JPS6197649A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain high whiteness without deteriorating sensitivity and gradation by incorporating a fluorescent whitening mordant in nonphotosensitive layers except the layer farthest from the side of a support, and hardening plural silver halide emulsion layers and nonphotosensitive layers with a specified hardener. CONSTITUTION:The nonphotosensitive layer located far from the support contains as a hardener for hardening the silver halide emulsion layers and the nonphotosensitive layers, such as interlayers, a compd. represented by formula I or II in which R1 is Cl, OH alkyl, or -NR'R'; R', R' are each H, alkyl, aryl, or OM; M is a monovalent metal; R2 is same as R1 except Cl; R3, R4 are each Cl, alkyl, alkoxy, or OM; Q, Q' are each -O-, -S-, or -NH-; L is alkylene or arylene; and l, m are each 0 or 1. The nonphotosensitive layer far from the support except the farthest layer, i.e., a protective layer, contains a fluorescent whitening mordant together with said hardener and a vinylsulfone type hardener, thus permitting the photosensitive material high in whiteness and superior in sctratch resistance, etc., to be obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), particularly a light-sensitive material suitable for direct viewing. This invention relates to a photosensitive material with improved gloss and scratch resistance.

[Prior Art and Problems] In light-sensitive materials for direct viewing, white skin in the background has an important effect on the image. Fluorescent brighteners are known as an effective means for improving white skin, and are used in developing solutions or photosensitive materials. In order for this fluorescent brightener to work effectively, a mordant for the fluorescent brightener must be used in the light-sensitive material.

In order to further enhance the whitening effect, it is desirable to include this mordant in the uppermost layer or a layer close to the uppermost layer, but in this case, the physical properties of the film, such as deterioration of gloss and scratch resistance, are significantly deteriorated.

On the other hand, various hardening agents have been used to act on gelatin,
The physical properties of gelatin films are improved by crosslinking them with functional groups such as amino groups, carboxyl groups, and amide groups in gelatin molecules.

In addition, hardening agents not only have excellent hardening effects, but also
It is required that photographic properties such as sensitivity, capri, and color density are not adversely affected. For this reason, various hardening agents have been investigated and proposed.

However, in a structure in which a mordant is contained in a layer above the uppermost emulsion layer as described above, the physical properties of the film are significantly deteriorated, and a large amount of hardener must be used in order to obtain sufficient physical properties of the film. This method not only causes desensitization and capri, but also has various drawbacks such as a reduction in covering power.

In a configuration in which a mordant is contained in a layer above the uppermost emulsion layer, among various hardeners, cyanuric chloride thread hardeners represented by general formulas [I] and [■] can be used to improve gloss. It is effective, but scratch resistance deteriorates.

Furthermore, if a vinyl sulfone hardener is used, it may not be effective in improving scratch resistance, but it tends to deteriorate gloss.

As described above, no matter which hardener is used, it is difficult to improve both gloss and scratch resistance in a structure in which a mordant is contained in a layer farther from the support than the uppermost emulsion layer. Therefore, it has been desired to develop a method for improving whiteness, gloss, and scratch resistance.

[Object of the invention] The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide a material with extremely high white skin, extremely little deterioration of gloss over time, and high scratch strength. Our purpose is to provide photosensitive materials.

A second object of the present invention is to provide a photosensitive material which is free from deterioration in sensitivity, gradation, and capri and has an improved whiteness of 1.

[Specific Structure of the Invention] As a result of various studies for this purpose, the present inventors have discovered that a plurality of silver halide emulsion layers are provided on a support, and among these emulsion layers, the emulsion layer furthest from the support is In a photosensitive material having a plurality of non-photosensitive layers on the side opposite to the support,
(a) at least one non-photosensitive layer of the plurality of non-photosensitive layers, excluding the non-photosensitive layer furthest from the support, contains a mordant for a fluorescent brightener; Each of the emulsion layer and the plurality of non-light-sensitive layers is hardened using at least one of the compounds represented by the following general formulas [I] and [II], and (c) at least the mordant for the fluorescent brightener. A photosensitive material characterized in that the layer containing the compound is coated with a vinyl sulfone hardener in addition to at least one of the compounds represented by the general formulas [1] and [■]. represent. ] or -0
It represents an M group (M is a monovalent metal atom), and the bird has the same meaning as R excluding the chlorine atom.

General formula [■] In the formula, Bl+ R4 is a chlorine atom, a hydroxy group,
An alkyl group, an alkoxy group or a 10M group CM represents a monovalent metal atom. Q, Q' are 10-, -S-.

The linking group representing -MW-, L represents an alkylene group or an arylene group. ! and m represents O or 1. The present inventors have discovered that the object of the present invention can only be achieved by the following methods, and have thus completed the present invention.

R of the hardening agent represented by the general formula [I] according to the present invention
The alkyl group represented by 1 and R1 is, for example, a methyl group, ethyl group, butyl group, etc., and the M in the 10M group represented by R+ and horse is, for example, a sodium atom, a potassium atom, etc.

Further, regarding the cyanuric chloride thread hardener represented by the general formula [I], US Pat. I47-6151, I47-33380,
No. 5l-96Q7, JP-A-48-18220, No. 5
No. 1-78788, No. 52-60612, No. 52-1
No. 2813Q, No. 52-430326, No. 56-10
No. 43, etc. include Kiga, which can be used in accordance with the above standards.

Next, the alkyl group represented by Ra and R4 in the general formula [n] is, for example, a methyl group, an ethyl group, a butyl group, etc., and the alkoxy group is a methoxy group, an ethoxy group, a butoxy group, etc.
M in the -0M group is, for example, a sodium atom, a potassium atom, or the like.

Further, the alkylene group represented by L is, for example, -OH, -1-C
am2) H-1-(OHt)j- group, and the arylene group is, for example, p-10- or m-7 enylene group.

The cyanuric chloride hardener represented by the general formula [■] is described in Canadian Patent No. 895,808, Japanese Patent Publication No. 58-33542, Japanese Patent Application Laid-open No. 57-40244, etc. It can be selected and used based on the following.

The compound represented by the general formula CI] or [II] according to the present invention may be added to at least one selected layer or multiple layers from the emulsion layer or auxiliary layer according to the present invention, but preferably in the layer farthest from the support. layer (protective layer).

The additive is dissolved in water or alcohol (eg, methyl alcohol, ethyl alcohol, etc.) and added in an amount of 0.5 to 1 ook, preferably 2 to 50 da, per 1 g of coated gelatin. The addition method may be either a batch method or an in-line method.

Typical specific examples of compounds represented by formula [I] or [II] are listed below, but the present invention is not limited thereto.

Compound represented by general formula [I]: Cl-1) (I-2) (I 5
)()-6ノ(I-7) CI-8
)Cl-11) Cl-12ノ(
I-43) Compound represented by general formula [11 = (II-17 (n-1 (n-nee 3) Cjl Li(II-B) ([-9) (n-10) Vinyl sulfone type according to the present invention Hardeners include aromatic compounds such as those described in Sayama Patent No. 1,100,942, Japanese Patent Publication Nos. 44-29622 and 47-25.
Alkyl compounds bonded with hetero atoms as described in Japanese Patent Publication No. 373, sulfonamides and ester compounds as described in Japanese Patent Publication No. 47-8736, and ester compounds as described in Japanese Patent Publication No. 47-8736.
1,3.5-) as described in No. 9-24435
Ris[β-(vinylsulfonylnopropionyl-cohexahydro-5-)riryozin or JP-A-51-44
This includes alkyl thread compounds such as those described in No. 164. Preferably, a vinyl sulfone hardener has a molecular weight of 1,000 or more, and more preferably a vinyl sulfone hardener has a molecular weight of 2,000 or more.

Typical specific examples are shown below, but are not limited to these 9 Vinyl sulfone type @! Eye agent: V-20 (OH, OH, So, 0H=OH, J.

V -31JH ((!H,OH,So,0H=OHri.

V-5So, 0H=OH.

Oh.

11-8 0H,Q(OH,OOH@f30,0
H=OH*).

V -90 (OH, OOH, So, 0H=OK,).

V-10N(O)1. OH, OOH, So, OH-O
Ht)sSo,01i-OHtV -130,H,0(OH,So,0H=OH,haV
-140,H,,O(CjH,SO,0H=OH1
J.

V-150H,-GH8O1OH,0HGH,So,
0H=G! H.

So, (!H=OH.

V-16(OH1=OH8O, CHIJloCiH
, BrV -1'7 (OH, -0H3O,0H
1), 0HOH (OH, So, 0H=OR, HaV-1+
3 (OH, -0H9O,OH,), OCR, 0
0) I, 0(OH, So, C!H=OHri.

V -190 (OH, So, 0H = GH! Ha CH3 0
H8O,so,cH=cu.

V -21COH, -0HF30. OH, ), COH,
So,CjH,OH,C1V-22CooH,OH,
So, 0H=OH.

So, OH-OH.

In addition to the above-mentioned exemplified compounds, vinylsulfone hardeners used in the present invention include compounds having at least three vinyl sulfone groups in their molecular structure, such as exemplified compounds [v-5
] ~ [v-22] A reaction product obtained by reacting a compound having a group that reacts with a vinyl sulfone group and a water-soluble group, such as jetanolamine, thioglycolic acid, sarcocinnatri'rum salt, and taurine potassium salt. including.

These vinyl sulfone hardeners are coated with 1g of gelatin.
The amount of σ0° is 5 to 100 degrees, preferably 2.0 to 507 degrees. The addition method may be either a batch method or an in-line method. The layer to which the vinyl sulfone hardener is added is the layer containing the mordant. The effects of the present invention are not exhibited in layers other than this layer.

As the mordant for the fluorescent brightener according to the present invention, many conventionally known compounds can be used. Particularly useful are hydrophilic polymers, such as polyvinylpyrrolidone, polymers containing vinylpyrrolidone as a repeating unit (monomers forming repeating units with vinylpyrrolidone include acrylic acid, methacrylic acid, acrylic acid and Amides of methacrylic acid (e.g. acrylamide,
methacrylamide, N,N-dimethylacrylamide,
N, N-diethylacrylamide, N-methylol acrylamide, N-hydroxyethylacrylamide, N
-tert-butylacrylamide, N-cyclohexylacrylamide, diacetone acrylamide, N-
(111-dimethyl-3-hydroxybutylnoacrylamide, N-(β-morpholizethylacrylamide, M-benzylacrylamide, N-acryloylmorpholine, N-methacryloylmorpholine, N-methyl-N+-7 chloroyl perazine, N-7 criloylpiperidine, N-7 criloylpyrrolidine, N-acryloylhexamethyleneimine, etc., alkyl esterates of methacrylic acid and methacrylic acid, 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), vinyl ethers (e.g. methyl vinyl ether, butyl vinyl ether, oleyl vinyl ether, etc.), vinyl ketones (
(e.g. methyl vinyl ketone, ethyl vinyl ketone, etc.)
, styrenes (e.g. styrene, methylstyrene, dimethylstyrene, 2,4.6-)dimethylstyrene, ethylstyrene, laurylstyrene, chlorostyrene, dichlorostyrene, methoxystyrene, cyanostyrene, dimethylstyrene, dimethylstyrene, chloromethylstyrene, vinyl Benzoic acid, styrene sulfonic acid, α-methylstyrene, vinyl heterocyclic compounds (e.g. vinyl pyridine,
(vinylpyrrolidone, vinylisoxazoline, vinylimidazole, etc.), acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, pyrene, butadiene, isoprene, chloroprene, maleic anhydride, itaconic anhydride, citraconic anhydride, vinylsulfonic acid, etc. In addition, poly-N-vinyl-5-methyl-2-oxazolidinone, general formula OH, described in Japanese Patent Publication No. 48-31842.

= 0) Polymer of N-vinyl phosphomide compound represented by INR, OOR, hydrophilic polymer containing a cationic nitrogen-containing active group described in JP-A No. 48-42723, JP-B No. 44-2522 Polymer of N-morpholinoalkylalkenoylamide described in Japanese Patent Publication No. 1983
A copolymer of vinyl alcohol and vinyl pyrrolidone described in Japanese Patent Publication No. 47-49028, OH0OONH, described in Japanese Patent Publication No. 47-49028.

□ = 0.05 to 0.25 polymer, general formula described in Japanese Patent Publication No. Sho x+y 48-384'11
R8 (wherein, R1 is -H or -OH; R1 is -H, -0H8
, -0tHss JHts CJ4H
@S RIGj-Is -OH@s-
0tHs)-O3H,,04Hi x/y = 95
/5 to 20/80. ) can be mentioned. Among these, particularly preferred mordants are polyvinylpyrrolidone and copolymers thereof.

The molecular weight of the hydrophilic polymer used in the present invention is preferably 1,000 or more, more preferably 10,000 or more in weight average molecular weight. Even more preferably 50.00
0 N1,000,000. The layer containing these mordants is at least one non-photosensitive layer other than the non-photosensitive layer that is faster than the support, and preferably the non-photosensitive layer that is in contact with the non-photosensitive layer that is furthest from the support. It is.

The mordant is usually used at a coating rate of 0.05 to 3.0 my/am.

Any type of color light-sensitive material can be used as long as it has a hydrophobic support.

In particular, Japanese color photosensitive materials, which 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 being projected onto a screen, such as color slides. In particular, the effects of the method of the present invention are preferably exhibited on color photographic paper. 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 cases, the combination of emulsion layers and couplers is usually a cyan coupler in the red-sensitive emulsion layer, a magenta coupler in the green-sensitive emulsion layer, and a yellow color coupler in the blue-sensitive emulsion layer. - are combined respectively. There are no particular restrictions on the order in which the emulsion layers are stacked. However, the color photographic paper to which the present invention is advantageously applied is coated in the order of the on coupler-containing layer, or in the order of the cyan coupler-containing layer, the magenta coupler-containing layer, and the yellow coupler-containing layer.

Any known yellow, magenta, and cyan couplers may be used in the present invention. Preferred yellow couplers include α-pivaloyl acetolysate couplers. Preferred magenta couplers include 1-7enyl-3-7nilino-5-
Included are pyrazolone couplers and pyrazolotriazole thread couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers contains 1 silver halide in the silver halide emulsion layer.
It is contained in an amount of about 0.05 to 1 mole per mole.

In addition to the above-mentioned emulsion layer, the light-sensitive material according to the present invention includes non-photosensitive layers such as a protective layer, an intermediate layer, a filter layer, a scavenger layer, etc. in an appropriate stratification and number of layers on the hydrophobic support. The amount of binder applied in these non-photosensitive layers is usually about 1 to 30 η/d in each layer.

Examples of the hydrophobic support 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, and glass. It will be done.

On this premise, the method for dispersing the diffusion-resistant coupler in the color photosensitive material of the present invention is as follows:
Various methods can be used, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc., and these methods can be selected as appropriate depending on the chemical structure of the diffusion-resistant coupler. Can be done.

In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods are well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open Nos. 49-7453B and 51-59943,
No. 54-32552 and Research Disclosure (R@gearchDisclosure) magazine, 19
August 1976, Al 485 Q, pages 77-79.

Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate), 2-acetoacetoxyethyl methacrylate,
-(methacryloyloxynoethyltrimethylammonium methosulfate, 3-(methacryloyloxylapropane-1-sulfonic acid sodium salt, N-isopropylacrylamide, h-[2-(g-methyl-4-oxopentylnocoacrylamide, 2- Seven polymers such as acrylamide-2-methylpropanesulfonic acid, etc.
It is a homopolymer of cobolymer Oyohita polymer. The oil-in-water type emulsification dispersion method can be used by conventional methods for dispersing icephobic additives such as couplers. Is there a way to finely disperse it inside?

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

The color photosensitive material according to the present invention thus configured,
The color development processing step is carried out by the following color development processing method. That is, after the color photosensitive 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 color photosensitive material, and this photosensitive material is color developed using 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, a method that has these functions,
It is also possible to carry out the process once (in one bath). In the present invention, the color development process includes operations such as color development, bleach-fixing, and washing with water. It is preferable that at least one of the liquids is more alkaline than pH 9.

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

Aromatic primary amine color developing agents include aminophenol and p-phenylenediamine derivatives, and these compounds can be used in the free state or in their hydrochloride, sulfate, p-toluenesulfonate, or tetrahydrochloride form. It can be used as an organic acid salt such as phenylborate and p-(t-octylnobenzene sulfonate).

Specific aromatic primary amine color developing agents include 0
-Aminophenol, p-7 minophenol, 5-minor 2-oxytoluene, 2-amino-3-o, xytoluene, 2-oxy-3-amino-1,4-dimethylbenzene, N,N-diethyl- p-7z nylenediamine hydrochloride, N-methyl-p-7, nylenediamine hydrochloride, N
, N-dimethyl-p-phenylenediamine salt Q salt, N
-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline and its sulfate, N-
Ethyl-N-β-hydroxyethylamino unilin H
, 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, 4-7mi/-N
-(2-methoxyethyl-N-ethyl-3-methylaniline tetraphenylborate, p-morpholino-uniline p-piperidino-niline, 4-minnow N, M
Typical examples include -diethyl-3-chloroniline.

The precursor of the color developing crude drug contained in the color photosensitive material is a compound that forms a color developing agent under alkaline conditions, such as a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, etc. , a phthalic acid imide derivative precursor, a phosphorus-accepting imide derivative precursor, a sugar amine reactant precursor, and a urethane type precursor.

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, JP-A-53-435,628, JP-A-54-79,03
No. 5, Research Disclosure Magazine No. 15159,
It is described in No. 12146 and 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 jj/l. In addition, when this is contained as a precursor in a sensitive material, 0.0. It is contained in an amount of about δ to 3 moles.

The color developing solution or activator solution used in the present invention includes alkaline agents such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate, sodium sulfite, potassium sulfite, etc. These include sulfites, bromide salts such as sodium bromide, potassium bromide, and ammonium bromide.

Furthermore, if necessary, known development inhibitors, thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, ammonium chloride,
Amount of chlorides such as potassium chloride and sodium chloride, organic solvents such as ethylene glycol, diethylene glycol, methanol, ethanol, n-butanol, pencil alcohol, acetone, dimethylform 7 ml', hydroxylamine, ethanolamine, ethylenediamine, jetanolamine The color developer or activator used in the present invention may contain amines such as sodium hexametaphosphate, sodium tripolyphosphate, water softeners such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and water-soluble fluorescent whitening agents. The liquid may contain an auxiliary developer. As such an auxiliary developer, 1-aryl-3-pyrazolidone derivatives are preferred, and the amount is 1 to 1 g, preferably 10 m to 500 m, per 11 of the color developer or activator solution.
Used within the range of Typical auxiliary developers include 1
-Phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone, 4.4-dimethyl-1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, Examples include 4-methyl-4-hydroxymethyl-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 can be appropriately selected depending on the type, composition, use, purpose, etc. of the photosensitive material according to the present invention to be processed, and is preferably 15°C to 70°C, more preferably 30°C to 50°C.

As the bleaching agent used in the bleach-fixing bath, known compounds can be used, such as ferric complex salts of 7-aminocarboxylic acids such as ferric sodium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, and ammonium persulfate. , persulfates such as sodium persulfate can be used.

Further, as the fixing agent used in the bleach-fixing bath, known compounds can be used, such as thiosulfates such as sodium thiosulfate and ammonium thiosulfate, 316-
Cythia 1,8-octanediol, 3,6,9.12
- Water-bathable sulfur-containing diols such as tetrathia-1゜14-tetradecanediol, ethylene-bis-thioglycolic acid, ethylene-bis-thioglycolic acid sodium salt, st 6+ 9-trithiahendecanedioic acid, etc. A sulfur-containing dibasic acid or the like can be used.

[Example 2] According to the method of the present invention, a photosensitive material with increased background whiteness, very little deterioration of gloss over time, and high scratch strength can be obtained.

Hereinafter, the present invention #==4 will be explained in detail by specifically showing examples, but the actual tif+D of the present invention is not limited to these examples.

Example 1 Color photographic paper was prepared by sequentially applying the following two constituent layers using gelatin as a binder to a paper support whose surface was coated with polyethylene containing anatase titanium oxide as a white pigment.

Ta.

The weights shown here are for each coated layer 10 unless otherwise specified.
This is the content per 0 cd.

Layer 1: Blue-sensitive emulsion layer Gelatin using a silver chlorobromide emulsion containing 5 mol% of silver chloride, the following yellow coupler, and an emulsified dispersion prepared by dissolving 2,5-dioctylhydroquinone in dioctyl phthalate. Coating liquid was applied 7 (silver 4.
Orn9, gelatin 15In9].

Y coupler single layer 2: first intermediate layer 2. A gelatin coating solution was coated using an emulsified dispersion prepared by dissolving 2.5-dioctylhydroquinone in dioctyl 7-talate (gelatin 1. Om9).

Layer 3: Green-sensitive emulsion layer Gelatin using a silver chlorobromide emulsion containing 15 mol% of silver chloride, and an emulsified dispersion prepared by dissolving the following magenta coupler and 2,5-dioctylhydroquinone in dioctyl 7-talate. Coating liquid was applied (silver 3.0
m9, gelatin 15rN9).

Layer 4: Second intermediate layer UV absorber 2- (2'-hydroxy-31,51-
A gelatin coating solution was applied using an emulsified dispersion prepared by dissolving di-t-pentylphenylrabenzotriazole and 2,5-di-octylhydroquinone in dioctyl phthalate (gelatin 10 duff).

Layer 5: Red-sensitive emulsion layer Gelatin coating using a silver chlorobromide emulsion containing 30 mol% of silver chloride and an emulsified dispersion prepared by dissolving the following cyan coupler and 2,5-dioctylhydroquinone in dioctyl phthalate. A liquid was applied (silver 3,0η,
gelatin 15■].

C coupler H layer 6: third intermediate layer ultraviolet absorber 2- (2'-hydroxy-31,5+-
Using an emulsified dispersion prepared by dissolving di-t-pentylphenylnobenzotriolizole and 2,5-dioctylhydroquinone in dioctyl phthalate, 0.8 μ of the above V-9 was added as a hardening agent. A gelatin coating solution was applied (gelatin 10 cm).

Layer 7: Protective layer A gelatin coating solution containing 0.4111p of the above-mentioned ■-1 as a hardening agent was coated (gelatin 101n9).

In addition, vinylpyrrolidone-vinyl acetate (7:3) copolymer is used as a mordant for the layer or skin 4. -1 (weight average molecular weight 220.0OO) was contained in 0.55 m9.

Each of the samples (&1 to 4) thus obtained was 3
After being stored at 5° C. and 80% RH for 7 days, it was treated with the following color development process and processing solution.

[Processing process Temperature: 0 Development color development
33 3 minutes 30 seconds bleach fixing 33
Wash with water for 1 minute and 30 seconds 33
3 parts Drying 80 [Color developing solution composition] The relative fluorescence intensity, glossiness, and scratch strength of each sample thus obtained were measured by the following methods.

[Measurement of Relative Fluorescence Intensity] Reflection density is measured using a color analyzer (model 6o7, manufactured by Hitachi Seisakusho). Furthermore, the light source of this analyzer is a colored glass filter (UV-39, Tokyo Shibaura Electric Co., Ltd.).
(manufactured by J.D.) and measure the reflection density of each sample through the filter. The difference in reflection density was measured when the light source had a filter and when there was no filter, and the difference in reflection density 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.

[Glossiness] Glossiness was measured using a gloss meter manufactured by Tokyo Denden Corporation.

[Scratch strength]

The aged sample without any development treatment was added to the color developing solution for 33 minutes.
℃ for 3 minutes, the scratch strength (g) at which scratches occur on the film surface is measured using a Hayton scratch meter.

The results are shown in Table-1.

Table 1 As is clear from the table, only the sample of the present invention has good fluorescence intensity, gloss, and scratch strength.

In the sample of the present invention, a mordant for the Noko brightener was contained in layer 6, a hardener (I-17 was contained in layer 6), and a hardener V-9 was contained in layer 6.

Print image G2 obtained from the sample of the present invention was a good photographic image (with high white discoloration of the background and high gloss of the surface). In addition, one comb sample showed no scratches on the surface.

Example 2 Same layer structure as Example 1, using polyvinylpyrrolidone P-2 (weight average molecular weight 360.000) as a mordant
Sample 10 containing 0.55μ of P-2 in layer 6 and having the hardening agent and hardening agent added layer shown in Table-2 Six types of samples (&15~
20) was created.

Table 3 vsM-1: The reaction product of Exemplary Compound V-9 and Taurinka-13um salt (molar ratio 1:0.5) was dissolved in water/ethanol (1/1% by volume), and phenylcarbamyl A water bath solution of Nanauchin was added.

After developing these samples in the same manner as in Example 1, the fluorescence intensity, glossiness and scratch strength were measured. The results are shown in Table 4.

Table 4 As is clear from the table, when hardener V-9 is added to layer 6 and hardener I-1 is used in combination, both gloss and scratch resistance are improved. This was not seen in other configurations and was completely unexpected.

Hardener 1-1 is more effective when used in a protective layer. With the samples of the present invention, photographic images with good whiteness, gloss, and scratch resistance are obtained.

Example 3 The layer structure was the same as Sample 14 of Example 2, or the compound shown in Table 5 was used instead of V-9 as a hardening agent.
5 Comparative Compound-1 00CH-OH.

(2) These samples were developed over time in the same manner as in Example 1, and the fluorescence intensity, glossiness and scratch strength were measured.

The results are shown in Table-6.

Table 6 As is clear from the table, the samples of the present invention using the hardener of the general formula [I] or [■°] and the vinyl sulfone hardener showed poor whitening, gloss, and scratch strength. It also improves.

This was achieved for the first time by the combination of hardeners according to the present invention, and was completely unexpected. Furthermore, when a photographic image was created using the sample of the present invention,
Good images with high whiteness were obtained without deterioration in sensitivity, -tone, etc.

Claims (1)

[Scope of Claims] A plurality of silver halide emulsion layers on a support, and a plurality of non-light-sensitive layers on the side opposite to the support of the emulsion layer furthest from the support among the silver halide emulsion layers. In the silver halide photographic light-sensitive material, (a) at least one non-photosensitive layer other than the non-photosensitive layer furthest from the support among the plurality of non-photosensitive layers contains a mordant for a fluorescent brightener; Ori,
(b) Each of the plurality of silver halide emulsion layers and non-photosensitive layers is hardened using at least one of the compounds represented by the following general formulas [I] and [II]; The layer containing a mordant for a fluorescent brightener is hardened using a vinyl sulfone hardener in addition to at least one of the compounds represented by the general formulas [I] and [II]. A silver halide photographic light-sensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a chlorine atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R', R'' each represents a hydrogen atom, an alkyl group, or an aryl group. -NHOOR'''(R'' represents a hydrogen atom, an alkyl group, or an aryl group) or an -OM group (M is a monovalent metal atom) , and R_2 has the same meaning as R_1 excluding the chlorine atom.] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_3 and R_4 are a chlorine atom, a hydroxy group, an alkyl group, and an alkoxy group, respectively. or -OM group (M is 1
(valent metal atom). Q, Q' are -O-, -S-, -
The linking group representing NH-, L represents an alkylene group or an arylene group. l and m represent 0 or 1. ]