JPH04163454A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide excellent picture sharpness by a method wherein a photosensitive material contains one kind of compound represented by a specified formula, and a water soluble and organic solvent soluble consisting of a repeat unit having an acid group in a main chain or a side chain polymer. CONSTITUTION:A photosensitive material contains at least one kind of compound represented by a formula II and a water soluble and organic solvent soluble polymer consisting of a repeat unit having no acid group in a main chain or a side chain. In a formula, R<12> indicates an aliphatic group, an aromatic group, or a heterocyclic group and M indicates -CO-, -SO2, -N(R<13>))C)-, -OCO-, and -N(R<15>)SO2-. R<14>, R<15>, and R<24> indicate a hydrogen atom, an alkyl group, or an aryl group. L is two coupling groups necessary to form a 5-membered ring or a 7-membered ring. R<11>, R<13>, and R<21> are a group replaceable with hydrokinon nucleus, time indicates a group discharging X after it is separated away from an oxidant of hydrokinon nucleus, X indicates a development inhibitor, and (t) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material, and more particularly to a silver halide color reversal photographic material with improved sharpness.

(Prior Art) Color reversal photographic materials usually have a plurality of silver halide emulsion layers having different color sensitivities, such as a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, on a support.

These color reversal photographic light-sensitive materials imagewise exposed for multicolor subjects are first subjected to black and white silver development in a first development step, and then undergo a chemical or optical detonation step to remove residual halogens in a second development step. Silver oxide is developed in color to form color images such as cyan, magenta, and yellow. By the way, 1. Normally, the dye image formed in each color-sensitive layer during multicolor exposure is different from the color image formed during monochrome exposure, and in the case of color reversal photographic materials, this difference is mainly caused by the first IJ image process. This occurs due to the movement of development inhibiting substances such as iodide ions between emulsion layers having different color sensitivities. The difference in color image between multicolor exposure and monochrome exposure caused by such development is described by Hudson and Horton, Journal of the Optical Society of America, Vol. 42, No. 9, pp. 663-669 (1976). This is called the multi-layer effect or inter-image effect, as described in the publication), and is known to be useful for improving sharpness and color reproducibility.

As a technique for increasing the multilayer effect, Japanese Patent Application Laid-Open No. 51-12
No. 8528 discloses a method of increasing the interlayer effect experienced by a light-sensitive silver halide emulsion layer by introducing into the light-sensitive silver halide emulsion layer an emulsion having a surface covered with silver halide grains.

Also, Re5earch Disclosure 13
553 (1975) describes a preferred method of applying an interlayer effect using iodine ions in a reversal photosensitive material, using AgBr 1. AgCl! I and AgB
It is possible to contain an emulsion containing silver iodide such as rCf I, and to contain a hydrophilic colloid in addition to normal emulsion grains as a layer that receives at least one interlayer effect, and to contain a surface fogging emulsion. is listed.

Another known method for increasing the interlayer effect, particularly for color photographic materials, is to use so-called DIR couplers. This is a technology in which a development inhibitor is released from a coupler as a color image is formed during color development of a color photosensitive material, and the difference in concentration of the development inhibitor produces an edge effect to improve sharpness. This method is effective only during color development, so it is applicable to color photosensitive materials such as color negatives and color papers, but it is applicable to color reversal photosensitive materials, where the main effect of image formation is determined by black and white development, and color photosensitive materials. It cannot be expected to be used for black and white photosensitive materials that do not require development.

DIR-hydroquinone, which releases a development inhibitor during development, is known as a technology that utilizes the edge effect during development and can be applied to many color photosensitive materials and especially black and white photosensitive materials without color development processing ( LIS-33
64022, US-3379529, Japanese Patent Publication No. 50-62
435, JP 50-133833, JP 51-51
941, JP-A-50-119631, JP-A-52-57
828). Since DIR-hydroquinone is effective not only in color development but also in black and white development, it can be applied to a wide range of silver halide photosensitive materials.

However, when DIR-hydroquinone is mixed and coated with conventionally used emulsions, it decomposes over time after the coating solution is prepared, causing adverse effects, and the photosensitive materials prepared can be stored for long periods of time. It was known to have problems with increased capri and decreased sensitivity when attempting to use it after storage.

The reason is that when DIR-hydroquinone and silver halide emulsion coexist, silver halide becomes a medium and DIR
- the oxidative decomposition of hydroquinone is greatly accelerated;
For this reason, not only does the aging of the coating solution affect the sensitivity and capri, but also this reaction occurs gradually during storage, resulting in deterioration of performance. Based on the above findings, side effects can be prevented by adding DIR-hydroquinone to an adjacent layer that does not substantially contain silver halide so as not to come into direct contact with the silver halide emulsion. It was believed that DIR-F (Q) was only effective when added to an emulsion layer containing silver halide, but even if it is added to an adjacent layer that does not contain silver halide, the conventional sharpening effect can be improved by adjusting the amount added. It has been found that the effect of improving the temperature is shown (Japanese Patent Application Laid-Open No. 64-546).

However, when DIR-HQ is added to an adjacent layer that does not substantially contain silver halide so that it does not come into direct contact with the silver halide emulsion, the oxidation reaction during photographic development is delayed, so it is difficult to improve sharpness. had the problem of requiring a large amount of addition.

Furthermore, even if DIR-HQ is added to an adjacent layer that does not substantially contain silver halide so as not to come into direct contact with the silver halide emulsion, oxidative decomposition of IR-HQ still occurs, so prevention of side effects is insufficient. However, when the prepared photosensitive materials are used after being stored for a long period of time, there are problems of increased fogging and decreased irritability.

(Problems to be Solved by the Invention) An object to be solved by the present invention is to provide a silver halide color reversal photographic material that has excellent image sharpness without deteriorating storage stability.

(Means for Solving the Problems) The object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support, the photographic material having the following general formula (1a) or (1b). This is achieved by a silver halide photographic material containing at least one of the compounds shown below and a water-insoluble and organic solvent-soluble polymer consisting of a repeating unit having no acid group in its linear or side chain. Ta.

General formula (1a) General formula (lb) 240H H In the formula, R12 represents an aliphatic group, an aromatic group, or a heterocyclic group, and M is -C0-1-SO, -1-N (R") C.O.
-1-〇CO- or -N CR") So, -.

RI4, RI5, and Rz4 represent a hydrogen atom, an alkyl group, or an atomyl group, and L is a divalent linking group necessary to form a 5- to 7-membered ring. R'', Rox and R2'
is a hydrogen atom or a group capable of substituting the hydroquinone nucleus, time represents a group that releases X after being separated from the oxidized product of hydroquinone, X represents a development inhibitor, and t represents 0 or 1.

The polymer of the present invention may be a single polymer having one type of repeating unit or a copolymer of two or more types of repeating units.

Further, the compound represented by formula (la) or (1b) of the present invention and the polymer may be contained in the same layer or in separate layers, but preferably each is contained in the emulsion layer. Most preferably, it is contained simultaneously in the red-sensitive emulsion layer containing the coupler.

To explain the general formula (1a) or (1b) in more detail, the substituents represented by R11, R13 to R2' include a hydrogen atom, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an amide group, and a sulfonamide group. , an alkoxycarbonylamino group, and a ureido group, and more preferably a hydrogen atom, an alkylthio group, an alkoxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, and a ureido group.

RI 1 or R2' is preferably a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a sulfonyl group, a cyano group, an acyl group, or a heterocyclic group, and more preferably a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, or a sulfamoyl group. group, cyano group.

To further explain R12 in detail, RI! Examples of aliphatic groups include straight chain, branched chain, and cyclic alkyl groups, alkenyl groups, and alkynyl groups having 1 to 30 carbon atoms. Examples of aromatic groups include those having 6 to 30 carbon atoms, such as phenyl and naphthyl groups. The Peter ring is nitrogen, oxygen,
It is a 3- to 12-membered compound containing at least one type of sulfur.

L represents a divalent linking group, preferably alkylene, alkenylene, arylene, oxyalkylene, oxyarylene, aminoalkyleneoxy, aminoalkenyleneoxy, aminoaryleneoxy, and oxygen atom.

%Time-), X is a group that is released as e(-Time+-,X) when the redox mother nucleus represented by A undergoes a cross-oxidation reaction during development and becomes an oxidized product.

Time is preferably connected through a sulfur atom, nitrogen atom, oxygen atom, or selenium atom.

Time represents a group that can further release X thereafter, and may have a timing adjustment function, and may also be a coupler or redox group that reacts with the oxidized developer to release X.

When 'l''ime is a group having a timing adjustment function, for example, U.S. Pat.
409,323, British Patent No. 2,096.783;
U.S. Patent No. 4,146.396, Japanese Patent Application Publication No. 51-14
6,828, JP-A No. 57-56,837, etc. The aTime may be a combination of two or more selected from those described therein.

Preferred examples of timing control groups include the following.

(1) Groups that utilize the cleavage reaction of hemiacetal For example, U.S. Pat. No. 4,146,396, JP-A-60-24
It is described in No. 9148 and No. 60-249149,
It is a group represented by the following formula.

Here, the main mark represents the bonding position on the left side in general formula (1a) or (1b), and the main mark represents the bonding position on the right side in general formula (1a) or (1b).

Formula (T-1) In the formula, W is an oxygen atom, a sulfur atom, or -N-R1? represents a group, R&S and R represent a hydrogen atom or a substituent, R&? represents a substituent, t represents 1 or 2, and when t is 2, two -W-C-Rb
& represent the same or different sWhen R&S and Rb2 represent a substituent, representative examples of Rht are Rh, group, R*vCO- group, R&? SO□- group,
Examples include I R to R groups such as R*wNCO- group or R&qNSOz- group. Here, Raw represents an aliphatic group, aromatic group or heterocyclic group, R1° represents an aliphatic group, aromatic group, heterocyclic group or a hydrogen atom, R61, R44 and R4?
Each represents a divalent group, and cases in which they are linked to form a cyclic structure are also included.

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction, such as a timing group described in US Pat. No. 4,248,962. It can be expressed by the following formula.

Formula (T-2) *-Nu-L ink-E-** In the formula, this mark represents the bonding position on the left side in general formula (1a) or (1b), and the ** mark represents the position bonded to the left side in general formula (1a) or (1b). ) or (1b), represents the bonding position on the right side, and N
u represents a nucleophilic group, an example of which is an oxygen atom or a sulfur atom, and E represents an electrophilic group, which is a group that can undergo nucleophilic attack from Nu to cleave the bond with the mark **. 1 inch
k represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction.

(3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system.

For example, U.S. Pat. No. a, 409.323 or 4.4.
It is a group described in No. 21,845 and represented by the following formula.

Formula (T-3) In the formula, this mark, ** mark, W, R, , R6 & and t represent the same meaning as explained for formula (T-4).

(4) A group that utilizes a cleavage reaction due to ester hydrolysis.

For example, West German Published Patent No. 2,626. The linking group described in No. 315 includes the following groups.

In the formula, * and ** have the same meaning as explained for formula (T-1).

Formula (T-4) Formula (T-5) S *-〇-C-＊＊＊-○-C-** (5) A group that utilizes the cleavage reaction of iminoketal.

For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following formula.

Formula (T-6) In the formula, this mark, ** mark and W have the same meaning as explained in formula (T-1), and R1 represents the same meaning as Rbl.

As a preferable example when Time is a coupler,
The following formulas (C-1) to C-4) can be mentioned.

Formula (C-1) Formula (C-2) Formula (C-3) Formula (C-4) In the formula, ■1 and v2 are! Represents a substituent, ■3, V,
, V, and V& represent a nitrogen atom or a substituted or unsubstituted methine group, ■ represents a substituent, X represents an integer from O to 4, and when X is plural, ■ is the same or different. , two V may be linked to form a cyclic structure, and v is a -C〇- group, -SO, -
represents a group, an oxygen atom or a substituted imino group, and ■ and Le
■ Represents a group of nonmetallic atoms that constitute the umbrella wheel. is a hydrogen atom or! Represents a substituent.

When the group represented by T im e in general formula (1a) or (1b) is a redox group, it is preferably represented by the following formula (R-1).

Formula (R-1) -P-(Y=Z), -Q-B In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and two Y and Z
At least one of represents a methine group having X as a substituent, the other Y and Z represent a substituted or unsubstituted methine group or a nitrogen atom, l represents an integer of 1 to 3, and 11 Y and Z represents the same or different), B represents a hydrogen atom or a group that can be removed by an alkali, where P, Y, Z, Q and B
The case where any two substituents become divalent groups and connect to form a cyclic structure is also included. For example, (Y-Z) forms a benzene ring, a pyridine ring, etc.

When P and Q represent a substituted or unsubstituted imino group, preferably an imino group substituted with a sulfonyl group or an acyl group.

At this time, P and Q are expressed as follows.

Formula (N-1) Formula (N-2) *-N-pieces**-N-** SO□-G'C〇-G' Here, the asterisk indicates the hydroquinone core in the case of P and the hydroquinone core in the case of Q. The case represents the bonding position with B, and the ** mark indicates -(Y-Z)
, − represents the position of bonding with one of the free bonds.

In the formula, the group represented by G' represents an aliphatic group, an aromatic group, or a heterocyclic group.

Particularly preferred groups among the groups represented by formula (R-1) are those represented by the following formula (R-2) or (R-3).

Formula (R-2) Formula (R-3) H In the formula, the * mark represents the position bonded to the hydroquinone mother nucleus, and the ** mark represents the position bonded to X.

Rk4 represents a substituent, and q represents an integer from 0, 1 to 3. When q is 2 or more, two or more R&4 may be the same or different, and two R1 are substituted on adjacent carbons. When it is a group, it also includes the case where each becomes a divalent group and is connected to form a cyclic structure.

Preferred examples of X include mercaptoazoles and benzotriazoles. Mercaptoazoles include mercaptotetrazoles and 5-mercapto-1,3,
4-thiadiazoles and 5-mercapto-1,3,4
-Oxadiazoles are more preferred.

Most preferably X is 5-mercapto-1°3.4-
They are thiadiazoles.

Specific examples of the compound represented by the general formula (1a) or (1b) of the present invention are listed below.

a-1 0Hl CH3 a-2 2715 71 ;-% la-3 0H H a-4 H la-5 a -6 00H If 1 H a-7 H H a-8 la-9 la-10 H H la -11 1l la (2 00R H la-13 H H la-14 H 1a-15 0H H a-16 H a-17 a-18 H a-19 il a-20 1a -21 00H H a-22 001' 1 a-23 a-24 0CsHI? (n) 0f(0)I
CH 0■ a-26 1a-27 H a-28 00H 0il 0 a-30 00H0 1a -31 υ11 SIUNt11. ; Coff a-33 H b-1 H H b-2 H b-3 H i b-4 H ) II H b-5 H 1 b-6 0H b-7 H H b-8 General of the present invention The compound represented by formula (1a) or (1b) is disclosed in JP-A-49-129536 and JP-A-52-57828.
No. 60-21044, No. 60-233642,
No. 60-233648, No. 61-18946, No. 6
No. 1-156043, No. 61-213847, No. 61
-230135, 61-236549, 62-
No. 62352, No. 62-103639, U.S. Patent No. 3,
379゜529, 3,620,746, 4,3
32.828, 4,377.634, 4゜68
It can be synthesized according to the method described in No. 4.604.

The compound represented by formula (1a) or (1b) may be added to any emulsion layer and/or non-photosensitive layer, or may be added to both.

The amount added is 0.001-column 01/bo~0.2mmo
It is preferable to use it in the range of l/m, more preferably 0°005
mmol/m~0. 1 mmoj! It is particularly preferable to use it within the range of /rrr.

The polymer used in the invention may be any polymer as long as it has at least one type of repeating position that does not have an acid group in the main chain or side chain, is insoluble in water, and soluble in a medium solvent. 10-bond? Polymers having the above are preferred from the viewpoint of color development and fading improvement effect. On the other hand, when a polymer consisting of a monomer containing all acid groups is used, the fading-improving effect of the polymer is markedly reduced, although the reason is not clear, and this is often undesirable.

In addition, monomers constituting the repeating base without acid groups in the polymer of the present invention include its homopolymer (molecular weight 2
It is preferable that the glass transition point (Tg) is 3060 or higher. More preferably, it is ro 0c or higher. When a polymer compound composed of a monomer having a Tg of ro 00 or higher as a homopolymer is used as a load, the improvement effect increases significantly as room temperature conditions are approached. This tendency is particularly remarkable when acrylamide-based and methacrylamide-based polymers are used, which is very preferable.

To be sure, the content of repeating units without acid groups constituting the polymer of the present invention is preferably 35 mol% or more, more preferably SO mol% or more, and even more preferably B
It is 70 mol% to 100 mol%.

Next, the oil bath polymer used in the present invention will be explained in more detail. The acid group of an oil-bathable polymer that does not have an acid group in its main chain or side chain is the remaining portion of an acid molecule after removing a hydrogen atom that can be substituted with a metal, and forms the negative portion of a salt.

Repeating units that do not have any acid groups include, for example, carmine powder,
Refers to repeating units that do not contain sulfonic acids, phenols with a pKa of approximately 10 or less, naphthols, active methylenes, and their salts, etc., which have at least one electron-withdrawing group at the ortho or para position of the hydroxyl group. do. Therefore, the coupler structure is considered an acid group here.

A preferable requirement for the structure of the oil-soluble polymer of the present invention is that the main chain or side chain has a group (G1 and 02 are each a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group). . The polymer according to the present invention will be explained below by giving specific examples; however, the present invention is not limited thereto.

(A) Vinyl polymer Monomers forming the vinyl polymer of the present invention include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and inbutyl acrylate. acrylate, 5ee-butyl acrylate,
tert-butyl acrylate, amyl acrylate,
hexyl acrylate, two-ethylhexyl acrylate, octyl acrylate), tert-octyl acrylate, λ-riQO ethyl acrylate, 2-bromoethyl acrylate, Hiro-chlorobutyl acrylate, anoethyl acrylate, 2-acetoxyethyl acrylate, dimethyl Aminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, λ-chloro/riguchihequinol acrylate, cyclohequinol acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate,! -Hydroxypentyl acrylate, co,2-dimethyl-3-
hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, -monoethoxyethyl acrylate), 2-4so-propoxy acrylate, coptoxyethyl acrylate, 2-
(,2-methoxyethoxy)ethyl acrylate, -1(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added = n) l-bromo 2-methoxyethyl acrylate, l,l-dichloro- Ni-ethoxyethyl acrylate and the like can be mentioned. In addition, the following nanatsumers can be used.

Methacrylic acid esters: Specific examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, 5e
C-butyl methacrylate-F, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chloroy/zyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylamino Ethyl methacrylate, 2-(j-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, -monohydroxyethyl methacrylate, hydroxybutyl methacrylate , triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, λ-methoxyethyl methacrylate, 3
-methoxybutyl methacrylate, λ-acetoquinethyl methacrylate, two-acetoacetoxyethyl methacrylate, two-ethoxyethyl methacrylate, λ-1
so-propoxyethyl methacrylate, λ-butquinethyl methacrylate, "2('-methoxyethoxy)
Ethyl methacrylate, u-(,2-ethoxy7ethoxy)ethyl methacrylate), u-(j-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added n = j), allyl methacrylate, methacrylic acid Examples include dimethylamine ethylmethyl chloride salt.

Vinyl esters: Specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl imbutyrate, vinyl acetate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. ; Acrylamides: For example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-7” tylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, metquinethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, Dimethylacrylamide, diethylacrylamide, β-cyanoethyl acrylamide, N-(coaceto7toxyethyl)acrylamide, diacetone acrylamide, etc.; Methacrylamides: For example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexynylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, metquinethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-nano Ethylmethacrylamide, N-(λ-acetoacetoquinethyl)methacrylamide, etc.; Olefins: For example, dicyclopentadiene, ethylene, propylene, /-propylene, /-hentene, vinyl chloride, vinylidene chloride, innobre/ , chloroprene, butadiene, λ, 3-dimethylbutadiene, etc.; styrenes:
For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methkinstyrene,
Acetoxystyrene, chlorstyrene, dichlorostyrene, flomstyrene, vinylbenzoic acid methyl ester, etc.; Vinyl ethers: for example, methyl vinyl ether, phthyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Butyl crotonate, hequinyl crotonate, dimethyl itaconate, dibuty itaconate/diethyl pemaleate, dimethyl maleate, diptyl maleinoate, diethyl fumarate, dimethyl fumarate, diptyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, Examples include metquinethylvinylketone, prendyl acrylate, glycidyl methacrylate, N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinyliso/rynylide, methylenemalonitrile, and vinylidene.

The monomers used in the polymer of the present invention (for example, the above monomers) may be used in combinations of two or more monomers depending on various purposes (for example, improving solubility). In addition, in order to control color development and solubility, monomers having acid groups such as those listed below may also be used as the monomer, as long as the copolymer does not have poor water solubility.

Acrylic acid; Methacrylic acid; Itaconic acid, Malay/acid;
Monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monomethyl itaconate; monoalkyl maleinoate, such as monomethyl maleate, monoethyl maleate, motupyl maleate; /traconic acid; styrene sulfonic acid; vinyl Benzyl sulfonate; vinyl sulfonic acid; acryloyloxyalkyl sulfonic acid, such as acryloyl oxine methyl sulfonic acid, acryloyl oxine ethyl sulfonic acid,
Acryloyloxypropylsulfonic acid, etc.; Methacryloyloxyalkylsulfonic acids, such as methacryloyloxy/methylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxy/methylsulfonic acid, etc.; Acrylamidoalkylsulfonic acids, such as
coacrylamidecomethylethanesulfonic acid, 2
-acrylamido-2-methylpropanesulfonic acid,!
-Acrylamide! -methylbutanesulfonic acid, etc.;
Methacrylamide alkyl sulfonic acids, such as λ-methacrylamide! -methylethanesulfonic acid, -methacrylamide λ-)tlupro/? Sulfonic acid!
- methacrylamide-co-methylbutanesulfonic acid, etc.; these acids contain alkali metals (e.g. Na, etc.)
Alternatively, it may be a salt of ammonium ion.

Among the vinyl monomers listed above and other vinyl monomers used in the present invention, hydrophilic monomers (
Here, it refers to a substance that becomes water-soluble when made into a homopolymer. ) is used as a comonomer, there is no limit to the proportion of hydrophilic monomer in the copolymer, as long as the copolymer is not subjected to a water bath process, but it is usually preferably μO
It is mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. Furthermore, the hydrophilic comonomer copolymerized with the monomer of the present invention has an acid group ffi! In this case, as mentioned above, from the viewpoint of image storage stability, the proportion of the comonomer having an acid group in the copolymer is usually less than 35 mol%, preferably 20 mol% or less, more preferably,
70% or less, most preferably when such comonomer is not included.

The monomers of the invention of the polymer molecules are preferably methacrylate, acrylamide and methacrylamide.

CB) As polyester resin polyhydric alcohol obtained by condensation of polyhydric alcohol and polybasic acid, )l(J-R1-OH(R1
Glycols or polyalkylene glycols having a structure consisting of a hydrocarbon chain (particularly an aliphatic hydrocarbon chain) having 12 to about 12 carbon atoms, or a polyalkylene glycol chain, are effective as polybasic acids.
Those having OOC-R2-COOH (R2 simply represents all bonds or a hydrocarbon chain having about 72 carbon atoms) are effective for 7.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, l
, Coprohirencricor, /.

3-propylene glycol, trimethylolpro, 2-l, 4t-butanediol, isobutylene diol,
/, S--: ntandiol, neopentyl glycol, /, J-hexanediol, /17-hebutanediol, 71g-octanediol, /, ternonanediol, /, 10-decanediol, l, // -undecanediol, /.

/codedecanediol, /, /3-4lysocandiol, /, 4t-diol, glycerin, diglycerin,
Examples include triglycerin, /-methylglycerin, erythritol, mannitol, norbit.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sepacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and fumaric acid. Acids, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, inhimelic acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc. It will be done.

(C) Other triester obtained by ring-opening polymerization as shown below. In the formula, m represents an integer from μ to 7. The -CH2- chain may be branched.

Suitable monomers which may be conveniently used to make this polyester include .beta.-propiolactone, .epsilon.-caprolactone, dimethylpropiolactone, and the like.

The molecular weight and degree of polymerization of the uninvented polymer do not substantially affect the effects of the present invention, but as the molecular weight increases, problems such as the time it takes to dissolve in the auxiliary bath agent and the problem that the solution viscosity increases. Because of the high content, it becomes difficult to emulsify and disperse, producing coarse particles, and as a result, problems such as decreased color development and poor coating properties are likely to occur. As a countermeasure to this problem, using a large amount of auxiliary solvent to completely lower the viscosity of the solution causes new process problems. From the above point of view, the viscosity of the polymer is 3% for 100cc of the adjuvant used.
0? The viscosity when dissolved is preferably at most so ocps, more preferably at most λ0OOCpS. Further, the molecular weight of the vine polymer that can be used in the present invention is preferably 1!
It is 10,000 or less, more preferably 10,000 or less, and even more preferably 30,000 or less.

The ratio of the polymer of the present invention to the co-solvent varies depending on the type of polymer used, and the solubility in the co-solvent,
Summerization occurs over a wide range depending on the degree of polymerization, solubility of the coupler, etc. Generally, the amount necessary to provide a solution of at least the coupler, high-boiling coupler solvent, and polymer in a cosolvent with a sufficiently low viscosity to be easily dispersed in water or an aqueous hydrophilic colloid solution. of co-solvents are used. The higher the polymerization degree of the polymer, the higher the viscosity of the solution, so it is difficult to uniformly determine the ratio of polymer to cosolvent regardless of the polymer type, but it is usually from about /:l to i:to The range of (weight ratio) is preferable. The ratio (weight ratio) of the polymer of the present invention to the coupler is preferably from /20 to 202/, more preferably /:I
It is 702/ from O.

Some specific examples of polymers used in the invention are described below, but the invention is not limited thereto.

Specific example A type of polymer Tg('C)P-
7) Polyvinyl acetate 32P-2) Polyvinyl propionate 20P-3) Polymethyl methacrylate 10! P-1A) Polyethyl methacrylate 6jP-ri Polyethyl acrylate
-, 24tP-4) Hinylruvinylalcoacetate (
32) -L copolymer (Ri!: RiP-7), +? Sn-butyl acrylate! Hiroto P-? ) Poly n-butyl methacrylate 20-P-ta) Polyisobutyl methacrylate 33-P-10) risopropyl methacrylate 11'/Rate P-//) Polyethyl acrylate-70F-/Co] n- Butyl acrylate = (-acrylamide copolymer (Ri!: RiP-/J) 4-lymethylchloroacrylate /≠0-toP-/μ)/, Hiro-butanediol--AI adipic acid polyester P- /ri Ethylene glycol sepacinic acid polyester P-#) Polycaprolactone P-/7) Poly(2-tert-butyl 7λ phenyl acrylate) P-i♂) Poly(lA-tert-butyl 7/phenyl acrylate) ] P-i) n-butyl methacrylate (uO)-N
-Vinyl pyrrolidone copolymer (?O: 1o) P-λO) Methyl methacrylate-Kaki <, ioB vinyl vinyl copolymer 0: P-λノ) Methyl methacrylide-dose (#)j) Tyrene copolymer Combined P-λ co) Methyl methacrylate toe (106゜Tyl acrylate copolymerization -1≠) Body (to:to) P-λJ) n-Butyl methacrylate (λO)-
Methyl methacrylate-styrene copolymer (!o:3o”, ro) P-2≠] Vinyl acetate-acrylica:: (Jl)
Copolymer (1'!:/riP-26) Vinyl chloride-vinyl acetate copolymer (r/ )
Polymer (Aj:Jt) P-2t) Methyl methacrylate (#)j)
Crylonitrile copolymer (63:33) P-27) Diacetone acrylamide (≦O1-
Methyl methacrylate) 10-tricopolymer (!0:jO) P-rr) Vinyl methyl ketone-iso (-.

Butyl methacrylate j3) Polymer (!!: Guri P-29) Ethyl methacrylate-n (4j)-
Butyl acrylate copolymerization (70:30) P-3o) Diacetone acrylamide (jO.

-n-butyl acrylate- Copolymer (tO:≠0) P-37) Methyl methacrylate (10!.

Chlorhexyl methacrylate 10-9-to copolymer (jO:5O) P-32) n-butyl acrylate-(-!≠) styrene methacrylate-diacetone acrylamide copolymer (70:λo:1o) P -33) N-tert-gfh) Tough (/l
o.

Lylamidomethylmethacrylate-acrylic acid copolymer (to: 3o: P-Jj) methyl methacrylate (ioB tyrene-vinyl sulfonamide copolymer (70: coo: 1o) P-33) Methyl methacrylate tofu (-10j
) enyl vinyl ketone copolymer (70:30) P-3) n-butyl acrylate (-jg.

Tyl methacrylate-n 10-butyl methacrylate copolymer (3!:3!: P-J7) n-butyl methacrylate (201-inchyl methacrylate)-N-vinyl-1-pyrrolidone copolymer ( 3g':3r:λ4L) P-JJ') Methyl methacrylate-n (-1
03)-Butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (J7:Jri:2!:ri] P-32) n-butylmethacrylate (,2o)-
Acrylic acid (ri!:!] P-≠O) Methyl methacrylate (-10 pieces acrylic acid copolymer (ri!:!) P-a) benzyl methacrylate-(6″) acrylic acid copolymer ( ri o: 1 o) P-gu j) n-butyl methacrylate) (, 2 o
.

-Methyl methacrylate 10) -Benzyl methacrylate- Acrylic acid copolymer (Jj:Jjlj:j) P-4t3) n-Butyl methacrylate (,!0)-
Methyl methacrylate-benzyl methacrylate copolymer (3!: J, t = 30] P-4tu) Poly-3-pentyl acrylate (-2)
Rate P-<tB cyclohexyl methacrylate (10<1
)-Tomethyl methacrylate-n-propyl methacrylate copolymer (3 7: Rich: 3hiro) P-at) Polyinthyl methacrylate-! P-
μ7) Methyl methacrylate-n (10!.

-Butyl methacrylate Co0) Copolymer (Otsu!: 3riP-at) Vinyl acetate-vinyl (3λ) Propionate copolymer (7j:uj) P-Hiroshi?) n-Butyl methacrylate (Co0) −
3-acryloxybutane-sodium norsulfonate copolymer (7 = 3) P-to)n-butyl methacrylate) (,!o.

-Methyl methacrylate 10 Monoacrylamide copolymerization Body C3! :31:30) P-tl) H-butyl methacrylate (!o.

-Methyl methacrylate 10) -Vinyl chloride copolymer (37:jg:27) P-zx)n-Butyl methacrylate (-.)-Styrene copolymer (R 0:10) P3) Methyl methacrylate- ) −N (101)
- Vinyl-2-pyrrolidone copolymer (0:10) P-t<t) n-butyl methacrylate (2°) - Vinyl chloride copolymer (0:10) P-s piece n-butyl methacrylate (, !(1))
-Styrene copolymer (7 0:30) p-t+) Poly(N-sec-butyl //7 acrylamide) P-t7) Poly(N-tert-7-tyl/21r
Acrylamide] P-tB Diacetone Acrylamide (tro.

-Methyl methacrylate 10 Copolymer (J:Jf) P-tri) Polycyclohexylmethac (104t.

Relayto Methylmeth　10j) rylate copolymer (t.

:4tO) P-AO) N-tert-butyl acrylic (,i,
2r.

ruamide methylmethac 103 sulfurate copolymer (g0:to) P-t/) poly(N-n-butyl ac 4L furylamide) P-ot2) poly(tert-butylmeth (//r.

tert-butyl acrylamide copolymer (!O: !0) p-13) tert-butyl methacrylate (//1f
)-to-methyl methacrylate copolymer (70:30] p-t4L) poly(N-tert-butyl it.

Methacrylamide) P-As) N-tert-buty/l/7cri(i
xr.

Ruami Do Methyl Methac 10ri rylate copolymer (t.

: μ0) P-tA) Methyl methacrylate (7or)
Crylonitrile copolymer (70:30) P-Otsu 7) Methyl methacrylate Copolymer (10!.

Nyl methyl ketone copolymer -) (JJ':Aλ) P-+♂) Methyl methacrylate-dose (10-tyrene copolymer (7!: +23) P-Otori) To methyl methacrylate- (,10- Quinl methacrylate copolymer (717:jO) P-70) Poly(benzyl acrylate-6) P-7/) Poly(4L-biphenylacrylate)
Ilo P-7, poly(≠-butoxycarbo/3-nylphenyl acrylate) P-73) poly(5ec-butyl ac-22 rylate) P-7g) poly(tert-butyl ac 413)
Relate] P-7j) Poly[3-chloro-! 1.2 μ6−
Bis(chloromethyl) propyl acrylate] P-7 O) Poly(2-chlorophenyl j3 acrylate) P-77) Poly(Hiro-chlorophenyl Jr acrylate) P-7,r) Poly(pentachlorophenylene/4t full acrylate) P -7ri), +? (Hiro-cyanobenzyl 4t≠acrylate p-to) Poly(cyanoethyl acrylic Hirolate P-,1'/) Poly(4-cyanophenyl ?0
Acrylate P-rλ) Poly(Hiro-cyano-3-thi--μbutyl acrylate) P-r3) Poly(cyclohexol ac/thallate) P-rq) Poly(-monoethoxycal i 3゜nylphenyl acrylate) - g) P-, rj) Poly(3-ethoxycarbo 24L)
Nilphenyl acrylate) P4A) Bo IJ (lA-xtoxycarbo 37 Nilphenyl acrylate) P-ry) Poly(2-nitoxyethyl-jO acrylate) P-rr) Poly(3-ethoxypropy-!!ruacrylate) P-rq) Bo+)(/H, /H,tH---J
t Octafluorobentyl acrylate P-ta θ poly(heptyl acrylate-t).

〕P-ta/) Poly(hexadenruacrylic 3!shi) -
) P-92) Poly(hexyl acrylate-!7) P-23) Poly(inobutyl acrylate-λkegut) P-24t) Poly(inpropyl acrylate-!late) P-Tari Poly(3-methoxybutyl-!2 acrylate) P-26) Poly(2-methoxycarbo 4♂nylphenyl acrylate) P-97) Poly(3-methoxycarbo 3♂nylphenyl acrylate) P-2 Poly (4-Methoxycarbo 7-nylphenyl acrylate 9 P-yri) Poly(co-methoxyethyl-jO acrylate p-1oo) Poly(≠-Methoquinphenylacrylate) p-10/) Poly(3- methoxypropyl-7! acrylate) P-102) Poly(3,!-dimethylamino 10damantyl acrylate) p-103) Poly(3-dimethylamino 4t7)
Phenyl acrylate) P-7ot, t) Polyvinyl-tert-butylene
FA rylate-IO poly(λ-methylbutylacetate) p-10) Poly(3-methylbutylacetate) P-i07) Poly(/, 3-dimethylphenyl-7!)
(tyl acrylate) P-10r)r (j-jfkbenfh -31r acrylate) P-tori) poly(cornaphthyl acrylic!!shi) -
〕 P-/io) Poly(phenylacryle-!7〕 p-///) Poly(propyl acrylate--37〕 P-//r) Poly(m-tolylacryle 2j-
P-//3-poly(o-tolyl acrylate !coat) P-//≠) poly(p-tolyl acrylate ≠3-t) P-//phantom poly(N, N-diptyla 6゜acrylamide) P- //A) Poly(isohexyl acrylic 71 amide) P-//7) Poly(inoctylacrylic JJ amide) P-//r) Poly(N-meth5- to -N-7/r.

enyl acrylamide) P-tttri) poly(adamantylmethacrylate 7hiro/relate] p-txo) rsu (benzyl methacrylate j4L-to) P-tλl) poly(l-promoethylmethacrylate) P-zl)z (2-N-tert-butyl methacrylate) p-1i3) Poly(see-i thyl meth 6° acrylate) P-7i<li Poly(tert-butyl meth//f acrylate) p-/2t) Poly (λ-rioa ether meta 2
tacrylate) Pl-j) Poly(2-cyanoethylmethacrylate) P-/27), +? IJ(2-'/7/'fk7
/2. renyl methacrylate) P-txt) poly(4L-cyanophenyl /!!
methacrylate) P-/Utah) Poly(cyclohexyl meth 104t acrylate) P-13o) Poly(dodecyl methacrylate -Aj-
P-/3/) Poly(dimethylaminoethyl-20-methacrylate) P-73x) Poly(2-ethylsulfico!nylethyl methacrylate) P-133), +? (hexadecylmetac/!polito) P-/J4t) poly(hexolmethalilate -!-to) P-/3r), 1'? (2-Hydroxypro7-Pyrmethacrylate-P-i3t) Poly(tA-Methoxycari 10
tNylphenyl methacrylate] P-/37) Poly(3,!-dimethylalyl tDamantyl methacrylate) P-7Jr) Poly(dimethylaminoethyl methacrylate) P-/Jri) Poly( 3,J-dimethylp4t!tyl methacrylate) P-/ao) Poly(3,3-dimethyA,-101coptyl methacrylate) P-not,tt)f! Su(3,!,!-)reme
Ethylhexyl methacrylate) P-i≠2) Poly(octadecyl methacrylate) P-/Hiroshi 3) Poly(tetradecyl methacrylate) t.

related) P-/≠≠), 1′? (4-butoxycardine ixr
(nylphenyl methacrylamide)

p-1ty;) poly(4t-ethoxycar 1161 nylphenyl methacrylamide) P-/Hiroshi 7) poly(≠-methoxycarbo/10 phenyl methacrylamide) P-/4Lt) poly(butyl butoxycar 2) !l
[Nil methacrylate] P-ta51) Poly(butyl chloroacrylate!7)
rate) P-/lo) Poly(butylcyanoacrylic?!shi-to) P-/!/) Poly(cyclohexylchloro //4t
= Acrylate) P-'/j2) Poly(ethyl chloroacrylate) 3
Rate) P-/s3), 1'? (ethyl ethoxyl j2
Poly(ethyl methacrylate) P-/!ri Poly(ethyl fluorometa 4t3 acrylate) P-/!J) Poly(hexylhexyl-≠xycarbonyl methacrylate) P- /! 7) Poly(inbutylchloroata-acrylate) P-/! r) Poly(isopropyl chloride acrylate) Note: () is the acid-free monopolymer of the present invention which forms 3 t mol % or more of the polymer. at least one silver halide emulsion layer of a blue-chromatic layer, a green-sensitive layer, and a red-sensitive layer is provided (the calendar number of the silver halide emulsion layer and the non-photosensitive layer and There is no particular restriction on the order of the layers; typically, at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same coloring property but different luminous intensity per layer is placed on the support. A multilayer silver halide color photographic light-sensitive material, in which the light-sensitive layer is a unit light-sensitive layer having an angry color property to any of blue light, green light, and red light; Generally, the unit photosensitive layers are arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer.However, depending on the purpose, the above arrangement order may be reversed. However, the arrangement may be such that different photosensitive layers are sandwiched between the same color-chromic layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
It may contain couplers, DIR compounds, etc. as described in No. 037 and No. 61-20037, and may also contain a color mixing inhibitor as commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer include a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121.470 or British Patent No. 923.045. A two-layer structure of 0 can be preferably used.
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, the low-intensity blue-photonic layer ([lL)/high-intensity blue-photonic II! (B)I)
/High-sensitivity green light-sensitive layer (G11) /Low-sensitivity green light-sensitive layer (GL) /High-sensitivity red light-sensitive layer 1i (R1+) /Low-sensitivity red light-sensitive layer (IIL), or old 1/BL /GL/
Gll/R) I/RL order or B II/11
L/G II/GL/RL/RI
They can be installed in the order of I, etc.

Furthermore, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G II
They can also be arranged in the order of /RII/GL/RL. Also, JP-A-56-25738, JP-A No. 62-
As described in No. 63936, from the side farthest from the support, the blue-sensitive layer/GL/RL/GH/R1
They can also be arranged in the order of 1.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-speed emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, preferred silver halides incorporated into the photographic emulsion layer include silver iodobromide, iodobromide, and silver iodide containing up to about 30 mol% silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, Any silver bromide/silver chloride can be used. This ratio can vary widely depending on the purpose, but the silver chloride ratio is 2 mol%.
The above can be preferably used. So-called high silver chloride emulsions containing a high silver chloride content are preferably used for light-sensitive materials subjected to rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.For the purpose of reducing the amount of replenishment of the processing solution, the silver chloride content is 98 to 100 mol%. Emulsions of nearly pure silver chloride, such as .

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or may be a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) N[L1T64
3 (December 1978) pp. 122-23, °"1. Emulsion preparation
and types)”, and Nα1871
6 (November 1979), 648 pages, E. Physics and Chemistry of Photography by Grafkide, published by Beaumontel (P, G
lafkides, Chemic et Ph1si
que Photography-4que, Paul
Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Duffi)
n.

Photographic Emulsion Che
mistry (Focal Press.

1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikm)
anet al, + Making and
Catrng Photographic Em
uI-sion, Focal Press, 196
It can be prepared using the method described in 4).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
U.S. Pat. No. 4,434,226, U.S. Pat. No. 4.414.310, U.S. Pat.
, 433,048, 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

It is also possible to use a mixture of particles of various crystal forms.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure 1--N.
o, 17643 and N (118716), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Drop plate■Dish plate and [Dan L Anal M group 1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity increasing agent Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Chromatic enhancer
Page 649 right column 4 Brightener Page 24 5 Antifoam agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25 Right B Page 650 Left-Right Column 8 Dye Image Stabilizer Page 25 9 Hardener Page 26 Page 651 Left Column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Patch agent Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, it is preferable to add a compound capable of reacting with and fixing formaldehyde, as described in US Pat. No. 4,411,987 and US Pat. No. 4,435,503, to the photonic material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,50.1, No. 4,022,620, No. 4,
No. 326,024, No. 4.401,752, No. 4
, 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476.760
No. 3,973,968, U.S. Patent No. 4.314
, No. 023, No. 4.511.649, European Patent No. 2
49.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0,619, European Patent No. 4.351.897, European Patent No. 73,636, U.S. Patent No. 3,061,432,
No. 3゜125.061, Research Disclosure Nα24220 (June 1984), JP-A-60
-33552, Research Disclosure Sou 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4゜500.63Q, No. 4,540.654
No. 4,556,630, International Publication WO3810
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052.212.
No. 4,146,396, No. 4.228,23
No. 3, No. 4,296,200, No. 2.369,9
No. 29, No. 2.801.171, No. 2,772.
No. 162, No. 2,895,826, No. 3,772
, No. 002, No. 3,758,308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
No. A, No. 249°453A, U.S. Patent No. 3.446
, No. 622, No. 4.333.999, No. 4,77
No. 5,616, No. 4,451,559, No. 4,4
No. 27,767, No. 4,690,889, No. 4,
Preferred are those described in No. 254.212, No. 4.296.199, and JP-A-61-42658.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Sou 17643.
- Section G, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146.36
No. 8 is preferred, and also US Pat. No. 4,7
No. 74.181, a coupler that corrects unnecessary absorption of a color-forming dye by a fluorescent dye released upon coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned 11017643
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248,96
No. 2, No. 4°782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131,188, JP 59-157638
No. 59-170840 is preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc.,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
Couplers that release dyes that recover color after separation, R, D, Nα11449, Nα24241, described in No. 02A, JP-A No. 6
Bleach accelerator-releasing couplers described in US Pat. No. 1-201247, Gantt-releasing couplers described in US Pat. No. 4,774,1
Examples include couplers that emit fluorescent dyes as described in No. 81.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high boiling point melting materials with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , decyl phthalate, bis(2,4-sheet amyl phenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid. Esters (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amide ltI (N, t'
l-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5- tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene,
diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, solvents having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, and methyl ethyl ketone. , cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat.
゜541.230 etc.

These couplers can also be prepared by impregnating the above-mentioned high boiling points into rhodapulu latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of organic solvents.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer to form an emulsified molecule in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. 088100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and Patent Application No. 1983-
Benziisothiazolone, n-butyl p-hydroxybenzoate, phenol, 2-
It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of NCL 17643, and k 18 of the same.
716, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side where the emulsion layer exists is preferably 28 μm or less, and the film swelling rate T, /2 is preferably 30 seconds or less.

The film thickness is 25°C and 55% relative humidity! II refers to the film thickness measured under humidity (2 days), and the film swelling rate TI/□ can be measured according to techniques known in the art. For example, according to Green et al. Photographic Science and Engineering (Photogr, Sci, Eng,), 1
T1
7° is the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developing solution at 30°C for 13 minutes and 15 seconds, and this T
, /2 is defined as the time required to reach a film thickness of .

The film swelling rate Tlzt can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (ffi large swelling film thickness - film thickness) / film thickness. .

The color photographic photonic material according to the present invention includes the above-mentioned RD, N
α17643 pages 28-29 and gap 111T16
615, left column to right column.

/ The present invention is particularly effective when processed with a developer containing a silver halide solvent such as sodium sulfite, potassium thiocyanate, or thioethers, and the first developer in reversal processing is one specific example. be.

The preferred amount of these silver halide solvents added is 0.1 g per 11, particularly preferably 0.5 g or more, and the upper limit is the saturated dissolution amount. Moreover, it is preferable to use two or more types in combination.

In addition, the effects of the present invention are particularly evident in processing steps that require speed.
The effect is large, and high temperature (33℃ or higher), short-term treatment,
It is desirable that the first development time is within 6 minutes. especially,
The effect is great when the first development is performed at 38° C. or higher and within 90 seconds. Furthermore, a remarkable effect was shown within 60 seconds.

The color reversal film processing process usually consists of black and white development (first development) → stop → washing → reversal → washing - color development → stop - washing → adjustment tower → washing → bleaching → washing → regular maintenance →
It undergoes a basic process of washing with water → stabilization → drying. This step may further include a pre-bath, a pre-hardening bath, a neutralization tower, etc. Also stop, reverse,
Washing with water after color development, conditioning bath or bleaching may be omitted. The reversal bath can be replaced with re-exposure,
It can also be omitted by adding a brushing agent to the color developing bath. Furthermore, the conditioning bath can also be omitted.

The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

In addition to the silver halide solvent mentioned above, this developer contains development inhibitors or antifoggants such as carbonates, borates, phosphates, sulfites, bromides, iodides, and organic antifoggants. be able to.

If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amine serum, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, US Pat. QB3,123
The polycarboxylic acid chelating agent described in No.
LS) No. 2,622,950, etc. may be included.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g. 4-
Amino-N, N-diethylaniline, 3-methyl-4
-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N- ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, F. A. Menn's “Photographic
"Processin Chemistry", published by Focal Press (
1966), pp. 226-229, U.S. Pat. No. 2,193.
, No. 015, No. 2,592゜364, Japanese Unexamined Patent Publication No. 48-6
Those described in No. 4933 may also be used.

In addition, it is possible to contain the additives described in the black and white developer.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (VI), and copper (n), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromic hydrochloride, organic complex salts of iron (I [[) or cobalt (II [)],
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1
, 3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid: persulfates, permanganates, and nitrosophenols. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (I
II) Sodium and iron ethylenediaminetetraacetate (DI
) Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron(I[I) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Patent 3,042.52
No. 0, No. 3,241,966, Special Publication No. 45-8506
Bleaching accelerators described in Japanese Patent Publication No. 45-8836, etc.
In addition to the thiol compound described in JP-A-53-65732, various additives can also be added.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 A color photographic material was prepared by coating the following 1st layer to 12th layer in multiple layers on a paper support laminated on both sides with polyethylene. 15% by weight on the first layer coating side of polyethylene
Contains anatase titanium oxide as a white pigment and a small amount of ultramarine as a bluish dye.

(Photosensitive layer composition) Below are the components and the amount of water f shown in g/ld.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin...1.30 2nd layer
Layer (anti-halic acid layer) Black colloidal silver...0.10 Gelatin...0.70 No. 311
(Low-sensitivity red-sensitive layer) Chloroiobromide ili spectrally sensitized with red sensitizing dyes (Equivalent amounts of ExS-1, 2, and 3)! (Chloride if 1 mol%, iodide w & 4 mol%, average particle size 0.3 μ, particle size distribution 10%, cubic, core shape modified core shell)
...Silver iodobromide (silver iodide 4 mol%, average grain size 0.5μ, grain size distribution 15%, cube)
...0.10 gelatin
...1.00 cyan coupler (ExC-1)
-0,16 cyan coupler (ExC-2) -0
,05 Anti-fading agent (Equivalent amounts of each of Cpd-2, 3, 4)...0,12 Coupler dispersion medium (Cpd-6)...0.03 Coupler solvent (Equivalent amounts of each of Solv-1, 2, 3) ) ...0.06 Development accelerator (Cpd-13) ...0.05 4th layer (highly sensitive red-sensitive layer) Spectral enhancement with red sensitizing dye (Equivalent amounts of ExS-1, 2, and 3) Sensitized silver iodobromide (silver iodide 6 mol%, average grain size 0.
8μ, particle size distribution 20%, flat plate (aspect ratio -8
, core change)) ...0.15 Gelatin ...1.00 Cyan coupler (ExC-1) -0,20 Cyan coupler (ExC-2) = -0,10 Antifading agent (Cpd-2, 3, 4 each equivalent) ...0.15 Coupler dispersion medium (Cpa-6) ...0.03 Coupler solvent (Solv-1, 2, 3 each equivalent) ...0.10 5th layer (Intermediate layer) Magenta colloid silver...0.02 Gelatin...1.00 Color mixing prevention agent (Cpd-7, 16 each in equal amounts)...0.08 Color mixing prevention agent solvent (Solv-4, 5 each) equivalent amount)...0.16 Polymer latex (Cpd-8)...0. lO 6th layer (low sensitivity green sensitive layer) Silver chloroiodobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver chloride 1 mol%, silver iodide 2.5 mol%, average grain size 0.28μ, particle size distribution 8%, cubic, core-shaped deformed core-shell)...0.04 Spectrally sensitized with green sensitizing dye (ExS-4) w
&(silver iodide 2.5 mol%, average grain size 0.48μ,
Particle size distribution 12%, cubic) ... 0.06 Gelatin ... 0.80 Magenta coupler (ExM-1) = 0.10 Anti-fading agent (Cpd-9) ... 0.20 Anti-staining agent (Cpd-5) ...0.001 Stain inhibitor (Cpd-12) ...0.01 Power puller dispersion medium (Cpd-6) ...0.05 Coupler solvent (
Solv-4)...0.20 7th layer (high sensitivity green-sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver iodide 3.5 mol%, average Particle size 1.0 μ, particle size distribution 21%, flat plate (aspect ratio = 9, uniform-moderate type)) ...0.10 gelatin
...0.80 magenta coupler (ExM-
1) ...0.10 anti-fading agent (Cpd-9)
...0.20 stain inhibitor (Cpd-5)
... o, ooi stain inhibitor (Cpd-12)
...0.01 force puller dispersion medium (Cpd-6)
...0.05 coupler solvent (Sol v-4)
-0,20 8th layer (yellow filter layer) Yellow colloid)'m ・0.20 Gelatin...1.00 Color mixing prevention solution (Cpd-7>...0.06 Color mixing prevention agent solvent (Solv-4) , 5 each equivalent amount) ...0.15 Polymer latex (Cpd-8) ...0.10 9th layer (low sensitivity blue-sensitive layer) Blue sensitizing dye (E X S-5, 6 each equivalent amount) ) spectrally sensitized with silver chloride iodobromide (ff12 chloride, silver iodide 2.
5 mol%, average particle size 0.33μ, particle size distribution 8%, cubic, core-shaped modified core-shell)
...0.07 blue sensitizing dye (E
Silver iodobromide (
Silver iodide 2.5 mol%, average grain size 0.55μ, grain size distribution 11%, cubic)
...0.10 gelatin
...0.50 Yellow coupler (Equivalent amounts of ExY-1 and 2) ...0.20 Anti-stinting agent (Cpd-5) ...0.001
Antifading agent (Cpd-14>...0.10 Coupler dispersion medium (Cpd-6)...0.05 Coupler solvent (So 1v-2) -0,05 10th layer (high sensitivity blue sensitive layer) Silver iodobromide (silver iodide 2.5 mol%, average grain size 1.4 μ, grain size distribution 21%, flat plate) spectrally sensitized with blue sensitizing dye (E x S -5, 6 equivalents) (Aspect ratio -14)) ...0.25 gelatin
...1.00 yellow coupler (
Equivalent amounts of EXY-1 and 2)...0.40 Anti-stinting agent (Cpd-5)...0. OO
2 Anti-fading agent (Cpd-14)...0.10
Coupler dispersion medium (Cpd-6)...0.15 Coupler solvent (So 1v-2) -0,10 11th
Layer (ultraviolet absorption layer) Gelatin...1.50 Ultraviolet absorption (Cpd-1, 2, 4, 15 each equivalent amount)...1.00 Color mixing prevention agent (Cpd-7, 16)...0 .06 Dispersion medium (Cpd-6) Ultraviolet absorber solvent (Solv-1, Solv-2, each equivalent amount) ...0.15 Irradiation prevention dye (Cpd-17, 18 each equivalent amount) ...0.02 Anti-irradiation dye (Equivalent amounts of Cpd-19 and 20)...0.02 No. 12
Layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
μ) ...0.07 modified poval ...0.02 gelatin
...1,50 gelatin hardening agent (H-
1,2 each equivalent amount)...0.17 Furthermore, each layer contains alkanol XC (
Du Pont Co., Ltd.) and sodium alkylhenzenesulfonate, and succinic acid ester and Magefac F 120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. (Cpd-2122, 23) was used as a stabilizer in the silver halide or colloidal silver containing layer. The compounds used in the examples are shown below.

xS-I xS-2 xS-3 xS-4 xS-5 xS-6 (cut)4sose (clm SOsH-N(CJs)s Cpd-I Cpd-2 Cpd-3 Cpd-4 Cpd-5 H i Cpd- 5 Cpd-7 H Cpd-8 Polyethyl acrylate (MW=10.000-100,000) Cpd-9 Cpd-12 Cpd-13 H cpct-t 4 pa-15 Cpd-16 H Cpd-17 Cpd-18 Cpd -19 5Uj8)
υkohe pd-20 Cpd-21 H Cpd-22 Cpd-23 xC-1 Shit xC-2 H xM-I xY-1 ExY-2 CL Solv -1 Di(2-ethylhexyl)phthalate o1v-2 Trinonyl Phosphate 5olv 3 Di(3-methylhexyl)phthalate olv-4 Tricresyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate CHz8CH-3ow-CL-CON)I-CLCHz
=CH-302-CHz-CON)I-CHz4,6-
Dichloro-2-hydroxy-1,3゜5-triazine N
The sample thus obtained was designated as 101.

Next, in sample 101, 310 g of compound t'kla-3 and 50 g of oil (Solv-5) were added to the third low-sensitivity red light layer.
g, 50 g of ethyl acetate, and log of sodium alkylhenzenesulfonate were dissolved by heating? 8 liquids dissolved in gelatin water!
Sample 102 was prepared by adding and applying 1000 g of the emulsion prepared by stirring with a mixer.

Compound 11kLla-3 of sample 102 was replaced with compound m1a-
Sample 103 was prepared by replacing sample No. 12 with Sample No. 12.

Compound NaLa-3 of sample 102 was replaced with compound Th1b-5.
Sample 104 was created by changing to .

Next, in sample 101, compound N was added to the third low-frequency red-sensitive layer.
wla-310g, polymer P-1210g, oil (S
Sample 105 was prepared by coating a solution obtained by heating and dissolving 50 g of olv-5), 50 g of ethyl acetate, 10 g of sodium alkylbenzenesulfonate, and adding 1000 g of an aqueous gelatin solution and an emulsion prepared by stirring with a mixer.

Compound Th1a-12 of sample 105
Sample 106 was created by changing to .

Sample 108 was prepared by replacing polymer P-12 in sample 106 with polymer P-33.

Sample 108 was prepared by replacing polymer P-12 in sample 106 with polymer P-61.

The obtained sample was exposed to a light source of 3200' and the illuminance of the exposed surface was 6.
It was exposed to white light at 30 lux through a pattern for measuring sharpness, and then developed as described below to obtain a color image.

The treatment steps and treatment liquid used here are as follows.

38℃ 75 seconds water development (black and white development)
Washing 38℃ 90 seconds Reverse exposure 1001ux or more 60 seconds or more Color development 38℃ 135 seconds Water washing
Bleach fixing at 38℃ for 45 seconds
Wash with water for 120 seconds at 38℃
38℃ 135 seconds drying history” mouth L1 precept.

(First developer) Nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt 0.6g
Diethylenetriaminepentaacid acetic acid pentasodium salt 4.0g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate
35.0g hydroquinone monosulfonate potassium salt 25.0g diethylene glycol 15.0dl-phenyl-4-
Hydroxymethyl-4-methyl-3-viladuridone 2.0g Potassium bromide 0.5g Potassium iodide
5. Add 0mg water
1e (pH 9,70) (color developer) Hensyl alcohol 15. (lddiethylene glycol 12.(lH13,6-cythia1.8-octanediol 0.2gnitrilo-
N,N,N-)rimethylenephosphonic acid pentasodium salt 0.5g
Diethylenetriaminepentaacetic acid pentasodium salt 2.0g Sodium sulfite 2.0g Potassium carbonate
25°Og Hydroxylamine sulfate sulfate 3.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g
Potassium bromide 0.5g iodizing power'
)')mu 1. (Add 1g water, 1l (pH 10,40) (bleach-fix solution) 2-mercapto-1,3,4-) Riazole 1.0g ethylenediaminetetraacetic acid disodium trihydrate 5.0g ethylenediaminetetraacetic acid Fe Cl11) Ammonium hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g/l liquid) 160.0d Ice vinegar #
5.0IR1 Add water and 1e (pH6
, 50) /' / The image sharpness of these sample method samples was measured.

Table 1 shows that the density through the red filter is 1. 1 at 0
The MTF values at frequencies of 10 lines per m are shown.

After the sample was placed under the following storage conditions, the sample was exposed to light through a wedge in which the amount of exposure light was changed continuously, and then the above-mentioned development process was performed to obtain a color image.

Storage conditions 1: 50°C 30% for 3 days 2: 45°C 80% for 3 days 3: Refrigerator 5°C for 3 days The density of the obtained color image was measured through a red filter.

ΔI) + ax = (maximum concentration of refrigerated product) - (maximum concentration of sample stored under condition 1 or 2) ΔSo, s = (sensitivity of concentration 0.5 of refrigerated product (j!og
E) 1-(Sensitivity at a concentration of 0.5 for samples stored under conditions 1 or 2 (j!ogE)1 The results are shown in Table 1.

Δ[1max, ΔS0. ．． The smaller the value, the better.

Table 1 shows that the sample using the present invention can improve the reduction in Dmax and sensitivity during storage without impairing sharpness.

Example-2 Sample 201 was created by changing the coating solution for the third low-sensitivity red-sensitive layer to sample 101 of Example-1 and aging it at 40°C for 8 hours using a constant temperature bath. did.

Sample 202 was prepared by changing the coating solution of the third low-sensitivity red-sensitive layer to sample 102 of Example-1, which had been aged at 40° C. for 8 hours using a constant temperature bath.

Compound 14hla-3 of sample 202 was replaced with compound Na1a-
Sample 203 was prepared by replacing sample No. 12 with Sample No. 12.

Compound k 1 a -3 of sample 202 was converted to compound 11hl
Sample 204 was created in place of b-5.

Sample 205 was prepared by changing Sample 105 of Example-1 to a coating solution for the third layer with low sensitivity red sensitivity that had been aged at 40° C. for 8 hours using a constant temperature bath.

Compound 11k11 a-3 of sample 205 was converted to compound m1
Sample 206 was created in place of a-12.

Sample 207 was prepared by replacing polymer P-12 in sample 206 with polymer P-33.

Sample 208 was prepared by replacing polymer P-12 in sample 206 with polymer P-61.

The obtained sample was exposed and developed in the same manner as in Example 1, and the sharpness was measured.

Table 2 shows the MTF values at frequencies of 10 lines per crane when the density through the red filter is 1.0.

After exposing the sample to light through a wedge in which the amount of exposure light changes continuously, the same development process as in Example 1 was performed to obtain a color image.

The density of the obtained color image was measured through a red filter.

ΔDmax' = (Maximum concentration of sample without aging of coating solution) - (Maximum concentration of sample with aging of coating solution) ΔSo, s' = (Sensitivity of concentration 0°5 of sample without aging of coating solution (zogE)l (ZogE) Table 2 shows the sensitivity (logE) 1 results at a concentration of 0.5 for the aged samples.

From Table 2, it can be seen that the present invention can improve the decrease in Dmax and sensitivity without impairing the sharpness even in samples in which the coating liquid has been used for a long time.

7・'/' / / / Example-3 Although it was added to the sixth low-sensitivity green-sensitive layer instead of the third low-sensitivity red-sensing layer of Example-1, the same effect as in Example-1 was obtained. Obtained.

Claims (3)

[Claims] (1) A photographic material having at least one silver halide emulsion layer on a support, in which the photographic material contains at least one compound represented by the following general formula (1a) or (1b) and a main chain or A silver halide photographic material comprising a water-insoluble and organic solvent-soluble polymer comprising repeating units having no acid group in the side chain. General formula (1a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (1b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R^1^2 is an aliphatic group, aromatic group, or heterocyclic group , M is -CO-, -SO_2-, -N(R^1
＾5) CO-, -OCO- or -N(R￣1￣5)S
Represents O_2-. R^1^4, R^1^5 and R^2^
4 represents a hydrogen atom, an alkyl group, or an aryl group, and L is a divalent linking group necessary to form a 5- to 7-membered ring. R^1^1, R^1^3 and R^2^1 are hydrogen atoms or groups that can be substituted for the hydroquinone nucleus, and ti
me represents a group that releases X after leaving the oxidized form of hydroquinone, and X represents a development inhibitor. t represents 0 or 1. (2) the silver halide emulsion layer is blue-sensitive and contains a coupler;
2. The silver halide photographic material according to claim 1, comprising a green-sensitive emulsion layer and a red-sensitive emulsion layer, each of which contains the compound and the polymer. (3) The silver halide photographic material according to claim (2), wherein the compound and the polymer are simultaneously contained in the red-sensitive emulsion layer.