JPS5971049A - Method for accelerating fluorescent whitening effect - Google Patents

Abstract

PURPOSE:To improve the white ground and to prevent the generation of any static mark by providing a layer contg. a whitening agent and a layer capturing the whitening agent on a substrate. CONSTITUTION:A color photographic material wherein a layer contg. a compd. capable of capturing a whitening agent is provided in the position further from a substrate than a layer contg. the whitening agent is subjected to a coloring development process after exposing so that the whitening agent is diffused and captured into the layer contg. the compd. capable of capturing the whitening agent. The layers contg. said compd. and said agent are separately formed and therefore the static mark by fluorescence is weakened, and since the layer contg. the compd. capable of capturing the whitening agent is provided in the position further from the substrate, the effect of fluorescent whitening is accelerated. Polyvinyl pyrolidone and its copolymer are preferred as the compd. capable of capturing the whitening agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for processing silver halide color photographic materials,
Regarding the processing method of silver halide color photographic light-sensitive materials particularly suitable for direct viewing, in more detail, a novel method for improving the whiteness of silver halide color photographic light-sensitive materials and preventing the generation of static marks. Concerning methods.

In photographic materials intended for direct viewing, the whiteness of the background has an important effect on the image. Improving the whiteness of the background increases contrast, improves color purity (coloring), and improves aesthetics. Therefore, fluorescent whitening agents are known as one of the effective means for improving the whiteness of zero silver halide photographic materials for which various methods have been devised for improving the whiteness.

One method of using this fluorescent whitening agent is to include it in any solution used for color development processing, for example, Japanese Patent Publication No. 46-35240, No.
It is described in each publication of No. 9-20975 and No. 50-25336. However, these methods have drawbacks such as insufficient fluorescent whitening effects and poor stability of the developing solution. This method is difficult to adapt to the current situation.

Another method of using a fluorescent brightener is to incorporate the fluorescent brightener into a light-sensitive material.
-21189, 48-27692, 49-10
No. 696, No. 51-28225 and No. 52-322
It is described in each publication No. 54. According to these methods, more preferable results can be obtained since the fluorescence intensity is increased and the whiteness of the unexposed areas is improved compared to the above-mentioned method in which a fluorescent whitening agent is included in the developer. However, in the conventional method of incorporating a fluorescent brightener into a light-sensitive material, the fluorescent brightener is added to one of the constituent layers of the light-sensitive material such as a support coating layer, an emulsion layer, or a non-emulsion layer. It has been used to contain a fluorescent whitening agent alone, or a fluorescent brightener and a compound that captures the fluorescent brightener and enhances the whitening effect.
According to such conventional methods, although the above-mentioned effect of improving the whiteness of the unexposed areas can be sufficiently obtained, when each constituent layer of the photosensitive material is coated on the support at high speed, there is a problem in the color printer during printing. There is a serious drawback in that static failures such as static marks occur during manufacturing or processing of the photosensitive material, such as when transporting it or peeling off the tape attached to the surface of the photosensitive material. Moreover, in conventional methods, static marks tend to occur more easily as the fluorescent light intensity is increased, and conventional methods cannot achieve equivalent solutions for both purposes of improving the white background and preventing static marks. had become impossible to find. Furthermore, in photosensitive materials using hydrophobic supports such as paper supports coated with polyolefin, static marks tend to occur frequently, and it has become urgent to find a solution to this problem. .

The present invention has been made in order to eliminate the above-mentioned drawbacks of the conventional processing method using a fluorescent brightener for silver halide photographic light-sensitive materials. The object of the present invention is to provide a new processing method that improves the whiteness of silver color photographic materials and prevents the generation of static marks.

The method for enhancing the fluorescent whitening effect of the present invention, which has been found to achieve this objective, is to provide a method for enhancing the fluorescent whitening effect of the present invention by applying
a silver halide emulsion layer, a layer containing a fluorescent brightener, and a layer containing a compound capable of trapping the fluorescent brightener; The layer and the layer containing the compound capable of capturing the fluorescent brightener are separate layers, and the layer containing the compound capable of capturing the fluorescent brightener is formed on the support. A silver halide color photographic light-sensitive material provided at a position farther than the layer containing the whitening agent,
After imagewise exposure, a color development process is performed to diffuse and trap the fluorescent brightener in a layer containing a compound capable of trapping the fluorescent brightener.

Examples of the fluorescent brightener used in the present invention include diaminostilbene-based, benzidine-based, imidazole-based, triazole-based, and imidasilone-based fluorescent brighteners.

A preferred fluorescent whitening agent is a water-soluble fluorescent whitening agent having in its molecule at least one organic acid group exhibiting a pKB of 6.0 or less or an organic base exhibiting a pKb of 7.5 or less.

More preferably, it is a water-soluble fluorescent brightener having in its molecule at least one organic acid group exhibiting a pKa of 5.0 or less, or an organic base exhibiting a pKb of 4.0 or more and 7.5 or less, More preferably at least one organic acid group having a C of 5.0 or less and a pK of 4.0 or more and 7.5 or less.
It is a water-soluble fluorescent brightener having at least one organic base having b in the same molecule. pK of organic bases
t) is most preferably 4.0 or more and 7.0 or less.

pKB in the present invention is a so-called acid dissociation constant, which is an ionization equilibrium constant of an acid, and is one of the measures showing the strength of an acid. For example, it is defined in Chemical Handbook' (Basic Edition ■) (edited by Japan Chemical Society) P4O10. The dissociation of acid HA is HA
It is expressed as ≠H+-1-A-, and the dissociation constant Ka at this time is K'=[H+][A-)/l:HA], and p
Ka is expressed as pKa=−4-layer gKa.

Similarly, pKb is the so-called base dissociation constant, and the base B
The dissociation of B -1-H2O,! BH" -1-OH-, the dissociation constant Kb = [BH+) [OH-]/
[B] and pKb is pKt) = -4o
gKt).

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

Diaminostilbene Fluorescent Brightener> General Formula I In the formula, R1, R2, R3 and R4 are each a hydrogen atom, a halogen atom, a sulfonic acid or its salt, a carboxylic acid or its salt, an alkylamino group, an arylamino represents a hydroxyl, amino, alkoxyl, aryloxy, or morpholino group. Xl represents a sulfonic acid, 1-< represents a carboxylic acid, or a salt of - of these.

Benzidine-based fluorescent whitening agent> General formula “In the formula, R5, R6 and R7 are each a hydrogen atom,
Represents a hydroxyalkyl group or an alkoxyl group. X2 represents a sulfonic acid or a carboxylic acid, or a salt thereof. A particularly preferred R7 is hydroxyl.

<Imidazole Fluorescent Brightener> General Formula In the formula, R8 and R11 each represent a hydrogen atom, an alkyl group, an alkoxyl group, a sulfonic acid or a salt thereof. R9 and R10 each represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group.

X3 represents a sulfonic acid or a carboxylic acid, or a salt thereof.

<Triazole type fluorescent brightener><Imidazole type fluorescent brightener> FB-6 Triazole type fluorescent brightener> B-7 <Other fluorescent brightener> B-8 \C/ 1 B -9 09 B-IQ The layer containing the fluorescent brightener used in the present invention is a different layer from the layer containing the compound that captures the fluorescent brightener and is described in detail below. , and is a layer closer to the hydrophobic support than the layer containing the compound capable of trapping the fluorescent brightener. The layer containing the fluorescent brightener may be any layer as long as it is closer to the hydrophobic support than the layer containing the compound that captures the fluorescent brightener, and is similar to the silver halide emulsion layer. They may form the same layer. However, when added to the silver halide emulsion layer, some of the fluorescent brighteners have an adverse effect on photographic performance such as storage stability, sensitivity, gradation, fog, etc. of raw samples. Therefore, the layer containing the fluorescent brightener is preferably a non-emulsion layer closer to the support than the layer containing the compound capable of trapping the fluorescent brightener. For example, a layer between a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer, and/or a layer between a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. be.

Further, the whiteness is improved more when the fluorescent whitening agent is contained in a layer as close as possible to the layer containing the compound capable of trapping the fluorescent whitening agent. Therefore, a particularly preferable fluorescent brightener-containing layer that captures the fluorescent brightener is a non-emulsion layer that is closer to the hydrophobic support than a layer containing a compound capable of capturing the fluorescent brightener. This is the layer closest to the layer containing the mineral compound.

For example, it is a layer between a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer.

When the layer containing the fluorescent whitening agent is coated, the coating amount of the fluorescent whitening agent is usually 0.1 to 0.5 mg//dm<2>.

Many conventionally known hydrophilic binders can be used in the layer containing the fluorescent brightener. Such a hydrophilic binder includes a hydrophilic binder having an organic acid group having a pKa of 6.0 or less or an organic base having a pKb of 7.5 or less, and furthermore, an organic acid group having a pKa of 6.0 or less and a pK
b Preferably, it is a hydrophilic binder having an organic base of 7.5 or less. In particular, the isoelectric point is from 4.5 to 8.0
Preferred are hydrophilic polymers ranging up to 100%, such as gelatin.

As the compound that captures the fluorescent whitening agent and enhances the whitening effect (hereinafter referred to as a scavenger), many conventionally known compounds can be used. Particularly useful are parent, aqueous polymers, such as polyvinylpyrrolidone, polymers containing vinylpyrrolidone as a repeating unit (monomers forming repeating units with vinylpyrrolidone include N,N-dimethylacrylamide, N , N-diethylacrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide, N-tert
-butylacrylamide, N-cyclohegizol acrylamide, diacetone acrylamide', N-(1,1-
dimethyl-3-hydroxybutyl)acrylamide, N
-(β-morphorino)ethyl acrylamide, N-benzylacrylamide, N-acroylmorpholine, N-
Methacryloylmorpholine, N-methyl-N'-acryloylpiperazine, N-acryloylpiperidine, N-
acryloylpyrrolidine, N-acryloylhexamethyleneimine, etc.), alkyl ester acids of acrylic and methacrylic acids (such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2-
Ethylhexyl acrylate, decyl acrylate, β
-cyanoethyl acrylate, β-chloroethyl acrylate, 2-ethoxyethyl acrylate, sulfopropyl methacrylate, etc.), vinyl esters (e.g. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl lactate, etc.), vinyl ethers (e.g. evamethyl vinyl ether, butyl vinyl ether, oleyl vinyl ether), vinyl ketones (e.g. methyl vinyl ketone, ethyl vinyl ketone), styrenes (e.g. evastyrene, methylstyrene, dimethylstyrene, 2,4.6
- Dolimethylstyrene, ethylstyrene, laurylstyrene, chlorostyrene, dichlorostyrene, methoxystyrene, cyanostyrene, dimethylaminostyrene, chloromethylstyrene, vinylbenzoic acid, styrenesulfonic acid, α-methylstyrene, etc.), vinyl heterocycle Compounds (e.g. vinylpyridine, vinylpyrrolidone, vinylisoxazoline, vinylimidazole, etc.), acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, propylene, phthalene, isoprene, chloroprene, maleic anhydride, itaconic anhydride, citraconic anhydride, vinyl sulfone (acids, etc.), and in addition, poly-
N-vinyl-5-methyl-2-oxazolidinone, N represented by the general formula CH2=C■l N R4C0R2
-Polymer of vinylamide compound, lK? Kaisho 48-42
A hydrophilic polymer containing a cationic nitrogen-containing active compound described in Japanese Patent Publication No. 723, a polymer of N-morpholinoalkylalkenoylamide described in Japanese Patent Publication No. 44-2522, and a polymer of N-morpholinoalkyl alkenoylamide described in Japanese Patent Publication No. 47-20738. A copolymer of vinyl alcohol and vinylpyrrolidone described in Japanese Patent Publication No. 47-49028.
8-38417 Publication δ (wherein, R1 is -H or -CH3, R2 is one-melon-C'H
3, -C2H5, -C3H7, C4H9, R3 is -H,
-CH5, -C2H5, -C3H7, -C4H9, χ/
)1. =9515 to 20/80. ) can be mentioned. However, particularly preferred scavengers are polyvinylpyrrolidone and copolymers thereof.

The molecular weight of the hydrophilic polymer used in the present invention is a weight average molecular weight of 1. It is preferably OO'0 or more, more preferably 10,000 or more. Even more preferably, 50,
000-i, ooo, ooo. The layer containing these scavengers is a layer different from the layer containing the fluorescent brightener, and is a layer farther from the support than the layer containing the fluorescent brightener.

The higher the content of the scavenger, the more the fluorescent whitening agent is captured and the whiteness is improved. However, the layer furthest from the support (protective layer)
If two or more scavengers are contained in the hydrophilic binder of the protective layer, serious drawbacks such as deterioration of the physical properties of the film and reticulation may occur. The preferred scavenger-containing layer is therefore the layer between the protective layer and the emulsion layer furthest from the support.

The scavenger is typically used at a coverage of 0.05 to 3.0 mf/dm2.

The color development processing step of the silver halide color photographic light-sensitive material according to the present invention thus constructed is carried out by the following color development processing method.

That is, after the silver halide color photographic light-sensitive material is imagewise exposed, it is first subjected to color development using a color developer containing a color developing agent. Alternatively, a color developing agent or its precursor is contained in the silver halide color photographic light-sensitive material, and this light-sensitive material is color-developed with a so-called activator liquid. If necessary, black and white development may be performed prior to the color development. After the color development is completed, bleach-fixing and water washing are usually carried out according to conventional methods. In this case, color development using a color developer or activator solution, bleach-fixing, and washing with water may be performed independently, but instead of performing two or more independently, these functions are provided in one bath. ) is also possible. In the present invention, the color development process includes operations such as color development, bleach-fixing, and washing with water, and at least one of the solutions used in these operations must be more alkaline than pi (9). is preferred.

The color developing agent is typically an aromatic primary amine color developing agent.

Aromatic primary amine color developing agents include amine phenolic and p-phenylenediamine derivatives, which can be used in the free state or as their hydrochlorides, sulfates, p-)luenesulfonates, It can be used as an organic acid salt such as tetraphenylborate and p-(1-octyl)benzenesulfonate.

Specific aromatic primary amine color developing agents include 0
-Aminephenol, p-Aminephenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino-1,4-dimethylbenzene, N,N-diethyl-p- Phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N
, N-dimethyl-p-phenylenediamine hydrochloride,
N-ethyl-N-β-methanesulfonaminoethyl-
3-Methyl-4-aminoaniline and its sulfate, N
-ethyl-N-β-hydroxyethylaminoaniline,
N,N-diethyl-3-(β-methanesulfonamidoethyl)-4-aminoaniline hydrochloride, 4-amino-N-
(2-methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate, N-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4-aminoaniline tetraphenylborate, 4-amino-
N-(2-methoxyethyl)-N-ethyl-3-methylaniline tetraphenylborate, p-morpholinoaniline, p-hyperidinoaniline, 4-amino-N
, N-diethyl-3-chloroaniline, etc. can be mentioned as representative examples.

The precursor of the color developing agent contained in the silver halide color photographic light-sensitive material is a compound that can form a color developing agent under alkaline conditions, such as a Schiff paste type precursor with an aromatic aldehyde derivative, a polyvalent metal, etc. Examples include ionic complex precursors, phthalimide derivative precursors, phosphoric acid amide derivative precursors, sugar amine reactant precursors, and urethane type precursors.

Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat. No. 3,342,599, U.S. Pat. , 492, British Patent No. 803, 783
Specifications of each issue, JP-A-53-135,628, JP-A No. 54
-79,035, Research Disclosure Magazine No. 15159, Research Disclosure No. 12146, and Research Disclosure No. 13924.

These aromatic primary amine color developing agents are usually contained in a color developing solution in an amount of about 1 to 20 f/L. When it is contained as a precursor in a sensitive material, it is contained in an amount of about 0.5 to 3 moles per mole of silver halogenide.

The color developing solution or activator solution used in the present invention includes potassium hydroxide, sodium hydroxide, sodium carbonate, etc.
alkaline agents such as potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sulfite), IJium,
These include sulfites such as potassium sulfite, bromide salts such as sodium bromide, potassium bromide, and ammonium bromide. Furthermore, if necessary, known development inhibitors, thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, chloride salts such as ammonium chloride, potassium chloride, and sodium chloride, ethylene glycol, diethylene glycol, methanol,
Organic solvents such as ethanol, n-butanol, benzyl alcohol, acetone, dimethylformamide, amines such as hydroxylamine, ethanolamine, ethylenediamine, jetanolamine, sodium hexametaphosphate, sodium tripolyphosphate, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. It may also contain a water softener, a water-soluble fluorescent brightener, and the like.

The color developing solution or activator solution used in the present invention may contain an auxiliary developer.

As such an auxiliary developer, 1-aryl-3-pyrazolidone derivatives are preferred, and 11 to 12, preferably 1 to 1 part of color developer or activator solution is used.
(Used in the range of IIF to 500W. Typical auxiliary developers include]-]phenyl-3-pyrazolidone 4-methyl-1-phenyl-3-pyrazolidone, 4.
4-dimethyl-1-7E-3-pyrazolidone, 4-
Mef-4-hydroxymethyl-1-phenyl-3
-Birasoliton, 4-methyl-4-hydroxymethyl-
Examples include 1-(p-)lyl)-3-pyrazolidone.

The color developing solution or activator solution used in the present invention is generally used within a certain temperature range. The temperature range depends on the type of printed photosensitive material according to the present invention to be processed;
It can be selected as appropriate depending on the composition, use, purpose, etc., but 15
C. to 70.degree. C. is preferred, and 30.degree. C. to 50.degree. C. is more preferred.

As the bleaching agent used in the bleach-fixing bath, known compounds can be used, such as ferric aminopolycarboxylic acid complex salts such as ferric sodium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium persulfate, Persulfates such as sodium persulfate can be used. In addition, as the fixing agent used in the bleach-fixing bath, known compounds such as thiosulfuric acid (17 um),
Thiosulfates such as ammonium thiosulfate, 3,6-cythia]18-octanediol, 3, 6, 9, 12
-Water-soluble sulfur-containing diols such as tetrathia-1,14-tetradecanediol, ethylene-bis-thioglycolic acid, ethylene-bis-thioglycolic acid sodium salt, 3,6.9-)lithiahendecanedioic acid, etc. water-soluble sulfur-containing dibasic acids, etc. can be used.

The silver halide color photographic light-sensitive material according to the present invention may be of any kind as long as it has a hydrophobic support. In particular, silver halide color photographic materials that are intended for direct viewing are preferably used. Examples of such photosensitive materials include those that are viewed using reflected light, such as color photographic paper, and those that are viewed by projecting onto a screen, such as color slides.In particular, the effects of the method of the present invention are shown in color photographic paper. is preferably exhibited. Color photographic papers typically have three light-sensitive silver halide emulsion layers with different spectral sensitivities, each emulsion layer containing one of three diffusion-resistant couplers: yellow, magenta, and cyan. Contains. In such a case, the combination of the light-sensitive silver halide emulsion layer and the coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer, Furthermore, a yellow coupler is respectively combined with the blue-sensitive silver halide emulsion layer. There are no particular restrictions on the order in which the emulsion layers are stacked. However, in the case of color photographic paper to which the present invention is advantageously applied, the sequence is usually a yellow coupler-containing layer, a magenta coupler-containing layer, a cyan coupler-containing layer, or a cyan coupler-containing layer, a magenta coupler-containing layer, starting from the hydrophobic support side. Coat the coupler-containing layer and the yellow coupler-containing layer in this order.

As the yellow, magenta and cyan couplers used in the present invention, any known couplers may be used.

Preferred yellow couplers include α-pivaloylacetanilide couplers. A preferred magenta coupler is 1-phenyl-3-anilino-5
- Mention may be made of pyrazolone couplers and pyrazolotriazole couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers contains silver fluoride 1 in the silver fluoride emulsion layer.
The silver halide photographic material of the present invention containing about 0.05 to 1 mole per mole has an appropriate layer sequence and number of layers on the hydrophobic support in addition to the silver halide emulsion layer described above. Then non-photosensitive layers such as a protective layer, an intermediate layer, a filter layer, a scavenger layer, etc. are provided. The coating amount of these non-photosensitive layers is usually about 1 to 30 .mu./dm@2 in each layer.

The hydrophobic supports used in the present invention include paper supports coated with polyolefins, polyolefins such as polypropylene, celluloses such as cellulose triacetate, plastic supports such as polyesters such as polyethylene terephthalate, or glass. .

On this premise, methods for dispersing the diffusion-resistant coupler in the silver halide color photographic light-sensitive material of the present invention include so-called aqueous alkali dispersion, solid dispersion, latex dispersion, and oil-in-water emulsification. Various methods such as a dispersion method can be used, and this method can be appropriately selected depending on the chemical structure of the diffusion-resistant coupler.

In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open Nos. 49-7453'8, 5]-59943, 54-32552, and Research Disclosure. (Disclosure)
Magazine, August 1976, Ya 14850, pages 77-79.

Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2
-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)
Homopolymers of monomers such as propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-2-methylpropanesulfone M, etc. , copolymers and terpolymers. In the oil-in-water emulsion dispersion method, a conventionally known method for dispersing hydrophobic additives such as couplers can be applied.The above-mentioned diffusion-resistant couplers are dissolved in a high boiling point solvent, and finely dispersed in a hydrophilic colloid such as gelatin. There are ways to disperse.

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

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100':] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art.

A silver halide photographic emulsion in which silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

In addition to the above-mentioned additives, the silver halide color photographic light-sensitive material according to the present invention further contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, DIR
Substances or other various additives useful in photographic materials may be added.

According to the method for enhancing the fluorescent whitening effect of the present invention, a fluorescent brightener and a compound capable of capturing the fluorescent whitening agent are added to each of the different layers of a silver halide color photographic light-sensitive material. A silver halide color photographic light-sensitive material is prepared by providing a layer containing a compound capable of containing a fluorescent brightener and capturing a fluorescent brightener with respect to a hydrophobic support at a position farther than the layer containing a fluorescent brightener. After imagewise exposure, color development is performed to diffuse the fluorescent whitening agent,
By trapping the fluorescent brightener in the layer containing the scavenging compound, the fluorescent whitening effect is enhanced and static defects such as static marks are avoided. Although the mechanism by which these effects are exerted has not yet been fully elucidated, because the fluorescent brightener and the compound that can capture the fluorescent brightener are contained in different layers, The generation of static marks is significantly weakened, and the layer containing the compound capable of capturing the fluorescent brightener is provided at a position farther from the support than the layer containing the fluorescent brightener. After imagewise exposure, such a silver halide color photographic light-sensitive material is subjected to color development treatment, and the fluorescent brightener is diffused and captured in a layer containing a compound capable of capturing the fluorescent brightener, thereby increasing the fluorescent light. It is speculated that this is to promote the whitening effect.

According to the method for enhancing the fluorescent whitening effect of the present invention, the effect of improving the whiteness of silver halide color photographic light-sensitive materials and the effect of preventing static marks can be achieved, as is clear from the following "Examples". It was confirmed that both effects could be sufficiently obtained.

Hereinafter, the method for enhancing the fluorescent whitening effect of the present invention will be explained in more detail with reference to specific examples, but the embodiments of the present invention are not limited to these examples.

Example 1 A silver halide photographic material having the layer structure shown in Table 1 was prepared and the method of the present invention was applied thereto.

In order from the top of the first Omotesawa, that is, the polyethylene-coated paper support,
The first to sixth layers containing silver halogenide in the amount of coated silver shown in Table 1 and gelatin in the amount of gelatin coated were laminated and coated. The fourth layer contains polyvinylpyrrolidone (military law average molecular weight 360,000, indicated as P-1 in Table 1) as a compound capable of trapping the fluorescent whitening agent of the present invention at a coating amount of 0 and 55mf/dm at a ratio of 20%. It was contained in Furthermore, the above-mentioned exemplary compound FB- is added as a fluorescent brightener related to the present invention to any layer from the first layer to the sixth layer.
1, (indicated by FB-1 in Table 1) at a coating amount of 1 mf/
Samples 1, 2 and 3, which are silver halide color photographic materials of the present invention, and Comparative Samples 1 (not containing FB-1), 2.3 and 4 were obtained.

Each unexposed sample of Samples 1 to 3 and Comparative Samples 1 to 4 thus obtained was heated using an automatic printing machine (Mengen name: Sukura Color Printer 7NN) under conditions of a temperature of 25°C and a relative humidity of 20%.
), the conveyance was repeated 50 times at a conveyance speed of 8,000 sheets/hour. Separately, adhesive tape (trade name Nislon NO360, manufactured by Sekisui Chemical Co., Ltd.) was applied to the emulsion surface of these samples, and after peeling off the tape, these samples were treated with the color development process and processing solution shown below.

Color development process> Temperature (℃) Time Color development 33 3'30'' Bleach fixing
33 1' 30”Wash 33
3' Drying 80 <Color developing solution composition> Bleach-fixing solution composition> [Ethylenediaminetetraacetate iron ammonium 61
2. The relative fluorescence intensity of each sample thus treated was measured by the method shown below, and the presence or absence of static marks was also observed. The results are shown in Table 2.Measurement of Relative Fluorescence Intensity> The reflection density of each developed sample was measured using a color analyzer (Model 607, manufactured by Hitachi). Furthermore, a colored glass filter (UV-39, manufactured by Tokyo Shibaura Electric Co., Ltd.) was installed in the light source of this analyzer.
The reflection density of each sample was measured through the filter. The difference in reflection density with and without the light source filter was measured, and the difference in the degree of reflection at the maximum fluorescence wavelength of each fluorescent brightener was defined as the fluorescence intensity. The relative value of this fluorescence intensity was defined as relative fluorescence intensity.

Table 2 As is clear from Table 2, it does not contain a fluorescent brightener.
Alternatively, compared to a silver halide photographic light-sensitive material in which a layer containing a fluorescent brightener is provided farther from the support than a layer containing a compound capable of trapping a fluorescent brightener, the silver halide color photograph of the present invention The light-sensitive material has a strong fluorescence intensity after color development processing, and the occurrence of static marks is reduced compared to silver halide photographic light-sensitive materials that contain a fluorescent brightener and a scavenger compound in the same layer. It is something. Therefore, the method of the present invention provides good effects in terms of improving whiteness and preventing static marks.

Example 2 A silver halide photographic material having the layer structure shown in Table 3 was prepared and the method of the present invention was applied thereto.

Table 3: Layers 1 to 7 containing the silver halide of the coated silver image shown in Table 3 and gelatin in the amount of coated gelatin are laminated in order from the top surface of the polyethylene-coated paper support. It was painted. The sixth layer contains vinylpyrrolidone-ff as a compound capable of trapping the fluorescent brightener related to the present invention.
l vinyl (7:3) copolymer (weight average molecular weight 220
, 000, indicated as P-2 in Table 3) with a coating amount of 0.5
The content was adjusted to 5 mP/dm2. Furthermore, the second layer,
The fourth layer or the sixth layer contains the above-mentioned exemplary compound F, 13-3 (indicated by FB-3 in Table 3) as a fluorescent brightener related to the present invention in a coating amount of 1 mf/drn2. Samples: ) 4 and 5, which are silver halide color photographic light-sensitive materials related to the present invention, and comparative sample 5 (FB-
3) and 6 were obtained.

Samples 4 and 5 thus obtained and comparative sample 5
The unexposed samples of Samples No. 6 and No. 6 were transported in a printing machine and subjected to an adhesive tape peeling test in the same manner and under the same conditions as in Example 1. Next, the same treatment steps as in Example 1 were carried out, and the relative fluorescence intensity was similarly measured to observe the occurrence of static marks. The results are shown in Table 4.

Table 4 As is clear from Table 4, the silver halide color photographic photosensitive material 1) processed by the method of the present invention has high fluorescence intensity and extremely little static mark generation.

Example 3 It has the same layer structure as Sample 2 prepared in Example 1, and FB
-1 instead of FB-10, FB-2, or FB-5
Samples 6.7 and 8 were prepared by preparing silver halogenide color photographic light-sensitive materials containing silver halide in the second layer.

The unexposed samples of Samples 6, 7 and 8 thus obtained were subjected to the same tests and treatments as in Example 1, and the relative fluorescence intensity was measured and the occurrence of static marks was observed. The results are shown in Table 5.

Table 5 As is clear from Table 5, the silver halide color photographic light-sensitive materials processed by the method of the present invention have high fluorescence intensity and have very few static marks.

Example 4 Three types of silver halide color photographic materials prepared using the same raw materials and methods as Samples 1 to 3 prepared in Example 1 were subjected to imagewise exposure and then subjected to the same color development treatment as in Example 1. As a result, good images were obtained without having the same adverse effects on photographic properties such as sensitivity, gradation, fog, and maximum color density.

Patent issuer: Konishiroku Photo Industry Co., Ltd. Procedural amendment (voluntary) November 19, 1980 Commissioner of the Patent Office Kazuo Wakasugi1, Indication of the case 1980 Patent Application No. 1809392 Name of the invention Fluorescent whitening How to increase the effect 3. Relationship with the case of the person making the amendment Patent applicant Name (127) Konishiroku Photo Industry Co., Ltd. Representative Director Nobuhiko Kawamoto 4, Agent 5, Date of amendment order Voluntary 6, Number of inventions increased by amendment None 1) Change "...coloring" on page 2, line 6 of the description to "...saturation."

(2) "...salts of these -" on page 7, line 13 of the specification are 1- as "...salts of these...".

(3) On page 17, line 4 of the specification, “...nitrogen-containing active group...
"..." is defined as "...nitrogen-containing active group...".

(4) On page 18 of the specification, line 1: “...but especially...
" is 1...especially...".

Claims (1)

[Claims] Provided on a hydrophobic support are at least one non-logenated steel emulsion layer, a layer containing a fluorescent brightener, and a layer containing a compound capable of scavenging the fluorescent brightener; A layer containing a fluorescent brightener and a layer containing a compound capable of capturing the fluorescent brightener are separate layers, and a layer containing a compound capable of capturing the fluorescent brightener is formed on the support. A silver halogenide color photographic light-sensitive material in which a layer containing the fluorescent brightener is provided at a position farther than the layer containing the fluorescent brightener is subjected to color development treatment after imagewise exposure to remove the fluorescent brightener. A method for enhancing the fluorescent whitening effect, which comprises diffusing and trapping the fluorescent whitening agent in a layer containing a compound capable of trapping the fluorescent whitening agent.