JPH02110448A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is photograhically inert and is caused easy decoloration and/or elution in a photographic processing by incorporating a specific mordant and dye into at least one hydrophilic colloidal layers. CONSTITUTION:The mordant expressed by formula I and the dye expressed by formula II are incorporated into at least one hydrophilic colloidal layers. In formula I, A, B denote a monomer unit forming the mordant by polymn. of different monomers; R1 denotes a hydrogen atom, lower alkyl group, etc.; Q denotes a single bond or alkylene group, phenylene group, etc.; G denotes formula III, etc. In formula II, R11 denotes an aryl group, aralkyl group, etc.; R12 denotes an alkyl group, cyano group, etc.; R13, R14 denote a hydrogen atom, halogen atom, etc.; R15, R16 denote a hydrogen atom, alkyl group, aralkyl group, etc.; L1 to L3 respectively denote a methyne group; n denotes 0 or 1. The hydrophilic colloidal layers are colored by the water soluble dye which is irreversibly decolored by a photographic processing and has no adverse influence on the photographic characteristics of photographic emulsions in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inactive and easily decolorized during photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted and/or a hydrophilic colloid layer.

(Prior Art) In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer may be reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enter the photographic emulsion layer again. Between the photographic emulsion layer and the support, in order to prevent blurring of images, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of multilayer color photosensitive materials,
An antihalation layer may be placed between each layer.

Furthermore, in X-ray photosensitive materials, a colored layer may be provided as a loss-over cant filter to reduce crossover light and improve sharpness.

Image sharpness decreases due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

These layers to be colored are often composed of hydrophilic colloids, and therefore, for coloring them, a water-soluble dye is usually incorporated into the layer. This dye must satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. In other words, it has an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense.
For example, it should not cause a decrease in sensitivity, latent image regression, or fog.

(3) Although it is decolored during the photographic processing process, it is dissolved and removed and does not leave any harmful coloring on the photographic material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known. For example, British Patent No. 506°385, British Patent No. 1,17
No. 7.429, No. 1,311.884, No. 1.338
, No. 799, No. 1385.371, No. 1,467.2
No. 14, No. 1.433, 102, No. 1.553.51
'6, JP-A No. 48-85.130, JP-A No. 41-114
No. 420, No. 50-147.712, No. 55161.
No. 233, No. 58-143, 342, No. 59-38.
No. 742, No. 59-111, 641, No. 59-111
, 640, U.S. Patent No. 3247.127, 3. ．．
No. 169,985, U.S. Pat. No. 4.078.933, etc., oxonol dyes having a pyrazolone nucleus or a barbylic acid nucleus;
79°533, other oxonol dyes described in British Patent No. 1.278.621, British Patent No. 575
．． 691, 680,631, 599.623, 786.90-7, 907°125, 1,
No. 045.609, U.S. Patent No. 4.255,326;
Azo dyes described in JP-A-59-211,043, etc., JP-A-50-100.116, JP-A-54-118,2
47, British Patent No. 2,014,598, British Patent No. 750.
Azomethine dye described in No. 031 etc., British Patent No. 2
．． anthraquinone dyes described in No. 865,752;
U.S. Patent No. 2,538,009, 2°688.54
No. 1, No. 2,538,008, British Patent No. 584. '
No. 609, No. 1,210.252, Japanese Unexamined Patent Publication No. 50-40
, No. 625, No. 51-3623, No. 51-10, 92
No. 7, 54-! No. 18.247, Special Publication 1974-3.2
Arylidene dyes described in No. 86, No. 59-37,303, etc., Japanese Patent Publication No. 2B-3,082, No. 44-16
．． Styryl dyes described in British Patent Nos. 594 and 59-28,898, British Patent No. 446,583, British Patent No. 1,33
5.422, JP-A-59-228.250, etc., triarylmecne dyes, British Patent No. 1,075
, No. 653, No. 1153.341, No. 1.284, 7
No. 30, No. 1.475,228, No. 1,542.80
Examples include merocyanine dyes described in US Pat. No. 2,843,486 and US Pat. No. 3,294,539.

Among these, arylidene dyes having two pyrazolone nuclei have the property of being decolorized in developing solutions containing sulfites, and are used as dyes for photosensitive materials as useful dyes that have little negative effect on photographic emulsions. did it.

On the other hand, if the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. It is usually necessary to ensure that the This is because, otherwise, not only the effect as a filter layer or an antihalation layer will be reduced, but also a harmful spectral effect will be exerted on other layers. There are several methods for selectively coloring a specific hydrophilic colloid layer. The most frequently used method is to localize the dye in a particular layer by interaction with the dye molecules (considered as charge attraction and hydrophobic bonding). As a mordant, for example, U.S. Pat. No. 2,548,564, U.S. Pat.
Vinylpyridine polymers and vinylpyridinium cationic polymers described in No. 061, Japanese Patent Publication No. 59-31696, etc.; U.S. Patent No. 4,124.386;
Vinylimidazolium cationic polymers disclosed in Japanese Patent Publication No. 55-29418, Japanese Patent Application Laid-Open No. 59-55436, etc.; Polymer mordants capable of crosslinking with gelatin, etc., disclosed in U.S. Patent No. 3,625,694, etc. ; U.S. Patent No. 3,958,995, JP-A-54-115228
Aqueous sol mordant type disclosed in US Patent No. 3,898.088, US Pat. A mordant having an ammonium structure;
US Patent 4. Reactive mordants capable of forming covalent bonds with dyes as disclosed in British Patent No. 685.476; derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in British Patent No. 685.475; British Patent No. 850281, U.S. Patent No. 2,882,156, Japanese Patent Publication No. 15820-1987
products obtained by the reaction of polyvinyl alkyl ketones with aminoguanidine as described in US Pat. No. 3,445°231;
Polymers derived from methyl-1=vinylimidazole are known.

(Problem to be Solved by the Invention) When using such a method of mordanting using a polymer, when a layer containing a dye and another hydrophilic colloid layer come into contact with each other in a wet state, a portion of the dye is transferred from the former to the latter. Diffusion often occurs. Such diffusion of the dye naturally depends on the chemical structure of the mordant, but also on the chemical structure of the dye used.

Further, when a polymeric mordant as described above is used, residual coloring is particularly likely to occur on the photosensitive material after photographic processing, particularly after photographic processing in which processing time is shortened. This is because although the binding force of the mordant to the dye becomes considerably weaker in an alkaline solution such as a developer, some binding force still remains, so the dye or reversible decolorization product remains in the layer containing the mordant. This is thought to be because. These difficulties are largely dependent on the chemical structure of the mordants and dyes.

In order to overcome these difficulties, Japanese Patent Application Laid-Open No. 513.623
A method of combining a basic polymer and a specific dye is known, as described in Japanese Patent Application No. 51-32.325, Japanese Patent No. 52-34,716, and Japanese Patent No. 62-242,933. However, with these methods, it is difficult to selectively dye only specific layers without leaving any coloring in the light-sensitive material after the photographic processing, due to the speeding up of photographic processing that has been carried out in recent years.

(Objectives of the Invention) Therefore, the first object of the present invention is to provide a hydrophilic colloid layer colored with a halogen dye that is irreversibly decolorized by photographic processing and has no adverse effect on the photographic properties of the photographic emulsion. An object of the present invention is to provide a silver oxide photographic material.

A second object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer in which only the hydrophilic colloid layer containing a mordant is sufficiently selectively dyed with a dye, and which has excellent decolorization properties through photographic processing. It is to be.

A third object of the present invention is to provide a silver halide photograph having a dyed hydrophilic colloid layer which does not adversely affect the photographic properties of the silver halide emulsion layer even with aging. The purpose of the present invention is to provide photosensitive materials.

(One Means for Solving the Problems) These objects of the present invention include a mordant represented by the following general formula (1) and a dye represented by the following general formula (II) in at least one hydrophilic colloid layer. This was achieved by a silver halide photographic material characterized by containing.

General formula (1) % formula % In the formula, A is a monomer copolymerized with a copolymerizable monomer having at least two copolymerizable ethylenically unsaturated groups and containing at least one of them in the side chain. Represents the unit of tsumar.

B represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated heptamer. R1 represents a hydrogen atom, a lower alkyl group or an aralkyl group. Q represents a single bond or a group represented by an alkylene group, a phenylene group, an aralkylene group, or -C-NR-L-. Here, L represents an alkylene group, an arylene group or an aralkylene group, and R represents an alkyl group.

good.

x, y, and Z represent mole percentages, X represents a value from 0 to 60, y represents a value from 0 to 60, and Z represents a value from 30 to 100.

)(e R2, Rs, Ra, Rs, R6, R?, Re,
Rq represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, which may be the same or different from each other, and may be substituted.

Xθ represents an anion.

Also, Q, R,, R,, R, or QSR,, R6R?
, Ra, and Rq may be bonded to each other to form a ring structure together with a nitrogen atom, where R1 is an aryl group containing at least one sulfonic acid group or carboxylic acid group. , represents an aralkyl group or an alkyl group, Rl
z is an alkyl group, an aryl group, an aralkyl group, a cyano group, -cooR+7-1CONR1? R11+, -COR
,,, -8O□R19, -5OR+q, SO□NR1?
R11+, -OR+t, -NR+J+a, -N
R+aCOR+q, NR17cONRI J l g or NR,, SD□RI9 (Here, Rlff, R11
1 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, R19 represents an alkyl group, an aralkyl group, or an aryl group, and R1? and Rlfl or R111 and R
19 may be connected to form a 5- or 6-membered ring. )
RI3 and R14 are hydrogen atoms, halogen atoms,
Alkyl group, aryl group, -0[++q-1NR+vR
+a, -NRl5cOR1q, -COOR,v, -C
ONR+vR+s (here, R1'l, R111, R1
9 is R1'l defined above, RI 11% RI 9
is synonymous with ) or represents a sulfonic acid group, R+5,
R16 represents a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and R1 and R16 may be linked to form a 5- or 6-membered ring, and R1 and RI5 or R14 and R16 may be linked to form 5 or 60 rings.

L+ and Lx -La each represent a methine group, and n is O
Or represents l.

To explain the above general formula (1) in more detail, examples of the monomer in A include divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate,
Tetramethylene dimethacrylate and the like, among which divinylbenzene and ethylene glycol dimethacrylate are particularly preferred.

Examples of ethylenically unsaturated heptamers in B are ethylene, propylene, 1-butene, isobutyne, styrene, α
- methylstyrene, vinyl ketones, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate) , rhohexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate,
n-hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (e.g. acrylonitrile) or dienes (e.g. butadiene, isoprene), among which styrene, n-butyl methacrylate, cyclohexyl methacrylate, etc. is particularly preferred, and B may contain two or more types of the above monomer units.

R8 is preferably a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (e.g. methyl, ethyl, n-propyl, n-7" thyl, n-amyl, n-hexyl) or an aralkyl group (e.g. benzyl); A hydrogen atom or a methyl group is particularly preferred.

Q is preferably a divalent optionally substituted alkylene group having 1 to 12 carbon atoms (for example, a methylene group or -(CH
z) a group represented by b-), an optionally substituted phenylene group, or an optionally substituted aralkylene group having 7 to 12 carbon atoms (for example, a group represented by -C-0-L- is also preferred. is preferably an optionally substituted alkylene group having 1 to G carbon atoms, an optionally substituted arylene group having 57FfA, or an optionally substituted aralkylene group having 7 to 12 carbon atoms; An optionally alkylene group is more preferred.

R is preferably an alkyl group having 1 to 6 carbon atoms.

Rz, R3, R4, R5, R&, Rt, R
e and R9 are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and are the same. may also be different. The alkyl group, aryl group, and aralkyl group include a substituted alkyl group, a substituted aryl group, and a substituted aralkyl group.

The alkyl group is an unsubstituted alkyl group (for example, methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-
hexyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n
-dodecyl); the carbon atom of the alkyl group is preferably 1 to
There are 12 pieces. More preferably, the number of carbon atoms is 4 to 10. Examples of substituted alkyl groups include alkoxyalkyl groups (for example, methoxymethyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl, methoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl, vinyloxyethyl), cyanoalkyl groups (
For example, 2-cyanoethyl, 3-cyanopropyl, 4-
Examples thereof include cyanobutyl), halogenated alkyl groups (eg, 2-fluoroethyl, 2-chloroethyl, 3-fluoropropyl), alkoxycarbonylalkyl groups (eg, ethoxycarbonylmethyl), allyl groups, 2-butenyl groups, and propargyl groups.

Examples of the aryl group include unsubstituted aryl groups (e.g., phenyl, naphthyl), and examples of the substituted aryl group include alkylaryl groups (e.g., 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl,
4-isopropylphenyl, 4-terL-butylphenyl), alkoxyaryl groups (e.g. 4-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl), aryloxyaryl groups (e.g. 4-phenoxyphenyl), etc. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

Aralkyl groups include vA1-substituted aralkyl groups (e.g. benzyl, phenethyl, diphenylmethyl, naphthylmethyl); substituted aralkyl groups, e.g. alkylaralkyl groups, (e.g. 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropyl); benzyl), alkoxyaralkyl groups (e.g. 4-methoxybenzyl, 4-ethoxybenzyl), cyanoaralkyl groups (e.g. 4-
cyanobenzyl), perfluoroalkoxyaralkyl group, (e.g. 4-pentafluoropropoxyhenzyl group,
4-undecafluorohexyloxybenzyl group, etc.),
Examples include halogenated aralkyl groups (eg, 4-chlorobenzyl group, 4-butmobenzyl group, 3-chlorobenzyl group, etc.).

The number of carbon atoms in the aralkyl group is preferably 7 to 15,
Preferably it is 7 to 11 pieces. Among these, benzyl group and phenethyl group are particularly preferred.

Xθ represents an anion, such as a halogen ion (e.g. chloride ion, bromide ion), an alkyl or aryl sulfonic acid ion (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, P-)luenesulfonic acid), acetate ion, Examples include sulfate ions and nitrate ions, with chloride ions, acetate ions, and sulfate ions being particularly preferred.

It is also preferable that two or more arbitrary groups of Q, Rz, Rs, and R4 bond to each other to form a cyclic structure together with a nitrogen atom. Examples of the cyclic structure formed include a loridine ring and a piperidine ring. , a morpholine ring, a pyridine ring, an imidazole ring, a quinuclidine ring, etc. are preferred, and particularly preferred are a pyrrolidine ring, a morpholine ring, a piperidine ring,
They are an imidazole ring and a pyridine ring.

Furthermore, any two or more groups of Q, R5, R6, Rt, Re, and R- may be bonded to each other to form a cyclic structure together with a nitrogen atom, and the cyclic structure formed is a 6-membered cyclic structure. Rings or 5-membered rings are particularly preferred.

X is from O to 60 mol%, preferably from 0 to 40 mol%, more preferably from O to 30 mol%. y is from 0 to 60 mol%, preferably from 0 to 40 mol%, more preferably from O to 30 mol%.

2 is 30 to 100 mol%, preferably 40
The amount is preferably from 50 to 95 mol%, more preferably from 50 to 85 mol%.

Among the mordants represented by the general formula (N), particularly preferred mordants are those in which, in addition to the above definition, at least one of R, R, and R represents a hydrogen atom.

Specific examples of the mordant represented by general formula (1) are listed below.

X: z = 50: 50 z=20:80 C1θ y: z = 50: 10: 40 C.I.

03e x:y:Z=45:5:50
C1+.

C.B.

IO X: z = 20: 80 4C-CL)
, + CFI.

IO x : y : z = 15:30:55x
: y : z=40:10:50l1i (CH2CHh- -4C1,CHh Js x:y:z 15: =80 H3 C=0 C4+0 C=0 le X: y: z=10:10:80 X: y : z = 20:10 near 0 C = 0 - (CC11□㽇C10゜C1!3 CH.

x:y:z 15: 15: 70 (I9) CH2 CI! ,○ 61 no.

x:y:z 20: 10: 70 CI! .

iC-C1h) CHl o4e X: z = 50: 50 CH2 11■ C) 13COOO (C CH,f x:z:y 40: 10: 50 C20 +CI(,C+- x: z: y=25:25:50H3 -(-CHzCH)nr (CIIzCH) -11° C20 CH8 C=N-NHC-NIIz CH3NH.

■ CH.

C00θ X : y : z =47.5 : 47.5 : CH3-N-CB5 C113N CH3 Hi C-C11゜ょx: )': z = 20:20:60 x of the compound represented by the general formula N) of the present invention:
The y:z=20:10 near-zero formation method will be explained below.

The polymer represented by the general formula (1) of the present invention comprises a copolymerizable monomer containing at least two of the above ethylenically unsaturated groups in -a, an ethylenically unsaturated monomer, and -
Unsaturated materials (e.g. N,N-dimethylamine ethyl methacrylate, N,N-diethylaminoethyl methacrylate , N,N-dimethylaminoethyl acrylate, NN-diethylaminoethyl acrylate, N-(N,N-dimethylaminopropyl)acrylamide, N-(NN-dihexylaminomethyl)
Acrylamide, 3-(4-pyridyl)propyl acrylate, NN-diethylaminomethylstyrene, NN-
Dihexylaminomethylstyrene, 2-vinylpyridine, or 4-vinylpyridine, particularly preferably ' is N
, N-diethylaminoethyl methacrylate, also-YoN,N-diethylaminomethylstyrene, N,N-
After polymerization with dihexylaminomethylstyrene), R
, -X (wherein R,, X are the same as shown above) (e.g. hydrochloric acid, nitric acid, sulfuric acid, P-
It can be obtained by converting it into an ammonium salt with toluenesulfonic acid, ethyl bromide, hexyl bromide, hensyl chloride, etc.).

In addition, the polymer represented by the general formula (r) of the present invention is a copolymerizable heptamer having at least two ethylenically unsaturated groups as described above, an ethylenically unsaturated monomer, and a formula (%). unsaturated monomers (same as those shown in ) (e.g. N,N-dimethylaminoethyl methacrylate hydrochloride, N,N-diethylaminoethyl methacrylate sulfate, N,N-dimethylaminoethyl acrylate hydrochloride, N, N-diethylaminoethyl acrylate acetate, N-(NN,N-)limethylammonioprobil)
Acrylamide chloride, N-(N,N,N-1-lyhexylammoniomethyl)acrylamide chloride, 3-(
4-N-methylpyridyl)propyl acrylate p-
) luenesulfonate, N,N-diethylaminomethylstyrene sulfate, 2-vinylpyridine hydrochloride, N,N,
N-) lyhexylammoniomethylstyrene chloride, N
, N,N-)lioctylammoniomethylstyrene chloride, N,N.

N-1-butylammoniomethylstyrene chloride, N
-benzyl-N,N-dimethylammoniomethylstyrene chloride or 4-vinylpyridine hydrochloride, particularly preferably N,N,N-trihexylammoniomethylstyrene chloride LN,N,N-trioctylammonio It can be obtained by polymerizing with methylstyrene chloride, etc.).

The polymer of the present invention represented by the general formula (e.g., chlorine atom, bromine atom), sulfonic acid ester (e.g., P-)luenesulfonyloxy group); chloroethyl methacrylate, β-P-)luenesulfonyloxyethyl methacrylate, chloromethylstyrene)
After polymerization, an amine having the structure R, -N-R3 (where Rz, Ri, Ra are the same as those shown above) (for example, dimethylamine, diethylamine, diisopropylamine, morpholine, piperidine, pyridine) , trimethylamine, N-methylmorpholine, tributylamine, trihexylamine, trioctylamine, triethylamine, etc.).

The method for synthesizing the compound represented by the general formula (1) of the present invention will be explained below.

The polymer represented by the general formula of the present invention includes a polymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula (wherein R+, Rs, and Q are unsaturated monomers (e.g., methyl vinyl ketone, methyl-(l-methyl vinyl) ketone, ethyl vinyl ketone, ethyl-(1-methyl vinyl) ketone,
After polymerization with n-propyl vinyl ketone, diacetone acrylamide, diacetone acrylate, etc., particularly preferably methyl vinyl ketone, ethyl vinyl ketone, diacetone acrylamide, diacetone acrylate),
- Compounds of the form (wherein the formulas R6, R1, Ra, and Rq are the same as shown above) (e.g., aminoguanidine bicarbonate, N-amino N'-methylguanidine bicarbonate, N-methylguanidine bicarbonate, N-amino N'-methylguanidine bicarbonate, -amino-N'-methylguanidine, etc.
Particularly preferably, aminoguanidine bicarbonate) is reacted,
Furthermore, it can be obtained by converting it into a guanidinium salt with a compound represented by H-X (H-X is the same as shown above) (for example, hydrogen chloride, hydrogen bromide, sulfuric acid, acetic acid, nitric acid).

The above polymerization reaction may be carried out by any of the generally known methods of solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization, and dispersion polymerization. Preferably? 8 Liquid polymerization and emulsion polymerization.

The above polymerization reaction, such as emulsion polymerization, is generally performed using an anionic surfactant (such as sodium dodecyl sulfate, Triton 770 (commercially available from Rohm & Haus), a cationic surfactant (such as octadecyltrimethylammonium chloride), a nonionic surfactant, etc. (for example, Emmalenx NP-20 (commercially available from Nippon Emulsion)), gelatin, polyvinyl alcohol, etc. (a combination of one emulsifier and a radical polymerization initiator (for example, potassium persulfate and sodium bisulfite), Wako 1→ (commercially available from Yakuza under the name ■-50) is generally heated at 30°C to about 100°C, preferably 40°C.
The temperature is between about 80°C and about 80°C.

The above reaction to form the ammonium salt is generally carried out at a temperature of 110°C to about 40"C, particularly 0°C to 30"C.
0″C is preferred.

The polymer of the present invention can be manufactured very easily since the entire manufacturing process can be carried out in one container.

Synthesis examples of representative polymers of the present invention are shown below.

Synthesis Example 1 Synthesis of poly(divinylbenzene-codiethylaminomethylstyrene sulfate) polymer skeleton Iik product (2) 1100 g of 7X distilled water was placed in a reaction vessel, degassed with nitrogen gas, and 16°6 g of sodium F-decyl sulfate was added. , sodium hydroxide 1.9g, sodium sulfite 1.4g, divinylbenzene 33.6g, diethylaminomethylstyrene 19
5.7 g was added and stirred.

After heating to 60°C, add 0.9 g of potassium persulfate to
A solution dissolved in 60 g of distilled water was added every hour for a total of 4 times.
Further, stirring was continued for 2 hours. After that, it was left to cool to room temperature, and 48.9 g of concentrated sulfuric acid dissolved in 313 g of distilled water was added. ! A polymer dispersion having a solid content concentration of 15.4 W% and an amine content of 15.29 x IO-' eqv/g was obtained.

The average particle size of this polymer is 0.054 μm, and its coefficient of variation (standard deviation/average particle size = 0.01110, 054
) was about 0.20.

Synthesis Example 2 In a reaction vessel for the synthesis of poly(ethyl glycol dimecrylate-cobutyl meccrylate-cordiethylaminomethylstyrene hydrochloride) polymer dispersion (9), Nirasantranx H-45 (commercially available as NOF) was added. 2.8 g of emulsifier, 75 g of distilled water, 5.95 g of ethylene glycol dimethacrylate, 1 butyl methacrylate-14,9
8g and 5□34g of chloromethylstyrene were added and stirred. After heating to 60°C, V-50 (Wako pure straw)
0.2 g of a commercially available polymerization initiator was added, and stirring was continued for 3 hours. Thereafter, it was cooled to 40"C, 108 g of residual water and 62 g of isopropyl alcohol were added, and 2.52 g of diethylamine was added dropwise over 15 minutes.
Continue stirring at 0°C and freeze to a solid concentration of 8.16 w
L%, amine included! +, a polymer dispersion of 31XIOeqv/g was obtained.

Synthesis Example 3 Synthesis of poly(divinylbenzene/-costyrene-NN-diethyl-N-meccryloyloxyedylammonium chloride) polymer dispersion 03).

108g of residual water was placed in a reaction vessel, degassed with nitrogen gas, heated to 60"C under a nitrogen stream, and then 7.9g of octadecyltrimethylammonium chloride (23%), 1,1 vinyl alcohol (saponification degree) 95%) 0.04g
, 0.78 g of styrene, 2.94 g of divinylbenzene,
N,N-diethylamine ethyl methacrylate 20.6
3 g was added and stirred. A solution of 0.44 g of potassium persulfate and 0.44 g of sodium bisulfite was added to 10.8 g of degassed distilled water surrounded by nitrogen gas, and stirring was continued for 5 hours. Then cool to room temperature,
A solution of 1016 g of concentrated hydrochloric acid in 100 g of residual water was added and filtered to obtain a polymer dispersion with a solid concentration of 14.0 W L% and an amine content of 4.59 X l O-' eqv/g. .

Other polymers can also be synthesized according to the synthesis method described above.

/ -8 Formula (II) will be explained in detail.

An aryl group, an aralkyl group, or an alkyl group having at least one sulfonic acid group or a carboxylic acid group represented by R11 is a substituent other than a sulfonic acid group or a carboxylic acid group [e.g., an alkyl group (e.g., methyl, ethyl) , alkoxy group (e.g. methoxy, ethoxy), halogen atom (e.g. chlorine, bromine, fluorine), amino group (e.g. dimethylamino, diethylamino), hydroxyl group, cyano group, phenoxy group].Also, sulfone Acid groups and carboxylic acid groups not only directly bond to aryl groups, aralkyl groups, and alkyl groups, but also bond to divalent linking groups (for example, -0(C
Ht )p-, -NR'(CHz)p-[R' is an alkyl group having 1 to 6 carbon atoms (e.g. methyl, ethyl, n
-hexyl, 3-sulfopropyl, 4-sulfobutyl)
and p represents an integer from 1 to 5. )).

Examples of the aryl group represented by R1 include 4-sulfophenyl, 2.5-disulfophenyl, 2methyl-4-
Sulfophenyl, 24-disulfophenyl, 4-(3-
sulfopropyl)oxyphenyl, 3-(2-sulfoethylcarbamoyl)phenyl, 3-(N,N-bis(4
-sulfobutyl)] phenyl, 2-methoxy-4-sulfophenyl, 2-hydroxy-4-sulfophenyl, 3
Examples include groups such as 5-disulfophenyl, 3,6-disulfo-2-naphthyl, 6,8-disulfo-2-naphthyl, and 4-carboxyphenyl.

The aralkyl group having at least one sulfonic acid group or carboxylic acid group represented by R11 is preferably a benzyl group or phenethyl group, and specifically, 2-sulfobenzyl, 4-sulfohensyl, 2゜4-disulfobenzyl. , 4
-Sulfophenyl, 2.4-di(4-sulfobutyloxy)benzyl, 4-(3-sulfopropyloxy)benzyl, 2-methyl-4-sulfobenzyl, 4-methoxy2-(3-sulfopropyloxy) Hensill, 4 (N-
Ejiru N-(2-sulfoethyl)amino)benzyl 1
, 1(2-sulfoethylcarbamoyl)benzyl, 4-
Examples include groups such as carboxyhensyl, 2-carboxybenzyl, and 4-carboxyphenethyl.

The alkyl group having at least one sulfonic acid group represented by R1+ is preferably an alkyl group having 1 to G carbon atoms,
Specifically, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl,
Mention groups such as 6-sulfobutyl 2-(3-sulfopropyloxy)ethyl, 3-hydroxy-3-sulfopropyl, 3-methyl-3-sulfopropyl, carboxymethyl, 2-carboxyethyl, 3-carboxyethyl, etc. Can be done.

R1□, R13, R14, RIS, R16, R17, R
1,.

The alkyl group represented by R17 and -octyl, isoamyl) are preferred 1, substituents [e.g. fluorine, chlorine,
Halogen atoms such as bromine, phenyl groups, hydroxyl groups, cyano groups, alkoxy groups (e.g. methoxy, ethoxy, hydroxyethoxy), aryloxy groups (e.g. phenoxy,
Pmethoxyphenoxy), carboxylno5. Sulfo group, amino group, substituted amino group (e.g. dimethylamino, diethylamino, alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycar, Jf-nyl, i-propoxycarbonyl), carbamoyl (e.g. methylcarbamoyl, ethylcarbamoyl, 2-hydroxyethyl) carbamoyl), sulfamoyl (eg methylcarbamoyl) 1.

R12, R13, R14, R81, R16, R37, R
As the aryl group represented by 18 and R19,
Phenyl groups and naphthyl groups are preferred, and substituents [e.g. halogen atoms such as fluorine, chlorine and bromine, sulfo groups, carboxy groups, hydroxyl groups, cyano groups, alkyl groups having 1 to 4 carbon atoms, (e.g. methyl, ethyl, n-propyl] ), alkoxy groups (e.g. methoxy, ethoxy), aryloxy,!
! ' (for example, phenoxy).

R1□, Rla, R16, R1? , R111, and R1
The aralkyl group represented by 9 is preferably an aralkyl group having 7 to 11 carbon atoms (e.g., benzyl, phenethyl, 1-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, naphthylmethyl), and a substituted group [e.g., fluorine, Halogen atoms such as chlorine, hydroxyl groups, cyano groups, alkoxy groups (e.g. methoxy, ethoxy), carboxyl groups,
It may have a sulfo group, an amino group, a substituted amino group (for example, dimethylamino, diethylamino), or an alkoxycarbonyl group (for example, ethoxycarbonyl).

R1? The 5- or 6-membered ring formed by connecting R111 and R11 or R15 and R1& includes a piperidine ring, a morpholine ring, and a pyrrolidine ring, and Rla and R1
Examples of the 5- or 6-membered ring formed by linking 9's include a pyrrolidone ring and a piperidinone ring.

The alkenyl group represented by Rla and R16 has 1 carbon number.
-6 alkenyl groups are preferred, specifically allyl groups,
Groups such as 3-hexenyl group can be mentioned.

RI 5. , RI 6 is preferably an acyl group having 2 to 8 carbon atoms, specifically acetyl, propionyl, pivaloyl, hexanoyl, benzoyl,
Groups such as 2-methylpropionyl can be mentioned.

The sulfonyl group represented by R15, RR6 is preferably a sulfonyl group having 1 to 8 carbon atoms, and specific examples include groups such as methanesulfonyl, ethanesulfonyl, butanesulfonyl, benzenesulfonyl, and P-tulfonesulfonyl. can.

The methine group represented by L+, Lx, and L3 may have a substituent (eg, methyl, ethyl, cyan, phenyl, chlorine atom, sulfoethyl).

In the above-format Nr), the sulfonic acid group or carboxylic acid group can be a free acid or a salt (e.g. Na salt, K salt, Li salt, (
C2R5) 3 NFT salt, pyridinium salt, ammonium salt) may be formed.

Preferred in the above-mentioned form (II) are those in which R1 represents an aryl group, an aralkyl group or an alkyl group having at least one sulfonic acid group, and more preferred one is one in which R1 represents an aryl group, an aralkyl group or an alkyl group having at least one sulfonic acid group. represents an aralkyl group having

Next, specific examples of the dye represented by the general formula (n) used in the present invention will be listed. ((n-1) to (n-44) are -
The group in the format (It) is represented in a specific form. ) ■-45 ■ ■ ■ -The synthesis of the dye represented by the format (n) is described in JP-A-51-
No. 3623, No. 48-68623, No. 52-2082
No. 2, No. 59-154439, No. 59-211,04
No. 1, No. 60-135937, No. 62-106455
No. 62-133453, etc.,
This can be easily accomplished by condensation of pyrazolones and benzaldehydes. A specific synthesis example will be shown below.

People 4. - Person 11-5 1-(2-sulfobenzyl)-3-carboxypyrazolone monosodium salt 32.0 g (0.1 mol), 2
-Methyl-4-(N-hexyl-N=(2-sulfoethyl)amino)benzaldehyde sodium salt 34.9
g (0.1 mol) was stirred in 250 mff1 of methanol, 2 d of acetic acid was added, and the mixture was heated under reflux for 1.5 hours.

After filtering to remove dust, 12.3 g of sodium acetate (0
, 15 mol) of methanol was heated, and 600 d of isopropyl alcohol was added to precipitate crystals.

The crystals were collected by filtration and washed with isopropyl alcohol.

aX H,0 64,18X10' aX Synthesis Example 5. (Synthesis of Exemplified Compound 11-8) 3-Methyl-
1-sulfophenyl-5-brassilone 27.2g, 4
- 28.4 g of (N-ethyl-N-methanesulfonamidoethylamino)-2-methylbenzaldehyde and 140 ml of triethylamine were dissolved in 330 ml of methyl alcohol and heated under reflux for 3 hours. Next, add a solution of 9.8 g of potassium acetate in 40 d of methyl alcohol,
When PAl↑ was heated at °C for 1 hour, crystals precipitated in a few minutes. After further cooling to room temperature and stirring for 1 hour, the precipitated crystals were filtered and recrystallized from methyl alcohol.

Yield 41.6g (70%) 11.0λ
503 nm ax H,0 ε 4.98X10' ax Other dyes can also be synthesized according to the alternative synthesis method described above.

When using the dye represented by the general formula (n) as a filter dye or antihalation dye, any effective number can be used, but the optical density is 0.05 to
It is preferable to use it in a range of 3.0, and it can be added at any step before coating.

The dyes according to the invention can be dispersed in interlayers, protective layers, antihalation layers, filter layers, bank layers, etc. in various known ways.

Especially when applying a hydrophilic colloid layer containing a mordant,
Although advantageously added to the coating solution, it may also be added to the coating solution of either other hydrophilic colloid layers, i.e. photographic emulsion layers or other non-light sensitive layers, in the latter case the dye contains a mordant. It is desirable to introduce the dye into a layer as close to the layer as possible, preferably into an adjacent layer. Even if the dye is introduced into a layer that does not contain a mordant, the dye will diffuse into the layer where the mordant is present and will be further concentrated there, resulting in the finished product. In the photographic material, the mordant is often selectively dyed.

The dye may be incorporated in more than one layer.

The mordant-containing hydrophilic colloid layer may be single or two or more, and its (or their) layer is above the photographic emulsion layer (different from the support).

The function of a layer selectively dyed by the presence of a mordant, which may be located either between multiple photographic emulsion layers when present, or between a photographic emulsion layer and a support, is to Depending on its location, it can be either a filter layer, an anti-haley silane layer, or a layer with other purposes.

Further, in the hydrophilic colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, may be added.

Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used.

The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

The silver halide grains used in the present invention include those having regular crystal shapes such as cubic and octahedral, and those having irregular crystal shapes such as spherical and plate shapes.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase.
For example, it may be a negative-tone emulsion), or it may be a grain that is mainly formed inside the grain (for example, an internal latent image type opalescent, a pre-fogged direct reversal type emulsion), and preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
A tabular grain emulsion in which grains having a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area, is statistically The above coefficient of variation (the value s/H obtained by dividing the Enoki deviation S by the diameter 1 when the projected area is held in a circle)
A monodisperse emulsion in which the emulsion is 20% or less is preferred, and two or more types of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is P. gelafchides (
Chimie er Phy Physique Photography Inc.
photographeque) (Ballmontel, 1967), written by G.F. Duffin, published by Photography Inc.
Emulsion Chemistry (Photograph)
ic Emulsion Chemistry) (Focal Press, 1966), V, L, Zelikman et al., Making and Coating Photographic Ink Emulsion (Making and Coating Ph
otographic Emulsion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, No. 628, No. 3,704,130, No. 4.297.439, No. 4.276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually chemically enlarged.

For chemical sensitization, for example H, Friesel (H.

Fr1eser) I, Die Grundlagen der Fotografisien Prozesse Mint Zilberhalogenden
rPhotographischen Prozess
e+wit Silberhalogeniden＞
(Academische Verlagsgesellschacht 196
8) The method described on pages 675 to 734 can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfines, silane compounds).
A noble metal sensitization method using complex salts of metals of Group 1 of the periodic table such as t, lr, and Pd can be used alone or in combination.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. Can be done. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (particularly 4-hydroxy substituted (13,3a,
7) Compounds known as antifoggants or stabilizers such as tetraazaindene, benzenethiosulfonic acid, benzenesulfinic acid, etc. can be added.

The silver halide photographic emulsion of the present invention can be used in colors such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, the oxidizing power with aromatic primary amine developers (for example, phenylene diamine derivatives, amine phenol derivatives, etc.) in color development processing.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, bilasolotriazole couplers, open-chain acylacetonitrile couplers, and yellow couplers. , acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include naphthol couplers, phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.

The coupler may be either 4-equivalent or 2-equivalent to the i-ion, and may also be a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (a so-called DIR coupler). .

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane derivatives. , urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The silver halide photographic emulsion of the present invention may contain known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. In addition, as a spectral sensitizer, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and improving contrast). good.

In addition, the photosensitive material of the present invention contains anti-fading agents, hardening agents, anti-color fogging agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as detailed in Research Disclosure Vol. 1.176 ( 1978, 'A>RD
-11643 etc.

As for hardening agents, N-carbamoylpyridinium salts such as bis(vinylsulfonylmethyl)ether, (1-morpholinocarbonyl-3-pyridinio)methanesulfonate, and 1(l-chloro-1-pyridinomethylene) are used. Hardeners such as haloamidinium salts such as pyrrolidinium 2-naphthalene sulfonate are preferred.

The finished emulsion can be prepared on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
Applied on other plastic bases or glass plates.

The silver halide photographic light-sensitive materials of the present invention include color positive films, color papers, color negative films, color reversals (which may or may not contain couplers), and photographic materials for platemaking (for example, lithium film, lithography), and color reversal films (which may or may not contain couplers). eup film, etc.), photosensitive materials for cathode ray tube displays (e.g., photosensitive materials for emulsion X-ray recording, materials for direct and indirect photography using screens), silver salt diffusion transfer process (Silver 5alt diffusion tr
photosensitive material for color diffusion transfer process, dye transfer, imbibi tion transfer process
photosensitive materials for use in the silver dye bleaching method, photosensitive materials for recording printout images, photosensitive materials for heat-developable printing (Direct Pr1nt image), photosensitive materials for heat development, photosensitive materials for physical development, etc. can be mentioned.

Exposure to obtain photographic images may be carried out using conventional methods: natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots. Any of a variety of known light sources can be used. n
The light time is usually an exposure time of 1/1000 second to 30 seconds, but exposures shorter than 1/1000 second, such as 1/10' to 1/10-second exposures using xenon flash lamps or cathode ray tubes, may be used. or exposures longer than 30 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. It is also possible to use Losee light for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Any of the known methods and known treatment liquids as described in J.D.T.S. Closure No. 176, page 28A-30 (RD-17643) can be used. This photographic processing may be either a photographic process that forms a silver image (black and white photographic process) or a photographic process that forms a dye image (color photographic process), depending on the purpose.The processing temperature is usually from 1B to 50℃. Selected between 18℃ and 18℃
Lower temperatures or temperatures above 50°C may also be used.

There are no particular restrictions on the color photographic processing method, and any method can be used. For example, a typical method is to perform color development, bleach-fixing processing after exposure, and further washing with water and stabilization processing as necessary. , After exposure, color development, bleaching and fixing are performed separately, and if necessary, further washing with water and stabilization treatment are performed. After exposure, development is performed with a developer containing a black and white developing agent to give -like exposure. After that, color development and bleach-fixing are carried out, and if necessary, washing with water and stabilization are carried out, or after exposure, development is carried out with a developer containing a black and white developing agent, and then a fogging agent (
For example, there is a method in which the image is developed with a color developing solution containing (for example, sodium borohydride) and then subjected to a bleach-fixing process, followed by washing with water and stabilizing process as required.

Next, the present invention will be specifically explained.

Example 1 109A gelatin water soluble ill! 95-, the dyes according to the invention and the comparative dyes listed in Table 1 were added 2.3x each.
25 d of an aqueous solution containing io-' moles, 0.6 g of the mordant shown in Table 1, a surfactant and a hardener were added, and distilled water was added to make the total volume 150-. This dye solution was coated on a cellulose triacetate film. A sample was prepared by coating and drying.

These samples were immersed in a pH 7.0 (p) (buffer) solution at 25° C. for 10 minutes and dried.

The visible spectrum of each sample before and after dipping was measured, and the fixation rate of the dye was determined from the optical density at the maximum absorption wavelength. The results are shown in Table 1.

Fixation rate (%) Fog x 100 (0+ is the concentration before immersion in distilled water, D2 is the concentration after immersion) Comparative dyes A, B, C, and D have the following structure.

((1,)ssO3K (CBri5sOsK) These samples were also processed at 35°C using a developer with the following composition.
It was immersed in water for 25 seconds, then washed with water for 20 seconds and dried.

Measure the visible spectrum of each sample before and after immersing it in the developer,
The decolorization rate was determined from the optical density at the absorption maximum wavelength. The results are shown in Table 1.

D+ (D+ is the concentration before immersion in the developer, D represents the concentration after immersion) Composition of developer 1-Phenyl-3-pyrazolidone 1.5g Hydroquinone 30g 5-Ditocentric indazole 0.25g Odor Potassium
3.0g anhydrous sodium sulfite 50
g Potassium hydroxide 30g Oxalic acid 10g Glutaraldehyde 5g Add water and make a panoramic view.
Let it be f.

(The pH was adjusted to 10.20.) As is clear from Table 1, samples 5 to 17 of the present invention were superior in fixation rate and decolorization rate compared to samples 1 to 4 (comparative examples). Also, from the comparison of 5 and 7, it was found that the tertiary ammonium type is superior to the guanidyl type in terms of fixation rate and decolorization rate, and from the comparison of 6 and 7, it is recommended to use a crosslinked mordant. It can be seen that the tertiary ammonium type is superior to the quaternary ammonium type from the comparison of 8 and 9.

On the other hand, in the case of dyes, the comparison of 13.14.15 shows that in order to achieve both fixation rate and decolorization rate, an aralkyl group having a sulfonic acid group is the best substituent at the 1-position of the pyrazolone ring.

In addition, these samples were treated with micro-sensitive material processing solution MD-28.
5 (manufactured by Fuji Photo Film Co., Ltd.) and processing liquid 0R-DI (manufactured by Fuji Photo Film Co., Ltd.) for printing sensitive materials.
The mordant and dye combination of the present invention showed excellent decolorization rates.

Example 2 A blue-colored polyethylene terephthalate base having a thickness of 175 μm was provided with an undercoat layer on both sides of the base in the coating amount of the dye shown below and in Table 2.

0 Gelatin 84 mg/nfO Mordant (2) 60 mg/rrr Emulsion A shown below and its coating solution were coated on both sides of this base together with the surface protective layer shown below so that the amount of coated silver per side was 1.95 g/n+.

(Preparation of emulsion A) In 1 liter of water, 5 g of potassium bromide, 0.05 g of potassium iodide, 30 g of gelatin, 80 thioether (C1lzhS(Cll□
), 5 (CI!□), 5% aqueous solution of Oll 2 , 5 c
An aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were added to the solution kept at 75°C while stirring (by double jet method). Added over 45 seconds, followed by 2.5 g of potassium bromide.
After that, an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of the addition was twice that at the start of the addition.

Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by a controlled double jet method while maintaining the potential at pAg 8.1. The flow rate at this time was accelerated so that the flow rate at the end of addition was eight times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 50 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After this, increase the temperature to 3
After lowering the temperature to 5°C and removing soluble salts by the sedimentation method,
The temperature was raised to 40° C., and 68 g of gelatin, 2 g of phenol, and 7.5 g of trimethylolpropane were added, and the pH was adjusted to 6.40 and pAg to 8.10 using soda and potassium bromide.

After raising the temperature to 56°C, a sensitizing dye with the following structure was added to 7
44 .mu./Ag-1 mole was added. After 10 minutes, sodium thiosulfate pentahydrate 8.2++t Potassium thiocyanate 16
At dawn 3, 5.4 quartz of chloroauric acid was added to each emulsion, and after 5 minutes, it was rapidly cooled and solidified to give emulsion A. In the obtained emulsion, 93% of the total projected area of all grains consisted of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more was 0.83 μm, with a standard deviation of 18.
．． 5%, the average thickness was 0.161/μm, and the aspect ratio was 5.16.

(CHg) 3(Cllz) s so, e SO, Na (Preparation of emulsion coating solution) The following chemicals were added to emulsion A per mole of silver halide to prepare a coating solution.

・4-hydroxy-6-methyl-1,3,3a,? -Tetrazaindene 1', 914...
・g.

・Polymer latex (poly(ethyl acrylate-methacrylic acid)-97/3) 25.0g ・Hardening agent l 2-bis(sulfonylacetamido)ethane ・26-bis(hydroxyamino)-4-diethylamino-1,3, 5-) Sodium riazine polyacrylate (average molecular weight 41,000) - Kalyrum polystyrene sulfonate (average molecular weight 600,000) (Contents of surface protective I1 layer) 11 points 1 star and Yoshida gelatin dextran (average molecular weight 1t4 10,000) ・Sodium polyacrylate (average molecular weight 400,000) ・Sodium salt of pt-ogtylphenoxy diglyceryl butyl sulfonate ・Poly(degree of polymerization 10) oxyethyl 2.3 g 80 ■ 4.0 g 1.0 g ”Ll 0.8g/IT? 0.8 0.02 0.02 Lencethyl ether 0.035 Poly (
Degree of polymerization: 10) Oxyethylene-poly (degree of polymerization: 3) Oxyglyceryl-ophthyl phenoxy ether 0.01・CsF+,
0.003sHv ・CeF+ tsOxN +CHz)r(CH*h a
sOJa 0.00IC3B?・C*F+tSOJ +CH*(J!*Oh ding → CHz
C) IzCHzO) -110,003 ・Polymethyl methacrylate (average particle size 3.5 pm) 0.02
5. Poly (methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) 0.020 Samples 1111 to 8 were obtained in this way.

For exposure of the sample obtained as above, a screen was used as a screen for Fuji Photo Film Co., Ltd. GRENEX series tDG-4/)I)-7(
Gd*O□S:Tb) was used. According to the usual method, G
-4 Photographic materials 1 to 8 were sandwiched between two screens so as to be in close contact with each other, and exposed to X-rays through a water fan dome in 10 countries. After processing, sharpness is 30μm x 500μ
It was measured with an aperture of m and evaluated using an MTF value with a spatial frequency of 2.0 cycles/tsuru. The MTF was evaluated on both sides with an optical density of 1.0.

Regarding MTF, The Theory or
Photographic Process 592~
It is described on page 618.

Further, the processing was carried out using an FPM-4000 automatic processor (manufactured by Fuji Photo Film Co., Ltd.), a developer RD-1 (manufactured by Fuji Photo Film Co., Ltd.), and a fixer solution Fuji F (manufactured by Fuji Photo Film Co., Ltd.).

An unexposed film was processed using the above-mentioned automatic processor and processing solution, and the level of residual color was sensory evaluated. As a guideline for evaluation, A... is a state where you can hardly notice that there is any residual color C...... you are aware that there is some residual color, but it is not really noticeable for practical purposes E... ...The remaining color was clearly left, and the remaining color was considered to be a problem in practice, and B and D were set as intermediate states.

The results of the above evaluation are shown in Table 2 together with the sample contents.

As is clear from Table 2, in the case of the comparative example, the relative sensitivity was significantly reduced due to the filter effect based on the diffusion of the dye from the undercoat layer to the emulsion layer, or, if it did not reduce, the residual color became large. On the other hand, samples t6 to 8 using the dyes of the present invention showed less desensitization and improved residual color.

Furthermore, it can be seen that the sharpness (MTF) is also improved by providing an undercoat layer using the dye of the present invention.

Example 3 The undercoat layer base and surface protection layer were prepared in the same manner as in Example 2, with the amount of hardener added to the emulsion coating solution being 20 m mol/100 g.
-gel An emulsion coating solution of Example 2 was prepared.

Samples 9 to 14 were thus obtained. Exposure and residual color evaluation were performed in the same manner as in Example 2.

However, the processing was changed to the same one as in the photographic performance evaluation described below.

Evaluation of Photographic Performance The same exposure as in Example 2 was applied, and the following developer (II) was used.
The film was processed using an automatic processor using a fixer and a fixer.

<Developer 'I! Near I condensate> Potassium hydroxide 56゜6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate
16.7 g boric acid
10g hydroquinone
83.3 g diethylene glycol
40g4-hydroxymethyl-4 methyl1-phenyl-3 pyrazolidone 11.085-methylbenzotriazole 2
Make IE with g water (adjust pH to 10.60).

Fixer Concentrate> Ammonium thiosulfate 560 g Sodium sulfite 60 g Ethylenediaminetetraacetic acid disodium dihydrate 0.10 g Sodium hydroxide 24 g Make up to 1 liter of water (adjust to pH 5, io with acetic acid).

Automatic developing machine Second processing developing tank
5.5ffi 35℃ x 12.5 seconds fixing tank 5.51 35℃ x 1O seconds washing tank
5.5f 20℃ x 7.5 seconds drying
50℃ Dry Lo Dr
y Processing time: 48 seconds When starting the developing process, each tank was filled with the following processing solution.

Developing tank: 333-1 of the above developer concentrate, 667 of water, and 10M1 starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.15.

Fixing tank: 250ml of the above fixer concentrate and 750ml of water The results are summarized in Table 3.

As is clear from Table 3, even in such a rapid processing system, the present invention is excellent in terms of relative sensitivity and residual color.

Patent applicant: Fuji Photo Film Co., Ltd. 1゜

Claims (3)

[Claims] (1) A silver halide photographic material characterized in that at least one hydrophilic colloid layer contains a mordant represented by the following general formula (I) and a dye represented by the following general formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A has at least two copolymerizable ethylenically unsaturated groups, and is copolymerizable with at least one of them included in the side chain. represents a monomer unit copolymerized with a monomer,
B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R_1 represents a hydrogen atom, a lower alkyl group, or an aralkyl group. Q is a single bond or an alkylene group, a phenylene group, an aralkylene group, ▲ formula,
Represents a group represented by chemical formulas, tables, etc.▼, ▲numerical formulas, chemical formulas, tables, etc.▼ or ▲numerical formulas, chemical formulas, tables, etc.▼. Here, L represents an alkylene group, an arylene group or an aralkylene group, and R represents an alkyl group. G stands for ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_2, R_3, R_4, R_5, R_6, R_7, R
_8, R_9 are hydrogen atoms, alkyl groups, aryl groups,
or represents an aralkyl group, which may be the same or different from each other, and may be substituted. X^■ represents an anion. Also, Q, R_2, R_3, R_4 or Q, R_5, R
Any two or more groups of _6, R_7, R_8, and R_9 may be bonded to each other to form a ring structure together with the nitrogen atom. x, y, and Z represent mole percentages, x represents a value from 0 to 60, y represents a value from 0 to 60, and z represents a value from 30 to 100. General formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_1 represents an aryl group, aralkyl group, or alkyl group having at least one sulfonic acid group or carboxylic acid group, and R_1_2 represents an alkyl group, Aryl group, aralkyl group, cyano group, -COOR_1_7-, -
CONR_1_7R_1_8, -COR_1_9, -S
O_2R_1_9, -SO_R_1_9, -SO_2N
R_1_7R_1_8, -OR_1_7, -NR_1_
7R_1_8, -NR_1_8COR_1_9, -NR
_1_7CONR_1_7R_1_8 or NR_1_8
SO_2R_1_9, (where R_1_7, R_1_
8 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, R_1_9 represents an alkyl group, an aralkyl group, or an aryl group, and R_1_7 and R_1_8 or R
_1_8 and R_1_9 may be connected to form a 5- or 6-membered ring. ), and R_1_3 and R_1_4 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, -
OR_1_7, -NR_1_7R_1_8, -NR_1
_8, COR_1_9, -COOR_1_7, -CON
R_1_7R_1_8 (here, R_1_7, R_1_
8, R_1_9 is R_1_7, R_1_ defined above
8, synonymous with R_1_9. ) or a sulfonic acid group, R_1_5 and R_1_6 represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and R_1_5 and R_1_6
may be linked to form a 5- or 6-membered ring, R_1_3
and R_1_5 or R_1_4 and R_1_6 are connected to 5
Alternatively, a 6-membered ring may be formed. L_1, L_2, L_3 each represent a methine group, and n is 0
Or represents 1. (2) In the mordant represented by the general formula (I), G represents ▲a mathematical formula, a chemical formula, a table, etc.▼, and at least one of R_2, R_3, and R_4 represents a hydrogen atom. A silver halide photographic material according to claim 1. (3) In the dye represented by the general formula (II), R
3. The silver halide photographic material according to claim 1 or 2, wherein _1_1 represents an aralkyl group having at least one sulfonic acid group.