or different. The alkyl group aryl group and aralkyl group include a substituted alkyl group, a substituted aryl group, and a substituted aralkyl group.

The alkyl group is an unsubstituted alkyl group (for example, methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-
Hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-
Dodecyl); the carbon atom of the alkyl group is preferably 1 to 12
It is an individual. More preferably, it has 4 to 10 carbon atoms.
Examples of the substituted alkyl group include an alkoxyalkyl group (for example, methoxymethyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl, methoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl, vinyloxyethyl), a cyanoalkyl group (for example, 2- Cyanoethyl, 3-cyanopropyl, 4-cyanobutyl), halogenated alkyl groups (eg 2-fluoroethyl, 2-chloroethyl, 3-fluoropropyl), alkoxycarbonylalkyl groups (eg ethoxycarbonylmethyl), allyl groups, 2-butenyl. Group, propargyl group and the like.

The aryl group is an unsubstituted aryl group (eg, phenyl, naphthyl), and the substituted aryl group is, for example, an alkylaryl group (eg, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropyl). Phenyl, 4-tert-butylphenyl), an alkoxyaryl group (for example, 4-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl), an aryloxyaryl group (for example, 4-phenoxyphenyl) and the like. The aryl group has preferably 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

As the aralkyl group, an unsubstituted aralkyl group (for example, benzyl, phenethyl, diphenylmethyl, naphthylmethyl); a substituted aralkyl group, for example, an alkylaralkyl group, (for example, 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropyl) Benzyl), alkoxyaralkyl groups, (eg 4-methoxybenzyl, 4-ethoxybenzyl), cyanoaralkyl groups, (eg 4-cyanobenzyl), perfluoroalkoxyaralkyl groups,
(For example, 4-pentafluoropropoxybenzyl group, 4
-Undecafluorohexyloxybenzyl group, etc.), a halogenated aralkyl group, (eg, 4-chlorobenzyl group, 4-bromobenzyl group, 3-chlorobenzyl group, etc.). The carbon number of the aralkyl group is preferably 7 to 15, and preferably 7 to 11. Of these, a benzyl group and a phenethyl group are particularly preferable.

X Represents an anion, such as a halogen ion (eg
(Chlorine ion, bromine ion), alkyl or aryl
Rusulfonate ion (eg methanesulfonic acid, ethane
Sulfonic acid, benzenesulfonic acid, p-toluenesulfo
Acid), acetate ion, sulfate ion, nitrate ion, etc.
Chlorine ion, acetate ion, and sulfate ion are particularly preferred.
Yes.

It is also preferable that any two or more groups of Q, R ₂ , R ₃ and R ₄ are bonded to each other to form a cyclic structure together with the nitrogen atom. The cyclic structure formed is preferably a pyrrolidine ring, piperidine ring, morpholine ring, pyridine ring, imidazole ring, quinuclidine ring or the like. Particularly preferred are pyrrolidine ring, morpholine ring, piperidine ring, imidazole ring and pyridine ring.

Further, any two or more groups of Q, R ₅ , R ₆ , R ₇ , R ₈ and R ₉ may be bonded to each other to form a ring structure together with a nitrogen atom. Particularly preferred is a 6-membered ring or a 5-membered ring.

x is 0 to 60 mol%, preferably 0 to
It is 40 mol%, and more preferably 0 to 30 mol%. y is 0 to 60 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%.
Is. z is 30 to 100 mol%, preferably 4
0 to 95 mol%, more preferably 50 to 85
Mol%.

G in the general formula (I) is preferably a basic residue having a pKa value of 4.5 or more, particularly 7 or more, in an aqueous solution.

Among the cationic polymers of the general formula (I), polymer latex is particularly preferable in terms of film quality.

Specific examples of the compound represented by formula (I) are listed below.

When making a fine particle dispersion of a cationic polymer,
Generally, a crosslinkable monomer such as divinylbenzene is used as the monomer, but the use of the crosslinkable monomer is not essential depending on the monomer used.

Among the compounds represented by the general formula (I) of the present invention, G is A method for synthesizing the compound represented by will be described below.

The polymer represented by the general formula (I) of the present invention is generally a copolymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (However, R ₁ , R ₂ , R ₃ and Q are the same as those shown above)
Unsaturated monomers represented by (for example, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N
-(N, N-dimethylaminopropyl) acrylamide,
N- (N, N-dihexylaminomethyl) acrylamide, 3- (4-pyridyl) propyl acrylate, N, N
-Dimethylaminomethylstyrene, N, N-diethylaminomethylstyrene, N, N-dihexylaminomethylstyrene, 2-vinylpyridine, 4-vinylpyridine, etc., particularly preferably N, N-diethylaminoethyl methacrylate, or N, N - dimethylaminomethyl styrene, N, N-a de after polymerizing diethylamino methylstyrene), a compound having a structure of R ₄ -X (wherein, R _4, X are the same as those shown above) (e.g. hydrochloride , Nitric acid, sulfuric acid,
It can be obtained by forming an ammonium salt with acetic acid, p-toluenesulfonic acid, etc.).

The polymer represented by the general formula (I) of the present invention includes a copolymerizable monomer having at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (Wherein R ₁ , R ₂ , R ₃ , R ₄ , X and Q are the same as those shown above) (for example, N, N-dimethylaminoethylmethacrylate hydrochloride, N, N -Diethylaminoethyl methacrylate sulfate, N, N-dimethylaminoethyl acrylate hydrochloric acid ring, N, N-diethylaminoethyl acrylate acetate, N, N-dimethylaminostyrene hydrochloride, N, N-diethylaminomethylstyrene sulfate, 2- It can be obtained by polymerizing with vinylpyridine hydrochloride or 4-vinylpyridine hydrochloride.

The polymer represented by the general formula (I) of the present invention includes a copolymerizable monomer having at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (I). (Wherein X represents a halogen atom (eg, chlorine atom, bromine atom), sulfonic acid ester (eg, p-toluenesulfonyloxy group), and R ₁ and Q are the same as those shown above) Monomer (eg β-chloroethyl methacrylate, β-p-toluenesulfonyloxyethyl methacrylate, chloromethylstyrene)
And after polymerization By an amine having the structure of (wherein R ₂ , R ₃ and R ₄ are the same as those shown above) (eg, dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, morpholine, piperidine, etc.) It can also be obtained by using an ammonium salt.

Of the compounds represented by the general formula (I) of the present invention, G is A method for synthesizing the compound represented by will be described below.

The polymer represented by the general formula of the present invention includes a polymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (However, R ₁ , R ₅ , and Q are the same as those shown above) (for example, methyl vinyl ketone, methyl- (1-methyl vinyl) ketone, ethyl vinyl ketone, ethyl- (1-methylvinyl) ketone, n-
Propyl vinyl ketone, diacetone acrylamide, diacetone acrylate, etc., particularly preferably methyl vinyl ketone, ethyl vinyl ketone, diacetone acrylamide, diacetone acrylate) (However, R ₆ , R ₇ , R ₈ and R ₉ are the same as those shown above) (for example, aminoguanidine bicarbonate, N-amino-N′-methylguanidine bicarbonate, N-amino-N'-methylguanidine bicarbonate, etc., particularly preferably aminoguanidine bicarbonate, is reacted, and H-
It can be obtained by forming a guanidinium salt with a compound represented by X (HX is the same as those shown above) (for example, hydrogen chloride, hydrogen bromide, sulfuric acid, acetic acid, nitric acid).

The above-mentioned polymerization reaction may be carried out by any of generally known methods such as solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization and dispersion polymerization. Solution polymerization and emulsion polymerization are preferred.

Among the above-mentioned polymerization reactions, for example, emulsion polymerization is generally anionic surfactant (for example, sodium dodecyl sulfate,
Triton 770 (commercially available from Rohm & House), cationic surfactant (eg octadecyltrimethylammonium chloride), nonionic surfactant (eg Emarex NP-20 (commercially available from Japan Emulsion)), gelatin, polyvinyl alcohol, etc. At least one emulsifier selected from the group and a radical polymerization initiator (for example, a combination of potassium persulfate and sodium bisulfite, Wako Pure Chemical Industries
Marketed under the name of 50), typically at 30 ° C.
To about 100 ° C, preferably 40 ° C to about 80 ° C.

The above-mentioned reaction with ammonium salt is generally carried out at a temperature of -10 ° C to about 40 ° C, with 0 ° C to 30 ° C being particularly preferred.

The polymer of the present invention can be manufactured very easily because the whole manufacturing process can be carried out in one container.

A synthesis example of a typical polymer of the present invention is shown below.

Synthesis Example 1 Synthesis of poly (divinylbenzene-co-diethylaminomethylstyrene sulfate) polymer dispersion (2)
00 g of distilled water was added and degassed with nitrogen gas, sodium dodecyl sulfate 16.6 g, sodium persulfate 1.9 g, sodium sulfite 1.4 g, divinylbenzene 33.6 g, and diethylaminomethylstyrene 195.7 g were added and stirred.

After heating to 60 ℃, 0.9g of potassium persulfate, 60g of distilled water
The solution dissolved in was added every 1 hour for a total of 4 times, and the stirring was continued for 2 hours. Then, let it cool to room temperature and distilled water 313g.
A solution prepared by dissolving 48.9 g of concentrated sulfuric acid was added to the mixture, and the mixture was filtered to obtain a polymer dispersion having a solid content concentration of 15.4 wt% and an amine content of 5.29 × ^-4 eqv / g.

The average particle size of this polymer was 0.054 μm, and the coefficient of variation (standard deviation / average particle size = 0.011 / 0.054) was about 0.20.

Synthesis Example 2 Synthesis of poly (ethylglycol dimethacrylate-co-butylmethacrylate-co-diethylaminomethylstyrene hydrochloride) polymer dispersion (6) In a reaction vessel, it is commercially available as Nissan Tracks H-45 (NOF Corporation). 2.8 g of an emulsifier, 75 g of distilled water, 5.95 g of ethylene glycol dimethacrylate, 4.98 g of butyl methacrylate and 5.34 g of chloromethylstyrene were added and stirred. After heating to 60 ° C., 0.2 g of a polymerization initiator commercially available as V-50 (Wako Pure Chemical Industries, Ltd.) was added and stirring was continued for 3 hours.
Then, the mixture was cooled to 40 ° C, distilled water (108 g) and isopropyl alcohol (62 g) were added, diethylamine (2.52 g) was added dropwise over 15 minutes, stirring was continued at 40 ° C for 2 hours, and the solid content concentration was 8.16.
A polymer dispersion having a wt% and an amine content of 1.31 × 10 ⁻⁴ eqv / g was obtained.

Synthesis Example 3 Synthesis of poly (divinylbenzene-co-styrene-co-N, N-diethyl-N-methacryloyloxyethylammonium chloride) polymer dispersion (12).

Put 108 g of distilled water in a reaction vessel, degas with nitrogen gas, heat to 60 ° C under nitrogen stream, then octadecyltrimethylammonium chloride (23%) 7.9 g, polyvinyl alcohol (saponification degree 95%) 0.04 g, 0.78 g of styrene, 2.94 g of divinylbenzene, and 20.63 g of N, N-diethylaminoethyl methacrylate were added and stirred. A solution prepared by dissolving 0.44 g of potassium persulfate and 0.14 of sodium hydrogen sulfite in 10.8 g of distilled water degassed with nitrogen gas was added, and stirring was continued for about 5 hours. After that, the mixture was cooled to room temperature, 100 g of distilled water and 10.6 g of concentrated hydrochloric acid were dissolved therein, and the mixture was filtered to obtain a polymer dispersion having a solid content concentration of 14.0 wt% and an amine content of 4.59 × 10 ^-4 eqv / g. Obtained.

Synthesis Example 4 Synthesis of poly (N, N-dimethyl-N-methacrylamidopropylammonium chloride) (Compound (17)) Concentrated hydrochloric acid (hydrogen chloride content 36 weight percent) was placed in a reaction vessel.
Add 50.7 g and 350 ml of distilled water and stir at room temperature while stirring N, N
85 g of dimethylaminopropyl methacrylamide were added slowly.

This solution was heated to 80 ° C under a nitrogen stream, and potassium persulfate was adjusted to 0.
What melt | dissolved 5 g in 20 ml of distilled water was added, and heating was continued as it was for 5 hours. After cooling, 100 g of distilled water was added and filtered to obtain a polymer aqueous solution of compound (17) having a solid content concentration of 17.0% and an amine content of 8.17 × 10 ⁻⁴ eqv / g.

Other polymers can also be synthesized according to the above synthetic method.

Examples of the hydrophilic protective colloid used for dispersing the cationic polymer according to the present invention include gelatin, modified gelatin, gelatin derivatives and graft polymers of gelatin and other polymers, and proteins such as albumin and casein: Hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates; saccharide derivatives such as dextran, sodium alginate and starch derivatives; polyvinyl alcohol, partially acetalized polyvinyl alcohol,
Homopolymers and copolymers such as poly-N-vinylpyrrolidone, polyacrylamide, acrylic acid or methacrylic acid copolymer, and polyvinylpyrazole can be used in combination. Particularly preferably, gelatin is used as the hydrophilic colloid, and so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin are used. It is particularly preferable for rapid processing that it has a narrow molecular weight distribution.

The molecular weight distribution of gelatin can be measured by the GPC method (gel permeation chromatography). Gelatin containing 12% by weight or more, preferably 14% by weight or more of the high molecular weight component is preferable. The GPC method is described in the text of JP-A-62-87952 and Example-1.

Cationic polymer dispersion layer used in the present invention, or
The other hydrophilic colloid layer is hardened by an inorganic or organic hardener. Examples of hardeners include chromium salts, aldehydes (formaldehyde, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), active vinyl compounds (1,3,5-triacryloyl-).
Hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis- [β-vinylsulfonyl) propionamide], etc., for example, active halogen compounds (2,4,4,3) described in US Pat. -Dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium salts (1-morpholinocarbonyl-3-pyridinio) methanesulfonate etc.), haloamidinium salts (1- (1 -Chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. In the present invention, a hardener having two or more vinylsulfonyl groups (for example, Japanese Examined Patent Publication Nos. 47-24259, 49-13563, and 57-2).
Compounds described in the specification such as 4902) and hardeners having two or more active vinyl groups (for example, JP-A-53-41220, JP-A-53-41220).
Compounds described in the specification such as 53-57257, 59-162546, and 60-80846), and others, JP-A-62-222242
No. 62-245261, No. 62-109050 and No. 61-139
The compounds described in the specification such as 713 can be stably used without damaging the cation site of the polymer used in the present invention.

The acid dye used together with the cationic polymer according to the present invention has a light absorption selected in the spectral sensitivity wavelength range of the light-sensitive layer of the color light-sensitive material of the present invention, and particularly has a molar extinction coefficient of 10 ² l · mol · cm ⁻¹ or more. The ones are good. In a color light-sensitive material using a reflective support, a dye that does not leave a residual color by being decolorized or eluted after development is particularly preferable.

It is preferable to use a dye, which has a pH of 7.0 or less and is substantially insoluble in water, as a light absorber together with a dispersion aid in the form of solid fine particles in a colloid. "Solid fine particles" means
The average particle size (projection, circle approximation) is 1 μm or less, preferably 0.5 μm to 0.01 μm, and it is substantially diffusion resistant to other adjacent layers in the colloid layer and does not aggregate coarsely above 3 μm. It refers to the dispersed state.

Examples of the dispersion aid include ordinary nonionic surfactants, anionic surfactants and amphoteric surfactants, for example, JP-A-62-215272.
Nos. 649 to 668, and the compounds represented by the specific compounds W-1 to W-99, Japanese Patent Publication Nos. 56-36415 and 59-31688, and Japanese Patent Application No. General formulas [VII] and [VIII] of the specification of Sho 62-118519,
It can be used by selecting it from the surfactants represented by the formula [IX]. For example A water-soluble organic solvent such as dimethylformamide, methyl alcohol, ethyl alcohol or dimethylsulfonylamide can be used as the dispersion aid. In addition, hydrophilic colloids such as gelatin, casein, hydroxyl ethyl cellulose, poly-N-vinylpyrrolidone, polyacrylic acid and gelatin derivatives are used as the dispersion medium.
Also, alkaline water can be used.

Solid fine particle dispersion is a method in which a dye solid is dissolved in a water-soluble organic solvent and dispersed in an aqueous colloidal solution having a neutral or acidic pH, particularly preferably, the dye solid is wetted with water or an insoluble liquid and kneaded with a dispersion aid. Then, a method of forming fine particles in a mill and dispersing in a colloidal aqueous solution, a method of making a dye solid into a fine powder by using ultrasonic waves, and then dispersing in a colloidal aqueous solution by using a surfactant as a dispersion aid, or the like, It can be produced by a method such as dissolving a dye in alkaline water and dispersing it in an acidic colloidal aqueous solution.

Organic acids such as citric acid, oxalic acid, acetic acid and tartaric acid are preferably used in combination with the dye or colloid aqueous solution.

The solid fine particles used in the present invention are microcrystals of a dye,
It may be fine particles having a micelle structure or fine agglomerated particles. The particle size of the solid fine particles can be measured by observing the cross section of the section of the colloid layer containing them using a transmission electron microscope.

The method for dispersing solid fine particles is substantially insoluble in water having a pH of 7 or less, and in the molecule, hydroxyl group, carboxyl group, amino group, sulfomoyl group, etc. Dyes containing groups are preferred. The term "substantially insoluble in water" means that the fine particle dispersion state is insoluble to the extent that it can be retained in a hydrophilic colloid having a pH of 7 or less, for example, an aqueous gelatin solution.

Dyes having a solubility in water of pH 7 at room temperature (24 ° C.) of 10% by weight or less, more preferably 5% by weight or less are preferable.

Commonly known dyes, for example, arylidene dyes, styryl dyes, butadiene dyes, oxysole dyes, cyanine dyes, merocyanine dyes, hexianine dyes, diarylmethane dyes, triaryl dyes, azomethine dyes, Azo dyes, metal chelate dyes, anthraquinone dyes, catilben dyes, chalcone dyes,
It can be selected from the group of indophenol dyes. Further, for example, U.S. Patent Nos. 3,880,658, 3,931,144, and
3,932,380, 3,932,381, 3,942,987, Jei Fabian, H.Hartm
ann), “Light Absorption of Organic”
Colorants), (Springer Verlag (Sprin
gerVerlag) published) (or diffusion-resistant analogs) can also be selected from.

The dyes used in the present invention include functional dyes disclosed in Japanese Patent Application No. 62-106892, Japanese Patent Application No. 62-21527, Japanese Patent Application No. 62-2.
No. 93243 (pages 109 to 117) and Japanese Patent Application No. 62-4370
No. 4 and Japanese Patent Application No. 62-153132, the dye represented by the general formula (I); and Japanese Patent Application No. 62-226131, the general formula (I
Among the dyes represented by I), it is possible to select a dye that has a spectral absorption characteristic and does not have a residual color after development. To prevent halation, a dye that absorbs light in the spectral sensitivity wavelength range of the photosensitive layer provided on the cationic polymer dispersion layer is used. A dye having light absorption is used. It is preferable that 80% or more of the dye used in the photographic emulsion layer or other layers of the light-sensitive material is contained in the cationic polymer-containing layer. The amount of dye added is cation
Advantageously, the number of anionic groups of the dye is 0.01 to 10, preferably 0.2 to 1, relative to the number of sites.

Preferred dyes used in the present invention include, for preventing halation, Japanese Patent Application Nos. 61-287295, 61-314428 and 62-7.
No. 9483, No. 62-110333, No. 62-226131, No. 62-277669
Nos. 62-284448 and 62-34264, 62-239032, and 6 for correcting spectral sensitivity.
The dyes described in 2-264396, 62-261052, 62-247477 and the like can be mentioned.

Particularly preferred dyes are Japanese Patent Application Nos. 61-287295 and 62-79.
483, 62-153132, 62-226131, 62-284448
And the dyes described in JP-A-62-123454.

Next, specific examples of the dye used in the present invention are shown. However, it is not limited.

Dye-18, -37 and -43 are suitable for solid fine particle dispersion, and Dye-45 can also be used for solid fine particle dispersion.

General formulas (II), (III), (IV), (V) according to the invention
The dyes represented by (VI) and (VI) are particularly suitable for solid fine particle dispersion. In particular, when used in a colored layer (compared to, for example, a method using colloidal silver or a method using a cationic polymer that provides a cation site as a mordant), the following features are exhibited.

(1) Appropriate spectral absorption characteristics can be easily selected according to the purpose of use, such as a filter layer or an anti-halation layer.

(2) Photochemically inactive. It does not chemically desensitize, fog, or degrade latent images in adjacent silver halide light sensitive layers.

(3) Elution and decolorization are easy during the development process. Leaves no residual color or stain.

(4) Solid fine particles do not diffuse into other layers. It also has good stability over time and does not discolor or fade.

These features are especially the color photographic material for printing using a reflective support, specifically color printing paper, anti-halation layer for direct positive / color printing paper and color reversal printing paper,
It is useful as a filter layer for correcting the spectral sensitivity distribution.
When used as a filter layer, it is preferable to appropriately provide a filter layer by changing the layer structure of the light-sensitive layer constituting the color light-sensitive material, for example, the blue-sensitive layer (BL), the green-sensitive layer (GL) or the red-sensitive layer (RL). . It is also possible to form a filter layer by incorporating fine dye solid particles in a usual intermediate layer. Dye solid fine particles,
It is preferable to use in combination with the above-mentioned acid dye.

Each group in the general formulas (II), (III), (IV), (V) and (VI) will be described in detail.

The carboxyphenyl group possessed by the acidic nucleus represented by A ₂ and the electron-withdrawing group represented by X ₃ or Y ₃ includes not only one but also a phenyl group having two or three carboxy groups, and Include a sulfamoylphenyl group, a sulfonamidophenyl group and a hydroxyphenyl group each including a sulfamoyl group, a sulfonamide group and a phenyl group having two or three hydroxy groups, and a carboxy group. , A substituent other than a sulfamoyl group, a sulfonamide group and a hydroxy group (as a substituent, a dissociable substituent having a pKa (acid dissociation constant) of 4 or more in a solution having a volume ratio of water to ethanol of 1 or more or There is no particular limitation as long as it is a dissociative substituent.) Specifically, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 3-carboxyphenyl, 2-methyl-3-carboxyphenyl,
3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2,5-
Dicarboxyphenyl, 2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl, 4- (p-
(Cyanobenzenesulfonamido) phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2,4-dihydroxyphenyl, 3,4,5-trihydroxyphenyl, 2-hydroxy-4- Carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2
Examples thereof include groups such as -methyl-4-phenylsulfamoylphenyl. These groups may be bound not only directly to the acidic nucleus but also via a methylene group, an ethylene group or a propylene group.

The carboxyalkyl group having an acidic nucleus represented by A ₂ and an electron-withdrawing group represented by X ₃ or Y ₃ preferably has 1 to 10 carbon atoms, for example, carboxymethyl,
2-carboxyethyl, 3-carboxypropyl, 2-
Examples include groups such as carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl and the like.

The alkyl group represented by R ₄₀ , R ₄₃ or R ₄₆ has 1 to 1 carbon atoms.
Alkyl groups of 0 are preferred, eg methyl, ethyl, n
Examples thereof include groups such as -propyl, isoamyl and n-octyl.

The alkyl group represented by R ₄₁ and R ₄₂ is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-
Butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferable, and a substituent [eg, halogen atom such as chlorine bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (eg, methoxy, ethoxy)] An alkoxycarbonyl group (eg, methoxycarbonyl, i-propoxycarbonyl), an aryloxy group (eg, a phenoxy group), a phenyl group,
It may have an amide group (eg, acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R ₄₁ and R ₄₂ is preferably a phenyl group or a naphthyl group, and has a substituent (the substituents include the groups and alkyl groups (the groups mentioned above as the substituents of the alkyl group represented by R ₄₁ and R ₄₂ ). For example, methyl, ethyl) are included. ] May be included.

The acyl group represented by R ₄₁ and R ₄₂ is preferably an acyl group having 2 to 10 carbon atoms, for example, acetyl, propionyl, n-
Examples thereof include groups such as octanoyl, n-decanoyl, isobutanoyl and benzoyl. Examples of the alkyl or arylsulfonyl group represented by R ₄ and R ₄ include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl,
Examples thereof include groups such as p-toluenesulfonyl and o-carboxybenzenesulfonyl.

The alkoxy group represented by R ₄₃ and R ₄₆ is preferably an alkoxy group having 1 to 10 carbon atoms, for example, methoxy, ethoxy, n-
Examples thereof include butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy and isopropoxy groups. Examples of the halogen atom represented by R ₄₃ and R ₄₆ include chlorine, bromine and fluorine.

Examples of the ring formed by linking R ₄₁ and R ₄₄ or R ₄₂ and R ₄₅ include a diurolidine ring.

The 5- or 6-membered ring formed by connecting R ₄₁ and R ₄₂ is
Examples thereof include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L ₁ , L ₂ and L ₃ may have a substituent (eg methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X ₃ and Y ₃ may be the same or different, and are a cyano group, a carboxy group, an alkylcarbonyl group (an optionally substituted alkylcarbonyl group, for example, acetyl, propionyl, heptanoyl, Dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl group, etc., arylcarbonyl group (which may be substituted arylcarbonyl group, for example, benzoyl, 4
-Ethoxycarbonylbenzoyl, 3-chlorobenzoyl group and the like), alkoxycarbonyl group (alkoxycarbonyl group which may be substituted, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t
-Amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2
-Cyanoethoxycarbonyl, 2- (2-chloroethoxy) ethoxycarbonyl, 2- [2- (2-chloroethoxy) ethoxy] ethoxycarbonyl group, etc., aryloxycarbonyl group (which may be substituted aryloxycarbonyl group) , For example, phenoxycarbonyl,
3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4
-Nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2,4-di- (t-amyl) phenoxycarbonyl group, etc., carbamoyl group (which may be substituted, for example, carbamoyl group) , Ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl,
4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,
4-di- (t-amyl) phenylcarbamoyl, 2-chloro-3- (dodecyloxycarbonyl) phenylcarbamoyl, 3- (hexyloxycarbonyl) phenylcarbamoyl group and the like), sulfonyl group (for example, methylsulfonyl, And a sulfamoyl group (which may be substituted, such as sulfamoyl and methylsulfamoyl group).

Next, specific examples of the dyes used in the present invention, which are particularly suitable for solid fine particle dispersion, will be given, but the present invention is not limited thereto.

The dyes used in the present invention include international patents WO88 / 04794, European patent EP0274723A1, JP-A-52-92716, and JP-A-55-15.
5350, 55-155351, 61-205934, 48-68623
U.S. Pat.Nos. 2,527,583, 3,486,897, 3,746,
539, 3,933,798, 4,130,429, 4,040,841 and the like, and can be easily synthesized according to the method.

Examples of the hydrophilic protective colloid used in the colored layer in the present invention include gelatin, modified gelatin, derivatives of gelatin, graft polymers of these with other polymers, proteins such as albumin and casein; hydroxycellulose, carboxymethylcellulose and cellulose sulfate. Cellulose derivatives such as esters; sugar derivatives such as dextran, sodium alginate and starch derivatives; polyvinyl alcohol, partially acetalized polyvinyl alcohol,
Homopolymers and copolymers such as poly-N-vinylpyrrolidone, polyacrylamide, acrylic acid or methacrylic acid copolymer, and polyvinylpyrazole can be used in combination. Particularly preferably, gelatin is used as the hydrophilic colloid, and so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin are used. From the viewpoint of rapid processing, those having a narrow molecular weight distribution are particularly preferable.

The molecular weight distribution of gelatin can be measured by the GPC method (gel permeation chromatography). Gelatin containing 12% by weight or more, preferably 14% by weight or more of the high molecular weight component is preferable. The GPC method is described in the text of JP-A-62-87952 and Example-1.

The cationic polymer used in the present invention is dispersed in the hydrophilic colloid as water-soluble or as a latex. In the case of a water-soluble cationic polymer, a dye may be further added to prepare a coating solution for a colored layer. In the case of a cationic latex, the master coating solution to which a dye is added in advance is preferably diluted and dispersed in a hydrophilic colloid to obtain a coating solution. A dispersion of a water-soluble cationic polymer is relatively prone to agglomeration, and a relatively small amount of dye is used for the cationic polymer. The cationic polymer according to the present invention varies depending on the use conditions, but it is a hydrophilic protective colloid.
It is preferable to use 1 to 100 g per 0 g, more preferably 1 to 50 g, and further preferably 1 to 120 g. Also, for example, for each anion group of the anionic compound such as dye used, the cation site of the cation polymer is 0.1 or more, preferably 0.3 to 50.
In particular, quantities corresponding to 1 to 30 are used. The water-soluble cationic polymer is preferably 1 to 20 g per 100 g of the hydrophilic protective colloid, and the anionic group of the acid dye is 1
An amount corresponding to 5 to 30 cation sites is preferable for each.

Furthermore, a nonionic, amphoteric or anionic surfactant is used in the coating liquid for the colored layer, and it is particularly preferable to use a cationic surfactant. In the case of a water-soluble cationic polymer, a polymer latex dispersion is preferably used in combination, and particularly preferably used in combination with a cationic polymer latex dispersion.

The colored layer or other hydrophilic colloid layer used in the present invention is hardened with an inorganic or organic hardener. Examples of the hardener include chromium salts, aldehydes (formaldehyde, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, Bis (vinylsulfonyl) methyl ether,
N, N′-methylenebis- [β-vinylsulfonyl) propionamide], etc.), for example, active halogen compounds (2,4-dichloro-6) described in US Pat. No. 3,325,287.
-Hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid etc.), N-carbamoylpyridinium salts (1-morpholinocarbonyl-3-pyridinio)
Methanesulfonate, etc.), haloamidinium salts (1
-(1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. In the present invention, a hardener having two or more vinylsulfonyl groups (for example, JP-B-47-242)
59, Doujin 49-13563, No. 57-240902 and the like), and hardeners having two or more active vinyl groups (for example, JP-A Nos. 53-41220 and 53-43). -57257, 59
-162546, compounds described in the specification such as JP-A-60-80846), and others, JP-A-62-222242, JP-A-62-245261,
The compounds described in the specifications such as JP-A-62-109050 and Japanese Patent Application No. 61-139713 can be stably used without damaging the cation site of the polymer used in the present invention.

The average particle size of the cationic polymer latex fine particles used in the present invention is 1 μm or less, preferably 1 to 0.
001 μm, particularly 0.2 to 0.01 μm is preferable, and a narrow particle size distribution is preferable. Further, in the photographic constituent layer, other polymer latexes described in US Pat. Nos. 3,411,911 and 3,411,912 and Japanese Patent Publication No. 45-5331 can be used in combination. For example, when an anionic compound such as an acid dye is adsorbed and dispersed, it is preferable that the anionic compound be adsorbed on the cation site of the polymer in advance. By using this dispersion method, it is possible to prevent desorption due to the anionic surfactant coexisting in the hydrophilic colloid layer, the anionic group of the hydrophilic colloid itself, and the like.

The colored layer according to the present invention can be directly applied and dried on the water resistant resin layer containing a white pigment. It can also be provided directly on the support side of the silver halide photosensitive layer. Further, it is preferable to provide an intermediate layer between the front two layers. Further, another silver halide light-sensitive layer can be inserted. The colored layer is preferably provided so that the spectral sensitivity distribution of the silver halide photosensitive layer provided on the support side of the colored layer is modified.

The colored layer of the present invention has a membrane layer of 0.1 to 10 μm, preferably 0.2.
To 5 μm is preferable. The maximum spectral reflection density is preferably 0.2 or more, particularly 0.3 to 1.5.

The silver halide emulsion used in the present invention, especially the silver chlorobromide emulsion, is
P. Glafkides "Chemie et Physique Photographique" (P
aul Montled, 1967), GF Duffin, "Photographic Emulsion Chemistry" (Photogra
phic Emulsion Chemistry) (Focal Press, 1966)
, VLZelikman et al, "Making End Coating Photographic Emulsion" (Ma
king and Coating Photographic Emulsion.) (Focal P
ress, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, but the acidic method is particularly preferable. As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. The simultaneous mixing method is preferred for obtaining the monodisperse particles of the present invention. A method of forming grains under the condition of excess silver ions (so-called reverse mixing method) can also be used. As one type of the simultaneous mixing method, a method of keeping the silver ion concentration in the liquid phase where silver chlorobromide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a monodisperse silver chlorobromide emulsion suitable for the present invention having a regular crystal shape and a narrow grain size distribution can be obtained. The above-mentioned particles preferably used in the present invention are desirably prepared on the basis of the double-blending method. The composition of silver halide preferably has a silver chloride content of 15 mol% or more, and particularly 98 mol% or more for a light-sensitive material which requires rapid processability. The silver iodide may be contained in the range of not more than 1 mol%, but it is preferable that the silver iodide is not contained in the light-sensitive material in which rapid processing property is particularly required.

Known silver halide solvents (for example, ammonia, potassium thiocyanate, or U.S. Pat.
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828, etc. in the presence of thioethers and thione compounds) Physical ripening is preferable because a monodisperse silver halide emulsion having a regular crystal shape and a narrow grain size distribution can be obtained.

To remove the soluble silver salt from the emulsion after physical ripening, it is possible to use Nudel water washing, flocculation sedimentation method, ultrafiltration method or the like.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc., alone or in combination. That is, a sulfur sensitization method using active gelatin or a compound containing sulfur capable of reacting with silver ions (for example, thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.) or a reducing substance (for example, stannous salt) , Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc., and reduction sensitization methods, and metal compounds (eg, complex salts, Pt, I
r, Pd, Rh, Fe, etc. Periodic table metal complex group VIII)
The noble metal sensitization method using can be used alone or in combination. In the monodisperse silver chlorobromide emulsion,
Sulfur sensitization or selenium sensitization is preferably used, and it is also preferable that a hydroxyazaindene compound is present in the sensitization.

In the present invention, the monodispersity of the silver chlorobromide emulsion is preferably 0.15 or less in terms of coefficient of variation, particularly preferably 0.1 or less.

The chemical sensitization applied in the present invention can be performed by a usual method as described above. Especially when the silver bromide grain has a silver bromide localized phase on the surface or subsurface thereof, it is important to control the balance between the substrate grain and the localized phase for chemical sensitization. For this control, Japanese Patent Application Nos. 61-311131 and 62-62
The methods described in the specifications of 86252, 62-86163 and 62-86165, especially the appropriate use of the CR compound, are used.

The light-sensitive material of the present invention may contain various compounds as stabilizers. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyridines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as Oxazoline thiones; azaindenes such as tetraazaindenes;
Many compounds known as stabilizers can be added (especially 4-hydroxy substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like.

In the present invention, the use of the spectral sensitizing dye is important. As the spectral sensitizing dye used in the present invention, a cyanine dye, a merocyanine dye, a complex merocyanine dye and the like are used.
In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As the cyanine dye, simple cyanine dye, carbocyanine dye and dicarbocyanine dye are preferably used.

The sensitizing dye used in the present invention is preferably added before or during the process of chemical sensitization, or during or after the formation of silver halide grains.

The cationic polymer used in the present invention captures iodine ions eluted during development or fixing of silver halide,
It has the effect of increasing the development processing speed.

Further, there is an effect that bromine ions that are eluted during the silver halide development processing step or that are brought into the developing solution or from the outside are captured to stabilize the color development processing and increase the development processing speed. Further, in the present invention, the effect of suppressing a change in photographic property due to a change in processing conditions is particularly large, and the gradation stability of the legs and shoulders in the characteristic curve is improved. This effect is particularly remarkable when a high-silver chloride emulsion in which silver bromide is localized on the grain surface (preferably a silver chlorobromide emulsion having AgCl of 98 mol or more) is used and subjected to rapid processing at high temperature.

Furthermore, if the amount of silver halide used is silver, for example, 0.9 g / m
² or less, preferably 0.7 g / m ² or less, and by increasing the light transmittance of the coating by selecting the size and shape of the silver halide grains, the sharpness of the image by the polymer-containing colored layer of the present invention. And the effect of improving the color reproducibility is remarkable.

In the color light-sensitive material according to the present invention, a yellow coupler, a magenta coupler and a cyan coupler which are coupled to each other as an oxidation product of an aromatic amine color developing agent to develop yellow, magenta and cyan, respectively, are usually used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as benzoylacetanilide and bivaloylacetanilide are preferable.

Among them, as the yellow coupler, the following general formula [Y-
Those represented by 1] and [Y-2] are preferable.

For details of the pivaloyl acetanilide type yellow coupler, see US Pat. No. 4,622,287 at column 3, line 15-
Col. 8, line 39 and col. 4,623,616, col. 14, line 50 to 19
It is written in line 41 of column.

For details of the benzoylacetanilide type yellow coupler, U.S. Pat. Nos. 3,408,194, 3,933,501 and 4,
046,575, 4,133,958, 4,401,752 and the like.

Specific examples of the pivaloyl acetanilide type yellow coupler include the compound examples (Y-1) to (Y-39) described in columns 37 to 54 of the above-mentioned U.S. Pat. No. 4,622,287. Among them, (Y-1) (Y-4), (Y-
6), (Y-7), (Y-15), (Y-21), (Y-22),
(Y-23), (Y-26), (Y-35), (Y-36), (Y-37),
(Y-38), (Y-39) and the like are preferable.

Moreover, the compound examples (Y-1) to (Y-33) in columns 19 to 24 of the above-mentioned U.S. Pat. No. 4,623,616 can be mentioned, among which (Y-2), (Y-7), (Y-8), (Y-1
2), (Y-20), (Y-21), (Y-23), (Y-29) and the like are preferable.

In addition, as a preferable example, a typical specific example (34) described in column 6 of US Pat. No. 3,408,194, 3,933,
Compound examples (16) and (1
9), compound examples (9) described in columns 7 to 8 of the specification No. 4,046,575, compound examples (1) described in columns 5 to 6 of the specification No. 4,133,958, Compound Example 1 described in column 5 and Japanese Patent Application No. 62-263318 Application Nos. 29-3
The compounds a to g described on page 0 can be mentioned.

Examples of magenta couplers that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, preferably 5-pyrzolone type couplers 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 typical examples thereof are U.S. Patent Nos. 2,311,082 and 2,343,703.
No. 2, No. 2,600,788, No. 2,908,573, No. 3,062,65
3, No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230
(June 1984), and pyrazolopyrazoles. Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds are represented by the following general formula (M-
It is represented by 1), (M-2) or (M-3).

Among pyrazoloazole-based couplers, U.S. Pat. No. 4,50 in terms of low yellow sub-absorption of a coloring dye and light fastness.
The imidazo [1,2-b] pyrazoles described in 0,630 are preferred, and the pyrazolo [1,5 described in U.S. Pat. No. 4,540,654.
-B] [1,2,4] triazole is particularly preferred.

In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly bonded to the 2,3 or 6-position of a pyrazolotriazole ring, as described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent (Publication) No. 226,849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described.

The most representative cyan couplers are phenol cyan couplers and naphthol cyan couplers.

Examples of phenol cyan couplers include U.S. Pat.
929, 4,518,687, 4,511,647 and 3,772,002, etc. have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position (including polymer couplers), and their representatives Specific examples thereof include the coupler of Example 2 described in Canadian Patent 625,822, compound (1) described in US Pat. No. 3,772,002, compound (I-4) and (I-5) described in US Pat. Compounds (1), (2), (3) and (24), 62 described in Kaisho 61-39045.
The compound (C-2) described in -70846 can be mentioned.

As a phenol-based cyan coupler, U.S. Pat.
772,162, 2,895,826, 4,334,011, 4,500,6
There are 2,5-diacylaminophenol couplers described in JP-A-59-164555 and JP-A-59-164555, and typical examples thereof include compound (V) described in US Pat.
Compounds (17) described in 57,999, compounds (2) and (12) described in 4,565,777, compounds (4) described in 4,124,396, compounds (I-19) described in 4,613,564, etc. I can name it.

As a phenolic cyan coupler, U.S. Pat.
327,173, 4,564,586, 4,430,423, JP-A-61-
390441 and Japanese Patent Application No. 61-100222 include those in which a nitrogen-containing heterocycle is condensed with a phenol nucleus, and typical examples thereof include couplers (1) and (3 described in US Pat. No. 4,327,173. ), And the compound (3) described in No. 4,564,586.
And (16), the compounds (1) and (3) described in 4,430,423, and the following compounds.

Other US patents for phenol cyan couplers
4,333,999, 4,451,559, 4,444,872, 4,42
There are ureido couplers described in 7,767, 4,579,813, European Patent (EP) 067,689B1, etc., and typical examples thereof include couplers (7) described in U.S. Pat. No. 4,333,999 and 4,451,559. Coupler (1), same as 4,4
44,872 couplers (14), 4,427,767 couplers (3), 4,609,619 couplers (6) and (24), 4,579,813 couplers (1) and (11) The couplers (45) and (50) described in European Patent (EP) 067,689B1 and the coupler (3) described in JP-A No. 61-42658 can be mentioned.

The naphthol cyan coupler has an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, US Pat. No. 2,313,586) and an alkylcarbamoyl group at the 2-position (for example, US Pat.
4,293, 4,282,312), those having an arylcarbamoyl group at the 2-position (for example, Japanese Patent Publication No. 50-14523), those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-60-237448, 61-145557, 61-153640
No.), those having an aryloxy leaving group (for example, US Pat. No. 3,476,563), those having a substituted alkoxy leaving group (for example, US Pat. No. 4,296,199), those having a glycolic acid leaving group (for example, JP-B-60-39217). and so on.

Also, as a cyan coupler, European Patent (EP) No. 0,24
The diphenylimidazole type cyan couplers described in 9,453A2 can also be used alone or in combination with the above cyan couplers.

The following can be mentioned as a specific example.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color antifoggant.

Other dye image stabilizers include, for example, JP-A-59-125.
The catechol derivatives described in JP-A No. 732 and JP-A No. 60-262159 can also be used.

The light-sensitive material produced by using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (e.g. 46-278
4), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3,707,375),
A butadiene compound (for example, one described in US Pat. No. 4,045,229) or a benzooxide compound (for example, one described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These UV absorbers may be mordanted in a specific layer.

The color light-sensitive material according to the present invention comprises a reflection support, an undercoat layer, at least three kinds of silver halide light-sensitive layers, an intermediate layer, and
Since it is composed of multiple layers of ultraviolet absorber layer and protective layer,
In particular, the effect of improving the antihalation layer is great.

On the other hand, in the multi-layered color light-sensitive material according to the present invention, the cationic polymer-containing layer has a planar shape by providing an intermediate layer (layer substantially not containing photosensitive silver halide grains) adjacent to the polymer-containing layer. It can be installed without failure. In particular, when the silver halide photosensitive layer is used in combination with the cationic polymer-containing layer, it is preferable to provide an intermediate layer containing no photosensitive silver halide grains therebetween.

In the photographic emulsion layer or other photosensitive material constituting layers of the light-sensitive material of the present invention, as a coating remover, an emulsifying dispersant, an anti-adhesive agent and for improving photographic characteristics (for example, development acceleration, contrast enhancement, sensitization), antistatic and sliding A surfactant may be included for various purposes such as improving the properties.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkylamides or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulfonates,
Alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene Anionic surfactants containing carboxylic groups such as alkyl phosphates, sulfo groups, phospho groups, sulfate groups, phosphate groups, sugar acid groups; amino acids, aminoalkyl sulfonates, aminoalkyl sulfates or phosphate esters , Alkylbetaines, amine oxides and other amphoteric surfactants; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and fats Cationic surfactants such as phosphonium or sulfonium salts containing group or a heterocyclic ring can be used. Among these surfactants, polyoxyethylene-based surfactants and fluorine-containing surfactants are particularly preferably used.

In particular, when the dispersion of the cationic polymer according to the present invention is used in combination with the above-mentioned cationic surfactant, the surface property, film quality or adhesion to the adjacent layer can be improved.

Various other additives are used in the color light-sensitive material of the present invention, and these additives are listed in Research Disclosure magazine No. 17643 (December 1978).
No. 18716 (November) and No. 18716 (November 1979), and the relevant parts are summarized in the table below.

The color light-sensitive material of the present invention is preferably an ordinary color light-sensitive material, particularly a color light-sensitive material for printing.

A color developer is used for the development processing of the light-sensitive material of the present invention. The color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component.
Although amine phenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-.
Amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline , 3-methyl-4-
Examples thereof include amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds may be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catacol sulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives such as, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, fogging agents such as sodium boron hydride, 1-phenyl-3 -Auxiliary developing agents such as pyrazolidone, tackifiers, aminopolycarboxylic acids,
Various chelating agents represented by aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene, 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'
Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

The pH of these color developing solutions is generally 9 to 12, but preferably 10 to 11. Further, the replenishing amount of these developing solutions is generally 3 liters or less per 1 square meter of the light-sensitive material, and it can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of fixing after bleaching may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates and nitrobenzenes can be used. . Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858
Compounds described in JP-A No. 1,290,812 and JP-A No. 53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is most preferred. Can be used extensively. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the amount of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, etc. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in “Journal of the Society of Motion Picture Tel”.
evision Engineers Volume 64, pp. 248-253 (May 1955 issue)
It can be determined by the method described in.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 seconds to 5 minutes at 25-40 ° C. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. 8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

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. For example, indaniline compounds described in U.S. Pat. Salt complex, JP-A-5
The urethane compound described in 3-135,628 can be mentioned.

In the silver halide color light-sensitive material of the present invention, various 1-phenyl-containing compounds may be used, if desired, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-11.
No. 5,438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 35 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality and the stability of the processing liquid. be able to. Further, the light-sensitive material may be subjected to processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 for silver saving.

In order to fully exhibit the excellent features of the silver halide photographic light-sensitive material of the present invention, the silver halide color photographic light-sensitive material is substantially free of benzyl alcohol, and 0.00
2 minutes 30 with a color developer containing 2 mol / 1 or less bromine ions
It is preferable to process with a developing time of not more than seconds.

The above-mentioned "substantially free of benzyl alcohol" means 1 to 2 ml or less of the color developing solution, preferably 0.5
It means less than or equal to ml, and most preferably does not contain at all.

(Example) Next, the present invention will be described in more detail based on examples.

Example-1 LBKP (hardwood bleached, sulfate pulp) 100% for photographic printing paper
(Weighed 175 g / m ² , thickness about 180 μ); A white pigment-containing resin layer made of water resistant titanium oxide having the following composition was provided on the surface of a white base paper, and Supports A, I to VI were obtained.

Support A: 90 parts by weight of polyethylene composition (density 0.920 g / cc, melt index (MI) 5.0 g / 10 min), 10 parts by weight of titanium oxide white pigment surface-treated with silicon oxide and aluminum oxide are added. After kneading, melt extrusion coating was performed to obtain a water resistant resin layer having a thickness of 30 μm. On the other hand, another polyethylene composition (density 0.950g / cc, MI8.0g / 10
Min) was coated to obtain a water resistant resin layer having a thickness of 20 μm.

Support I: 89 parts by weight of the polyethylene composition used for Support A was treated with the following surface-treated anatase-type titanium oxide white pigment
After adding 11 parts by weight and kneading in the same manner, a water-resistant resin layer of 30 μm was obtained by melt extrusion coating.

The same titanium oxide powder as that used for the support A was immersed in an ethanol solution of 2,4-dihydroxy-2-methylpentane, heated and evaporated with ethanol to obtain a surface-treated titanium oxide white pigment. The alcohol was coated on the surface of particles corresponding to about 1% by weight of titanium oxide. A water resistant resin layer was provided on the back surface of the blank base paper using the polyethylene composition as in the case of the support A.

Samples II to V were obtained in the same manner except that the composition shown in Table 1 was used.

Support sample VI A composition of 50 parts by weight of hexaacrylate ester of 12 mol equivalent of dipentaerythritol propylene oxide and 50 parts by weight of rutile-type titanium oxide was mixed and dispersed in a ball mill for 20 hours or more, and then the dry film thickness was 20 μm. The following base paper was coated and dried so that The base paper used is support A
The thickness of the polyethylene composition on the white base paper used in
m layer, and the polyethylene composition (density
It was obtained by providing a 20 μm layer of 0.960 g / cc, MI 25 g / 10 min).

The coating layer was irradiated with an electron beam having an acceleration voltage of 200 kv and an absorbed dose of 5 megarads in a nitrogen atmosphere to obtain a support sample VI.

Regarding the dispersibility of the white pigment particles on the surface portion of the water-resistant resin layer of the support according to the present invention, the resin of about 0.05 μm was etched from the surface by the ion sputtering method, the white pigment particles were observed by an electron microscope, and continuous 6 μm × 6 μm
Of the projected area ratio Ri of each particle for 6 unit areas of The average particle occupation area ratio (%) was calculated.

The results are shown in Table 1-a.

In comparison with the support sample A, the support samples I to VI are excellent in dispersibility of the white pigment. In particular, Samples I, VI and VI are substantially uniformly dispersed.

Using Supports A and I to V, an undercoat layer (gelatin layer) is provided after corona discharge treatment, and a colored layer, a silver halide photosensitive layer, an intermediate layer, a protective layer, etc. are further provided as described below to perform color printing. Paper samples a to g and 1 to 6 were obtained.

The following coating amount values represent g / m ² . However, the silver halide emulsion represents the equivalent amount of silver.

First layer (colored layer) (shown in Table 2) Second layer (blue-sensitive silver halide emulsion layer) Coating amount Monodispersed silver chlorobromide emulsion (EM- with added spectral sensitizer (Sen-1) 1) 0.16 Monodispersed silver chlorobromide emulsion (EM-2) with 0.16 spectral sensitizer (Sen-1) 0.10 Antifoggant (Cpd-1) 0.004 Gelatin 1.83 Yellow coupler (ExY-1) 0.83 Color image stability Agent (Cpd-2) 0.03 Polymer (Cpd-3) 0.08 Solvent (Solv-1 and Solv-2 volume ratio 1: 1) 0.35 Hardener (Hd) 0.02 Third layer (color mixing prevention layer) Gelatin 1.25 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-3 and Solv-4 volume ratio 1: 1) 0.20 Hardener (Hd) 0.02 Fourth layer (Green-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-2, 3) Monodispersed silver chlorobromide emulsion (EM-3) 0.05 Monodispersed silver chlorobromide emulsion (EM-4) with spectral sensitizer (Sen-2,3) 0.11 Antifoggant (Cpd -5) 0.001 Gelatin 1.79 Magenta coupler (ExM-1) 0.32 Color image stabilizer (Cpd- 6) 0.20 Color image stabilizer (Cpd-7) 0.03 Color image stabilizer (Cpd-8) 0.03 Solvent (Solv-3 and Solv-4 volume ratio 1: 2) 0.65 Hardener (Hd) 0.01 Fifth layer ( UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1 / 2/3 molar ratio 1: 4: 4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Hardener (Hd) 0.01 No. Six layers (red-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-5) with spectral sensitizer (Sen-4,5) added 0.07 Spectral sensitizer (Sen-4,5) Monodispersed silver chlorobromide emulsion (EM-6) 0.15 Antifoggant (Cpd-9) 0.0002 Gelatin 1.34 Cyan coupler (ExC-1) 0.33 UV absorber (UV-1 / 3/4 molar ratio 1 : 3: 3) 0.17 Solvent (Solv-1) 0.23 Hardener (Hd) 0.01 7th layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1 / 2/3 molar ratio 1: 4: 4) 0.21 Solvent (Solv-6) 0.08 Hardener (Hd) 0.01 Eighth layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer The body (modification degree 17%) 0.17 Details of silver halide emulsions used in the liquid paraffin 0.03 the sample shown in Table 1.

Coefficient of variation = normal standard deviation in statistics / average particle size For the definition and measurement method of the above coefficient of variation, see TH James (The Theory of the Photographic Process) The Macmillan Company (Th
e Theory of the Photographic Process, the Macmillan
Company) 3rd edition (1966), page 39.

Photosensitizer (FWH manufactured by Fuji Photo Film Co., Ltd.)
Sequential exposure for sensitometry was performed using each of blue, green and red filters using a mold and a color temperature of a light source of 3,200 ° K. On the other hand, exposure for measurement of resolution (CTF) was performed, and then the following development processing was performed.

The density of the developed strips is measured and the Dm
in (minimum density of non-image area) was determined. The whiteness is Dmin (Dmin
(Yellow)). The results are shown in Table 3.

Treatment process temperature Time Color development 33 ° C. 3 minutes 30 seconds Bleach fixing 33 ° C. 1 minute 30 seconds Water washing 24-34 ° C. 3 minutes Drying 70-80 ° C. 1 minute The composition of each processing solution is as follows. Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Nitrilotriacetic acid 1.5 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 0.5 g Potassium carbonate 30 g N-ethyl-N- (β-methansulfonamidoethyl) -3 -Methyl-4-amino aniline sulphate 5.0 g Hydroxylamine sulphate 4.0 g Fluorescent brightener (WHITEX4B, Sumitomo Chemical Co., Ltd.) 1.0 g Add water to 1000 ml pH (25 ° C) 10.20 Bleach fixer water 400 ml Ammonium thiosulfate (70 %) as 150ml sodium sulfite 18 g ethylenediaminetetraacetic acid (III) ammonium 55 g disodium ethylenediaminetetraacetate sodium 5 g water to make 1000ml pH (25 ℃) 6.70 clear from the results of table 3, the support of the present invention The color photographic paper using the body (Samples c to g and 1 to 7) has improved whiteness and resolution compared to conventional ones. It is further color photographic paper using a colored layer of the present invention (Sample 1-7) are
It can be seen that the resolution is synergistically improved. Sample 6 having a colored layer containing a latex polymer having a small variation coefficient of titanium oxide particles and a high titanium oxide content, and a latex polymer having an ammonium group having at least one hydrogen atom at the cation site as a cationic polymer. In the case of, the resolution is good and the whiteness is excellent.

ExC-2, ExC- instead of ExC-1 as cyan coupler
Similar results can be obtained by using 3 or ExC-4. Example-2 Supports A, I, III, and V were obtained in the same manner as in Example-1.
Using I, samples h, 8 to 10 having the following layer constitutions were produced. The coating amount shown below represents g / m ² unless otherwise specified. However, the silver halide emulsion is the coating amount in terms of silver.

1st layer (blue layer) Coating amount Gelatin 1.0 Cationic polymer (5) 0.50 Dye (12) 5.0mg / m ² (8) 8.5〃 Second layer (blue sensitive silver halide emulsion layer) Spectral sensitizer (Sen -6) added monodispersed silver chlorobromide emulsion (EM-7) 0.27 Zetitin 1.86 Yellow coupler (ExY-1) 0.82 Polymer (Cpd-3) 0.08 Solvent (Solv-4) 0.35 Hardener (Hd) 0.02 3rd layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.06 Solvent (Solv-3 and Solv-4 volume ratio 1: 1) 0.12 Hardener (Hd) 0.02 Fourth layer (Green-sensitive halogenation) Silver emulsion layer) Monodispersed silver chlorobromide emulsion (EM-8) with spectral sensitizer (Sen-7,3) 0.45 Gelatin 1.24 Magenta coupler (ExM-1) 0.35 Color image stabilizer (Cpd-6) ) 0.20 Color image stabilizer (Cpd-7) 0.03 Color image stabilizer (Cpd-8) 0.03 Solvent (Solv-3 and Solv-5 volume ratio 1: 2) 0.65 Hardener (Hd) 0.01 Fifth layer (UV) Absorption layer) Gelatin 1.20 UV absorber (UV-1 / 2/3 molar ratio 1: 4: 4) 0.62 Color mixture inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Sixth layer (intermediate layer) Gelatin 0.50 Cationic polymer (1) 0.24 Dye (40) 5.3 (mg / m ² ) (41) 4.0 (〃) Seventh layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-9) with spectral sensitizer (Sen-4,5) added 0.20 Gelatin 0.92 Cyan coupler (ExC-1) 0.33 UV absorber (UV-1 / 3/4 molar ratio 1: 3: 3) 0.17 Solvent (Solv-4) 0.20 Hardener (Hd) 0.01 Eighth layer (UV Absorption layer) Gelatin 0.53 UV absorber (UV-1 / 2/3 molar ratio 1: 4: 4) 0.21 Solvent (Solv-6) 0.08 Hardener (Hd) 0.01 Ninth layer (protective layer) Gelatin 1.33 Polyvinyl alcohol Acrylic modified copolymer (17% modification degree) 0.17 liquid paraffin 0.03 The symbols of the additives used in the above sample have the same meanings as in Example 1. The structural formulas of other symbols are shown below.

Table 4 shows the details of the silver halide emulsion used in the above sample.

Cpd-1 and Cpd-9 used in Example 1 were added to the emulsions of EM-7 to 9 above.

In accordance with Example-1, stair step exposure for sensitometry and exposure for resolution measurement were performed. In addition, Fuji color in advance
Using a SUPER HR-100, printing exposure was performed from a color negative / original image obtained by photographing a person, a Macbeth color chart and fresh flowers.

Processing was carried out by the rapid color development processing step shown below, and the density was measured to obtain the results shown in Table 5.

As is clear from the results shown in Table 5, in the case of the silver halide color light-sensitive materials (Samples 8 to 10) according to the present invention, the sharpness of the image can be improved without deteriorating the whiteness.

Furthermore, by observing the characteristic curve, it is possible to compare
In addition to having a low Dmin, it was found that the gradation of the legs was sharply cut and extended, and it was found by visual observation of photographs that the gradation reproducibility of highlight details was excellent.

When a bluish colorant such as ultramarine is used for the support according to the present invention, it is possible to further enhance the apparent whiteness (visual whiteness). Processing step Temperature Time Color development 35 ° C. 45 seconds Bleach fixing 30- 36 ℃ 45 seconds Stability 30-37 ℃ 20 seconds Stability 30-37 ℃ 20 seconds Stability 30-37 ℃ 20 seconds Stability 30-37 ℃ 30 seconds Dry 70-85 ℃ 60 seconds (Stable → 4 The composition of each processing liquid is as follows. Color developer water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-Ethyl-N- (β-methansulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-diethyl hydroxylamine 4.2 g 5,6-dihydroxy benzene 1,2,4 Torisuru acid 0.3g fluorescent whitening agent (4,4'-Zia Minosuchiruben system) was added to 2.0g water 1000ml pH (25 ℃) 10.10 Bleach-fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 3g Glacial acetic acid 8g Water added 1000ml pH (25 ℃) 5.5 stabilizing solution formalin (37%) 0.1 g formalin - sulfite adduct 0.7 g 5-chloro-2-methyl-4 - isothiazolin-3-on-0.02 g 2-methyl-4 1000 ml pH by adding isothiazoloxy phosphorus-3-one 0.01g of copper sulfate 0.005g water (25 ° C.) 4.0 Example -3 support VII (support with acid paper) LBSP (hardwood bleached sulfite pulp) 20 parts, LBKP (Hardwood bleached sulfite pulp) 80 parts of wood pulp is beaten up to 300 cc in Canadian Freeness with a disc refiner, and sodium stearate 1.0 part, anion polyacrylamide 1.0 part, aluminum sulfate 1.5 parts, polyamide polyamine epichlorohydrin 0.5 parts are all wood pulp. As a surface sizing agent,
Polyvinyl alcohol (PVA) (adhesion amount: 1 g / m ² ) was used to make a paper with a weighed amount of 180 g / m ² by a Fourdrinier paper machine. The density was 1.0 g / m ² with a machine calender.

The pH value was 4.3.

A substrate VII provided with a water-resistant resin layer (25 μ layer) containing 15% by weight of trimethylolethane surface-treated anatase type titanium oxide according to the substrate II using the acid paper thus obtained as a paper substrate. Got Support VIII (support using neutral paper) Wood pulp consisting of 20 parts of LBSP and 80 parts of LBKP was beaten to a Canadian freeness of 300 cc with a disc refiner, and 0.5% to the pulp as a fixing agent (weight percentage to absolute dry pulp, below. The same) polyamide polyamine epichlorohydrin (manufactured by Dick Hercules, trade name Kaimen 557), followed by cationic polyacrylamide (manufactured by Arakawa Chemical Co., Ltd.), trade name Polystron 705) and anionic polyacrylamide (manufactured by Hamano Industry Co., Ltd., trade name Polyacron). ST-13) was added at 0.5% to each. Alkyl ketene dimer (Dick Hercules,
0.5% (trade name: Accorpel) was added, PVA (adhesion amount: 1 g / m ² ) was used as a surface sizing agent, and a paper having a basis weight of 180 g / m ^{2 was made} by a Fourdrinier paper machine. The density was 1.0 g / cm ³ with a machine calender. The pH value was 5.5.

Using the obtained neutral paper as a paper substrate, a water resistant white pigment-containing resin layer was obtained in the same manner as in Support VII.

Each of the supports VII and VIII was subjected to corona discharge treatment to form a colored layer having the following composition.

Composition of first layer (colored layer) Gelatin 0.50 g / m ² Black colloidal silver 0.18 g Cpd- (9) 0.001 Next, the second layer to the ninth layer were coated and dried in the same manner as in Example-2. Then, color photosensitive material samples 11 and 12 were obtained. However, the hardener was changed to 1,2-bis (vinylsulfonyl) ethane.

Cut into 12 cm width to make a roll, and after exposing the image by printing,
After making it into a roll and rubbing the cut surface under constant conditions, color development processing was performed according to the color development processing step shown in Example-2. In addition, 40 roll prints
The contamination on the cut surface was observed after aging at 5 ° C for 5 days (spread in a roll and observed from the side). The results are shown in Table 6.

Sample i was prepared by using Support B obtained in the same manner as in Sample 11, except that the water-resistant white pigment-containing resin layer was used in Support A in Support VII, and each layer was provided in the same manner as in Sample 11. It is a sample.

It has been shown that, in the color light-sensitive material according to the present invention, the use of neutral paper as the substrate for the support is more advantageous in obtaining whiteness than the acidic paper. This is probably due to additives, sizing and pH.

Example-4 Dye Fine Particle Dispersion Method Dispersion Method A Dye crystals having the following composition were kneaded and ground by a sand mill.

Dye −45 …… 0.3g −37 …… 0.7g −43 …… 0.8g 5% aqueous solution of the above-mentioned surfactant (5) …… 5ml Furthermore, in 25ml of 10% lime-treated gelatin aqueous solution by dissolving 1g of citric acid. And the sand used was removed using a glass filter. Dye adsorbed to the sand on the glass filter is also washed off with hot water and added, adding a 7% gelatin solution.
I got 100 ml.

Using the supports obtained in Example-1 and Example-3,
Corona discharge treatment was performed to provide a gelatin subbing layer, and the following first layer (colored layer) was obtained. Next, the second to ninth layers were obtained according to Example-2.

The cross section of the section of Sample-13 was observed using a transmission electron microscope. The average particle size of the fine dye powder according to Sample-13 is about 0.
It was 3 μm. The fine dye powder was in the first layer and was not found in the adjacent layer.

According to Example-1, stepwise exposure for sensitometry and exposure for resolution measurement were performed, and the rapid development processing shown in Example-2 was performed. The residual color due to the dye and the yellow stain were less than those of Samples 11 and 12 of Example-3. The results are shown in Table 8.

When each sample including the first layer of Samples 13 to 16 was immersed in the color developing solution, it was observed that the color was rapidly decolorized and flowed out in about 15 to 20 seconds.

Example-5 A dye crystal having the composition shown below and a dispersion aid were kneaded and ground by a ball mill, and further dispersed in 25 ml of a 10% lime-treated bone gelatin aqueous solution in which 1 g of citric acid was dissolved. Next, the beads used for the refinement were removed from the mixture by the filter, and the dye adsorbed on the filter and the beads was washed off with hot water and added to obtain 100 ml of 7% gelatin solution.

The average particle size of the fine crystal particles of the dye in the dispersion methods B, C, D and E was 0.1, 0.3, 0.15 and 0.2 μm. All were 0.3 μm or less, and haze was slight or nonexistent.

The first layer was provided by using a predetermined support as shown in Table 9. Samples 17 and 18 contained the dye fine particle dispersions according to the present invention using Dispersion Methods B and C, respectively. The second to ninth layers were provided in the same manner as in Example-2. However, Sample-19 contained fine particles of Dye IV-24 according to Dispersion Method D in the ninth layer. Stepwise exposure for sensitometry and exposure for resolution measurement were performed in the same manner as in Example-2.

As in Example-2, by the rapid color development processing step,
The treatment was performed and the concentration was measured, and the results shown in Table 9 were obtained. In particular, Samples 17, 18 and 19 have lower Dmin, no residual color or stain, excellent whiteness (visual observation), and excellent resolution.

(Sensitization Test with Safelight Light) Two sets of each of Samples 9, 16, 17, and 19 were subjected to stepwise exposure through a predetermined red filter for sensitometry (200 CMS, 0.1 second exposure). Sensitization test with safelight light was performed on one of the two samples.
The other set served as the control.

Mount the safelight filter 103A for color paper manufactured by Fuji Photo Film Co., Ltd. on a 10W (100V) light bulb, and
After irradiating the photosensitive surface of the sample perpendicularly for 20 minutes from a distance of m, color development processing was performed together with another set of samples. After the development processing, the density was measured, and the increase in the density of the sample at the image exposure amount corresponding to the reflection cyan image density of 0.5 of the control sample was compared to obtain the results shown in Table 10. This value is a measure of resistance to safelight light.

From the results shown in Table 10, it can be seen that Sample 19 has high resistance to safelight light and has a low white background density after the treatment.

(Effects of the Invention) According to the present invention, a photographic print that is less likely to have stains due to processing stains on a print obtained by photographic processing, has excellent whiteness, has excellent image sharpness, and has excellent tone reproducibility of highlight details. The silver halide photographic light-sensitive material provided can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Ono 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. Examiner Kayoko Yasuda (56) Reference JP-A-58-60738 (JP, A) JP-A-SHO 62-275246 (JP, A) JP-A-59-215334 (JP, A)

Claims (4)

[Claims] 1. A photographic light-sensitive material having at least one silver halide light-sensitive layer on a reflective support containing white pigment particles in the water-resistant resin layer, wherein the white pigment particles are contained in the water-resistant resin layer. It is contained at a density of 10% by weight or more, and the coefficient of variation of the occupied area ratio (%) per unit area in which the dispersibility of the white pigment particles is specified is s / (here, the average occupied area ratio per unit area). And s represents a standard deviation of an occupied area ratio per unit area) of 0.20 or less, and further has a colored layer which can be decolorized by photographic processing between the support and the silver halide photosensitive layer. And a silver halide photographic light-sensitive material. 2. A photographic light-sensitive material having at least one silver halide light-sensitive layer on a reflective support having a water-resistant resin layer coated on a support substrate, the silver halide light-sensitive layer being coated. White pigment particles are contained in the waterproof resin layer on the exposed side.
It is contained at a density of more than weight% and is 6μm × 6μ
The coefficient of variation s / of the occupied area ratio of the white pigment particles per m (unit area) is 0.20 or less, and further, a colored layer that can be decolorized by photographic processing is provided between the support and the silver halide photosensitive layer. A silver halide photographic light-sensitive material characterized by: 3. A pH value of 7.
The silver halide photograph according to claim (1) or (2), which comprises a solid fine particle dispersion of a dye which is substantially insoluble in water of 0 and has a pH higher than 9.0. Photosensitive material. 4. A coloring layer which can be decolorized by photographic processing, and has the following general formula (II), (III), (IV), (V) and (V
The silver halide photographic light-sensitive material according to any one of claims (1) to (3), which contains a solid fine particle dispersion of a dye selected from the compounds represented by I). General formula (II) General formula (III) General formula (IV) A ₂ = L ₁ − (L ₂ = L _{3 n} A ₂ General formula (V) General formula (VI) (In the formula, A ₂ represents an acidic nucleus having at least one substituent selected from a carboxyphenyl group, a sulfamoylphenyl group, a sulfonamidephenyl group, a carboxyalkyl group and a hydroxyphenyl group, As, 2-pyrazolin-5-one, rhodanin, hydantoin, thiohydantoin, 2,4-oxazolidinedione,
It is selected from the group consisting of isoxazolidinone, barbituric acid, thiobarbituric acid, indandione and hydroxypyridone. B ₂ represents a basic nucleus having at least one substituent selected from a carboxyl group, a sulfamoyl group and a sulfonamide group, and the basic nucleus includes pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole and pyrrole. Is selected from the group consisting of. R ₄₀ represents a hydrogen atom or an alkyl group, R ₄₁ and R ₄₂ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group, and R ₄₁ and R ₄₂ are linked to each other. To form a 5- or 6-membered ring. R ₄₃ and R ₄₆ each represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a halogen atom, and R ₄₄ and R ₄₅ each represent a hydrogen atom or R _41.
And R ₄₄ or R ₄₂ and R ₄₅ are connected to each other to represent a nonmetallic atom group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represent a substituted or unsubstituted methine group, X ₃ and Y ₃ each represent an electron-withdrawing group, and at least one carboxy group is present in either X ₃ or Y _3. It has an enyl group, a sulfamoylphenyl group, a sulfonamidephenyl group, a carboxyalkyl group or a hydroxyphenyl group. m represents 0 or 1, and n represents 0, 1 or 2. p represents 0 or 1, but when p is 0, R ₄₃ represents a hydroxy group or a carboxy group and R ₄₄ and R ₄₅ represent a hydrogen atom. )