JPH05303168A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material improved in lightfastness, balanced in photofading, small in rise or minimum density even in the case of running processing, and freed of bleeding on an image even at the time of storage under high temperature and high humidity. CONSTITUTION:The silver halide color photographic sensitive layer has at least each one of silver halide emulsion layers containing a yellow coupler, a magenta coupler, and a cyan coupler, respectively, on a reflective support, and the silver halide emulsion layer containing the yellow coupler is arranged farthest from the support, and one of photographic constituent layers contains a liquid ultraviolet absorber being liquid at normal temperature.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having improved image storability and processing stability (hereinafter, also simply referred to as "color light-sensitive material"). Regarding

[0002]

BACKGROUND OF THE INVENTION There are many known effects of ultraviolet light on photographic products. For example, static light generated during coating and drying of a photographic product and static light generated during transportation may cause unfavorable photosensitivity in photographic performance, and deterioration in color reproducibility due to different ultraviolet intensities of various light sources during photographing.

Further, in a photographic product in which an image is formed by a dye other than metallic silver, the fading of the dye image by ultraviolet rays is particularly large. Therefore, when the photographic product is displayed for appreciation, it is remarkably exposed to the sun rays containing a large amount of ultraviolet rays. Discoloration occurs.

Further, when polyethylene-coated paper is used as a support, polyethylene is deteriorated by ultraviolet rays, and the support is cracked.

In addition to these, various organic additives have been introduced into photographic products, and photodecomposition products produced by the photodecomposition reaction are often colored. It is also a phenomenon that often occurs. For example, it is also known that the uncolored part (white background) of color photographic paper causes yellowing due to light irradiation (called light stain), and its improvement is desired. Further, since the above problems become remarkable when the support is a reflective support,
Stronger improvements are required.

It is well known and widely used to incorporate an ultraviolet absorber into a silver halide emulsion layer or a non-photosensitive layer in a photographic product in order to mitigate the above-mentioned effects of ultraviolet rays. And, a great number of ultraviolet absorbers have been proposed for this use, and it is generally required to have the following properties. That is, (1) it has no absorption in the visible light region, (2) it has no effect on photographic products, (3) it has high solubility in high-boiling organic solvents, and the effect of long-time light irradiation To be used for the purpose of suppressing, (4) the light fastness of itself is high, and the like.

Proposals for using these ultraviolet absorbers in color light-sensitive materials have been proposed, for example, in JP-A-60-222853 and 62-1789.
54 and 62-178961.

Although the fastness of the image is obviously improved by using these ultraviolet absorbers, it is
When used in a color light-sensitive material that forms images of magenta and cyan dyes, there is a difference in light fastness between the coloring dyes, and the yellow image layer is positioned farther from the support than the magenta image layer and the cyan image layer. In general, the discoloration balance is lost and the image quality is significantly deteriorated. As a method of improving this, if an ultraviolet absorber layer is positioned on the side farther from the support than the yellow image layer to improve the color fading balance, the developing treatment is usually carried out while replenishing the developer replenisher with the developer replenisher. It was found that the white background is greatly deteriorated during the so-called running process.

This phenomenon is particularly remarkable when the silver halide emulsion layer is a direct positive light-sensitive material containing internal latent image type silver halide grains, and improvement has been desired.

The layer structure in which the yellow image layer is disposed farthest from the support further has a problem that the yellow image is bleeded especially when the image is stored in a high humidity or high temperature environment for a long period of time. It was understood that the improvement was desired.

[0011]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to improve the light fastness, to maintain the balance of photobleaching, to prevent the increase of the minimum density even after the running treatment, and to keep it at high temperature and high humidity. An object of the present invention is to provide a silver halide color photographic light-sensitive material that does not cause image bleeding.

[0012]

The above object of the present invention is:
A silver halide color photographic light-sensitive material comprising at least a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler, the silver halide emulsion comprising: Among the layers, a silver halide emulsion layer containing a yellow coupler is arranged at a position farthest from the support, and any one of photographic constituent layers of the photographic light-sensitive material contains a liquid ultraviolet absorber which is liquid at room temperature. Was achieved by a silver halide color photographic light-sensitive material.

The present invention will be described in more detail below.

In the present invention, a liquid ultraviolet absorber which is liquid at room temperature is used. In the present invention, “liquid at room temperature” means that at 25 ° C., as defined in “Chemical Dictionary (1963) Kyoritsu Shuppan” and the like, it does not have a certain shape, has fluidity, and has a substantially constant volume. Show things. Therefore, the melting point is not particularly limited as long as it has the above-mentioned properties, but a compound having a melting point of 30 ° C. or lower, particularly preferably 15 ° C. or lower is preferable.

The liquid ultraviolet absorber of the present invention may be a single compound or a mixture, and as the mixture, those composed of structural isomers can be preferably used. (Structural isomers are described in US Pat. No. 4,587,346 and the like.) The liquid ultraviolet absorber of the present invention can have any structure as long as the above is satisfied, but From the viewpoint, a 2- (2-hydroxyphenyl) benzotriazole compound represented by the following general formula (A) is preferable.

[0016]

[Chemical 1]

In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a dichloro group or a hydroxyl group.

Examples of the halogen atom represented by R ₁ , R ₂ and R ₃ include a fluorine atom, a chlorine atom and a bromine atom, and a salt atom is particularly preferable.

An alkyl group represented by R ₁ , R ₂ and R ₃ ,
The alkoxy group preferably has 1 to 30 carbon atoms, and the alkenyl group preferably has 2 to 30 carbon atoms, and these groups may be linear or branched. Further, these alkyl group, alkenyl group and alkoxy group may further have a substituent.

Specific examples of the alkyl group, alkenyl group and alkoxy group include methyl, ethyl, i-propyl, t-butyl, sec-butyl, butyl, pentyl, sec-pentyl, t-pentyl, octyl and nonyl. Groups such as dodecyl, eicosyl, α, α-dimethylbenzyl, octyloxycarbonylethyl, methoxy, ethoxy, octyloxy and allyl.

An aryl group represented by R ₁ , R ₂ and R ₃ ,
The aryloxy group is particularly preferably a phenyl group or a phenoxy group, and may have a substituent. For example, phenyl, 4-t-butylphenyl, 2,4-
Di-t-pentylphenyl and the like can be mentioned.

Of the groups represented by R ₁ and R ₂ , a hydrogen atom, an alkyl group, an alkoxy group and an aryl group are preferable, and a hydrogen atom, an alkyl group and an alkoxy group are particularly preferable.

Among the groups represented by R ₃ , a hydrogen atom,
A halogen atom, an alkyl group, and an alkoxy group are preferable, and a hydrogen atom, an alkyl group, and an alkoxy group are more preferable from the viewpoint of bright and fading.

Among the groups represented by R ₁ , R ₂ and R ₃ , at least one is preferably an alkyl group, and more preferably at least two are alkyl groups in order to be liquid at room temperature. is there.

The alkyl group represented by R ₁ , R ₂ and R ₃ may be any alkyl group, but at least one is preferably a tertiary alkyl group or a secondary alkyl group. Particularly, at least one of the alkyl groups represented by R ₁ and R ₂ is preferably a tertiary alkyl group or a secondary alkyl group.

Typical examples of the liquid ultraviolet absorbent according to the present invention are shown below, but the invention is not limited thereto.

[0027]

[Chemical 2]

[0028]

[Chemical 3]

The liquid ultraviolet absorber according to the present invention may be added in any amount, but in the range of 0.1 to 300% by weight with respect to the binder of the photographic constituent layer containing the ultraviolet absorber. It can be used and is preferably in the range of 1 to 200%, more preferably 5 to 100%.
The coating amount is preferably 0.01 to 100 mg / 100 cm ² .
Further, it is preferably used at 0.1 to 50 mg / 100 cm ² , particularly 0.5 to 30 mg / 100 cm ² .

The layer containing the liquid ultraviolet absorber of the present invention may be any of the photographic constituent layers of the present invention, but preferably at least 60% by weight of the total liquid ultraviolet absorber contained in the light-sensitive material further comprises Preferably at least 80% by weight
Are preferably contained in a photographic constituent layer located farthest from the light-sensitive silver halide emulsion layer farthest from the support.

The color light-sensitive material of the present invention comprises a silver halide emulsion layer containing at least a yellow coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a reflective support. And a silver halide emulsion layer containing a yellow coupler is disposed farthest from the support. The silver halide emulsion layer containing a yellow coupler may be one layer or two or more layers. Among them, the yellow coupler-containing emulsion layer farthest from the support is better than any magenta coupler-containing emulsion layer or cyan coupler-containing emulsion layer. Is also located far from the support.

As the reflective support that can be used in the color light-sensitive material of the present invention, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, or a cellulose acetate in which a white pigment which has been subjected to undercoating is kneaded if necessary. Examples thereof include polymer films such as films, baryta paper, and polyolefin laminated paper such as polyethylene. As the reflective support, one having a diffuse transmission density measured at 650 nm of 0.5 or more can be preferably used.

The silver halide emulsion used in the present invention is
Any conventionally known silver halide emulsion can be used. The silver halide grains may be surface latent image type silver halide grains or internal latent image type silver halide grains. For example, in the case of surface latent image type silver halide grains, a negative image can be obtained by a normal developing treatment, or a positive image can be obtained by developing by a reversal developing treatment. The effects of the present invention are more effectively exhibited when the internal latent image type silver halide grains are used.

The non-pre-fogged internal latent image type silver halide emulsion preferably used in the present invention forms a latent image mainly inside the silver halide grains and has most of the photosensitive nuclei inside the grains. An emulsion having silver halide grains, including any silver halide such as silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. .. Grains containing silver chloride are particularly preferable because they have excellent developability and are suitable for rapid processing.

Particularly preferably, the coated silver amount is about 1 to 3.5 g.
A portion of the sample coated on a transparent support to a range of / m ² was exposed to a light intensity scale for a defined period of time from about 0.1 second to about 1 second and was substantially halogenated. When only the surface image of a grain containing no silver halide solvent is developed for 4 minutes at 20 ° C., another part of the same emulsion sample is similarly exposed to expose the inside of the grain. Is an emulsion having a maximum density which is not larger than 1/5 of the maximum density obtained when the image is developed with the following internal developer B at 20 ° C. for 4 minutes. More preferably, the maximum density obtained with surface developer A is less than the maximum density obtained with internal developer B.
It is not larger than 1/10.

(Surface developer A) Metol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water was added to 1000 cc. (Internal developer B) Metol 2.0 g Sodium sulfite (Anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water is added to 1000 cc. The internal latent image type silver halide emulsion preferably used in the present invention is , Prepared by various methods are included. For example, a conversion type silver halide emulsion described in U.S. Pat.No. 2,592,250, or U.S. Pat.No. 3,206,316,
Silver halide emulsions having internally chemically sensitized silver halide grains described in U.S. Pat. Nos. 3,317,322 and 3,367,778, or U.S. Patents 3,271,157, 3,447,927 and
No. 3,531,291, emulsions having silver halide grains containing polyvalent metal ions, or U.S. Pat.
No. 761,276, a silver halide emulsion containing weakly chemically sensitized grain surfaces of silver halide grains containing a dopant, or JP-A Nos. 50-8524, 50-38525 and 53-2.
Silver halide emulsions composed of grains having a laminated structure described in JP-A-408156 and others.
Examples thereof include silver halide emulsions described in No. 55-127549.

The shape of the silver halide grains may be cubic, octahedral, tetrahedral composed of a mixture of (100) plane and (111) plane, a shape having (110) plane, spherical, tabular or the like. Good.

The average grain size of silver halide grains is 0.05 to 3 μm.
Those of m can be preferably used. The grain size distribution may be a monodisperse emulsion having uniform grain size and crystal habit, or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having uniform grain size and crystal habit. Is preferred.

In the present invention, the monodisperse silver halide emulsion means that the weight of silver halide contained within a grain size range of ± 20% around the average grain size rm is the total weight of silver halide grains.
It means 60% or more, preferably 70% or more, and more preferably 80% or more. Here, the average particle size rm is the product ni of the frequency ni and ri ^{3 of} particles having the particle size r i.
It is defined as the particle size ri when xri ³ becomes maximum. (3 significant digits, rounded down to the nearest digit.) The grain size referred to here is the diameter of a spherical silver halide grain,
Further, in the case of particles having a shape other than spherical, it is the diameter when the projected image is converted into a circular image having the same area. The particle size can be obtained by, for example, magnifying the particles with an electron microscope at a magnification of 10,000 times to 50,000 times, and measuring the diameter of the particles on the print or the area at the time of projection. (The number of measured grains is indiscriminately 1000 or more.) A particularly preferable highly monodisperse emulsion has a distribution width defined by the following that is 20% or less.

(Particle size standard deviation / average particle size) × 100 = width of distribution (%) Here, the average particle size and the particle size standard deviation are obtained from ri defined above.

The monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution in a gelatin solution containing seed grains to pAg and pH.
Under the control of the double jet method. To determine the addition rate, refer to JP-A-54-48521.
No. 58-49938 can be referred to. As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied.

The silver halide in the present invention can be optically sensitized with a commonly used sensitizing dye. It is also useful for the silver halide emulsion of the present invention to use a combination of sensitizing dyes used for supersensitization such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion. For sensitizing dyes, Research Disclosure (hereinafter abbreviated as RD) Nos. 15162 and 17643 can be referred to.

The fog treatment preferably used in the present invention can be carried out by using a compound which gives an overall exposure or produces a fog nucleus, that is, a fog agent.

The whole surface exposure is carried out by immersing the imagewise exposed light-sensitive material in a developing solution or other aqueous solution or moistening it and then uniformly exposing the whole surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the photosensitive material,
Further, high illuminance light such as flash light may be applied for a short time, or weak light may be applied for a long time. Further, the time of the whole surface exposure can be varied within a wide range so as to finally obtain the best positive image depending on the light-sensitive material, the development processing conditions, the type of the light source used and the like. Further, it is most preferable that the exposure amount of the whole surface exposure gives a certain range of exposure amount in combination with the photosensitive material. Usually, if the exposure amount is excessively increased, the minimum density is increased or desensitized, and the image quality tends to be deteriorated.

Next, the fog agent preferably used in the present invention will be described.

A wide variety of compounds can be used as the fog agent, and it is sufficient that the fog agent is present at the time of development processing. For example, in the constituent layers other than the support of the light-sensitive material (in particular, the silver halide emulsion layer). Medium) is preferred, or it may be contained in a developing solution or a processing solution prior to the development processing. The amount used can be varied over a wide range according to the purpose. The preferable amount added is 1 per mol of silver halide when it is added to the silver halide emulsion layer.
~ 1,500 mg, preferably 10-1,000 mg. When it is added to a processing solution such as a developing solution, the preferable addition amount is 0.01 to 5 g, and particularly preferably 0.05 to 1 g per liter of the processing solution.

Examples of the fogging agent used in the present invention include hydrazines described in US Pat.
615, 3,718,479, 3,719,494, 3,734,738 and 3,759,901 and heterocyclic quaternary nitrogen salt compounds; further silver halides such as acylhydrazinophenylthioureas described in U.S. Pat. No. 4,030,925. Examples thereof include compounds having an adsorption group on the surface. Further, these fogging agents can be used in combination. For example, RD15 mentioned above
162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent, either an adsorption type or a non-adsorption type can be used, or they can be used in combination.

Specific examples of useful fogging agents include hydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-acetyl-2-phenylhydrazine, 1-formyl-2- (4-methylphenyl) hydrazine, 1 Hydrazine compounds such as -methylsulfonyl-2-phenylhydrazine, 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine, 1-benzoyl-2-phenylhydrazine and formaldehydephenylhydrazine; 3- (2-formylethyl ) -2-Methylbenzothiazolium bromide, 3- (2-acetylethyl) -2-benzyl-5-phenylbenzoxazolium bromide, 3- (2-acetylethyl) -2-benzylbenzoselenazolium bromide , 2-methyl-3- [3- (phenylhydrazino) propyl] benzothiazolium bromide, 1,2
-Dihydro-3-methyl-4-phenylpyrido [2,1-b] benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] benzoselenazolium bromide,
4,4'-Ethylenebis (1,2-dihydro-3-methylpyrido [2,1
-b] N-substituted quaternary cycloammonium salts such as benzothiazolium bromide; 5- (3-ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] Rhodanine, 1,3-bis [4- (2-formylhydrazino) phenyl] thiourea, 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3,4- Examples thereof include tetrahydroacridinium trifluoromethanesulfonate, 1-formyl-2- [4- {3- (2-methoxyphenyl) ureido} phenyl] hydrazine and the like.

The light-sensitive material having the silver halide emulsion layer according to the present invention forms an image by developing after the image exposure.

When the light-sensitive material is an internal latent image type silver halide emulsion, a positive image is directly formed by imagewise exposure followed by overall exposure or development in the presence of a fogging agent.

As the developer that can be used in the developer used for developing the light-sensitive material of the present invention, a conventional silver halide developer, for example, polyhydroxybenzenes such as hydroquinone, aminophenols and 3-pyrazolidone can be used. , Ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or a mixture thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N- ( β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline, etc. Can be mentioned. It is also possible to incorporate these developers in the emulsion in advance so that they act on the silver halide during immersion in a high pH aqueous solution.

The developer used in the present invention may further contain a specific antifoggant and development inhibitor, or these developer additives may be optionally incorporated in the constituent layers of the light-sensitive material. It is possible.

The developing solution can be continuously developed while replenishing the replenishing developing solution. In the present invention,
When the replenishment amount of the developing solution is 500 cc./liter or less, the effect of the present invention can be more effectively exhibited.

Known photographic additives can be used in the light-sensitive material of the present invention.

Known photographic additives include, for example, the compounds described below in RD17643 and RD18716.

Additives RD17643 RD18716 Page Classification Page Chemical sensitizer 23 III 648 Top right Sensitizing dye 23 IV 648 Top right Development accelerator 29 XXI 648 Top right Antifoggant 24 VI 649 Bottom right Stabilizer 〃 Color stain preventive 25 VII 650 Left to right Image stabilizer 25 VII UV absorber 25 to 26 VII 649 Right to 650 left Filter dye 〃 〃 Whitening agent 24 V hardening agent 26 X 651 Right coating aid 26 to 27 XI 650 Right surfactant Agent 26 to 27 XI 650 Right Plasticizer 27 XII 650 Right Sliding agent 〃 〃 Antistatic agent 〃 〃 Matt agent 28 XVI 650 Right binder 29 IX 651 Right In the emulsion layer of the light-sensitive material of the present invention, a color developing agent is used. A dye-forming coupler is used which forms a dye by a coupling reaction with an oxidant. The dye-forming couplers are usually selected for each emulsion layer so that a dye that absorbs the light in the light-sensitive spectrum of the emulsion layer is formed, and in the blue-sensitive emulsion layer the yellow dye-forming coupler is the green dye. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, the color light-sensitive material may be manufactured by a method different from the above combination depending on the purpose.

These dye-forming couplers preferably have a group called a ballast group having a carbon number of 8 or more, which makes the coupler non-diffusible, in the molecule. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye. Even if they are 4-equivalent, only 2 molecules of silver ions need to be reduced. Either equivalence may be used. Releases a development inhibitor along with development, releases a development inhibitor at the same time as a DIR coupler that improves image sharpness and image graininess, and produces a colorless compound by coupling reaction with an oxidized product of a developing agent. DIR compounds may be used.

The DIR coupler and the DIR compound used have an inhibitor bound directly to the coupling position and an inhibitor bound to the coupling position via a divalent group, and are released by the coupling reaction. Those which are bound so as to release the inhibitor by intramolecular nucleophilic reaction or intramolecular electron transfer reaction (referred to as timing DIR coupler and timing DIR compound) are included. or,
A colorless coupler (also referred to as a competing coupler) that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with the dye-forming coupler.

Known acylacetanilide type couplers can be preferably used as the yellow dye-forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As the magenta dye forming coupler, known 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers, acylacetonitrile type couplers, indazolone type couplers and the like can be used. Examples of specific compounds of preferred magenta couplers are described in European Patent Publication No. 0327272, page 5, line 23 to page 8, line 52.

As another specific example, European Patent Publication 0273
Nos. 712, pages 6 to 21 Compounds M-1 to M-61
And the compounds 1-2 described in No. 0235913, pages 36-92.
There are other than the above representative examples in 23.

As the cyan dye-forming coupler, known phenol type, naphthol type or imidazole type couplers can be used. For example, a phenol-based coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol-based coupler formed from a 5-aminonaphthol skeleton, and a 2-equivalent naphthol-based coupler having an oxygen atom introduced as a leaving group are representative. It

The total amount of the binder on the side of the light-sensitive material of the present invention where the light-sensitive silver halide emulsion layer is present is preferably 10 g / m ² or less, more preferably 9 g / m ² or less.

The support used for the light-sensitive material of the present invention may be subjected to a treatment for enhancing the adhesiveness, antistatic property and the like.

[0065]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 A paper support (thickness 14
A multilayer color light-sensitive material was prepared by coating the following first to seventh layers on the front side (5 μm) and the eighth layer on the back side. Titanium white is included as a white pigment on the coating side of the first layer of polyethylene.

(Photosensitive layer composition) The components in each constituent layer and the coating amount shown in g / m ² are shown below. Silver halide is converted to silver. The silver halide emulsions used were each silver chlorobromide (AgB in molar ratio) optimally sensitized with sulfur and gold.
r: AgCl = 70: 30) emulsion. SA-1 and SA-2 were used as coating aids, and HA- was used as a hardener.
1, HA-2 was used.

SA-1: sulfosuccinic acid di (2-ethylhexyl) ester sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester Sodium H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: tetrakis (vinylsulfonylmethyl) methane 7th layer (protective layer) gelatin 1.23 6th layer (ultraviolet absorbing layer) gelatin 0.54 UV absorber (UV-1) 0.40 Solvent (SO-2) 0.12 Fifth layer (red photosensitive layer) 0.30 μm cubic chlorobromide spectrally sensitized with red-sensitizing dyes (D-3 and D-4) Silver emulsion 0.22 Gelatin 1.38 Cyan coupler (CC-1) 0.21 Cyan coupler (CC-2) 0.21 Image stabilizer (AO-3) 0.22 Solvent (SO-1) 0.33 Dye (AI-2) 0.02 Stabilizer (ST-1 , ST-2, T-1) 4th layer (intermediate layer) gelatin 0.7 5 Anti-color mixing agent (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer (green photosensitive layer) 0.30 μm cubic silver chlorobromide emulsion spectrally sensitized with a green sensitizing dye (D-2) 0.22 Gelatin 1.30 Magenta coupler (MC-1) 0.12 Magenta coupler (MC-2) 0.24 Image stabilizer (AO-1) 0.24 Image stabilizer (AO-2) 0.17 Solvent (SO-1) 0.31 Anti-stain agent (AS-2) ) 0.015 Dye (AI-1) 0.01 Stabilizer (ST-1, ST-2, T-1) Second layer (intermediate layer) Gelatin 0.75 Color mixing inhibitor (AS-1) 0.055 Solvent (SO-2) 0.12 1 layer (blue light-sensitive layer) 0.55 μm cubic silver chlorobromide emulsion 0.41 spectrally sensitized with a blue-sensitizing dye (D-1) 0.41 gelatin 1.35 yellow coupler (YC-1) 0.84 stain inhibitor (AS-2) ) 0.02 Image stabilizer (AO-3) 0.25 Solvent (SO-1) 0.52 Stabilizer (S T-1, ST-2, T-1) Eighth layer (back surface layer) Gelatin 4.00 SO-1: trioctyl phosphate SO-2: dioctyl phthalate AS-1: 2,4-di-t-octylhydroquinone AS- 2: 2,4-di-t-butylhydroquinone ST-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-2: N-benzyladenine T-1: 4-hydroxy-6-methyl-1 , 3,3a, 7-Tetrazaindene

[0069]

[Chemical 4]

[0070]

[Chemical 5]

[0071]

[Chemical 6]

[0072]

[Chemical 7]

The obtained sample is referred to as sample B-1. Then, the first layer (blue photosensitive layer) and the fifth layer (red photosensitive layer) of Sample B-1 were exchanged to replace the blue photosensitive layer with the fifth layer and the red photosensitive layer with the first layer.
Sample A-in the same manner as Sample B-1 except that the layer was used.
Created 1.

Further, the ultraviolet absorbers of the second layer (intermediate layer) and the sixth layer (intermediate layer) of Samples A-1 and B-1 were changed as follows to obtain Samples A-2 to A-11, Sample A-1. B-2 and B-3 were created.

UV absorber (g / m ² ) Sample No. Y layer 2nd layer 6th layer A-1 (comparative) 5th layer-UV-1 (0.40) A-2 (comparative) 5th Layer-UV-2 (0.40) A-3 (comparative) Fifth layer UV-1 (0.20) UV-2 (0.20) A-4 (comparative) Fifth layer UV-1 (0.40) -A-5 (Invention) Fifth Layer-UV-4L (0.40) A-6 (Invention) Fifth Layer-UV-13L (0.40) A-7 (Invention) Fifth Layer-UV-23L (0.40) A- 8 (Invention) Fifth Layer-UV-25L (0.40) A-9 (Invention) Fifth Layer UV-25L (0.20) UV-25L (0.20) A-10 (Invention) Fifth Layer UV-25L (0.40) -A-11 (Invention) Fifth layer UV-2 (0.10) UV-1 (0.20) UV-23L (0.10) UV-23L (0.20 B-1 (Comparative) First layer-UV- 2 (0.40) B-2 (comparison) 1st layer-UV-16L (0.40) B-3 (comparison) 1st layer-UV-23L (0.40) Samples A-1 to A-11 and B-1 to B-3, were exposed through an optical wedge using a sensitometer usual manner,
It processed according to the process step-1 shown below. (Development with a new solution) The same processing as above, but the processing steps-
The developing solution in Example 1 was treated with the developing solution obtained after running the sample A-1 until the total amount of the replenished replenishing solution reached 3 times the capacity of the developing tank. (Development with running solution) Processing step-1 Processing time Processing temperature (1) Current image 37 ° C 120 seconds (2) Bleach fixing 35 ° C 30 seconds (3) Stabilization processing 25-30 ° C 40 seconds (4) Drying 60 ~ 85 ℃ 40 seconds The composition of the processing solution is as follows.

(Color developer) Benzyl alcohol 15.0 cc. Cerium (III) sulfate 0.015 g Ethylene glycol 8.0 cc. Potassium sulfite 2.5 g Potassium bromide 0.6 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate Salt 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline 3/2 sulfate monohydrate 4.0 g N-ethyl-N-β-hydroxyethyl -4-Aminoaniline 3.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Diethylene glycol 15.0cc. Add water to bring the total volume to 1 liter and adjust to pH 10.15. ..

(Bleach-fixing solution) diethylenetriaminepentaacetic acid ferric ammonium 90.0 g diethylenetriaminepentaacetic acid 3.0 g ammonium thiosulfate (70% aqueous solution) 180.0 cc. Ammonium sulfite (40% aqueous solution) 27.5 cc. 3-mercapto-1,2, 4-Triazole 0.15 g Adjust pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to make 1 liter.

(Stabilizing liquid) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12.0 cc. Ethylene glycol 10.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Water is added to bring the total volume to 1 liter and hydroxylated. Adjust to pH 7.5 with ammonium or sulfuric acid.

The stabilization treatment was a countercurrent system having a two tank structure.

The formulation of the replenisher for running is shown below.

(Color development replenisher) benzyl alcohol 18.5cc. Cerium (III) sulfate 0.015g ethylene glycol 10.0cc. Potassium sulfite 2.5g potassium bromide 0.3g sodium chloride 0.2g potassium carbonate 25.0g T-1 0.1g hydroxylamine Sulfate 5.0 g Sodium diethylenetriamine pentaacetate 2.0 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline 3/2 Sulfate monohydrate 4.8 g N-Ethyl-N-β-hydroxy Ethyl-4-aminoaniline 3.6g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Diethylene glycol 18.0cc. Add water to make the total volume 1 liter and adjust to pH 10.35. To do.

(Bleach-fixing replenisher) The same as the above-mentioned bleach-fixing solution.

(Stabilizing Replenisher) Same as the above stabilizing solution.

The replenishing amount is a color developing solution, a bleach-fixing solution,
The stabilizing solution was 320 cc / m ^{2 of} the photosensitive material.

A part of the sample developed with the above-mentioned new solution was
Image bleeding was visually observed after storage for 1 week in an environment of a temperature of 85 ° C. and a relative humidity of 60%.

The following evaluations were performed on the obtained samples.

<Sensitometry> The sensitivity and the minimum density of the obtained treated sample measured with blue light using a PDA-65 densitometer (manufactured by Konica Corporation) were determined. Sensitivity was expressed as the relative value of the reciprocal of the exposure dose that gave a density 1.0 higher than the minimum density.

<Image bleeding> Visual observation was performed. The yellow image is greatly blurred from the outline of the image (x), slightly blurred (△), and no blur is observed (○).
The grade was evaluated.

The results are summarized below.

New liquid Running liquid Sample No. Sensitivity Dmin Dmin Image blur A-1 (Comparison) 100 0.25 0.32 × A-2 (Comparison) 102 0.25 0.32 × A-3 (Comparison) 98 0.25 0.29 △ A -4 (Comparison) 98 0.25 0.30 △ A-5 (Invention) 102 0.24 0.26 ○ A-6 (Invention) 103 0.24 0.26 ○ A-7 (Invention) 100 0.24 0.26 ○ A-8 (Invention) 100 0.24 0.26 ○ A-9 (Invention) 100 0.25 0.27 ○ A-10 (Invention) 100 0.25 0.27 ○ A-11 (Invention) 104 0.24 0.26 ○ B-1 (Comparison) 91 0.25 0.29 △ B- 2 (Comparison) 89 0.25 0.30 △ B-3 (Comparison) 89 0.25 0.29 △ As is clear from the above results, in the sample of the present invention, the processed photosensitive material was stored under high temperature and high humidity conditions. Even in this case, there is no blurring of the image, the sensitivity is high, and a small minimum density is maintained even when treated with the treatment liquid in the running state. Further, it is more preferable that the ultraviolet absorber of the present invention contains 60% or more of the hydrophilic colloid layer on the far side of the emulsion layer farthest from the support of the light-sensitive material.

Example 2 A paper support (thickness 14
A multilayer color light-sensitive material was prepared by coating the following first to ninth layers on the front side (5 μm) and the tenth layer on the back side. Titanium white is included as a white pigment on the coating side of the first layer of polyethylene.

The emulsions used were all core / shell agents prepared by the same method as the emulsion EM-1 below.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate and potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added simultaneously with the control double jet method to obtain a particle size of 0.30μ.
A cubic silver chlorobromide core emulsion of m was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added to the obtained core emulsion by a control double jet method. To form an average particle size of 0.42 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of the distribution of this emulsion was 8%.

(Composition of Photosensitive Layer) Components and coating amounts are shown below, but the display is the same as in Example 1. Incidentally, coating aid,
The same hardener as in Example 1 was used.

Ninth Layer (Protective Layer) Gelatin 1.23 Eighth Layer (UV Absorbing Layer) Gelatin 0.54 UV Absorber (UV-1) 0.40 Solvent (SO-2) 0.12 Seventh Layer (Blue Photosensitive Layer) Blue Sensitization 0.31 μm 14-sided silver chlorobromide emulsion 0.12 spectrally sensitized with dye (D-1) 0.55 μm cubic silver chlorobromide emulsion 0.18 blue sensitized spectrally sensitized with dye (D-1) 0.75 μm cubic silver chlorobromide emulsion 0.30 spectrally sensitized with dye (D-1) 0.30 gelatin 1.35 yellow coupler (YC-1) 0.84 stain inhibitor (AS-2) 0.02 image stabilizer (AO-3) 0.25 solvent (SO-1) 0.52 Stabilizer (ST-1, ST-2, T-1) Sixth layer (intermediate layer) Gelatin 0.40 Color mixing inhibitor (AS-1) 0.027 Solvent (SO-2) 0.036 Fifth layer ( Yellow filter layer) Gelatin 0.42 Yellow colloidal silver 0.10 Color mixing inhibitor (AS-1) 0 .04 Solvent (SO-2) 0.05 Fourth layer (intermediate layer) Gelatin 0.75 Color mixing inhibitor (AS-1) 0.055 Solvent (SO-2) 0.072 Third layer (green photosensitive layer) Green sensitizing dye (D- 0.18 µm cubic silver chlorobromide emulsion 0.06 spectrally sensitized in 2) 0.30 µm cubic silver chlorobromide emulsion spectrally sensitized with green sensitizing dye (D-2) 0.09 green sensitizing dye (D- 0.55μm cubic silver chlorobromide emulsion 0.15 gelatin 1.30 magenta coupler (MC-1) 0.12 magenta coupler (MC-2) 0.24 image stabilizer (AO-1) 0.24 image stabilizer (AO-) 2) 0.17 Solvent (SO-1) 0.31 Anti-staining agent (AS-2) 0.015 Dye (AI-1) 0.01 Stabilizer (ST-1, ST-2, T-1) Second layer (intermediate layer) Gelatin 0.75 Anti-mixing agent (AS-1) 0.055 Solvent (SO-2) 0.12 First layer (red photosensitive layer) Red-sensitive sensitizing dye 0.18 μm cubic silver chlorobromide emulsion spectrally sensitized with (D-3 and D-4) 0.06 0.30 μm cubic chlorobromide spectrally sensitized with a red-sensitizing dye (D-3 and D-4) Silver emulsion 0.09 0.55 µm cubic silver chlorobromide emulsion spectrally sensitized with red sensitizing dyes (D-3 and D-4) 0.15 Gelatin 1.38 Cyan coupler (CC-1) 0.21 Cyan coupler (CC-2) 0.21 Image stabilizer (AO-3) 0.22 Solvent (SO-1) 0.33 Dye (AI-2) 0.02 Stabilizer (ST-1, ST-2, T-1) 10th layer (backside layer) Gelatin 4.00 Obtained The samples C-1 to C- were prepared by changing the UV absorbers of the fifth layer (yellow filter layer) and the eighth layer (UV absorbing layer) of the sample C-1 as follows.
Created 11.

UV absorber (coating amount g / m ² ) Sample No. 5th layer 8th layer C-1 (Comparative example) -UV-1 (0.40) C-2 (Comparative example) -UV-2 ( 0.40) C-3 (Comparative example) UV-1 (0.20) UV-2 (0.20) C-4 (Comparative example) UV-1 (0.40) -C-5 (Invention) -UV-8L (0.40) C -6 (Invention) -UV-15L (0.40) C-7 (Invention) -UV-23L (0.40) C-8 (Invention) -UV-24L (0.40) C-9 (Invention) UV- 25L (0.20) UV-24L (0.20) C-10 (Invention) UV-25L (0.40) -C-11 (Invention) UV-2 (0.10) UV-1 (0.20) UV-23L (0.20) UV -23L (0.10) Each sample was exposed through an optical wedge using a sensitometer according to a conventional method and processed according to the following Process Step-2 (new liquid process). However, in the fogging exposure, the surface of the photosensitive material was uniformly exposed on the entire surface through a layer of the developing solution having a thickness of 3 mm while being immersed in the developing solution.

Similar to the above, but obtained by running the developer in processing step-2 on the above sample C-1 until the total amount of the replenished replenisher replenished is 3 times the capacity of the developing tank. Processing was performed using the latter developer. (Running solution treatment) Treatment step-2 Treatment temperature Treatment time (1) Immersion (developer) 37 ° C 8 seconds (2) Fog exposure-5 seconds (1 lux) (3) Development 37 ° C 95 seconds (4) Bleach fixing 35 ° C. 30 seconds (5) Stabilization treatment 25-30 ° C. 40 seconds (6) Drying 60-85 ° C. 40 seconds The composition of the color developing solution, bleach-fixing solution and stabilizing solution in the processing step-2 is the same as in Example 1. Is exactly the same as each of the treatment solutions used in the treatment step-1 and each of the replenishers for running has the same composition.

Similarly, for the stabilization treatment, a countercurrent system having a two tank structure was adopted.

[0102] Incidentally, replenishing amount developing solution replenisher, bleach-fixing solution, stabilizing solution together, and the photosensitive material 1 m ² per 320 cc..

The obtained sample was evaluated in the same manner as in Example 1 for sensitometry and bleeding. The results are shown below.

New liquid Running liquid Sample No. Sensitivity Dmin Dmin Image blur C-1 (Comparison) 100 0.25 0.37 × C-2 (Comparison) 102 0.25 0.37 × C-3 (Comparison) 98 0.25 0.34 △ C -4 (comparative) 98 0.25 0.32 △ C-5 (invention) 102 0.24 0.27 ○ C-6 (invention) 103 0.24 0.27 ○ C-7 (invention) 100 0.24 0.27 ○ C-8 (invention) 100 0.24 0.27 ○ C-9 (invention) 100 0.25 0.29 ○ C-10 (invention) 100 0.25 0.29 ○ C-11 (invention) 104 0.24 0.27 ○ As is clear from the results, the present example The sample of the invention does not cause image bleeding even when the processed light-sensitive material is stored under high temperature and high humidity conditions, has high sensitivity, and maintains a minimum minimum density even when processed with a running liquid. Further, the ultraviolet absorber of the present invention is more effective when the hydrophilic colloid layer on the far side of the emulsion layer farthest from the support of the light-sensitive material contains 60% or more thereof.

Example 3 The silver halide emulsion contained in each emulsion layer of Sample C-11 of Example 2 was replaced with an octahedral silver bromide emulsion prepared by a method according to EM-2 shown below, Further, FA-1 and FA-2 as fog agents were added to each emulsion layer in an amount of 6 mg and 25 mg per mol of silver halide, respectively.
Sample D-1 was prepared in the same manner as in.

Further, the silver halide emulsion contained in each emulsion layer of Sample C-1 was replaced with an octahedral silver bromide emulsion prepared by a method according to EM-2 shown below, and each emulsion layer was further replaced. Sample C except that FA-1 and FA-2 were added as fog agents in an amount of 6 mg and 25 mg, respectively, per mol of silver halide.
Sample D-2 was prepared in the same manner as -1.

(Preparation of Emulsion EM-2) An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added over 15 minutes while the aqueous gelatin solution was vigorously stirred and kept at 75 ° C., and the average particle size was 0.35 μm. An octahedral silver bromide emulsion was obtained. 0.1 g of 3,4-dimethyl-1,3-thiazoline per mol of silver was added to this emulsion.
2-Thion, 4 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added and chemically sensitized by heating at 75 ° C. for 25 minutes.

Using the obtained particles as a core, the particles were further grown under the same particle growth conditions as the first time, and finally the average particle size was changed.
A 0.58 μm octahedral monodisperse core / shell silver bromide emulsion was obtained. To this emulsion, 1.5 mg of chloroauric acid (tetrahydrate) was added per mol of silver, and the mixture was heated at 60 ° C for 45 minutes for chemical sensitization to obtain an internal latent image type silver bromide core / shell emulsion EM-2. Obtained.

FA-1: 7- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,4
-Tetrahydroacridinium trifluoromethanesulfonate FA-2: 1-formyl-2- {4- [3- (2-methoxyphenyl)
Ureido] -phenyl} hydrazine Further, as in the case of Sample D-1, as shown below, Sample D-1 in which the total amount of gelatin from the first layer to the ninth layer was changed
~ D-4 was created.

Sample No. Total gelatin loading (g / m ² ) D-1 (invention) 8.12 D-2 (comparative) 8.12 D-3 (invention) 9.50 D-4 (invention) 10.32 Sample With respect to D-1 to D-4, the treatment was performed in the same manner as the treatment step-1 of Example 1, and the same evaluation was performed. (New liquid treatment) Further, although it is the same as the treatment step-1, the treatment step-
Using the same replenisher as 1 replenisher performs running the sample D-1, a developing solution, the bleach-fixing solution, in 400cc photosensitive material 1 m ² per the replenishing amount of the stabilizing solution. And 600cc., Respectively replenisher amount Was processed up to twice as much as the developer tank, and the processing was performed using the processing solution. (Treatment of running liquid) The composition of the treatment liquid is as follows.

(Color developing solution and color developing replenishing solution) The same as the color developing solution and color developing replenishing solution of the processing step-1 of Example 1.

(Fixing bleaching solution and fixing bleaching replenishing solution) The same as the bleach-fixing solution and fixing bleaching replenishing solution of processing step-1 of Example 1.

(Stabilizing Solution and Stabilizing Replenishing Solution) The same as the stabilizing solution and stabilizing replenishing solution of the processing step-1 of Example 1.

The minimum density of each image developed with a fresh processing solution (new solution processing) measured with blue light, and the minimum density of each image developed with a running solution (running solution processing) measured with blue light The difference is shown below.

Sample No. 400 cc./m ² replenishment 600 cc./m ² replenishment D-1 (invention) +0.03 +0.03 D-2 (comparative) +0.07 +0.04 D-3 (invention) ) +0.04 +0.03 D-4 (invention) +0.05 +0.03 From the above results, in the sample of the present invention, the replenishment amount is 500 cc./m ²
It can be seen that it is more effective when the number is smaller. Further, when the total amount of gelatin is 10 g / m ² or less, the effect of the present invention can be more exerted.

[0115]

EFFECTS OF THE INVENTION According to the present invention, high sensitivity and light fastness are maintained, the balance of photobleaching is not disturbed, image bleeding does not occur even during running processing, and the processed light-sensitive material is kept under high temperature and high humidity conditions. A silver halide color photographic light-sensitive material having no increase in fog even after storage can be obtained.

Claims (1)

[Claims] 1. A silver halide having, on a reflective support, a silver halide emulsion layer containing at least a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler. In a color photographic light-sensitive material, a silver halide emulsion layer containing a yellow coupler in the silver halide emulsion layer is arranged at a position farthest from a support, and in any of photographic constituent layers of the photographic light-sensitive material, A silver halide color photographic light-sensitive material containing a liquid ultraviolet absorber which is liquid at room temperature.