JPS59149350A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance photosensitivity by forming a silver halide emulsion layer located farthest from a support and contg. monodispersed silver halide grains highest in photosensitivity among silver halide emulsion layers constituting photosensitive layers, and a nonphotosensitive layer contg. a specified compd. and neighbouring to said photosensitive layer on the side reverse to the support side. CONSTITUTION:Photosensitive layers consisting of silver halide emulsion layers same in color sensitivity but different in photosensitivity, and a nonphotosensitive layer are formed on a support. The photosensitive silver halide emulsion layer located farthest from the support contains monodispersed silver halide grains, and the nonphotosensitive layer formed adjacently to said layer on the side reverse to the support contains compds represented by formulae I -IV in which R<1>, R<22>, R<8> are each H, alkyl, or aryl; R<3> is alkyl, aryl, or alkenyl; A, B are each -CN, -SO2R<15>, -COOR<16>, -CONR<17>R<18>, or -COR<1>; R<4>-R<7> are each H or alkyl; G is an electron acceptor; R<13> is H or lower alkyl; R<14> is 1-20C alkyl; R<15>, R<16> are each alkyl or aryl; and R<17>, R<18> are each H, alkyl, or aryl.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to photographic materials.

(Prior Art) In recent years, in silver halide photographic light-sensitive materials, improvements in sharpness and graininess have been strongly desired as small formers and dual tones have been introduced. There is also a demand for highly sensitive silver halogenide photographic materials for indoor photography.

In order to meet these demands, various efforts have been made, such as increasing the quantum efficiency of silver halide grains contained in silver halide photosensitive materials, using monodispersed emulsions with low light scattering, and preventing light scattering by thinning the film. Studies have been carried out and some results have been achieved.

However, although these technical measures have brought good results in many respects, higher sensitivity or thinner films have the disadvantage that pressure blurring is more likely to occur in photosensitive materials due to external physical pressure. Ta.

That is, during manufacturing, pressure blurring is likely to occur due to pressure and abrasion during each process of coating and drying, cutting, and packaging, and during each operation process during photographing.

The occurrence of fog due to pressure, scratching, etc. generally increases as the quantum efficiency of 7. silver halide grains increases and as the absolute sensitivity increases, such as as the size of the silver halide grains increases.

Methods for preventing pressure fog include, for example, certain heterocyclic compounds (British Patent No. 738.618), alkyl phthalates (British Patent No. 738.637), alkyl esters (British Patent No. 738.639), and 2-pyrrolidone. derivatives (JP-A-48-24725) or certain hydrophilic compounds (U.S. Pat. No. 2.960.404, U.S. Pat. No. 3.520)
．． No. 094), organic high-boiling compounds (Japanese Patent Application Laid-open No. 57-392)
A method of adding silver halide emulsion layer or non-emulsion layer to a silver halide emulsion layer or a non-emulsion layer has been proposed.

However, if this method is used in an amount that is effective, it may cause excessive stickiness on the surface of the photosensitive material or cause some negative effects on the properties of the photosensitive material such as desensitization, sensitization, changes in gradation, fogging, etc. give. Improved brightness 4
Making the means thinner goes against the direction of absorbing and buffering the applied pressure, which goes against the purpose of preventing pressure blurring, and as a whole does not sufficiently meet the above-mentioned requirements for sharpness, graininess, and high sensitivity. is the current situation.

(Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide photosensitive material with improved fogging caused by pressure or abrasion.

A second object of the present invention is to provide a silver halide photosensitive material that is less prone to fog due to pressure or scratching and has improved sharpness and graininess.

A third object of the present invention is to provide a silver halide photographic material that has less fog due to pressure and abrasion and is not sticky.

(Structure of the Invention) As a result of intensive research in accordance with the object of the present invention, a high-sensitivity emulsion layer sensitive to pressure capri or abrasion fog has been prepared using the general formulas [I], (II), l] according to the present invention. By coating with a hydrophilic colloid layer containing at least one of the compounds represented by (1) and (2) in a manner that protects it from external pressure and abrasion, the fog resistance is significantly improved compared to a simple coating, and stickiness is also reduced. It has been found that stickiness does not occur if the above-mentioned substance that is produced is eliminated and the compound represented by the above-mentioned general formula is added.

Based on this knowledge, the present invention achieves the objects of the present invention, and provides a photosensitive material comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. In a silver halide photographic light-sensitive material in which at least one of the layers and at least one of the non-photosensitive layers are provided, the layer is provided at the farthest position from the support, which is easily affected by pressure from the outside and from scratches. Among the plurality of silver halide emulsion layers constituting the photosensitive layer, the silver halide emulsion layer having the highest sensitivity and containing monodisperse silver halide grains, which is particularly susceptible to the above-mentioned problems, is selected as the photosensitive layer. It is constructed by providing a non-photosensitive layer containing at least one compound represented by the general formula [■] to [h] on the outside of the layer (on the side farther from the support).

Furthermore, it is preferable that a non-photosensitive layer is further provided outside (on the side farther from the support) the non-photosensitive layer containing the compound represented by the general formula [ID to ID].

The effectiveness of the compound represented by the general formula [ID or ID] according to the present invention can be further increased by including it in a protected and dispersed manner in the non-photosensitive layer. Note that the non-photosensitive layer may be composed of multiple layers.

Furthermore, the layer structure of the emulsion layer in the photosensitive layer, which is composed of a plurality of silver halide emulsion layers having one color sensitivity and different sensitivity, is not particularly limited. , are preferably provided in order from the outside to the inside (towards the support) from the highest sensitivity to the lowest sensitivity. In high-sensitivity multicolor photographic materials, the photosensitive layers are generally blue-sensitive, green-sensitive, and red-sensitive photosensitive layers are arranged close to the support from the outside.

Next, the present invention will be explained in more detail.

In the present invention, monodisperse silver halide grains refer to those whose standard deviation S divided by the average grain size T is 0.15 or less as defined by the following formula. Furthermore, the value of 0.
A value of 10 or less is preferable because it has a large sharpness improvement effect.

1≦0.15 The average particle size here refers to the diameter of a spherical silver particle, or the projection image of a particle with a shape other than a cube or sphere to a circular image of the same area. It is the average value of the particle size (diameter) when calculated, and when the individual particle size is ri and the number (ni), it is defined by the following formula.

Σn1ri − Σni In the present invention, zri is preferably 0.3μ to 1. 5μ
is within the range of

When mixing two or more emulsions with different average grain sizes in order to widen the exposure latitude, it is necessary to ensure that the silver halide grains are appropriately sensitized. The same effect as the present invention can be obtained even when the emulsions defined above are mixed and used. Therefore, in the present invention, two or more types of monodisperse silver 10-genide grains having different average grain sizes are mixed and used, and A may also be used.

As a method for preparing the monodisperse silver halide grains of the present invention, grains of a desired size can be obtained by a stable table method without controlling PAg and P.

It is also highly monodisperse.

The agent is described in JP-A No. 54-48521 and is
This method can be applied. In a preferred embodiment of the method, O is produced by a method in which potassium compound, an aqueous gelatin solution, and an ammoniacal nitric acid aqueous solution are denatured and added as an aqueous gelatin solution containing silver seed particles. By appropriately selecting the speed time function, pH/PAg temperature, temperature, etc., highly monodisperse silver halogenide can be obtained.

In the present invention, the following general formula CI), CID, [■] or & In the compound represented by the following general formula, in the general formula [■] Oryl group or alkenyl group, A and B are each -CN, -8O2R15-COOR16-CONRl
A group represented by lR''-COR'9 (R15 and R'' each represent an alkyl group or an aryl group, R17R
"represents a hydrogen atom, an argyl group, or an aryl group, and R17 and R18 may be linked to each other to form a piperidi/ring, a mo/l/phorino ring, a pyrrolidino ring, or a piperazino ring. ” represents an alkyl group or an aryl group).

Each of the above groups mentioned herein also includes those having a substituent. Furthermore, regarding the number of carbon atoms in the alkyl group mentioned above, R1
, R2 is ■ to 4, RB is 1 to 6
In particular, those substituted with hydrophilic groups such as carboxylic acids, sulfonic acids, or salts thereof are desirable.

Preferred examples of aryl groups include unsubstituted or substituted phenyl groups. Typical examples of the alkyl group for R1 include methyl, ethyl, n-propyl, and n-butyl groups. Typical examples of the aryl group for R1 include phenyl group, tolyl group, and xylyl group.

Typical examples of alkyl and aryl groups for R1 include R1
The same examples can be given as for alkyl groups and aryl groups.

Typical examples of alkyl groups for R3 include methyl, ethyl, sulfoethyl, and benzyl groups.
It will be done. Examples of alkenyl groups include allyl groups.

Also, A and B are -CN, -8o2RI5-COOR16
-COOR17R' or COR'', but preferably A and B are different groups.

R'' and R'' are as described above, typical examples of alkyl groups include methyl group, ethyl group, n-butyl group, and aryl groups include ha, fe=/l' group, etc. Examples include a lyle group, a t-butylphenyl group, and a methoxyphenyl group.

Also, R1? ' and R'' are as described above, and typical examples of alkyl groups include methyl group, ethyl group, n
-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, etc.

Further, typical examples of the teryl group for R', o, and R18 include phenyl group, tolyl group, methoxyphenyl group, and the like. R'' is as described above, and representative examples of the aryl group include the same examples as the aryl groups of R17 and R18 above.

In the general formula [IT], R4, R5, R6, and R7 each represent a hydrogen atom or an alkyl group, R8 represents an alkyl group, an aryl group, or an allyl group, and R' and R10 each represent a hydrogen atom, an alkyl group, or an aryl group. represents a group, G
represents an electron-withdrawing group.

Each of the above groups mentioned herein includes those having a substituent, and the L1 alkyl group is preferably an alkyl group having a total number of carbon atoms of 1N2O. Further, a preferable example of the aryl group is an unsubstituted or substituted phenyl group.

Representative examples of alkyl groups for R4, R5, R6, R7 and R8 include methyl group, ethyl group, n-propyl group n-
Butyl group, RQs and R10 are as mentioned above, but typical examples of alkyl group are methyl group, ethyl group,
Examples include i-propyl group, n-butyl group, and benzyl group. R' and R'' are as described above, but representative examples of the aryl group include phenyl group, ethylphenyl group, n-
Examples include butylphenyl group and chlorophenyl group.

G is an electron-withdrawing group, for example CN or SO, R(R
is an alkyl group having 1 to 10 carbon atoms or 7 carbon atoms
-15 groups) and the like.

In the general formula [■I], rr = 1 or 2 and n is 1
In the case of R'' and R12 may be the same or different from each other, and include a cyano group, an alkyl group having 1 to 10 carbon atoms having a substituted alkyl group (e.g., a cyanoalkyl group, an alkoxyalkyl group), a substituted aryl group. represents a ring group or a cyclic alkyl group having 6 to 20 carbon atoms.

Furthermore, when n is 2, at least 1 of R'' and R12
One represents an alkylene group or an arylene group, and when one is as described above, the other represents an alkyl group or an aryl group.

G is an electron-withdrawing group, for example CN or 5O2R (R is an alkyl group having 1 to 10 carbon atoms or 7 to 1 carbon atoms)
It is an arylalkyl group having 5 groups. ).

In the general formula, R" represents a hydrogen atom or lower argyl having 1 to 5 carbon atoms, and R14 represents an alkyl group having up to 1 carbon number.

Specific compound examples are shown below, but the present invention is not limited thereto.

Compound examples of general formula [■] CH.

1-(2) 1-(3) 1-(4) (CH2) to 3808 1-(5) (C)I 2)3 SosK 1-(7) Hs l-(10) (CH2), SO, to -02 (CH2)3SO,K (CH2) 380sK 1-(1,6) l-Ken 1-(19I C2Hfi 1 - (22) 1 - (27+ 1-(281 c2i-r.

■-(29! (CI(2)3SO3K H3 General formula [■] Compound example 2-(2) CeH+a(n) 2-(3) 02H.

2-(4) CH2CH=CH2 2-(5) C2H.

CH3 2H5 2-(8) 2H5 (CH2)zO8o3Na 2-(1(1! 2-[1) (CH2)8SO3K (CH2)4So3 2-inch (CH2)45OsK CI(.

(CI(2), SO3K (CH2)4SosNa 2-(181 C,H.

C), l2CH=C) (2 General formula order) Compound example 3-(1) 3-(2) 3-(3) 3-(5) General formula ■] Compound example C2H* Said general formula CI) Generally, an effect is recognized when the compound I#J (compound according to the present invention) represented by CI[)(T[I:](5) is added in an amount of 1 to more than 100%, but especially when the total amount is 51n9 ~600 叡 is preferred.

The compounds according to the present invention can be used in water, water-miscible organic solvents (
in a coating liquid containing hydrophilic colloids to form the constituent layer dissolved in methyl alcohol, ethyl alcohol, isopropyl alcohol, dioxanetetrahydrofuran, tetra70lopropyl alcohol, dimethylformamide, dimethylsulfoxide, etc.) or mixtures thereof. It can be added to. At this time, if necessary, a mordant (for example, U.S. Pat. No. 2.548.564, U.S. Pat.
882°156, 3.706.563, 3.7
09.690, 3゜788, 855, 3.79
5.515, Japanese Patent Publication No. 51-1418) can also be used together. If necessary, a substantially water-insoluble high-boiling organic solvent (e.g. dibutyl phthalate, diotatylphthalate, triphenyl phosphate, F recresyl phosphate, acetyl tributyl citrate,
N,N-diethyldodecaneamide, N-dodecylpyrrolidone, octafluoropentyl dodecanoate, etc.),
It can be emulsified and dispersed and added to the hydrophilic colloid layer.

The ratio of the compound according to the present invention to the high boiling point solvent is preferably about 0.1 to 30, more preferably 0.5 to 10 rfLl, per 1 g of the compound.

Furthermore, the compounds according to the present invention can be incorporated into the coating solution after being emulsified and dispersed. More preferably, each compound is simultaneously dissolved in a high boiling point solvent and emulsion dispersed in an aqueous hydrophilic colloid solution.

The silver halide photographic materials of the present invention include color negative materials, black and white photographic materials, color aerial photographic films, X-ray photographic materials, printing materials, color photographic papers, etc. that contain couplers in their photosensitive films. It can be applied to light-sensitive materials such as type silver halide color photographic light-sensitive materials, but is preferably useful for so-called color negative films for photography.

The silver halide photographic material of the present invention has one or two types of coupler-containing silver halide emulsion layers on a support which has been subjected to corona discharge treatment, flame treatment, ultraviolet irradiation treatment, and subbing treatment as required. The above layers are appropriately combined with an intermediate layer, a single filter layer, an antihalation layer, a protective layer, and the like.

Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate,
For example, there are polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

In the silver halide photographic light-sensitive material of the present invention, hydrophilic colloids advantageously used to prepare the emulsion of the light-sensitive layer include gelatin, colloidal albumin, agar, gum arabic, alginic acid, for example, acetyl content 19-2
Cellulose derivatives such as cellulose acetate hydrolyzed to 6%, acrylamide, imidized polyacrylamide, zein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymer, polyvinyl Included are alcohols, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, and the like.

The silver halide grains used in the silver halide photographic material of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. Alternatively, for example, a method may be used in which seed particles are produced using an acidic method, and then grown using an ammonia method, which has a faster growth rate, to grow to a predetermined size. When growing silver halide grains, I)H, EAg, etc. in the reaction vessel are controlled to match the growth rate of silver halide grains, as described in JP-A-54-48521, for example. It is desirable to sequentially and simultaneously implant and mix silver ions and halide ions.

These silver halides include activated gelatin; sulfur sensitizer;
For example, sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers,
For example, gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-ourosulfo2
- Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as palladium, platinum, ruthenium, rhodium, iridium, etc., specifically ammonium opparadate, potassium chlorooleate, sodium chlorovaladate, etc. (These kinds of substances act as sensitizers, fog suppressants, etc. depending on the amount.)
For example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc. ) may be chemically sensitized.

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, using cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or optical sensitizers such as merocyanine dyes alone. To,
Alternatively, optical sensitization can be achieved in combination (for example, superchromatic sensitization).

This emulsion may also contain dihydroxyalkanes such as glycerin 1°5-bentanediol, esters of ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate, water-dispersible fine particulate polymeric compounds obtained by emulsion polymerization, etc. In addition, ethyleneimine compounds, dioxane derivatives, oxypolysaccharides, dicarboxylic acid chlorides, methanesulfonic acid bisesters, vinylsulfonyl type hardeners, etc.
Various photographic additives such as coating aids such as saponin and sulfosuccinate, optical brighteners, antistatic agents, and antistaining agents can be contained.

The blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion used in the silver halide color photographic light-sensitive material of the present invention are optically processed using appropriate sensitizing dyes in order to impart photosensitivity to the desired wavelength range. Sensitized. Various sensitizing dyes can be used, such as cyanine dyes, merocyanine dyes, and composite cyanine dyes, and each sensitizing dye can be used singly or in combination of two or more.

The coupler used in the silver halide color photographic light-sensitive material according to the present invention is a Fischer type coupler or an oil-soluble coupler.
It may be either an equivalent coupler or a 2-equivalent coupler, and of course a mixture of both may be used.

The coupler used in this case may be, for example, a colorless 2-equivalent or 4-equivalent coupler, or a so-called masking coupler having, for example, an arylazo group at the active site. In addition, the above couplers include yellow, -
The coupler is of the benzylua heptanilide type, or
The magenta coupler may be a pivaloylacetanilide type coupler, and the magenta coupler may be a 3-acylamino-5-virazolone type coupler or a 3-anilino-5-pyrazolone type coupler. In addition, so-called DIR couplers (British Patent No. 953.454 and U.S. Pat. No. 3,227,554) have a group introduced into the active site of the coupler that forms a compound that exhibits a development inhibiting effect when separated from the active site.
couplers specified in each specification of the above issue. In addition, in order to improve photographic properties, couplers called so-called beating couplers, or compounds that release a development inhibitor in accordance with the density of the image during development, so-called development inhibitor-releasing compounds, are used in combination with various couplers to improve photographic properties.
German Patent No. 2.362.752 and Japanese Unexamined Patent Publication No. 1977-77
No. 635 or U.S. Patent No. 3.632.345,
U.S. Patent No. 3.297°445, U.S. Patent No. 3.37
9.529 etc.) may be included. When the coupler used in the silver halide color photographic light-sensitive material according to the present invention is contained in the light-sensitive material, it can be contained in the coating solution of the constituent layer in various forms, such as Fischer type couplers can be added in the form of a solution, and oil-soluble: HL-type molecules can be added in the form of an emulsion by dissolving them in a HL-based solvent. A high boiling point organic solvent that is immiscible with water is used, such as n-butyl phthalate, benzyl phthalate, triphenyl phosphate, )! J-o-cresyl phosphate, monophenyl salt, p-t-butyl 5-enyl phosphate, etc.

In the present invention, the selection of coating methods for the protective layer, silver halide emulsion layer, and other constituent layers of the light-sensitive material is important in order to ensure uniform quality and productivity. For example, you can choose from dip coating, double roll coach ink, air knife:ff-7 ink, extrusion coating, curtain coating, etc. Among them, extrusion coating allows you to apply two or more layers at the same time. and curtain coatings are particularly useful. Also, the coating speed can be selected arbitrarily, but from the viewpoint of productivity, 30 r + y'n1
A speed of i n or higher is preferred.

Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is recommended to mix them using a static mixer or the like just before coating. preferable.

(Examples) Next, the present invention will be explained in detail by examples, but the embodiments of the present invention are not limited thereto.

In the examples, pressure blurring of the silver halide photosensitive emulsion due to scratching was removed by the following method.

A load was applied to the unexposed sample from the photosensitive surface of a needle-pull hardness tester with a needle head of 0.3, and then processed according to the following processing steps, and the load at which pressure capri occurred was measured.

Processing process (38°C) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes Second water Wash 3 minutes 15 seconds Fixation 6 minutes Second water Wash 3 minutes 15 seconds The processing solution composition used in each processing step is as follows. It is.

Color developer composition: 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.8, F anhydrous sodium sulfite 0.14 g hydroxyamine 1/2 sulfate 1. ．． 98.9 sulfur
Acid 0.
74g anhydrous potassium carbonate 28.85
, p anhydrous potassium hydrogen carbonate 3.46
g Anhydrous potassium sulfite 5.10 g
Potassium bromide 1.16, p
Sodium chloride O, 14g2)
IJ l:2) diacetic acid trisodium salt (water@)
1.20 g potassium hydroxide
Add 1.48g water to make 11.

Bleach composition: ethylenediaminetetraacetate iron ammonium i 1
00. Op ethylenediaminetetraacetic acid diammonium salt 10.0g ammonium bromide
150.0.9 Ice Vinegar @
Add 10.0 g of water to bring the mixture to 11, and adjust the pH to 6.0 using aqueous ammonia.

Fixer composition: Ammonium thiosulfate 175.09 Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to l
The pH was adjusted to 6.0 using acetic acid.

Stabilizing liquid composition: Formalin (37% aqueous solution) 'i,
5ml Konidax (manufactured by Konishi Rokuyushin Kogyo Co., Ltd.)
7.5 Add water to make up to 1 liter.

Example 1 Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, a red-sensitive layer, a light-sensitive layer, and a light-sensitive layer were layered from the support, with various auxiliary layers interposed. The effect of the present invention is obtained by disposing a monodisperse high-sensitivity emulsion layer on the outermost side of the blue-sensitive layer, and further coating a non-sensitive layer containing the compound according to the present invention on the outer side thereof. In order to verify this, 10 types of samples were created: samples A, B..., ■, and J.

Layer 1: antihalation layer containing 0.4 g of black colloidal silver and 3 g of gelatin.

Layer 2: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (A
gI; 6 mol%), l. 6g gelatin and O,SO
g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy) -N-(・δ-(2,4-di-
t-amylphenoxy)butyl]-2-naphthamide [
Hereinafter, it will be referred to as cyan coupler (Cr). ],]002
8 g of l-hydroxy-4-[4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-(δ-(2°4-di-t-amylphenoxy) ) butyl-2-naphthonamide disodium [hereinafter referred to as colored cyan coupler (CC-1)] containing 0.4.9 triresyl phosphate [hereinafter referred to as TCP]. A low-sensitivity green-sensitive emulsion layer.

Layer 3...1.1 g of highly sensitive red-sensitive silver iodobromide emulsion (
AgI; 7 mol%), i, 2y gelatin and 0.2
0, in which 3 g of cyan coupler (C-1'), 0.0209 of colored cyan coupler (CC-1) was dissolved;
A highly sensitive red-sensitive emulsion layer containing 159 TCP.

Layer 4: 0.07 g of 2.5 size G-t-octylhydroginone [hereinafter referred to as anti-fouling agent (HQ-1)]. ]
004 g of di-n-butyl phthalate [hereinafter referred to as DBP]. ] and an intermediate layer containing 1.2 g of gelatin.

Layer 5: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (A
gI; 5 mol%), 1.79 gelatin and 0.30
9 1-(2,4,6-)-lichlorophenyl)-3-
43-(2,4-di-t-amylphenoxyacetamide)benzenamide)-5-pyrazolone [hereinafter referred to as magenta coupler (M-1). ], 4,4 of 0.209
-methylenebis-11-(2,4,6-)lichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide)-5-pyrazolone[
Hereinafter, it will be referred to as magenta coupler (M-2). ], 0.0
66.9 1-,,(2,4,6-)IJ chlorophenyl)-4-(t-naphthylazo)-3-(2-
Chloro-5-octadecenyl succinimide anilino)
-5-pyrazolone [hereinafter referred to as colored magenta coupler (
CM-71). ] in which three types of couplers were dissolved.
, a slow green-sensitive emulsion layer containing 3 g of TCP.

Layer 6...1.5y high-sensitivity green-sensitive silver iodobromide emulsion (A
gI; 7 mol%), 1.9. ! 9 gelatin and 0.
093g magenta coupler (M-1), 0.09
4 g of magenta coupler (M-2), O,,049
, 9 colored magenta coupler (CM-1') Highly sensitive green-sensitive emulsion layer containing dissolved TCP of 0,12.9.

Layer 7...0.211 yellow colloidal silver, 0.119 DBP dissolved in 0.2 g antifouling agent (HQ-1) and 2.1. One layer of yellow filter containing li+ gelatin.

Layer 8...0.95 g of low-speed blue-sensitive silver iodobromide emulsion (AgI; 6 mol %), 1.9 g of gelatin and 1,
849 α-(4-(1-benzyl-2-phenyl-3
,5-dioxo-1,2,4-doriasilishell)]-
] α-pivaloyru 2-10 rho 5 [γ-(2,4-di-t-amylphenoxy)butanamide] acetanili V [hereinafter referred to as yellow coupler (Y-1). ] was dissolved. , a low-speed blue-sensitive emulsion layer containing DBP of 93p.

Layer 9: 1.2 g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (AgI; 7 mol %), 2.0 g gelatin and 0.0 g of gelatin.
0 in which 46 g of yellow coupler (Y-t) was dissolved,
High speed blue sensitive emulsion layer containing 23 g of DBP.

N10: A second protective layer made of gelatin was provided.

The second protective layer is referred to as layer 10, and various compounds as shown in Table 1 are added to the layer at a concentration of 0.1 g/n? A sample was prepared by applying the following coating.

Compound emulsion dispersion t tx b t: Comparative and exemplary compounds were added to a mixed solvent of dibutyl phthalate and ethyl acetate and heated to 50°C, and this solution was added to a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate. In addition, the mixture was emulsified and dispersed using a colloid mill.

N11...First protective layer containing 2.3 g of gelatin.

Table 1 The above coated sample was applied a load from the photosensitive surface side with a scratched hard layer of a needle with a needle head of 0.3 mm as described above, and then processed according to the processing procedure described above, and the load at which pressure fog occurred was measured. .

Table-2 J[Compound-1=dibutyl phthalate Comparative compound-2': 2-(2-hydroxy-5-ter
t-Butyl)phenylbenzo' triazole From Table 2, samples (F-J) according to the present invention are samples A to E.
It is clear that the resistance to pressure force burr due to friction is significantly superior to that of the conventional method.

In addition, sample A-J was cut into a size of 5 crn square, and 23
After being stored at 180% RH (RH represents relative humidity) for 1 day, the protective layers of the same samples were brought into contact with each other, a load of 800I was applied, and the samples were stored at 40°C and 80% RH for 2 days. Samples B and C were stored for several days and then peeled off to test for adhesion.

E was completely glued. In all other samples, the adhesive area was in the range of 0 to 15%, and no adverse effect on the adhesive properties of the present invention was observed.

In addition, with the sample according to the present invention, images with good photographic characteristics were obtained.

Agent Yoshimi Kuwa Hara

Claims (1)

[Scope of Claims] At least one light-sensitive layer and a non-light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. In the silver halide photographic light-sensitive material provided with at least one of The highest silver halide emulsion layer contains monodisperse halogenated silver grains, and adjacent to the photosensitive layer and on the opposite side from the support, the following general formulas CI), (TI),田〕or〔v〕
1. A silver halide photographic light-sensitive material, comprising a non-photosensitive layer containing at least one of the compounds represented by: General formula [I[) (1 General formula [where R' and W each represent a hydrogen atom, an alkyl group, or an aryl group. W represents an alkyl group, an aryl group, or an alkenyl group, and A and B Each -CN
, -3O,RI', -C0NRI? , C0NRI? H
lg or -COR" (R15 and R
"represents an alkyl group or an alkyl group, and R1
7, R'8 is a hydrogen atom, an alkyl group, an aryl group,
Furthermore, R17 and R'' may be linked to each other to form a piperidino ring, a morpholino ring, a bis-dino ring, or a pipetedine ring. R19 represents an alkyl group or an aryl group, R4, R5, R6, and R each represent a hydrogen atom or an alkyl group, R8 represents an alkyl group, an aryl group, or an alkenyl group, and R9 and RlO represent a hydrogen atom or an alkyl group, respectively. group or an aryl group, and G represents an electron-withdrawing group. n is l or 2, and when n is 1, R1', R''
may be the same or different from each other and represent an alkyl group, an aryl group or a cyclic alkyl group, and n is 2
In the case of R" It represents alkyl, and R14 represents an alkyl group having 1 to 20 carbon atoms.]