JPH0442225A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a mordant property by providing a mordant layer formed by adding a specific polymer dispersion or an ethylenic unsatd. monomer having an anionic group to another specific polymer dispersion, then polymerizing the mixture. CONSTITUTION:The mordant layer formed of the polymer dispersion obtd. by adding the polymer dispersion expressed by formula I or the ethylenic unsatd. monomer having the anionic group to the polymer dispersion expressed by formula II, then polymerizing the mixture is provided. In the formulas I, II, X<1>, X<2> denote a hydrogen atom, etc.; X<3> denotes a halogen atom, etc.; X<4> denotes >=9C hydrocarbon group, etc.; A denotes the repeating unit having a protonized ammonium structure; D denotes the repeating unit derived from the ethylenic unsatd. monomer having the anionic group; B denotes the repeating unit formed by copolymerizing the copolymerizable ethylenic unsatd. monomer; w to z and x' to z' respectively denote the weight per cents of the respective components. The excellent mordant property is obtd. in this way and the rapid releasing of the dyestuff is possible.

Description

DETAILED DESCRIPTION OF THE INVENTION ``Industrial Application Field'' The present invention relates to a novel polymer dispersion effective as a good mordant for dyes used in photographic systems, and a photographic method using this polymer dispersion. It's about systems.

"Prior Art" Traditionally, in the field of photographic technology, in order to prevent the scattering (irradiation) or reflection (halation) of light in the photosensitive dye and improve the sharpness of the resulting image, It is known to provide a layer containing a substance that absorbs light in a photosensitive material. For example, an antihalation layer is provided on the back side of the support, an antihalation layer is provided between the support and the photosensitive layer, an antihalation layer is provided between the photosensitive layers, or the emulsion layer is dyed. There is a method of using it as an irradiation prevention layer.

These antihalation layers or antiirradiation layers generally contain light-absorbing substances such as dyes, carbon black, or colloidal silver. However, when these light-absorbing substances are applied in the photosensitive layer or in a layer adjacent to the photosensitive layer, they have adverse effects such as desensitization and increased fog on the photographic emulsion. That is, when an antihalation layer containing a dye is provided adjacent to a photosensitive layer, the dye diffuses into the photosensitive layer and absorbs even 1 of the light necessary for the photosensitive layer, causing desensitization. Alternatively, even if colloidal silver is used, there is no adverse effect such as increased fog on the adjacent photosensitive layer.

In order to prevent such deterioration of photographic performance due to dye diffusion, techniques have been developed that use various polymers as dye mordants to mordant diffusible dyes to prevent diffusion.

These polymeric mordants include, for example, U.S. Pat.
．． 21. , Oj No. 7 discloses a mordant using alkylamines, and West German patent /, 09jr, /,
No. 20 discloses a reaction product of urea and polyethyleneimine. However, these polymeric mordants
Since the ability to support dyes is insufficient, a considerable amount of the dyes supported on the adjacent photographic light-sensitive layer diffuse and migrate, causing deterioration of photographic properties such as desensitization.

On the other hand, Tokukai Akira! j-! The latex mordant described in No. 3/72 and the latex mordant described in U.S. Pat.
．． It has been shown that polymer mordants having a guanidyl ketimine structure, such as those described in 74tO, +2+2g, and Tokko Sho Geta/3g2o, have an excellent ability to mordant dyes and do not cause the above problems. ing.

However, it has been shown that silver halide photographic materials using polymer mordants having such excellent mordant power do not necessarily have good dye desorption properties during high pH processing.

Originally, such a polymer mordant carries a dye during exposure and becomes fc4. It is possible to improve the sharpness of images until the end of processing, and to release the dye into the processing solution by losing the ability to mordant during processing, so that the remaining dye does not affect the image obtained after the development process. is necessary.

Recently, the development time of photosensitive materials has been shortened along with advances in photosensitive materials and processing agents, and polymer mordants used in antihalation and irradiation prevention layers have the ability to fix dyes. There was strong hope for the development of a technology that would not only have superior properties but also rapidly release dyes.

``Problems to be Solved by the Present Invention'' The purpose of the present invention is to develop a polymer that has excellent mordant properties, does not deteriorate the photographic properties of other layers, and can rapidly release dyes during processing. An object of the present invention is to provide a mordant and a photographic feed containing the same.

"Means for Solving the Problems" As a result of extensive studies, the present inventors have determined that the object of the present invention is to obtain a polymer dispersion having a protonated ammonium structure and anionic groups represented by [1] below. A polymer obtained by carrying out polymerization after adding at least seven ethylenically unsaturated monomers having The present invention has been found to be achieved by a silver halide photographic material characterized in that a mordant layer constituted by a polymer dispersion (hereinafter referred to as polymer dispersion (C)) is discarded to a minimum.

- Shipman [I] Xl, X3 Shipman Cl1) i X3 In the formula, Xl and X2 each represent a hydrogen atom or a fluorine atom.

X3 represents a hydrogen atom, a halogen atom, or an alkyl group having a carbon number of /≠. X4 represents a hydrocarbon group having 9 or more carbon atoms or a monovalent group containing at least 7 fluorine atoms.

A represents a repeating unit having a protonated ammonium structure.

D represents a repeating unit derived from at least seven ethylenically unsaturated monomers having an anionic group.

B represents a repeating unit copolymerized with a copolymerizable ethylenically unsaturated monomer other than the above.

w, x, y, z and y', y', 2' are the weight percentages of each component.
%y is O to '70. z takes a value between 1 and 0,
y' means evening and go, y' means 20! , 2' is O
It takes a value between 70 and 70.

Among the polymer dispersions in the present invention, the polymer dispersion represented by general 2N) will be described in detail.

In the general formula [I], X 1 and X 2 represent a hydrogen atom and a fluorine atom, respectively. X3 is a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom), a carbon number/~μ
Table the alkyl groups (methyl group, ethyl group, butyl group) of
However, hydrogen atoms and methyl groups are particularly preferred.

Among X4, examples of the hydrocarbon group having at least 70 carbon atoms include an alkyl group having at least 70 carbon atoms (for example, an n-decyl group,
F"7' syl &, n-hexadecyl i X3 Alkylene group having 7 or more carbon atoms (e.g. +Cll2)
, n-10, /11. , /J's, C1oI-12,
C11c)12) Among the ethylenically unsaturated monomers that give repeating units represented by aralkylene having 9 or more carbon atoms, examples of monomers in which X4 contains a hydrocarbon group having 9 or more carbon atoms are listed below. , but is not limited to this.

The aryl group above ( tylphenyl group, ! -G (-Ami) ruphenyl group), For example, tolyl group, coated t-butyl group, etc. g-1-butylphenyl group, co.

ruphenyl group, ≠-1-octyl group Arylene group with 7 or more carbon atoms These groups may further have a substituent.

Among these, alkyl groups, alkylene groups, and aryl groups having at least the number of carbon atoms are preferred, and alkyl groups are particularly preferred.

Cl-12=CH COOC16H33, C)] 2 =C C00C12■-129, Cl-13 C)+2=C C00C18■137, II3 112-C C00, (l-CI-12fOC113, CH2-CH C0NHC1oH21, C) 12=cll QC-CgHlg, CH2=CI(C0NHC1oH21, CI-]2-Q]0CC11H23 Containing at least 7 fluorine atoms, preferable examples include F, +CF2-), -F group (n-7 ~/θ), R4
-o + cF'2), -, F group (n = / ~ / 0
), -0+C1i"2-)-006F'5 group (n-,2
~J), -COO(-Q(z rabbit tongue CF2 thick) group (m =
/ ~tt, n = /~lO), -COO+el(□VCF2)IT group (m =: /
~II, n = /~10), -COO+OH□-)-NR” 80□-(CF2)F
group (m = i ~ p.

mnn = /~l
o, R5 is an alkyl group having a carbon number of 1 to t), -C(JO(7CH2-)7NR6CO(-CF2-)
-I! ' group (m = / ~ q, n = / ~ 10.R
6 is an alkyl group with carbon number/~≠), 100W) l + C1 (2 → JCF2-iF group (m =
/ ~ II, / ~ 10), 100NN (+CH2 thick CIF'2 YaH group (m =
/ to ~411770), 1000℃C) 12-1. -NR7CO+CF2 Kikukawa group (m = / ~ II.

n = /~/θ, ■ (7 is an alkyl group with carbon number/~t), 10CO+CF2-)-H group (n =-/~/0
), -CO+CF2) F group (1=/~10), -C0
0CH2CH20CO+c)H2SeeCF2GoF Group(m
-/~μ, 0-/to 10), -CO0C)I2CH20CO+CH2廿CF2-H group (m-7~μ, n = /~10'').

Among these, -CO(J(-c)12'), fcF2F group (m-/
Hehiro, n == /~/11)),~OCO+C■I2
(-CFz theory F group (m = / to ≠, xl- / to 1
0), -C00 mark 2CH20CU (CH2seCF2kiF
Group (m2]~μ, n = /~10), -C6H4-COO+CH2-)(-CB'2-)-
The F group m n (m-INμ, n = /~70), -〇〇N)l÷CH2viewCF2yaF group (to m-7≠, n = /~lO) is particularly preferred.

Examples of monomers having at least 7 fluorine atoms in R4 among the ethylenically unsaturated monomers providing repeating units are listed below, but are not limited thereto.

CH3 CH2-C CONHC)1203 F7 (n-)C112-
CH CON(Cold 2CF3)2 CH3 a(2-C COOCH2CH20CC7F15(n-)I CH2=CH Q(2NH8O2CBF17(n-) CH2-C Old Chu2CH2CH3COOCH
2CHCH2N-8O2CBB"17(n -)H (n 7.5) CI-12-C1-1 ■ CF 2CF2 ・Nl-ICH2C31!"7 (n
-)CH3 c')12-C Cαχ old 2CH2C10F21(n-)C112=C,
')4 COOCH2CI'2CgF1g(n)CF2-C
F2 a-12-CF2 / j -/, 4 G set = 01 CH3 CONHC) I2CH2N-C-C2F5Cl-12-
CI4CF3 COOCH2 (-CF20F-i) f H3 C) 12=C coo's 2 mo CF2 YaH CH2-CI (CO0CI-12+CF2 now-H C) I2-CH COOO-12+2 CFs-H CH3 12-C COoCI-12CF The repeating unit having a protonated ammonium structure represented by 20B'HCF 3H2-CH OCO-f-CF2)H A is specifically represented by the following - Shipman [■].

General formula [■] In the formula, 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 group, / g- OOO II II l
l-C-0-1, -1-C-N)] -L- or -C-N
Represents a group represented by R-L-. Here, ■ represents an alkylene group, an arylene group, or an aralkylene group, and I
(represents an alkyl group.

R3, R4, R5, R6, R7, R8, and 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, Q, R2, R3, R4- or Q%R”R1R,R
, H may be bonded to each other to form a ring structure together with the nitrogen atom.

\ At least one is a hydrogen atom.

To explain in more detail, R1 is a hydrogen atom or a lower alkyl group (for example, methyl, ethyl,
n-propyl, n-butyl, n-amyl, n-hexyl)
An aralkyl group (eg benzyl) is preferred, and among these, a hydrogen atom or a methyl group is particularly preferred.

Q is preferably a divalent optionally substituted alkylene group having up to 7 carbon atoms (for example, a methylene group or -(CI
-12) A group represented by 6-), an optionally substituted phenylene group, or an optionally substituted aralkylene group having 7 to 2 carbon atoms (for example, a group represented by Also preferred are the groups shown. -〇-0-L---C-
NI (-LC-N-L) Here, 1 represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted arylene group, having 7 to 1 carbon atoms. An aralkylene group is preferred, and an optionally substituted alkylene group having 1 to 2 carbon atoms is more preferred.

R is preferably an alkyl group having a carbon number of 1 to 3 carbon atoms.

R3, R4, R5, R6, R7, R8, R9 are hydrogen atoms or 7 to . Alkyl radicals having 20 carbon atoms or aryl radicals having 2 to 20 carbon atoms or 7 to! Preference is given to 2/aralkyl groups having 0 carbon atoms, which may be the same or different in each case. The alkyl group, allyl group, and aralkyl group include substituted alkyl groups, substituted aryl groups, and substituted aralkyl groups.

The alkyl group is an unsubstituted alkyl group (for example, methyl,
Ethyl, n-propyl, inpropyl, n-butyl, inbutyl, t-butyl, n-amyl, isoamyl, n-
hexyl, cyclohexyl, n-heptyl, n-octyl, coethylhexyl, n-nonyl, n-decyl, n
-dodecyl); the carbon atom of the alkyl group is preferably 1 to
There are 72 pieces. More preferably, the number of carbon atoms is 70 to 70. 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, ≠-
cyanobutyl), halogenated alkyl groups (e.g. l-fluoroethyl, λ-chloroethyl, 3-fluoropropyl), alkoxycarbonylalkyl groups (e.g. ethoxycarbonylmethyl), allyl groups, 2-butenyl groups, propargyl groups Examples include bases.

Examples of the aryl group include unsubstituted aryl groups (e.g., phenyl, naphthyl), and examples of substituted aryl groups include alkylaryl groups (e.g., comethylphenyl, 3-methylphenyl, Hiro-methylphenyl, gouethylphenyl,
Guisofurohylphenyl, l! -tcrt-i tylphenyl), alkoxyaryl groups (eg, ≠-methoxyphenyl), 3-methoxyphenyl, l-ethoxyphenyl), and aryloxyaryl groups (eg, t-phenoxyphenyl). The number of carbon atoms in the aryl group is preferably J-/≠, more preferably 4-1
There are 0 pieces. Particularly preferred is a phenyl group.

Aralkyl groups include unsubstituted aralkyl groups (e.g. benzyl, phenethyl, diphenylmethyl, naphthylmethyl); substituted aralkyl groups such as alkylararalgyl groups (e.g. goomethylbenzyl, co,!-dimethylbenzyl, t-isopropyl); benzyl), alfkyl/aralkyl groups, (e.g. u<z-methoxybenzyl, Hirokotogishibenzyl), cyanaralkyl groups, (e.g. guccianobenzyl), perfluoroalkoxyaralkyl &
, (Example: Id'y--intafluoropropoxybenzyl group, couundecafluorohexyloxybenzyl group, etc.), halogenated aralkyl group, (Example: Eva, chlorobenzyl a, 4'-bromobenzyl group, 3-chlorobenzyl group, etc.).

The number of carbon atoms in the aralkyl group is preferably 7 to 0! individual,
Preferably it is 7 to // 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 awarsulfonic acid ion (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-)luenesulfonic acid), acetate ion , sulfate ion, nitrate ion, etc., and chloride ion, acetate ion, and sulfate ion are particularly preferred.

It is also preferred that one or more arbitrary groups of Q1R2, R3, and R4 bond to each other to form a cyclic structure together with the nitrogen atom. The cyclic structure formed is preferably a pyrrolidine ring, a piperidine ring, a morpholine ring, a pyridine ring, an imidazole ring, a chimeclidine ring, or the like. Particularly preferred are a pyrrolidine ring, a morpholine ring, a piperidine ring, an imidazole ring, and a pyridine ring.

Furthermore, any two or more groups of Q s ” ”, R6, R7, R8, and R9 may be bonded to each other to form a cyclic structure together with a nitrogen atom, and the cyclic structure formed is Particularly preferred are rings or j-membered rings.

Examples of ethylenically unsaturated monomers in 13 are ethylene, propylene, l-duthene, isobutyne, styrene,
α-methylstyrene, vinyl ketones, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acid monoesters or amides (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, rhohexyl acrylate, coethylhexyl acrylate-1,
acrylamide, N-methylacrylamide), monoethylenically unsaturated compounds (for example, acrylonitrile), or dienes (for example, butadiene, isoprene), among which styrene, n-butyl methacrylate, methyl methacrylate, etc. are particularly preferred. B may contain two or more types of the above monomer units.

Of the ethylenically unsaturated monomer units represented by, those in which G does not form a salt structure can also be excluded.

, 2 z- That is, B includes an ethylenically unsaturated monomer represented by the following -shipman.

Examples include a 5O2H group, a -0PO3H2 group (or a monoalkyl ester group thereof), a -0803FI group, and the like. These anionic groups each have their own salts, such as alkali metal salts (e.g. Na salts), ammonium salts (
For example, it may be in the form of a salt with ammonia, methylamine, dimethylamine, etc.

Examples of ethylenically unsaturated monomers having such anionic functional groups are shown below in non-dissociated form, but are not limited thereto.

(R1, R5, R6, R7, R8, R9, Q are the same as above) The anionic functional group of the ethylenically unsaturated monomer having at least one kind of anionic functional group represented by D is -Cool group, -803I-1 group, a-12-a-
1coocn2cF12ococn2a-+2cooH.

CH3 CH3 2 CH3 C) 12-C COOC) I2CH20S03H As mentioned above, each of these monomers may be used in the form of a salt structure.

WlX, yl z represents the heavy charge percentage of each component, and W is! to 79, or 20 to ”5yFiO to 701
z is / or so, preferably wi; tJ or zOlX is 30fzishiri 0, y is O or! 0. z is from 3 to jO, particularly preferably W is from j to 0
, X is HiroO or ZS.

y is O to 30. z is 3 to aO.

Representative examples of mordants of the present invention represented by the general formula CI) are listed below, but the present invention is not limited thereto (the ratio of each component is expressed in weight percentage).

/ x/y/z, 20/73/j ko3 / low p- p-// C) T3 I-J3 The synthesis of the polymer represented by the general formula [■] of the present invention is carried out by emulsion polymerization. is preferred.

To explain in detail, the polymer of the present invention is the above-mentioned XI
R1CH3COO" x / y / z = 2!; /! 0 /
2! p-/, I I-13 CH3COO0 N-dimethylaminoethyl acrylate hydrochloride, N,N-dimethylaminoethyl acrylate acetate, N.

N-dimethylaminomethylstyrene sulfate, N.

N-diethylamine methylstyrene sulfate, N-vinylbenzyl bilysine hydrochloride, N-vinylbenzylmorpholine acetate, covinylpyridine hydrochloride, υH31Ntj 2 3'1 3! - C) T2. =CHCI (copolymerizable ethylenically unsaturated monomer represented by 3 B,
It is preferable to synthesize it by a polymerization reaction using an ethylenically unsaturated monomer having an anionic group.

In addition, the polymer 2 X2 of the present invention represented by the general formula [I] may be an ethylenically unsaturated monomer, an ethylenically unsaturated monomer having an anion l, and a general formula (where X is...
unsaturated monomers (e.g. β-chloroethyl methacrylate, β-p-)luenesulfonyloxyethyl meccrylate, chloromethylstyrene), R, R
%R is the same as shown above) (for example, dimethylamine, diethylamine, moro-propylamine, morpholylamine, piperidine, etc.) to form an ammonium salt.

Emulsion polymerization is generally carried out by emulsifying monomers in water or a mixed solvent of water and water-miscible organic solvents (for example, methanol, ethanol, acetone, etc.) using an emulsifier as necessary, and using a radical polymerization initiator. to about 10 o 0 C1 preferably a, o 0 c to about 1 o l
)C. The organic solvent miscible with water has a volume ratio of O to 300 ($, preferably O to
I'm in charge of iro.

In the polymerization reaction, the monomers to be polymerized are usually
! % by weight of radical polymerization initiator and optionally 0.7~
10 layers! -% emulsifier. Examples of polymerization initiators include azobis compounds, peroxides, hydroperoxides, redox catalysts, etc., such as potassium persulfate, ammonium persulfate, and tert-butylnoξ-
1.2. ! -dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydro/me oxide, dicumyl peroxide, azobisisobutyratetrile, λ1.2' azobis(2-amidinopropane) hydrochloride, and the like.

Examples of emulsifiers include anionic, cationic, amphoteric, and nonionic surfactants as well as water-soluble polymers. For example, sodium laurate, sodium dodecyl sulfate, l
-octoxycarbonylmethyl-/-sodium octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, lithium laurylbenzenesulfonic acid, sodium lauryl phosphate, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, Examples include N-J-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, hollyhinyl alcohol, an emulsifier described in Japanese Patent Publication No. 33-J/90, and water-soluble polymers.

In emulsion polymerization, depending on the purpose, a polymerization initiator,
It goes without saying that the concentration, polymerization temperature, reaction time, etc. can be varied widely and easily.

The above reaction to form the ammonium salt is generally carried out at a temperature of about 0C to about 0C, but especially at a temperature of 2oC-
1o'C is preferred.

Furthermore, it is also possible to synthesize the polymer dispersion mordant of the present invention by performing the above polymerization reaction by means such as solution polymerization and then dispersing it in water.

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

Synthesis Example/(Synthesis of Exemplary Compound p-/) A stirring device and a reflux condenser were equipped. In a goOml Mitsuro flask, Emarex NP-3o (commercially available from f3 emulsion ■)/Og, lauryl methacrylatene,
Og, N, N-diethylamine methylstyrene 2.91
g1 concentrated sulfuric acid 0.77g.

Acrylic acid 0.23g, ethanol 7s mA's
7 ml of distilled water was added, and the mixture was heated and stirred at RO 0C under a nitrogen stream. Dimethyl λ,2'-azobisisobutyreto0. Ojg was added to ethanol/jm/ and the mixture was stirred for to minutes.

Then, add 7.0 g of lauryl methacrylate 1 dimethyl co, 2'-azobisisobutyrate O0l O 0 g to ethanol! ;Those combed to 0ml/l, and
N,N-diethylamine methylstyrene//, 9g concentrated sulfuric acid, 0♂g, acrylic acid/, Og and distilled water 70m7
of each dissolved in a solution of l.

The dropwise addition was carried out at a uniform rate so that it was completed in 1 hour. After finishing dropping, dimethyl! ,,2'-azobisisobutyrate 0.1g
was dissolved in 1 ml of ethanol and added twice every hour. After stirring with a TOOC for 2 hours, 1 ml of distilled water was added, the temperature was raised, and the ethanol was distilled off.

After cooling, the polymer dispersion obtained by e-filtering had a solid fraction of 9.
．． The particle diameter was 0.3.2 μm (measured by Coulter submicron particle analyzer, Nikkaki ■).

Synthesis Example 2 (Synthesis of Exemplary Compound P-q) In a 6 ooml three-necked flask equipped with a stirring device and a reflux condenser, Emarex NP-30 (commercially available from Nippon Emulsion Mari)/
Add Og, 7.0 g of lauryl methactulate, 3.7 g of cationic monomer A (see below), 0.3 g of acrylic acid, 76 ml of distilled water and 76 ml of distilled water under a nitrogen stream.
The mixture was heated and stirred at 0°C. Dimethylco, 0.0g of 2'azobisinbutyrate in ethanol! The dissolved material was added to m7, and stirring was continued for ≠θ minutes.

After that, 41.0g of lauryl methacrylate and 0010g of dimethyl co-2'-azobisisobutyrate were added to ethanol! and cationic monomer Alt, 1g1 acrylic acid/.

A solution of Kog in 70 rrJ of distilled water was added dropwise at a uniform rate to complete the addition in 7 hours. After finishing dropping, add dimethyl, 2. ．． 2'-azobisisobutyre) (Ill.

/g dissolved in ethanol tm7 7:1141
Add distilled water every other time and continue stirring at 0°C for 2 hours. 0 ml was added and the temperature was raised to distill off the ethanol.

After cooling and filtering, the obtained polymer dispersion had a solid content of 7.
2% by weight, and a particle size of 0.2jtμm (measured by Coulter submicron particle analyzer, Nikkaki ■).

Monomer A (obtained by reaction of diacetone acrylamide and aminoguanidine bicarbonate) C'l-12=CHC)13 Next, among the polymer dispersions of the present invention, a polymer represented by general formula [II] A polymer dispersion (C) obtained by adding at least one ethylenically unsaturated monomer having an anionic group to the dispersion (a) and then performing polymerization.
I will explain about it.

-Xl, X', X3, X4, A, and B of the boatman [■] are the same as those mentioned in the explanation of general 2N) above.

X', y/z/ represents the weight percentage of each component,
X' is O or Shiri" s Y' is 2! O or Shiri!, 2
' is from O to 1,70, preferably X' is from 0 to 0, y' is from 4 to 9, and Z' is from 0 to 10.
Especially, X' is especially good! No, O1y' is I
O to 9, Z' is O to 30.

At least the ethylenically unsaturated monomer having an anionic group/glaze added to the above polymer dispersion (a) is of the same group of compounds as explained under D in the above-mentioned item [l]. It is chosen from among them.

In the present invention, two or more types of ethylenically unsaturated monomers having at least seven types of anionic groups may be added to the polymer dispersion (a).

Moreover, at that time, an ethylenically unsaturated monomer having no anionic group may be used in combination.

Examples of the ethylenically unsaturated monomer that may be used in combination include compounds selected from the same group as the ethylenically unsaturated monomer represented by B, as described above.

In the present invention, the amount of the ethylenically unsaturated monomer having an anionic functional group to be added is determined based on the monomer dispersion (a
The total amount of amino groups and their ammonium salts in ) can be changed as necessary, but it is preferable that the molar range is from < to SOO, and 4141° is particularly preferable! % to 20,000 mol%.

However, when the monomer having an anionic group is used in the form of a salt structure, the amount added is preferably in the range of J mole to the ammonium salt in the polymer dispersion (a).
Particularly preferred is 3 to 70 mol%.

In addition, the ethylenically unsaturated monomer that does not have an anionic group and is used in combination can be added in any amount as needed, but the monomer that has an anionic group has a
The amount added is preferably from 0 to 100 molar, particularly preferably from 0 to 100 molar.

Below, the polymer dispersion (C) used in the present invention
A polymer dispersion (a) having a protonated ammonium salt for However, the present invention is not limited thereto.

(Ratio of each component in polymer dispersion (a) and polymer (b)
) The ratio of each component in weight<zt represents the weight percentage ratio, and the ratio of (a) and (b) is the total amount of amine groups and their ammonium salts and the anionic functional group (a) having I-13 Represents the molar percentage ratio of monomers.

/ (a) H3 COO)l x/y y7r3 (a): (b) 33.3 x / y = / 7/za3 (weight ratio) (a) 0 (3) (b) +Cl-12C14-) (a) (b) 2g3 / (b) (-(J, 12CH→.

X / y = / 7 / J’ 3ψ o’3 Inside ゛1′ σ　′seedling゛ During ~ 3'8 σ　9 ε.

o'8 σ 0'3 - Polymer dispersion (a) represented by Shipman CI (') is an emulsion 1 similar to the polymer dispersion represented by - Shipman [1] above.
It is legal and can be synthesized conveniently.

It can also be obtained by performing a polymerization reaction by means such as solution polymerization and then dispersing it in water.

Next, the polymerization solution of ethylenically unsaturated monomers containing anionic monomers in the present invention will be explained.

First, a polymer dispersion (a
), an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having at least /i anionic functional groups is added. The entire amount may be added instantly, or may be added dropwise over several minutes to about an hour.

The temperature during addition of the monomer is not particularly limited, but is preferably in the range of z'C to go 0c. It is still preferable to stir the polymer dispersion during addition. The addition of ethylenically unsaturated monomers makes the monomer itself
If necessary, a co-solvent (e.g., water or methanol, ethanol, zolopanol, etc.) may be added.
The solution may be diluted and dissolved in an organic solvent such as acetone, ethyl acetate, acetonitrile, or a mixed solvent thereof.

Polymerization of these post-added ethylenically unsaturated monomers can be carried out using a method similar to that of a normal solution polymerization reaction.

The polymerization reaction is generally carried out at a temperature of from about 300C to about 100C, preferably from about 100C to about 900C.

In addition, the polymerization reaction can be carried out using a radical initiator with a heavy lid for the ethylenically unsaturated monomer to be polymerized. Radical initiators that can be used include:
Those selected from the same group as those mentioned above can be used. This radical initiator may be added after the addition of the ethylenically unsaturated monomer is completed, or may be added simultaneously with the ethylenically unsaturated monomer or before addition.

Further, in the polymerization reaction, the above-mentioned emulsifier may be further added as necessary.

It goes without saying that in the polymerization reaction of ethylenically unsaturated monomers of the present invention, the polymerization initiator, concentration, polymerization temperature, reaction time, etc. can be varied widely and easily.

The polymerization rate of the polymer dispersion when adding the ethylenically unsaturated monomer of the present invention is preferably higher, preferably from 0% to 00%, and particularly preferably from 100% to 100%.
It is.

As mentioned above, in the present invention, the addition needle of the ethylenically unsaturated monomer south of the anionic functional group to be added is necessary for the total amount of amino groups and their ammonium salts in the polymer dispersion (a). It can be changed depending on the situation, but preferably/no! 00 moles, especially preferably! It's about 200 moles.

However, when using a hexamer having an anionic group in the form of a salt structure, the amount added is preferably from / to 9 t mol based on the ammonium salt in the polymer dispersion (a).
Particularly preferred is 3 to 70 mol.

In addition, the ethio-3-lenically unsaturated monomer that does not have an anionic group and is used in combination can be added in any amount as required, but the amount is between O and 200 mol relative to the monomer that has an anionic group. The amount of deer added is preferably 1,000 to 100 mol, which is favorable for erection.

The polymer dispersion (C) of the present invention is produced by first adding an anionic single needle to a cationic polymer dispersion and then carrying out polymerization in order to coexist with an anionic polymer. It has characteristics. As a result, a stable polymer dispersion can be obtained even when an anionic polymer is present.

Furthermore, the polymer dispersion (C) of the present invention can be produced in all steps in one container, is extremely easy to produce, and does not require the use of a large amount of solvent.

A synthesis example of the polymer dispersion (C) of the present invention is shown below.

Synthesis Example 3 (Synthesis of Exemplified Compound Q-2) Synthesis of Polymer Dispersion (a) A stirrer and a reflux condenser were equipped. j00m13 Into a Mitsuro flask, put Emmalex NP-30 (commercially available from Nippon Emulsion ■) 1. Og, lauryl meta! 73 ml of Guclidi-1/0, 73 ml of distilled water and 7 ml of distilled water were added, and the mixture was heated and stirred at 0°C under a nitrogen stream. A solution of 0.03 g of dimethylco,2'azobisin butyrate in 1 ml of ethanol was added, and stirring was continued for ≠θ minutes.

After that, lauryl methacrylate≠. Og1 dimethyl2
,, 0.10g of 2'-azobisisobutyrate in ethanol! and N,N-diethylamine methylstyrene it. .

g dissolved in a solution of 11.3 Ag of starch sulfuric acid and 70 mJl of distilled water were added i.g. was added dropwise at a uniform rate so that it was completed within an hour. After the dropwise addition, 0.1g of dimethyl 2,,2'azobisisobutyrate dissolved in Sml of ethanol was added once every hour, and stirring was continued for 2 hours at go 0c, followed by distilled water/30m13 was added, and the temperature was raised to distill off the ethanol.

After cooling, the obtained polymer dispersion had a solid content of 10
．． 1% by weight, particle size/#Opm (measured by Coulter submicron particle analyzer, Nikikaki ■).

0 Polymerization of acrylic acid in polymer dispersion (a) 100 g of the synthesized polymer dispersion (a) was placed in a reaction vessel, and acrylic acid/. Koi g (
A solution of -COOH/total nitrogen atoms -l/λ) dissolved in 20 g of distilled water was added dropwise over 2 minutes. After dropping, heat to 700C and add λ1.2'-azobis(,2-amidinopropane) hydrochloride (v
- Commercially available from Wako Tsumugi Pharmaceutical ■ under the name of jo) 0.02g was added to distilled water jm. The solution dissolved in d was added twice every hour, and the temperature was further raised to 1rO0C and stirring was continued for 3 hours.

After cooling, filter thoroughly to reduce the solid content. O≠% by weight, particle size l.

A polymer dispersion of 0.05 μm (measured by the same method as above) was obtained.

Synthesis Example t (Synthesis of Exemplified Compound Q-//) Synthesis of Polymer Dispersion (a) In a 300ml Mitsuro flask equipped with a stirrer and a reflux condenser, Emarex NP-J o (commercially available from Nippon Emulsion G) )1. Og, lauryl methacrylate/. Og, cationic monomer A (see below) 'l,
O g, Erno/shi7 jtJ, distilled water 73ml
The mixture was heated and stirred at 0°C under a nitrogen stream. Dimethyl λ,2'-azobisisobutyreto o. org dissolved in ethanol jm7 was added, and stirring was continued for μθ minutes.

Then, 0.10 g of lauryl methacrylate II, Og, dimethyl, 2,,2'-azobisisobutyrate dissolved in ethanol, and cationic monomer A ll,, Og dissolved in 70 ml of distilled water were each dissolved. The dropwise addition was carried out at a uniform rate so that it was completed in 1 hour. After finishing dropping, add dimethyl co. λ′Azobisisobutyrate O0
/g dissolved in ethanol jm13 was added once every 7 hours, and stirring was continued for 2 hours at go 0c, then 110ml of distilled water was added, the temperature was raised, and the ethanol was distilled off.

After cooling and filtering, the obtained polymer dispersion had a solid size of 3" 7 !% by weight particle diameter of 0.30 μm (as measured by Coulter Submicron Particle Analyzer, Nikikaki ■).

Polymerization of acrylic acid in monomer A-0 polymer dispersion (a) The synthesized polymer dispersion (a) was placed in a 100-gum reaction vessel, and while stirring at room temperature under a nitrogen stream, acrylic acid O, I 7
t (C0OH/a%iWt./JL child-containing key=
' /λ :) The mixture was dissolved in distilled water λθV and added dropwise for a total of 2 minutes. After dropping, heat to 7θ0C and add λ1.2'-Azohis(2-amidinopropane).
Hydrochloride (under the name of V-so, sold by Wako Tsumugi (Kikieri)) O002V Total 7 bath liquids dissolved in 1ml of distilled water
Add 11-2 times every hour, add to V, gooC, and stir for 3 hours. continued. During cooling, solid concentration J and g, 3% overlapping, particle size/. A polymer dispersion vIJ of λjμm (M11′)j: ) was obtained using the separate description and circular method.

g Dyes that can be mordanted using the polymer dispersion of the present invention include acid dyes (for example, dyes having a sulfone group, carboxyl group, sulfonamide group, phenolic hydroxyl group, etc.); Preference is given to acidic dyes having groups, such dyes being described, for example, in British Patent No. JOt, 313, Ibid., /77, l
/-2nd issue, same/.

3//, za, r4 issue, same/, 331,799, same/
, 3zaj, 37/issue, same/, 4+, Otsu 7. ．． 2/j issue,
Same/, No. 4133.102, Same/, 333. Jet issue, JP-A-13,130, same≠9-/141.1
No. 120, same J Co.//7. /No.23, same jj-/l/
, No. 233, same! Tar///, 1g O, special public service 1977-
2.2. Ot9, 4t3-13゜lt1, U.S. Patent No. 3. Ko≠7, /, No. 27, Same 3,≠tq, Riza!
The oxonol dyes having a pyrazolone nucleus or a barbylic acid group described in US Pat. J'33.4! No. 72, 3,379,3
Other oxonol dyes described in British Patent No. 33, British Patent No. 1.27g, T, 2j, etc., British Patent No. 373.79
/ issue, same AIO, t3/ issue, same! 99, t23, F
J7J &, Pθ7, same 07, /, 2! No., same/,
04tj, t09, U.S. Patent No. 11,2j, f, 3
．． No. 2, azo dyes described in JP-A No. 1989-1999-/θθ, No. 0413, etc., No. 2//Z, (
6JJ4-//1,2117, British Patent No. 2,0/I
I.

59g issue, same 7! θ, No. 037, etc., and the azomethine dyes described in U.S. Patent No. 2. ZaA! , No. 732, U.S. Pat. 31
．． No. 00za, British Patent No. sgt, t, t.

No. 9, same/, No. 210.23.2, JP-A-Sho to-vo
, tJj number, same j/-J, t+23 number, same ri10.9
．． No. 27, 41-//♂, 24t77-1 Special Publication Showa 41
．． The azomethine dye described in Za-3, 21, No. 37,303, etc., Tokko Sho 2g3.0! , No. 2,
Same goo/ni,! Styryl dye described in Tag No., f9-2za, No. 19g, etc., British Patent No. 4tllt, 6
No. 13, same/, 333.4t, No. 22, JP-A-Sho J-9-
2,21,230 etc., British Patent No. 1°07, f, t! No. 3, same / ,
/! 3.3111, same/, 21! -, 730th issue, same/, 4t7ta, 22g issue, same/,! 41. ．． 2,107
Merocyanine dyes described in U.S. Patent Nos. 1 and 1
113. 'Art No. 3, . Examples include cyanine dyes described in No. 2911,639 and the like. In addition, U.S. Patent No. ,! t3. Za09
No., European Patent No. 111,0j, International Patent (WO), rI
Dyes described in R10'179'1 etc. can also be used. 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.

II-/ ■-17/ ■ Geyu■ 20■ / 3 ■ /1% ■ j ■ / ■ / ■ / ♂ ■-2! [-21 11-, 27 ■--ta■-27 Various additives are further used in the photosensitive material of the present invention, and these additives are listed in Research Disclosure I
tem/7&4tJ (/97J', July 2, 2015) and Item/J'7/& (/ri7, July 1997), and the relevant parts are summarized in the table below. .

Chemical sensitizer 2 Sensitivity enhancer/Brightener Anti-stain agent Dye image stabilizer Hardener Binder Plasticizer, lubricant, p. 23, 241. page,! ! Page right column 2! Page 2A page 2 to page, page 27 high page right column ditto 2! θ Page left to right column tsi Page left column Same as above tto right column Regarding various additives and development processing when the light-sensitive material of the present invention is an X-ray film, see, for example, JP-A-KOKAI Hirakoto tl.
Those described in the following relevant sections of Publication No. J39 can be used.

Item Relevant location/Halogenated milk JP-A No. 6 and J39 Agent Toso TVFJJ method From the second line from the bottom of the bottom column of No. g to the second line from the bottom of the bottom column of page io of the same page.

λ Chemical sensitization method From the top column/line 3 of page io of the same page to the line 2 of the bottom left column of the same page.

3. Antifoggant - Stable from line 7 in the lower left column of page 1 O of the same page] Line 7 of the upper left column of page 1 and from line λ of the upper and lower left column of the 3rd page to the negative pressure lower column of the same page.

G Spectral sensitizing dye From the Hiro row of the lower column of the μth column to the lower column of the same column.

! Surfactant / When charged from line 7 μ in the upper left column on page 11 J)-Sai 1 Skin 2 on page 72, upper left column, line 9
Slippery agents and plasticizers from line IO in the upper left column of No. 1.2. line,.

7 / The the law of nature / 0 hydrophilic colloid hard film agent support Hold body Processing power method From line 7.2, upper column // line Same lower left column/second row.

From line 1/7 of the upper and lower left columns of 7.2 Page 13, top right column, line A.

From page 73, top right column, line 7, Oth row.

Same number 1! From the top left column of the page Line 13 in the lower left column.

Example/A dye layer was coated on a polyethylene terephthalate transparent support having a thickness of 0 μm to which an undercoat layer was coated so as to have the structure shown in Table 1 below.

Here, the polymer mordant was 0.0% in sample 1. The amount of AAg/m2 was applied, and samples λ to g were applied so that the number of cation sites was the same as that of sample 1.

The depth of the trench was 0, If 3 g/m 2 , and the coating was performed so that the numbers of cation sites in Samples 9 and 10 were the same.

The gelatin concentration of the coating solution used here was 3°, twt
%, and the surfactant was applied to this pH 7.0 buffer solution at 2j 0C at 7.
After being immersed for 0 minutes, it was washed with water and dried. In cases where the immobilization was insufficient, the optical density of the dye decreased due to this treatment.

As a hardening agent, 2-bis(sulfonylacel-amido)ethane was used.

The p■■ of the coating solution was adjusted to S and O using NaOH.

The value obtained was evaluated as a fixed rate.

Evaluation of residual color (decolorization): Automatic processing was carried out at the following time intervals.

0 Evaluation of dye fixation rate: A buffer solution of pH 7.0 was prepared using potassium dihydrogen phosphate/sodium hydroxide system.

Dry to Dry processing time 4j seconds The developer and fixer used had the following compositions.

(Developer) Potassium hydroxide Potassium sulfite Sodium bicarbonate Boric acid Diethylene glycol Ethylene diamine Tetraacetic acid j-Methylbenzotriazole Hydroquinone Glacial acetic acid Triethylene glycol! -Nitroindazole l-phenyl-3-pyrazolidone geltaraldehyde (jOwt/wt) Add sodium metabisulfite potassium bromide water (fixer) Ammonium thiosulfate (70wt/vo1%) t 9g 4t41. , +2g 7, jg /, Og 12g /, 7g O, Otg 2jg 1g 12g O, +23g λ, fg 9, IAg /2. Ag 3.7g l, θl,! 00m/1 Ethylenediaminetetraacetic acid disodium dihydrate 0.02g Sodium sulfite 13g Boric acid
10g sodium hydroxide
&, 7g glacial acetic acid
13g aluminum sulfate 10g
Add sulfuric acid (77N) J and 9g water to make the total amount/73 (pl (adjusted to ldg 0.2o)) After this automatic processor treatment, the optical density of the dye of the treated sample was measured. .

The above experimental results are summarized in Table-λ.

In addition, the dye fl-po is the G concentration of Macbeth, and ■≠3 is B
The density was measured and defined as optical density.

From the results shown in Table C, it is clear that the polymer dispersion of the present invention has a fixation rate equivalent to that of the comparative sample, and is superior in that it has extremely little residual color.

Example! (1) Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring, and silver iodobromide (average iodine content 10 mol%) was prepared. After that, it is washed with water by the usual precipitation method, and Dye-/
(7) After that, chemical sensitization was carried out by a gold/sulfur sensitization method using chlorauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A.Similar to silver halide emulsion A, however, By adjusting the amount of potassium iodide and the temperature of preparation, o, 7
μ plate-like silver halide emulsion B (average iodine content 2
(mol%) and C (average iodine content iomol%) were prepared.

(2) Preparation of coated samples Samples // to /9 were prepared by sequentially applying each layer of the following formulation on a triacetyl cellulose support at the same time from the support side.

C bottom layer) Binder; Gelatin / g 7 m 2 Coating aid; Poly p-styrene sulfonic acid potassium salt 10. Omg/m2 (binder layer) Surfactant: Binder (intermediate layer) Binder coating aid (emulsion layer-/coating silver amount binder sensitizing dye additive 'coating aid, gelatin 1g7m2: gelatin 0,4tg/m2 poly p-
Potassium styrene sulfonate salt 3.3 mg/m2 Emulsion 13 1.5 g 7 m2 Gelatin 2 g 7 m 2Dye-/
, 2. /mg/Ag/ gC18H350+CH2C
H2O H j , I mg /A, g / g poly■) - styrene g.

Hardener: (Emulsion layer-2 Coated silver amount Binder Sensitizing dye additive: Sulfonic acid potassium salt jOmg/m2 /, 2-bis(vinylsulfonylacetamide) ethane jmg/m2
Emulsion A g/m2 gelatin
t, zag/m 2Dye-/, 2. /m
g/Ag/g01811350(-CII.Cl-12
0 Momme evening, g mg / Ag / g Ruatrimethylololopane poly p-styrene sulfonic acid potassium salt II, 20 mg / m2 Coating aid / 70 mg / m2 g' / Sensitizing dye: Dye- / has the following structure Formula (surface protective layer) Binder: Gelatin 0, 7 g/m
2 Coating aid, N-oleoyl-N-methyltauric acid sodium salt 0.2 mg/m2 Matting agent: Polymethyl methacrylate fine particles (average particle size 3p) 0,/jmg/m2 (3
) Measurement of Sensitivity Each sample was exposed to ttoolux tungsten light for 1710 seconds through an optical wedge, and then subjected to the following automatic processor treatment.

Processing solution temperature x time development I-IPD x A,
s 0CX/min (manufactured by Fuji Photo Film ■) Gradual Super Fuji Fix DP 2A, s 0C
X/min (manufactured by Fuji Photo Film) Rinse with running water #;'CX/
Dry for 0 minutes
The same method was used for each sample fixed for cX 1 minute, washed with water, and dried at a constant density (O) higher than the fog density.

Photographic sensitivity was measured at (optical density).

The results are summarized in Table 3.

(4) Evaluation of residual color Each sample was processed in an automatic processor as described above ((3) Measuring sensitivity) in an unexposed state. The residual color at this time was measured using a spectrophotometer. The residual color was composed of the mordant dye Ti's[-1 and the sensitizing dye Dye-/;
3 summarizes each contribution by acceptable level.

From the results in Table 3, it can be seen that the compounds of the present invention are excellent in dye mordanting properties, and are particularly excellent in terms of residual color. However, when evaluating the sharpness, the sample &/J' was
It showed a sufficiently superior image quality compared to A/-2.

Example 3 A biaxially stretched polyethylene terephthalate film with a thickness of 7 J-μm was subjected to corona discharge treatment, and a first undercoating liquid having the composition shown below was applied in an amount of 3. /cc/m2
Apply with a wire percoter so that /73
It was dried at 0C for 7 minutes. Next, a first undercoat layer was provided on the opposite side in the same manner.

A first undercoat liquid having the composition shown below was coated on the first undercoat layer on both sides at a coating amount of 1. The coated film was coated on one side and both sides at a rate of jcc/m2 and dried to complete a primed film.

First undercoat liquid 10 Gelatin log 0 g Lamb solution 2 0, 3 cc Average particle size,! μm polymethyl methacrylate 0, jg, 1-■
Preparation of additive emulsion layer coating solution so that 20 dota... is 71. Jg of potassium bromide and 0.0 of potassium iodide in water il! g.

Gelatin 30g 1 thioether HO (Q(.)2S(CI-(2)28(CI-42)
201-((7) j % water m liquid J.

Into the solution to which jCC was added and maintained at 73°C, an aqueous solution of 33 g of silver nitrate was added with stirring, and the bromidation power IJ, f.

911 g and an aqueous solution containing 0.72 tg of iodizing power I) by the double jet method. Added in seconds. Subsequently, calico bromide (Jg) was added, and then an aqueous solution containing 33g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of addition was twice that at the start of addition. Subsequently, an aqueous solution of 3.3 kg of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 2j minutes by a controlled double jet method while maintaining the potential at pAgJ',/. The flow rate at this time was accelerated so that the flow rate at the end of addition was r times the flow rate at the start of addition. After the addition is complete, 2N potassium thiocyanate solution/! Add cc and further 1% potassium iodide aqueous solution! Occ was added over 30 seconds. After that, the temperature was lowered to 3!0C and soluble salts were removed by the sedimentation method, and then the temperature was raised to Hiro00C, gelatin zrg, phenol 2g1 and trimethylolpropane 7.3g were added, and soluble soda and potassium bromide were added. pI4x, tt, pAgJ',
/θ.

After increasing the temperature to tx 0c, t-hydroxy-
t-methyl-/,3,3a,7-chitrazaindene/7
jmg and t2jfIng of a sensitizing dye having the following structure were added. Thiosulfuric acid after 70 minutes) IJumj hydrate 3.3m
g1 Potassium thiocyanate/l! , 3mg.

Chloroauric acid 3. tmg was added, and the mixture was rapidly cooled to a boiling point and solidified. The resulting emulsion has a total projected area of 93
is composed of particles with an aspect ratio of 3 or more, and the average projected area diameter of all particles with an aspect ratio of - or more is 0. The average thickness is 5μm, the standard deviation is g, 23, and the average thickness is 0.7ta sμ! η and the aspect ratio was &, /.

Copolymerized plasticizer with a composition ratio of 0 ethyl acrylate/acrylic acid/methacrylic acid = 9 nitrone/2/3. Og 60mg 2H5 The following chemicals were added per mole of silver halide to this emulsion to form a coating solution (~).

0,! , 4Nibis(hydroxyamino)-≠-diethylamino-/, 3. j-) Reazine
gOmgo Sodium polyacrylate (average molecular weight 1%, /10,000) II, OgThe resulting emulsion layer coating solution and the surface protection layer solution were coated in the same manner on both sides of the support by a coextrusion method. At this time, the amounts of the emulsion layer and surface protective layer coated on one side were as follows.

<Emulsion layer> 0 Coated silver amount /, 9 g/m20 Coated gelatin amount /, tg/m2 Surface retention layer> O gelatin O0♂/ g/m
20 dextran (average molecular weight 390,000) 0.1/g/m2Q matting agent (average particle size 3.5 μm) copolymer of polymethyl methacrylate/methacrylic acid = 9/l 0,01 g/m2JOm
g/m2. 20mg/m2 o CBF17SO2N(CH2CH20)4(CH2
)4SO3NaC3H7umg/m2 oC8F17SO2N(a-■2C)I20)□5I]
4t hydroxymethyl- /, 3.3a, 7 tetrazaindene /! , jmg/m2 0 Sodium polyacrylate (average molecular weight, / 10,000) 70mg/m2 The hardener is I1.2-bis(sulfonylacetamido)ethane on one side! ; It was coated so that it became Amg/m2. In this way, photographic materials 20 and 27 of the present invention were obtained.

Evaluation of photographic performance Photographic materials 20 to 27 include Fuji Photo Film GREN
EX Orthoscreen HR-p was brought into close contact with both sides using a cassette, and X-ray sensitometry was performed. The exposure needle was adjusted by changing the distance between the X-ray tube and the cassette. After exposure, processing was carried out using an automatic processor using the developer and fixer described in Examples. Sensitivity was determined by photographic standard and specific sensitivity with 20 as ioo.

Measurement of Sharpness (MTF) The MTF was measured using the combination of the above-mentioned 11R-Hiro screen and automatic processor processing. Measured with an aperture of 30 μm x 00 μm, and the spatial frequency is /, 0 cycles/m
Using the MTF value of m, the optical density/tachometer was estimated at the portions i and o.

Measurement of remaining color After the unexposed film was subjected to the above-mentioned automatic development process, it was passed through a Macbeth Status A filter and the green transmission density was measured. On the other hand, the green transmission density of the unprimed back dyed polyethylene terephthalate support was measured, and the net value obtained by subtracting this value was evaluated as the residual color density value.

The following results are listed in Table 1.

Note/) Amount of mordant: sample &20 /2. Ag, sample shop 2
For cores 7 to 7, the amount of mordant was changed so that the molar ratio of the cation site of the mordant to the dye was the same as Samples A and 20.

From the table results, it is clear that the compounds of the present invention are excellent in that they can significantly improve residual color without impairing the sensitivity and sharpness levels.

Claims (1)

[Scope of Claims] A polymer dispersion represented by the following general formula [I] having a protonated ammonium structure or at least one ethylenically unsaturated monomer having an anionic group is prepared by the following general formula [II] 1. A silver halide photographic light-sensitive material, comprising at least one mordant layer composed of a polymer dispersion obtained by polymerization after addition to a polymer dispersion represented by the formula. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, X^1 and X^2 each represent a hydrogen atom or a fluorine atom. represent. X^3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. X^4 represents a hydrocarbon group having 9 or more carbon atoms or a monovalent group containing at least one fluorine atom. A represents a repeating unit having a protonated ammonium structure. D represents a repeating unit derived from at least one ethylenically unsaturated monomer having an anionic group. B represents a repeating unit copolymerized with a copolymerizable ethylenically unsaturated monomer other than the above. w, x, y, z and x', y', z' represent the weight percentage of each component, w is 5 to 70, x is 20 to 90,
y takes a value from 0 to 70, z takes a value from 1 to 50, and x'
takes a value of 5 to 80, y' takes a value of 20 to 95, and z' takes a value of 0 to 70.