JPH02140738A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the viscosity of a coating soln. without deteriorating the properties of a coated surface and to enhance the dye retaining ability of a mordant-contg. layer by incorporating a specified polymer having anionic functional groups into a layer adjacent to the mordant-contg. layer. CONSTITUTION:This silver halide photographic sensitive material has a layer contg. an acid dye, a high molecular mordant and gelatin. A compd. represented by formula I is incorporated into a layer adjacent to the mordant-contg. layer. In the formula I, A is monomeric unit copolymerized with a copolymerizable monomer having at least two copolymerizable ethylenic unsatd. groups and contg. at least one of the groups in the side chain, B is a monomeric unit copolymerized with a copolymerizable ethylenic unsatd. monomer, E is a monomeric unit copolymerized with a copolymerizable ethylenic unsatd. monomer having at least one anionic functional group, x is 0-50mol%, y is 0-99mol% and z is 1-90mol%. The compd. represented by the formula I is an anionic polymer thickening agent having superior viscosity increasing property and nontransferability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material.
A silver halide photographic material having at least one layer containing an acidic dye, a polymeric mordant, and gelatin, which uses a compound that increases the viscosity of a coating solution without impairing the coated surface condition. .

(Prior art) Silver halide photographic materials are generally produced by coating a coating solution in which silver halide and other various additives necessary for photographic materials are dispersed in a gelatin solution on a support such as triacetyl cellulose or polyethylene terephthalate. Manufactured by coating. It is a well-known fact in the coating industry that various coating aids are used to uniformly and evenly apply a coating solution during the manufacturing process of such silver halide photographic materials. Among these, anionic polymers such as potassium polystyrene sulfonate are often used for the purpose of adjusting the viscosity of the coating solution.

For example, Tokukai Akihirotar l/j3// issue, same! /-rt
ixJ issue, 32-47311, same! J-39//r
No. 13-3L? //No.9, same j7-10!177/
No., t/-20!111/No.
! No., British Patent T76, ≠J No., same l,! 3ri, 24
No. 6, U.S. Patent No. 3゜022, /7.2, same! , 6j!
, μ07, same j, 70j, 791, same J, r//
, R. No. 7 discloses that the viscosity of a coating liquid can be increased by adding a polymer having anionic groups to the coating liquid.

However, when these anionic polymers are used in photosensitive materials containing polymers containing cationic sites, undesirable results often occur. for example,
When a layer containing a cationic polymer is provided for the purpose of mordanting an antihalation dye, if an anionic polymer is added to a layer other than the layer containing the cationic polymer, the anionic polymer will diffuse into the mordant layer and prevent halation. Causes demordanting of the dye. As a result, the antihalation dye cannot remain in the antihalation layer and diffuses into the emulsion layer, which not only impairs the original antihalation effect but also causes adverse effects such as a decrease in sensitivity.

Another problem was that diffusion of the anionic polymer into the adjacent layer causes interaction with the cationic polymer mordant in the mordant layer, often deteriorating the coated surface condition.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a novel anionic polymer thickener that has excellent thickening properties and excellent non-migration properties.

A second object of the present invention is to provide a silver halide photographic material in which the mordant layer has an excellent ability to retain dye by having an adjacent layer coated with the above-mentioned thickener. .

A third object of the present invention is to provide a photographic material with an excellent coated surface.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide film having at least one silver halide photosensitive layer on a support, and at least one layer containing an acid dye, a polymer mordant, and gelatin. This was achieved by a silver halide photographic material characterized in that a layer adjacent to the mordant-containing layer contains a compound represented by the following general formula [1].

General formula [I] + A + c + B + y ÷ E Nine formula chunin copolymerizes a copolymerizable monomer having at least λ copolymerizable ethylenically unsaturated groups and containing at least 7 of them in the side chain. Represents a monomer unit.

B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. E represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer having at least one anionic functional group. x, y, z represent the mole percentage of each component, and X is θ~! 0. y takes a value from O to Tata, and 2 takes a value from / to O.

The compound represented by the general formula [I] of the present invention will be explained in detail below.

Examples of monomers in A are divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, l,t-hexanediol diacrylate, neopentyl glycol dimethacrylate, tetra Methylene dimethacrylate and the like, with divinylbenzene and ethylene glycol dimethacrylate being particularly preferred.

Examples of ethylenically unsaturated monomers in B are ethylene, propylene, l-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) , n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate,
n-hexyl acrylate, λ-ethylhexyl acrylate) monoethylenically unsaturated compounds (e.g. acrylonitrile) or dienes (e.g. butadiene, imbrene), among which styrene, n-butyl methacrylate, methyl methacrylate, etc. are particularly preferred. preferable.

B may contain two or more types of the above monomer units.

E represents a copolymerizable ethylenically unsaturated monomer unit having an anionic functional group. Preferred examples of such anionic groups include -COOH group, -8O3H group, -
Examples include -8O2H group, -F-(-OH+2 group, or salts thereof, -COOH group, -8O3H group,
-8O2H group or a salt thereof is particularly preferred.

Examples of ethylenically unsaturated monomers having anionic functional groups that provide monomer units represented by E are shown below.
It is not limited to this.

CH3 Ha CH2=CH C0N)(+CH2yaC(i)Hl) These anionic group-containing monomers are salts thereof, such as alkali metal salts (eg, Na.

K salt), ammonium salt (for example, salt with ammonia, methylamine, dimethylamine, etc.) may be present in the polymer main chain.

These monomer units represented by E may be used alone or in combination of two or more.

x, yX zVi, represents the molar percentage of each component, X is θ
~! OX y is θ~ri7.2 is 1~riO.

Among these, when x = 0, the preferred range of yl Z is y! O~Tata, 2 is/~! 01 Particularly preferably,
y is 7Q-2t, z is evening to 30.

Also, when xNO, the preferred range of x, y, and z is when X is 0
．． /-,,! OX'j is 0~ri0. z to i-t.

Especially preferably, X is 3~! 0, y to O-10
, z is 3 to 70.

Examples of the compound represented by the general formula [1] of the present invention are shown below, but the present invention is not limited thereto. (x, y, z in the example represent the mole percentage of each component.) A-/ x:y:z=10:♂j:j A-j x:y:z=10 near 1:/j C=0 CH3 -j CH3 x:y:z=/j near 0:/j C)I2 C=0 -(-CCH2-)- x:y=≠j:jI CH3 -r a(3 CH3 CH2 C )′12 x:y:z=/! :Aj:20 x:y:z=/j Near! :10 C=0 +Cc1(2+ CH3 A-taHa c)(2 x:y:z=/l:♂O:I CH2 C=0 x:y=20:10 +CcH2+ c)I3 A-73 a( 3 x:y:z=10 near 3 2 /j x: y=27.j'ko, j A-/ / ≠ Ha x:y=30 near 0 A-/λ x:y=rij:j A −)! x:y=ri! :j x:y:z=10 near j near, 7 7,! A-/, < A-/ / r x:y=IO H3 x: y: z=≠O'HiroO x:y=7j: Ko! The compound represented by the general formula [I] of the present invention generally comprises a copolymerizable monomer containing at least λ of the above ethylenically unsaturated groups, an ethylenically unsaturated monomer, and at least one anionic functional group. Ethylenically unsaturated monomers having groups can be synthesized using generally well-known emulsion polymerization methods. When the anionic functional group in the polymer is used in the form of a salt, the monomer may be polymerized in the form of a salt, or a basic compound may be added after the polymerization.

The above emulsion polymerization is generally carried out using an anionic surfactant (e.g. sodium dodecyl sulfate, Triton 77Q (commercially available from Rohm & Haus), a nonionic surfactant (e.g. Emarex NP-λO (commercially available from Nippon Emulsion)), At least one emulsifier selected from gelatin, polyvinyl alcohol, etc. and a radical polymerization initiator (for example, a combination of potassium persulfate and sodium bisulfite, commercially available from Wako Tsumugi under the name V-to) is generally carried out at a temperature of 3θ0C to about /θθ0C.

In addition, among the compounds represented by the general formula (I), especially when synthesizing a polymer containing a large amount of anionic functional groups, You can refer to the method.

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

Synthesis Example 1 Poly(cypinylbenzene-costyrene-co-p-styrenesulfonate) polymer dispersion (Exemplary Compound A-
2) Nirasantrax H-111 for the synthesis reaction vessel! , 30% aqueous solution, NOF■)r, 77g, sodium bisulfite O, 72g, sodium p-styrenesulfonate 9.2
7g, divinylbenzene.

lrGg, Kutylev 3, 3 were added, and the mixture was heated and stirred at RO 0 cw under a nitrogen stream. Add 0.1 g of potassium persulfate dissolved in 10 ml of distilled water, continue heating and stirring for 2 hours, and then add 0.3 g of potassium persulfate.
g dissolved in 10 ml of distilled water was added, and the mixture was heated and stirred for an additional hour.

After cooling, the polymer dispersion obtained by r-filtration has a solid content/A.
It was a stable polymer dispersion with a particle diameter of 0.03 μm (measured by Coulter Submicron Particle Analyzer Nikikaki ■).

The amount of the compound represented by the general formula [I] of the present invention ranges from o-i to 100% by weight of gelatin, preferably o
．． j-to weight%.

If the amount added is less than 0.1%, the viscosity of the mixed solution of gelatin and the compound is too low to be used for practical use;
If it is 0% or more, the viscosity of the liquid mixture becomes abnormally high, making it impossible to put it into practical use.

The layer adjacent to the polymer mordant-containing layer of the present invention may be a photosensitive emulsion layer or a non-photosensitive layer, but is preferably a layer that does not substantially contain silver halide grains.

The cationic polymer mordant used in the present invention will be explained below.

The polymer in the present invention has the following general formula % Formula % General formula [I[] A group or an aralkylene group, and R represents an alkyl group.

In the formula, the compound represents a monomer unit copolymerized with a copolymerizable monomer having at least λ copolymerizable ethylenically unsaturated groups and at least one of which is included in a side chain. B
represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R1 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 L-C-0-L-
1R3.R4, R5, R6.R7.R8.R9 represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and these may be the same or different from each other, and may be substituted. Xo represents an anion.

Also, Qs R 2, R3, R4 or Qs R s, R
Any λ or more groups of 6, R7, R8, and R9 may be bonded to each other to form a ring structure together with the nitrogen atom.

represents. Here, L is an alkylene group, a phenylene group which may be arylene, or an optionally substituted aralkylene group having 7 to 7.2 carbon atoms (for example, it is particularly preferable that at least one of R4 is a hydrogen atom).

pS q and r represent molar percentages, p represents a value from 0 to to, q represents a value from O to AO, and r represents a value from 30 to ioo.

To explain the above general formula [■] in more detail, the monomers A and B each represent a compound selected from the same group as the compounds represented by A and B of the above general formula [I].

R1 is preferably a hydrogen atom or a lower alkyl group (e.g. methyl, ethyl, n-propyl, n-7" thyl, n-amyl, n-hexyl) or aralkyl group (e.g. benzyl) having a carbon number of /~ A hydrogen atom or a methyl group is particularly preferred.

Q is preferably a divalent optionally substituted alkylene group having 1 to 1 carbon atoms (for example, a methylene group or -(CH
2) A group represented by 6-), a substituted group) is preferable, and a group represented by the following formula is also preferable, where L is an optionally substituted alkylene group having a carbon number of /~B, or an unsubstituted group. An optionally substituted arylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms is preferable, and an optionally substituted alkylene group having 1 to t carbon atoms is more preferable.

R is preferably an alkyl group having carbon number/~t.

几2, R3, R4, R5, R6, R7, R8, R9 are
Hydrogen atom or 7~. Preference is given to an alkyl group having 20 carbon atoms or an aryl group having A-20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, each of which may be the same or 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, cyclohegycyl, n-heptyl, n-octyl, coethyl xyl, n-nonyl, n-decyl,
n-dodecyl); the carbon atoms of the alkyl group are preferably 7
~lλ pieces. More preferably, the number of carbon atoms is μmIO. Examples of substituted alkyl groups include alkoxyalkyl groups (e.g., methoxymethyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl, methoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl, vinyloxyethyl), cyanoalkyl groups (e.g., no/ Anoethyl, 3-cyanopropyl, ≠
-cya7noptyl), halogenated alkyl groups (e.g. λ
-fluoroethyl, λ-chloroethyl, 3-fluoropropyl), an alkoxycarbonyl alkyl group (eg, ethoxycarbonylmethyl), an allyl group, a -1-butenyl group, a propargyl group, and the like.

Examples of the aryl group include unsubstituted aryl groups (e.g. phenyl, naphthyl); examples of substituted aryl groups include alkylaryl groups (e.g. -1-methylphenyl, 3-methylphenyl, μm methylphenyl, μm methylphenyl,
≠-isopropylphenyl, +1- ter t-
) f ruphenyl), alkoxyaryl groups (eg, coumethoxyphenyl, 3-methoxyphenyl, Hiro-ethoxyphenyl), and aryloxyaryl groups (eg, Hiro-phenoxyphenyl). The aryl group preferably has 6 to 10 carbon atoms, more preferably 2 to IO carbon atoms. Particularly preferred is a phenyl group.

Examples of aralkyl groups include unsubstituted aralkyl groups, (e.g.
tJj: benzyl, phenethyl, diphenylmethyl, naphthylmethyl): substituted aralkyl group, e.g. alkylaralkyl group, (e.g. goomethylbenzyl, 2.!-dimethylbenzyl, μm isopropylbenzyl), alkoxyaralkyl group, (e.g. j-methoxybenzyl) , Hiro-ethoxypenzyl), cyanoaralkyl group, (e.g. evagus cyanobenzyl), barfluoroalkoxyaralkyl group, lJt≠-pentafluoropropoxypenzyl group, ≠-undecafluorohexyloxybenzyl group, etc.), halogen aralkyl groups (eg, c, 'I-chlorobenzyl groups, μm-bromobenzyl groups, 3-chlorobenzyl groups, etc.).

The number of carbon atoms in the aralkyl group is preferably 7 to /j,
Preferably it is 7 to 1 piece. Among these, benzyl group and phenethyl group are particularly preferred.

Xe represents an anion, such as a halogen ion (e.g. chloride ion, bromide ion), an alkyl or arylsulfonic acid ion (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic 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%"2, R3, and R4 bond with each other to form a cyclic structure together with a nitrogen atom. Examples of the cyclic structure formed include a pyrrolidine ring and a piperidine ring. , a morpholine ring, a pyridine ring, an imidazole ring, a quinuclidine ring, etc. Particularly preferred are a pyrrolidine ring, a morpholine ring, a piperidine ring, an imidasyl ring, and a pyridine ring.

Further, any two or more groups of Q% R5, 几6, R7, R8, 几9 may be bonded to each other to form a cyclic structure together with a nitrogen atom, and the cyclic structure formed is 2. Member ring or! Particularly preferred are ring members.

p is from O to 100%, preferably from O to μO0%, more preferably from 0 to 30%. q is from O to to molar, preferably from 0 to ≠O molar, more preferably from O to 30 molar.

r is 30 to ioo morti, preferably ≠0
Naishiri! Molch, more preferably! O to rz morch.

Preferred specific examples of the compound represented by the general formula [11] are listed below.

C-(1) x;z=10:90 C-(2) x: z 20 = 80 C-(3) x:z-25:15 C-(4) C-(5) C-(6) Ko-(10) CHl CH.

C-0 ACHtC square = Hj C-(11) C-(7) 1e x:z-50:50 x;z=20:80 C-(8) x:)’:z-50:10:40 CH.

CH.

CH.

■ Shiri aHq O3e -(C-CH2)- x:y:z-45:5:50 CH.

Xl:z=30:35:35 C-(12> CI! ,0 CXθ x:y:z=17.2 5:80 C-(13) X:Y:z=40:10:50 CH) zHs x:y:z=15:5:80 x；z 30 near 0 C-(14) CH.

1e -O x:y:z=20:10 near 0 (CCH, Masu- CH.

CH.

x: y: z plot 25; 15:60 〇-(18) CH.

304' x:Y:z-25:10:65 C○ One + C C1 (tto CH.

C-(+9) H@ Xl=15:35 -(CHCH,)- C-(16) C-(1n C-(20) C-(21) CH.

Hs X2y:z=35:5:60 CH3 'ASOaθ X:y:z-20:10 near 0 A　S　Oa　” x:z=so:s.

C-(22) CH3 Ken CH, CH stone 1+cHz CHhz C-(25) →CCH*)− x:z:y:ko40:10:50 Hs C-(26) C;0 One + CH! CH x:z:y:=25:25:50 CH2 CH.

To prepare a cationic polymer as a fine particle dispersion,
Generally, a crosslinking heptamer such as divinylbenzene is used as a monomer, but depending on the monomer used, the use of a crosslinking heptamer is not essential.

The compound represented by the general formula (It) of the present invention / will be explained below.

The polymer represented by the general formula (II) of the present invention generally comprises a copolymerizable monomer containing at least two of the above ethylenically unsaturated groups, an ethylenically unsaturated monomer, and a general formula % formula % (provided that , R1, R2, R3, Q are the same as shown above) Ethyl acrylate N, N-diethylaminoethyl acrylate, N-(N,N-dimethylaminepropyl)acrylamide, N-(N,N-dihexylaminomethyl)acrylamide, J-(<z-pyridyl)propyl acrylate, N,N -diethylaminomethylstyrene, N,
N-cyhexylaminomethylstyrene, λ-vinylpyridine, or t-vinylpyridine, particularly preferably N,N-diethylaminoethyl methacrylate, or N,N-diethylaminomethylstyrene, N,N-diethylaminomethylstyrene). After polymerization, R4-X
(wherein R4, It can be obtained by converting it into ammonium salt.

The polymer represented by the general formula (II) of the present invention may still be a copolymerizable monomer having at least two ethylenically unsaturated groups as described above, an ethylenically unsaturated monomer having the general formula % as shown above. unsaturated monomers represented by Diethylaminoethyl acrylate acetate, N-(N.

P -1-luenesulfonate, N,N-diethylamine methylstyrene sulfate, 2-vinylpyridine hydrochloride, N,N,NF-lyhexylammoniomethylstyrene chloride, N,N,N-triof.

Tylammoniomethylstyrene chloride, N,N.

N-tributylammoniomethylstyrene chloride, N-
Benzyl-NN-dimethylammoniomethylstyrene chloride or 4-vinylpyridine hydrochloride, particularly preferably N,N,N-)lyhexylammoniomethylstyrene chloride, N,N,N also the general formula of the invention The polymer represented by (I) has at least two ethylenically unsaturated groups.
Copolymerizable monomers, ethylenically unsaturated monomers, and general formulas (where X represents a halogen atom (e.g., chlorine atom, bromine atom), a sulfonic acid ester (e.g., P-toluenesulfonyloxy group), R+, Q is the same as shown above) (e.g. β-chloroethyl methacrylate, β-P-)luenesulfonyloxyethyl methacrylate, chloromethylstyrene)
After polymerization, an amine having the structure R, -N-R3 (where Rz, Rs, R4 are the same as shown above) (for example, dimethylamine, diethylamine, diisopropylamine, morpholine, piperidine, pyridine) , trimethylamine, N-methylmorpholine, tributylamine, trihexylamine, trioctylamine, triethylamine, etc.).

In the compound represented by the general formula (IL) of the present invention, G is The method for synthesizing the compound will be explained below.

The polymer represented by the general formula of the present invention includes a polymerizable monomer containing at least two of the above ethylenically unsaturated groups, an ethylenically unsaturated monomer and a general formula R C , Q are the same as shown above) (e.g., methyl vinyl ketone, methyl-(1-methyl vinyl) ketone, ethyl vinyl ketone, ethyl-(1-methyl vinyl) ketone, n
-propyl vinyl ketone, diacetone acrylamide,
After polymerization with diacetone acrylate, particularly preferably methyl vinyl ketone, ethyl vinyl ketone, diacetone acrylamide, diacetone acrylate), the general formula (however, the formula, R,, R,, R,, R, is (e.g., aminoguanidine bicarbonate, N-amino-N'-methylguanidine bicarbonate, N-amino-N'-methylguanidine bicarbonate, etc.), particularly preferably aminoguanidine bicarbonate. aminoguanidine), and further H-X (H-X is the same as shown above)
It can be obtained by converting it into a guanidinium salt with a compound represented by (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 such as solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization, and dispersion polymerization, preferably solution polymerization and emulsion polymerization.

In the above solution polymerization reaction, for example, in emulsion polymerization, -IQ is added an anionic surfactant (e.g. sodium dodecyl sulfate, Triton 770 (commercially available from Rohm and Haus), a cationic surfactant (e.g. octadecyltrimethylammonium chloride), a nonionic Surfactant (e.g. Emarex NP-20 (commercially available from Nippon Emulsion))
, gelatin, polyvinyl alcohol, etc., and a radical polymerization initiator (for example, a combination of potassium persulfate and sodium bisulfite, commercially available from Wako Tsumugi under the name V-to) ), generally from 3o'c to about 10O0C1, preferably 1I
It is carried out at a temperature of O0C to about rO0C.

The reaction to form the above ammonium salt is generally carried out at -10'C
or at a temperature of about ≠ O 0 C, but especially o 0 C
~300C is preferred.

The amount of polymer mordant added varies depending on the type of photosensitive material to be applied, the purpose of use, and the type of layer to be applied.
2 to 100 g per 00 g is preferable, and the amount of dye to be mordanted at this time is preferably 7 to 10 g.

The silver halide photographic light-sensitive material of the present invention has the purpose of absorbing light in a specific wavelength range, that is, preventing halation and irradiation, and controlling the spectral composition of light incident on the photographic emulsion layer by providing a filter layer. The photographic emulsion layer or other layers may be colored with a dye for the purpose of coloring.

Examples of dyes that can be mordanted using the polymer mordant of the present invention include acid dyes (e.g., sulfone group, carboxyl group,
Dyes with sulfonamide groups, phenolic hydroxyl groups, etc.)
Acidic dyes having a sulfone group or a carboxyl group are preferred, and such dyes are described, for example, in British Patent No.! Oh, 31! No., same/, /77.12 No., same/,
J//.

tr No. 1, same/, 331, 79, same/, 3gj, 3
7/issue, same/, ≠t7, 2/g issue, same/.

≠33.10th issue, same/,! ! 3. JLT issue, Tokukai Akihiro? -♂t, i3o, sameμter//4t, ≠λθ,
same! λ-//7. /λ3, same! ! -/1, /, 233
Same issue! 9-/ / /, No. 6410, Special Public Sho JP-
22,0 Otori No., Dohiro 3-/3. Ltr No. 3,21A7,127, 3゜≠Otori, 91r! issue,
Same 4! , 07/i', 233, etc.; ! 33°17! No. 3,372. !
Other oxonol dyes such as British Patent No. 33, British Patent No. 1.271r, tλ/, etc., British Patent No. 37! ,,
4ri No. 7, 410.1.31, same j! F? , 62
No. 3, No. 78't, No. 907, No. 907.72! No. 41,23! ,3
Issue 2, Tokukai Akira! Azo dyes described in Patent Publication No. 2//, No. 011.3, etc.; Azomethine dyes described in oihiro, No. 2, No. 730.03/etc.
US Patent No. 2. It, the anthraquinone dye described in '732, U.S. Patent No. 2°131.00? No., same co.
If,! II No. 1, II No. 2, 331, OCn No.
British Patent No. trtt, t.

ri issue, same/, 210, 2j issue 2, JP-A-Shozo-μ0,
A247, same j/-3. T23 issue, same! /10.92
No. 7, q, t! -//r, No. 211-7, Special Publication Showa 4
Azomethine dyes described in Japanese Patent Publication No. 2g-3,012, 4t4L-/l, 3;9', ', Tatar 2♂ ,!
Styryl dye described in No. 2 etc., British Patent No. 1 Bow,
! ♂No. 3, same/, 332r, μλλ, JP-A-Shojter 2
21.230 etc., British Patent No. 7゜07! ,t! No. 3, same /, /! 3.3
≠ / issue, same! , 2rlA, No. 730, same/ , 4Z7j
, No. 221, same/ , ! ;112, merocyanine dye described in ♂07 etc., U.S. Patent No. ko, r≠J,
1Itt issue, same 3.2? Examples include cyanine dyes described in II, E. No. 32, etc. Among the above dyes, oxonol dyes having a pyrazolone nucleus are particularly preferred.

Examples of dyes that can be used in the present invention are listed below, but the present invention is not limited thereto.

■ I-go (J3L S3 to 03H S (J3H ■! r-+ I-ta 1-/ 0 ■ / Gu1-/! 1-/ & ■ I-2/ ■-Here ■-77 1-/♂ 1-/ri1-.2j l-2hiro■ 2 yo8 (J3Na ■ 2 Otsu■ ■-cor SO3■ ■-33 1-3≠ ■-λri■-37 -3j ■ -34 ■-37 ((,H2)4sU3 (GHz)4S03■-μ0 l-31 1-4/ 1-J) The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention are cubic. , octahedron, rhombus/lambda hedron, /≠hedron, or irregular crystal shapes such as spherical, plate-like, etc.
It may have a regular crystal form or a composite form of these crystal forms. Also, research
Research Disclosure
sure) 2! Volume +20~! Tabular grains having an aspect ratio of 5 or more as described on page ♂ (/♂3 years/month) may be used.

Further, the particles may have an epitaxial structure, or may have a multilayer structure in which the inside and the surface of the particle have different compositions (for example, halogen composition).

Further, it is preferable that the average size of the particles is 03μ3μ. More preferably, the average size is 0°7μ or more j, Oμ
It is as follows.

Also, the particle size distribution may be broad or narrow. The latter is known as a so-called monodisperse emulsion, and has a dispersion coefficient of 20% or less, more preferably is% or less. (Here, the dispersion coefficient is the standard deviation divided by the average grain size.) These photographic emulsions are published by Chimie et Ph.
(Published by Paul Montel)
/ri 47 years) G.F. Dauphin, (G,F,Du
ffin) 7. t-spiky emulsion
Chemistry (Photographic Emul)
sion Chemistry) (The Focal Chemistry)
Pleine (The Foca I Press, / 6z), Bui El Zelikman (V, L, Z)
May 4. by Erikman et al. :ygu77)'-Coating Photographic Emulsion (Ma
king and coating photogra
phicEmulsion) (The Four Forces/L, -zo v, x, (The Focal Press), /
9t'i), etc. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble silver salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good too.

These photographic emulsions may be any combination of silver chloride, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.

Preferably, the average iodine content of all photographic emulsions is 3 molar or more, more preferably 3 molar or more and 0 gm or less.

Further, the coating silver amount of the photosensitive material of the present invention is /~λoy/m2,
In particular, it is preferably λ~10/7 m2.

In addition, the total amount of iodine contained in the silver halide photosensitive material (
AgI) is preferably 4'X/I:) -3 mol/rIL2 or more. More preferably 6×/o-3
mol/m2 or more and te4'X/o-2 mol/m2 or less.

At the stage of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or a complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof, etc. may be present.

Binders for the emulsion layer and other layers of the silver halide photographic material of the present invention include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; starch derivatives such as agar, dextran sodium alginate, and starch derivatives; Synthetic hydrophilic colloids such as polyvinyl alcohol, polyN
-Vinylpyrrolidone A polyacrylic acid copolymer, polyacrylamide, or a derivative thereof, a partial hydrolyzate, etc. can also be used.

Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Further, the photographic light-sensitive material of the present invention has US Patent No. 3. Gu//, ri No. 77, same 3. Gu//.

72, Japanese Patent Publication No. 4 TJF-J33/, etc., may be included.

The emulsion used in the photosensitive silver halide emulsion layer of the present invention is preferably chemically sensitized.

For chemical sensitization, the aforementioned Glafkides or Zelikuma 7 is used.
ikman) et al. or Ecchi Freezer' (
Di, e Grundlagen (H, Fr 1eser) ed.
derPhotographischen Pro
zesse mat3i1berhalogenide
n) Akademitsuie Felleragsgesellschaft (
AkademischeVerlagsgesel l
5chaft), (/rixr) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a cyclic substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, palladium, etc., can be used.

The light-sensitive material of the present invention can contain various compounds as stabilizers. That is, atoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-phenyl-j-mercaptotetrazole), mercaptopyri The above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; Thioketo compounds such as oxazolinthione; Azaindenes such as tetraazaindenes, (
Especially Hiro-hydroxy substitution (/ + 3+ 32 + 7
A number of compounds known as stabilizers can be added, such as) tetraazaindene; benzenethiosulfonic acids; benzenesulfonic acid; and the like.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention may contain various additives such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). A surfactant may also be included for this purpose.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate,
Polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters (polyethylene glycol esters), polyalkylene glycol alkyl amides or amides, polyethylene oxide adducts of silicones), glycidol Nonionic surfactants such as derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates Acid salts, alkyl naphthalene/sulfonate salts, alkyl sulfate esters, alkyl phosphate esters, N-acyl-N-furkyl tauric acid, sulfosuccinate esters, sulfoalkyl phorioxoethylene alkylphenyl ethers, polyol carboxy group, sulfo group, honuho group, sulfate ester group, such as ethylene alkyl phosphate esters,
Anionic surfactants containing acidic groups such as phosphate groups;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate ester foams, alkyl betaine systems,
Ampholytic surfactants such as amine oxides: alkylamine salts, aliphatic or aromatic secondary ammonium salts, heterocyclic cylindrical V-class ammonium salts such as pyridinium and imidazolium, and phosphonium or nuphonium containing aliphatic or heterocycles. Cationic surfactants such as salts can be used. Among these surfactants, polyoxyethylene surfactants and fluorine-containing surfactants are particularly preferably used.

The polyoxyethylene surfactant used in the present invention preferably has at least 2 or more oxyethylene groups, more preferably 1 to io.

It has individuality.

As the polyoxyethylene surfactant, in particular, the following general formulas CI [l-/], (III--2) and [■-3
] Preferred are surfactants represented by the following.

General formula CI-/) R1-A+CH2CH2O+-R2 General formula [■-2] General formula (III-J) In the formula, R1 is a hydrogen atom or a substituted or unsubstituted alkyl group having up to 30 carbon atoms, an alkenyl group, or The aryl group, A
is 10- group, -8- group, -COO- group, -N-R15 group, -CO-N R1s group, -8O2N-R15 group (here, R14 is a hydrogen atom, a substituted or unsubstituted alkyl group) ).

R2 has the same meaning as the above-mentioned R1 or R knee.

R3, R4, R8, RIO, R12 and R14 hydrogen atom, substituted or unsubstituted alkyl group, alkyl group, alkoxy group, halogen atom, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group represent. In the formula, R7, R9, R11 and R13 represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.

R5 and R6 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heteroaromatic ring.

R5 and R6, R7 and R8, R9 and RIO, R11 and R1
2 and R13 and R14 may be linked to each other to form a substituted or unsubstituted ring. nl, R2, na and R4 are average degrees of polymerization of ethylene oxide and are numbers from λ to 100.

Also, m is the average degree of polymerization, and! ~! It is the number of O.

The amount of the polyoxyethylene surfactant used in the present invention varies depending on the type, form, coating method, etc. of the photographic material used, but in general, the amount used is 1 mole of A g of the photographic material. The amount may be .0 mg or more, especially 60 mg.
mg or more is preferable.

The polyoxyethylene surfactant of the present invention is preferably added to a light-sensitive emulsion layer of a photographic light-sensitive material, but it may also be added to a non-light-sensitive layer.

For the purpose of increasing the viscosity of the coating liquid in the photosensitive material of the present invention, special public Shoj! No. 7-772, special public Shoj7-! No. 3233,
Patent Application No. Showa A/-t/2C# and U.S. Patent No. 3022/
Compounds described in No. 7.2 etc. can be added. Especially polystyrene sulfonic acid or poly-3,3
Water-soluble polymers such as -acrylamide-methyl-propanesulfonic acid can be preferably used. however,
It is preferable that these compounds are not used in the layer containing the polymer mordant and the adjacent layer in the light-sensitive material of the present invention.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, chromium salts, aldehydes (formaldehyde, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), activated vinyl compounds (i, 3.s
-Triacryloyl-hexahydro-5-) IJ 7
gin, bis(vinylsulfonyl) methyl ether, N,
N'-methylenebis[β-vinylsulfonyl)propionamide, etc.), active halogen compounds (2,≠-dichloro-A-hy)'fuxyS-triazine, mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium Salts ((/-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium iu (/-</-chloro-/-pyridinomethylene)pyrrolidinium 2-naphthalenesulfonate, etc.) can be used alone or in combination. can. Among them, Tokukai Akira! 3-4'/ko20. Same j3-j7.2 tough, same tater 7t! YollZ, same 60-? Preferred are the active vinyl compounds described in 0r4 (A) and the active halides described in U.S. Pat. No. 3.323.2f7.

The photographic emulsions of this invention are spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful pigments are those belonging to cyanine pigments, melonanine pigments and complex merocyanine pigments. Any of the nuclei commonly used in cyanine dyes can be used as the basic heterocyclic nucleus for these colors 1i. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, 2-thioxazolidine-λ
, ≠-dione nucleus, thiazolidine-λ, Hiro-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and other S-X member heteroartic ring nuclei can be applied.

The amount of the sensitizing dye used in the present invention is silver mole/×l0-6~! x70-3 mol is preferred.

The photographic emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) that reacts with the oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule. The coupler may be either ≠ equivalent or diisomeric with respect to silver ions. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The coupler may be such that the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, indiylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. An example of a matting agent is polymethyl methacrylate having an appropriate particle size (preferably a particle size of 0.3 to !μ or a particle size of at least twice the thickness of the protective layer, especially at least 10 times the thickness of the protective layer). Organic compounds such as water-dispersible vinyl polymers, and inorganic compounds such as silver halide and barium strontium sulfate are preferably used. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture film related to camera compatibility during shooting or projection; specific examples include liquid paraffin, Preferred are waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, silicones such as polyalkylpolysiloxanes, polyarynubolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxide addition derivatives. used.

The silver halide photographic material of the present invention also includes:

Provide intermediate layers, filter layers, etc. as necessary.

I can do that.

Specific examples of the silver halide photographic material of the present invention include X-ray photosensitive materials, Lithium photosensitive materials, black and white photosensitive materials, color negative photosensitive materials, color reversal photosensitive materials, and color photographic paper.

Preferably, a negative photosensitive material is used. Particularly preferred is a black-and-white photographic negative light-sensitive material.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include development accelerators, fluorescent whitening agents, color antifoggants, and ultraviolet absorbers. Specifically, research disclosure (RES)
EARCHDISCLO3URE)/7 whistle J, l'
Those described on pages 30 to 30 (RD-tyttx3/ri7) can be used.

Typical supports used in the light-sensitive material of the present invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, and other polyesters, as well as glass, paper, metal, wood, and the like.

Furthermore, regarding the development treatment of the photosensitive material of the present invention, R]) −
/71. '73, pages 2g to 30 may be referred to.

1. Fixing solutions for processing the light-sensitive material of the present invention include 7ji Fix, Super Fuji Fix, Fuji DP Fix, and Super Fuji Fix D manufactured by Fuji Photo Film ■.
P, F-O made by Kodanok in the United States, KODAK Fixe
r + Konishi Rokusha Conifix, Conifix Rabbit, other Orifix, My Fix, Niwa Fix 1 Nissan Rabbit Fixer F2 Nissan Rabbit Fixer P, Hanfix Fl Pan Fix P
, Myroll F, Oriental QF, etc.

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

(Example/) (1) Preparation of silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring. The average iodine content (tmolti) was prepared. Thereafter, it was washed with water by a conventional precipitation method, and then chemically sensitized by a gold/sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A.

Silver halide emulsion B (thick silver iodobromide emulsion with an average iodine content of t mol and an average grain size of 0 μm) was prepared in the same manner as A, except that the preparation temperature and the amount of potassium iodide were adjusted.

(2) Preparation of coating samples Samples 1 to 6 were prepared by forming the following layers on a triacetyl cellulose support in order from the support side.

(Antihalation layer) Binder: Gelatin /g/m2 Polymer mordant: Compound C-(2) 0, / 1. g
7m2 Dye: Compound I-31μmg/m2 Compound 1-/jmg/m2 (intermediate layer) Binder: Gelatin O1μg/m21μ Auxiliary agent: Listed in Table 1 (emulsion layer -/) Emulsion: Emulsion A Amount of coated silver used: /,, tg/m2 Binder: Gelatin 2 g/m2
Sensitizing dye: Dye-/2, /mg/Ag
/ g (CH2) 4803 (CH2) 480
3 Na hard FA agent: /, -2-bis(vinylsulfonylacetamido)ethane 3 mg/m2 additive:
ClBH350+CH2CH20-body-Ht, I
mg/Ag/g Coating aid (IJ-p-styrenesulfonic acid) I
Jum 2 μmg/m2 (Emulsion Layer-2) Emulsion: Emulsion B Coated amount of silver: Hiroshi, Ag/m2 Binder: Gelatin 7.0 g/m2 Sensitizing dye: D
ye-/2, /mg/Ag/g additive:
, Cl8H350-(-CH2CH20ChiH!-r
mg/Ag/g Trimethylolpropane l/LλOmg/m2 Coating aid: Sodium poly-p-styrene sulfonate
taJmg/m2 (Surface protective layer) Binder: Gelatin 0. rg/m2/jm
g/m2/, J' mg 7m2 Sodium poly-p-vinylbenzenesulfonate Amg/m2 Sliding agent: lIt, 2mg/m2 Matting agent Polymethyl methacrylate fine particles (average particle size 3μ) 0./3mg/m2 Additive : Hydroquinone 200mg/m2 (3)
Measurement of viscosity Table 1 Comparative Compound -/: Sodium poly p-styrene sulfonate From Table 7, adding the compound represented by the general formula [I] of the present invention increases the viscosity of the coating liquid. It turns out that you can. For sample/, before the applied coating solution gelatinized, the coating solution of the layer adjacent to the layer containing the polymer mordant, gelatin, and acidic dye was measured using a B-type rotational viscometer (Newly manufactured by Tokyo Keiki Seisakusho). using aO±o, r
Viscosity was measured at oc.

(4) Evaluation of coated surface condition The coated surface condition of coated samples/~3 was evaluated.

○゛problem ×: There is a surface failure The results are shown in Table 1.

(5) Sensitometry These samples are measured at 2jt 0Ct! It was stored for 7 days after application at a temperature and humidity of %RH. Each sample! After exposure for 17,100 seconds through an optical wedge using a light source with a color temperature of j00, each sample was developed for 206Cy minutes with the following developer. For each fixed, washed, and dried sample,
Photographic sensitivity was measured at a constant density (θ,/optical density) higher than Capri density. These results are shown in Table 1.

As a result, surface defects such as unevenness in the thickness of the emulsion layer occurred, and sample λ caused a decrease in sensitivity due to demordanting of the antihalation dye, but Samples 3 and 2 of the present invention suffered from loss of sensitivity. The coated surface condition can be improved without any problems.

EXAMPLE Samples 7-// were prepared by providing the following layers on a cotriacetylcellulose support.

(Bottom layer) Binder: Gelatin /g/m2 Coating aid: Listed in Table 2 (Antihalation layer) Same as Example-(Intermediate layer) Same as Example-/(Emulsion layer-/) Example- Same as / (emulsion layer-2) Emulsion: Emulsion B used Coating silver: 0g/m2 Binder gelatin Og/m2 High molecular weight dextran/, 2Ag/m2 Sensitizing dye Dye -/ 2, / mg ,
/Ag/g Additive: Cl8H3,0+CH2CH
20-Ming-H! , I mg/Ag/g Trimethylolpropane 4t+20mg/m2 Coating aid: Sodium poly-p-styrene sulfonate
22 mg/m2 (Surface protective layer) Same as Example-/ Regarding these samples, the viscosity measurement of the coating liquid, the evaluation of the coated surface condition, and the measurement of sensitivity were performed in the same manner as in Example-/. The results are summarized in Table 2.

As can be seen from Table 2, the samples of the present invention can improve the coating surface condition without impairing the sensitivity.

Procedural amendment

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide light-sensitive layer on a support, and at least one layer containing an acidic dye, a polymer mordant, and gelatin; A silver halide photographic material characterized in that a layer adjacent to the containing layer contains a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A has at least two copolymerizable ethylenically unsaturated groups, and at least one of them is included in the side chain. represents a monomer unit copolymerized with monomers. B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. E represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer having at least one anionic functional group. x, y, z represent the mole percentage of each component, x is 0 to 50, y is 0 to 99
, z take values from 1 to 90.