JP2676421B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a novel polymer dispersion which is a good mordant for dyes used in photographic systems, and a photographic system using this polymer dispersion. It is about.

"Conventional Technology" In the field of photographic technology, extra light is conventionally added to prevent scattering (irradiation) or reflection (halation) of light in a light-sensitive material to improve the sharpness of the obtained image. It is known to provide a layer containing a substance to be absorbed in a light-sensitive material. For example, an anti-halation layer is provided on the back surface of the support, an anti-halation layer is provided between the support and the photosensitive layer, or an anti-halation layer is provided between the photosensitive layers, or an emulsion layer is dyed to form an anti-irradiation layer. There are ways to do it.

These anti-halation layers or anti-irradiation layers are generally substances that absorb light, such as dyes,
It contains 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 adversely affect the photographic emulsion such as desensitization and fog. That is, when an anti-halation layer containing a dye is provided adjacent to the photosensitive layer, the dye diffuses into the photosensitive layer and absorbs even light necessary for the photosensitive layer to cause desensitization. Alternatively, even if colloidal silver is used, an adverse effect such as an increase in fog is exerted on the adjacent photosensitive layer.

In order to prevent the deterioration of photographic performance due to the diffusion of the dye, a technique has been developed in which various polymers are used as a mordant for the dye, and the diffusion is prevented by mordanting a diffusible dye.

As these polymer mordants, for example, U.S. Pat.
No. 057 discloses a mordant using an alkylamine, and West German Patent No. 1,095,120 discloses a reaction product of urea and polyethyleneimine. However,
Since these polymer mordants lack the ability to carry dyes, the dyes carried on the adjacent photographic light-sensitive layers diffuse and migrate to a considerable extent, causing deterioration of photographic characteristics such as desensitization.

On the other hand, the polymer mordants having a guanidyl ketimine structure described in U.S. Pat.Nos. 2,882,156, 3,740,228, and Japanese Patent Publication No. 49-15820 have excellent mordanting ability with dyes and have the above-mentioned properties. It has been shown to not cause problems.

However, such a polymer mordant requires a large amount of an organic solvent at the time of production, and the production process becomes complicated.
If a large amount of this type of mordant is added to prevent the diffusion of the dye, the adhesion with the adjacent emulsion layer will be deteriorated.

As a means for solving the deterioration of the adhesiveness between the mordant-containing layer and other layers due to the addition of a large amount of these mordants, JP
A method using a polymer dispersion mordant as described in 55-33172 has been proposed, and such a polymer dispersion has excellent ability to mord a dye, and even when used in a large amount, It is shown that the adhesiveness with other layers is not deteriorated.

However, silver halide photographic materials using polymer mordants having such excellent mordant power have high pH.
It was shown that the desorption property of the dye during the treatment was not always good.

Originally, such a polymer mordant improved the sharpness of the image while carrying the dye at the time of exposure, and at the time of processing, lost the mordant ability to release the dye into the processing solution and develop it. It is necessary to prevent the residual dye from affecting the image obtained after the process.

Recently, influence sensitive materials have been shortened in development time with the progress of sensitive materials and processing agents, and a layer containing a higher concentration of dye is provided for the purpose of improving the image quality of the sensitive material. Is desired.

Therefore, even in the polymer mordant used in the anti-halation layer or the anti-irradiation layer, the technique has excellent ability to fix the dye, and can rapidly release the dye, and does not deteriorate the adhesion between the layers. Was strongly desired.

"Problems to be Solved by the Present Invention" The first object of the present invention is that it has excellent mordability, does not deteriorate the photographic characteristics of the other layers, and can rapidly release the dye during processing. Another object is to provide a polymer mordant, and a photographic light-sensitive material containing the same.

A second object of the present invention is to provide a photographic light-sensitive material having the above-mentioned excellent properties and containing a mordant which can be incorporated into a light-sensitive material without deteriorating the adhesion between layers. .

"Means for Solving the Problems" As a result of earnest studies, the present inventor has as a result the following general formula [I] having a protonated ammonium structure.
It has been found that a silver halide photographic light-sensitive material characterized by having at least one mordant layer composed of a polymer dispersion represented by

General formula [I] In the formula, X ¹ and X ² each represent a hydrogen atom or a fluorine atom.

X ³ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. X ⁴ represents a monovalent group containing an alkyl group composed of a hydrocarbon having 9 or more carbon atoms.

A represents a repeating unit having a protonated ammonium structure.

B represents a repeating unit obtained by copolymerizing a copolymerizable monoethylenically unsaturated monomer other than the above.

x, y, and z represent the weight percentage of each component, and x is 5 to 6
The values of 0 and y are 40 to 95, and the values of z are 0 to 55.

The polymer dispersion represented by the general formula [I] in the present invention will be described in detail below.

In the general formula [I], X ¹ and X ² are each a hydrogen atom or
Represents a fluorine atom. X ³ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), or an alkyl group having 1 to 4 carbon atoms (a methyl group, an ethyl group or a butyl group), and a hydrogen atom or a methyl group is particularly preferable.

Among X ⁴ , the hydrocarbon group having 9 or more carbon atoms is an alkyl group having 10 or more carbon atoms (for example, n-decyl group, n-
Dodecyl group, n-hexadecyl group, n-octadecyl group, An alkylene group having 9 or more carbon atoms (for example, CH _{2 n} ,
n = 10, 14, 16 Aralkylene group having 9 or more carbon atoms Aryl groups having 9 or more carbon atoms (for example, 2-t-butylphenyl group, 4-t-butylphenyl group, 2,5-di-t-
Amylphenyl group, 4-t-octylphenyl group), arylene group having 9 or more carbon atoms Is raised. These groups may further have a substituent.

Among these, an alkyl group having 9 or more carbon atoms, an alkynylene group, and an aryl group are preferable, and an alkyl group is particularly preferable.

Represented by the general formula [I] of the present invention Among the ethylenically unsaturated monomers giving the repeating unit represented by the following, examples of monomers in which X ⁴ contains a hydrocarbon group having 9 or more carbon atoms are listed below, but the present invention is not limited thereto.

The repeating unit having a protonated ammonium structure represented by A is specifically represented by the following general formula [II].

General formula (II) In the formula, R ¹ represents a hydrogen atom, a lower alkyl group or an aralkyl group. Q is a single bond or an alkylene group, a phenylene group, an aralkylene group, Represents a group represented by Here, L represents an alkylene group, an arylene group or an aralkylene group, and R represents an alkyl group.

 G isOrAnd R^Two, R^Three, R^Four, R^Five, R⁶, R⁷, R⁸, R⁹Is hydrogen field
Represents an atom, an alkyl group, an aryl group, or an aralkyl group.
However, they may be the same or different from each other,
May have been substituted. X Represents an anion.

Further, any two or more groups of Q, R ² , R ³ , R ⁴ or Q, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are mutually bonded to form a ring structure together with the nitrogen atom. It may be formed.

However, In the formula, at least one of R ² , R ³ and R ⁴ is a hydrogen atom.

More specifically, R ¹ is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl) aralkyl group (eg, benzyl). Are preferred, with a hydrogen atom or a methyl group being particularly preferred.

Q is preferably a divalent optionally substituted alkylene group having 1 to 12 carbon atoms (for example, a methylene group or-(C
H ₂₎ 6 _- group represented by), optionally substituted phenylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms (e.g. Is preferable, and a group represented by the following formula is also preferable.

Here, L is preferably an optionally substituted alkylene group having 1 to 6 carbon atoms, an optionally substituted arylene group or an optionally substituted aralkylene group having 7 to 12 carbon atoms, and preferably has 1 to 6 carbon atoms. Is more preferably an alkylene group which may be substituted.

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

G is The ^{stands, R 2, R 3, R} 4, R 5, R 6, R 7, R 8, R 9 represents an alkyl group or 6 to 20 carbon atoms having a hydrogen atom or 1 to 20 carbon atoms Or an aryl group having 7 to 20
Aralkyl groups having 4 carbon atoms are preferred and may be the same or different. The alkyl group, the aryl group, and the aralkyl group include a substituted alkyl group, a substituted aryl group, and a substituted aralkyl group.

Examples of the alkyl group include unsubstituted alkyl groups (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, cyclohexyl, n-heptyl, n-
-Octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl); the alkyl group preferably has 1 to 12 carbon atoms. More preferably 1 to 10 carbon atoms
Individual. Examples of the substituted alkyl group include an alkoxyalkyl group (eg, methoxymethyl, methoxyethyl,
Methoxybutyl, ethoxyethyl, ethoxypropyl,
Methoxybutyl, butoxyethyl, butoxypropyl,
Butoxybutyl, vinyloxyethyl), cyanoalkyl group (eg, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl), halogenated alkyl group (eg, 2-fluoroethyl, 2-chloroethyl, 3-fluoropropyl), alkoxycarbonylalkyl Group (for example, ethoxycarbonylmethyl), allyl group, 2-butenyl group, propargyl group and the like.

The aryl group is an unsubstituted aryl group (eg, phenyl, naphthyl), and the substituted aryl group is, for example, an alkylaryl group (eg, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4). -Tert-butylphenyl), an alkoxyaryl group (for example, 4-methoxyphenyl), 3-methoxyphenyl, 4-ethoxyphenyl), an aryloxyaryl group (for example, 4-phenoxyphenyl), and the like. The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

As the aralkyl group, an unsubstituted aralkyl group (eg, benzyl, phenethyl, diphenylmethyl, naphthylmethyl); a substituted aralkyl group, eg, an alkylaralkyl group, (eg, 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropylbenzyl) ), Alkoxyaralkyl groups (eg, 4-methoxybenzyl, 4-ethoxybenzyl), cyanoaralkyl groups, (eg, 4-cyanobenzyl), perfluoroalkoxyaralkyl groups,
(For example, 4-pentafluoropropoxybenzyl group, 4
-Undecafluorohexyloxybenzyl group), an aralkyl halide group (eg, a 4-chlorobenzyl group, a 4-bromobenzyl group, a 3-chlorobenzyl group, etc.). The aralkyl group preferably has 7 to 15 carbon atoms, and preferably 7 to 11 carbon atoms. Of these, a benzyl group and a phenethyl group are particularly preferred.

 X Represents an anion, for example, a halogen ion (eg,
For example, chloride ion, bromide ion), alkyl or ant
Sulfonic acid ions (eg, methanesulfonic acid, ethanol
Sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid
Acid, acetate, sulfate, nitrate, etc.
Yes, chloride ion, acetate ion and sulfate ion are particularly preferred.
New

It is also preferable that any two or more groups of Q, R ² , R ³ , and R ⁴ are bonded to each other to form a cyclic structure together with a nitrogen atom. As the cyclic structure formed, a pyrrolidine ring,
Preferred are a piperidine ring, a morpholine ring, a pyridine ring, an imidazole ring, a quinuclidine ring and the like. Particularly preferred are a pyrrolidine ring, a morpholine ring, a piperidine ring, an imidazole ring and a pyridine ring.

In addition, any two or more groups of Q, R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be bonded to each other to form a ring structure together with a nitrogen atom. Is a 6-membered ring or 5
A membered ring is particularly preferred.

Examples of monoethylenically unsaturated monomers in B are ethylene, propylene, 1-butene, isobutene, styrene, α-methylstyrene, vinyl ketone, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate, allyl acetate), Esters or amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (for example methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-
Butyl acrylate, n-hexyl acrylate, 2-
Examples thereof include ethylhexyl acrylate, acrylamide, N-methyl acrylamide), monoethylenically unsaturated compounds (eg, acrylonitrile), and among them, styrene, n-butyl methacrylate, methyl methacrylate and the like are particularly preferable. B may contain two or more of the above monomer units.

Further, as B, in the general formula [II] Among the ethylenically unsaturated monomer units represented by, those in which G does not form a salt structure are also included.

That is, B includes ethylenically unsaturated monomers represented by the following general formulas [III] and [IV].

General formula (III) (R ¹ , R ² , R ³ and Q are the same as above) General formula [IV] ^{(R 1, R 5, R} 6, R 7, R 8, R 9, Q have the same meanings as defined above) x, y, z represent the weight percentages of each component, x is 5
80, y is 20 to 95, z is 0 to 75, preferably x is 5 to 60, y is 40 to 95, z is 0 to 55, and particularly preferably x is 5 to 50, y. Has a value of 50 to 95 and z has a value of 0 to 45.

Hereinafter, examples of preferred mordants of the present invention are listed,
The present invention is not limited thereto (the ratio of each component is expressed as a weight percentage).

The polymer represented by the general formula [I] of the present invention may be directly obtained as a polymer dispersion by emulsion polymerization, or may be obtained as a water dispersion after polymerization by means such as a solution platform. You can

More specifically, the polymer of the present invention is A monomer represented by (for example, N, N-dimethylaminoethyl methacrylate hydrochloride, N, N-diethylaminoethyl methacrylate sulfate, N, N-dimethylaminoethyl acrylate hydrochloride, N, N-diethylaminoethyl acrylate acetate, N , N-Dimethylaminomethylstyrene sulfate, N, N-diethylaminomethylstyrene sulfate, N
-Vinylbenzylpiperidine hydrochloride, N-vinylbenzylmorpholine acetate, 2-vinylpyridine acetate, It can be obtained by a polymerization reaction using a copolymerizable ethylenically unsaturated monomer represented by B.

Further, the polymer represented by the general formula [I] of the present invention is A monomer represented by, an ethylenically unsaturated monomer represented by B, and a general formula (Wherein X represents a halogen atom (eg, chlorine atom, bromine atom), sulfonic acid ester (eg, p-toluenesulfonyloxy group), and R ₁ and Q are the same as those shown above) Monomer (eg β-chloroethyl methacrylate, β-p-toluenesulfonyloxyethyl methacrylate, chloromethylstyrene)
And after polymerization An amine having a structure of (wherein R ² , R ³ and R ⁴ are the same as those described above), (for example, dimethylamine, diethylamine, di-n-propylamine, morpholine, piperidine, etc.) It can also be obtained by doing

Also, G The method for obtaining the polymer represented by A monomer represented by, an ethylenically unsaturated monomer represented by B, and a general formula (Wherein R ¹ , R ⁵ and Q are the same as those described above) (for example, methyl vinyl ketone, methyl- (1-methyl vinyl) ketone, ethyl vinyl ketone, ethyl- (1-methylvinyl) ketone, n-
Propyl vinyl ketone, diacetone acrylamide, diacetone acrylate, etc., particularly preferably methyl vinyl ketone, phenyl vinyl ketone, diacetone acrylamide, diacetone acrylate) (However, R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same as those shown above) (for example, aminoguanidine bicarbonate, N-amino-N′-methylguanidine bicarbonate, N-amino-N'-ethylguanidine bicarbonate, etc., particularly preferably aminoguanidine bicarbonate) is reacted and H 2
It can be obtained by forming a guanidinium salt with a compound represented by -X (H-X is the same as those shown above) (for example, hydrogen chloride, hydrogen bromide, sulfuric acid, acetic acid, nitric acid). .

The above polymerization reaction is preferably carried out by emulsion polymerization.

Emulsion polymerization is generally carried out by using a radical polymerization initiator by emulsifying a monomer in water or a mixed solvent of water and an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.) using an emulsifier, if necessary. ℃ to about 10
It is carried out at a temperature of 0 ° C, preferably 40 ° C to about 90 ° C. The amount of the organic solvent miscible with water is 0 to 300% by volume, preferably 0 to 150% with respect to water.

The polymerization reaction is usually performed for 0.05 to 5
The reaction is carried out by using a radical polymerization initiator by weight and optionally 0.1 to 10% by weight of an emulsifier. Examples of the polymerization initiator include azobis compounds, peroxides, hydroperoxides, redox catalysts, and the like, such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, and 2,4-dichlorobenzoyl peroxide. oxide,
Examples include methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, and 2,2'-azobis (2-amidinopropane) hydrochloride.

Emulsifiers include anionic, cationic, amphoteric and nonionic surfactants as well as water-soluble polymers.
For example, sodium laurate, sodium dodecyl sulfate,
Sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, N-2-ethylhexyl Examples include pyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, emulsifiers described in JP-B No. 53-6190, and water-soluble polymers.

In emulsion polymerization, it goes without saying that the platform initiator, the concentration, the polymerization temperature, the reaction time and the like can be widely and easily changed depending on the purpose.

The above-mentioned reaction with ammonium salt is generally carried out at a temperature of about 5 ° C to about 90 ° C, with 20 ° C to 80 ° C being particularly preferred.

It is also possible to synthesize the above-described polymerization reaction by means of solution polymerization or the like and then dispersing in water to obtain the polymer dispersion mordant of the present invention.

 The synthesis examples of typical polymers of the present invention are shown below.

Synthesis Example 1. (Synthesis of Exemplified Compound P-1) In a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, Emarex NP-30 (Nippon Emulgin Young Co., Ltd.)
1.0 g, lauryl methacrylate 1.0 g, N, N-
Diethylaminomethylstyrene 4.0 g, concentrated sulfuric acid 1.09 g, ethanol 75 ml, and distilled water 75 ml were added, and the mixture was heated and stirred at 80 ° C. under a nitrogen stream. Dimethyl 2,2'-azobisisobutyrate
What melt | dissolved 0.05 g in ethanol 5 ml was added, and stirring was continued for 40 minutes.

Then, 4.0 g of lauryl methacrylate, dimethyl 2,
Each of 2'-azobisisobutyrate 0.10 g dissolved in 50 ml of ethanol and N, N-diethylaminomethylstyrene 16.0 g dissolved in a solution of concentrated sulfuric acid 4.36 g and distilled water 70 ml, respectively, in 1.5 hours. A constant velocity was added dropwise to complete the process. After completion of the dropping, 0.1 g of dimethyl 2,2'-azobisisobutyrate dissolved in 5 ml of ethanol was added twice every 1 hour, and stirring was continued at 80 ° C for 2 hours, and then 150 ml of distilled water was added. Then, the temperature was raised and ethanol was distilled off.

After cooling, the solid support dispersion obtained by passing the solid content 1
The content was 0.1% by weight and the particle size was 1.20 μm (measured by Coulter submicron particle analyzer, Nikkaki Co., Ltd.).

Synthesis Example 2. (Synthesis of Exemplified Compound P-15) In a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, 1.0 g of Emarex NP-30 (commercially available from Nippon Emulsion Co., Ltd.), 1.0 g of lauryl methacrylate, and a cationic monomer. A (see below) 4.0 g, ethanol 75 ml, distilled water
75 ml was added, and the mixture was heated and stirred at 80 ° C under a nitrogen stream. Dimethyl
2,2'-azobisisobutyrate 0.05g ethanol 5ml
The melted mixture was added and stirring was continued for 40 minutes.

Then, 4.0 g of lauryl methacrylate, dimethyl 2,
2'-Azobisisobutyrate 0.10 g dissolved in 50 ml of ethanol, and 16.0 g of cation monomer A in distilled water 70
Each of those dissolved in ml was added dropwise at a constant speed so as to be completed in 1 hour. After completion of the dropping, 0.1 g of dimethyl 2,2'-azobisisobutyrate dissolved in 5 ml of ethanol was added twice every 1 hour, and stirring was continued at 80 ° C for 2 hours, and then 150 ml of distilled water was added. Then, the temperature was raised and ethanol was distilled off.

After cooling, the solid support dispersion obtained by passing the solid content 9.
The content was 5% by weight and the particle size was 0.30 μm (measured by Coulter submicron particle analyzer, Nikkaki Co., Ltd.).

Monomer A (obtained by reaction of diacetone acrylamide with aminoguanidine bicarbonate) Examples of dyes that can be mordanted using the polymer dispersion of the present invention include acid dyes (for example, dyes having a sulfone group, a carboxyl group, a sulfonamide group, a phenolic hydroxyl group, etc.), a sulfone group and a carboxyl group. Acid dyes having the following are preferred, and such dyes include, for example, British Patent Nos. 506,385, 1,177,429, and 1,311,884.
No. 1,338,799, No. 1,385,371, No. 1,467,214,
No. 1,433,102, No. 1,553,516, JP-A-48-85,130,
49-114,420, 52-117,123, 55-161,233
No. 59-111,640, Japanese Patent Publication No. 39-22,069, No. 43-13,
168, U.S. Pat.Nos. 3,247,127, 3,469,985 and 4,0
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in 78,933 etc., U.S. Pat.No. 2,533,472
No. 3,379,533, other oxonol dyes described in British Patent No. 1,278,621, British Patent No. 575,691,
680,631, 599-623, 786,907, 907,125
No. 1,045,609, U.S. Pat.No. 4,255,326, JP-A-59
Azo dyes described in JP-A-211,043, JP-A-50-100,1
No. 16, No. 54-118,247, British Patent No. 2,014,598, No. 75
Azomethine dyes described in U.S. Pat.
Anthraquinone dyes described in 65,752, U.S. Pat.
2,538,009, 2,688,541, 2,538,008, British Patents 584,609, 1,210,252, JP-A-50-40,625,
No. 51-3,623, No. 51-10,927, No. 54-118,247, Japanese Patent Publication Nos. 48-3,286, 59-37,303, etc., arylidene dyes, Japanese Patent Publication Nos. 28-3,082, 44-16,594. ,
59-28,898 and the like styryl dyes, British Patent Nos. 446,583 and 1,335,422, JP-A-59-228,250 and the like triarylmethane dyes described, British Patent No. 1,07
5,653, 1,153,341, 1,284,730, 1,475,228
No. 1,542,807 and the like, merocyanine dyes,
Examples thereof include cyanine dyes described in US Pat. Nos. 2,843,486 and 3,294,539. Also, U.S. Pat.
6, 4294917, JP-A-56-12639, 63-27838.
No. 63-197943, British Patent 1,563,809, European Patent 1
The dyes described in 5601, International Patent (WO) 88/04794 and the like can also be used. Of the above dyes, oxonol dyes having a pyrazolone nucleus are particularly preferable.

Hereinafter, examples of the dye that can be used in the present invention will be described, but the present invention is not limited thereto.

Various additives are further used in the light-sensitive material of the present invention, and these additives are used as research materials.
Item17643 (December 1978) and Item18716 (1979.11)
), And the relevant locations are summarized in the table below.

With respect to various additives and development processing when the light-sensitive material of the present invention is an X-ray film, see, for example, JP-A-2-68
It is possible to use the materials described in the following relevant parts of Japanese Patent No. 539.

Example 1 (1) Preparation of Photosensitive Silver Halide Emulsion Potassium bromide and potassium iodide and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to form a plate-shaped silver iodobromide having an average particle size of 1 μm (average iodine). (10 mol% content) was prepared. Thereafter, the precipitate was washed with water by an ordinary precipitation method, Dye-1 was added thereto, and then chemically sensitized by a gold-sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A. A silver halide emulsion B having a thickness of 0.7 μm (average iodine content: 6 mol%) was prepared in the same manner as in silver halide emulsion A except that the amount of potassium iodide prepared and the preparation temperature were adjusted.
C (average iodine content 10 mol%) was prepared.

(2) Preparation of Application Samples Samples 1 to 9 were prepared by sequentially providing each layer having the following formulation on the triacetyl cellulose support from the support side at the same time.

(Bottom layer) Binder: Gelatin 1 g / m ² Coating aid: Poly p-styrene sulfonate potassium salt 10.0
mg / m ² (Intermediate layer) Binder: Gelatin 0.4 g / m ² Coating aid: Poly p-styrene sulfonate potassium salt 3.3 m
g / m ² (emulsion layer-1) Coating silver amount: Emulsion B 1.5 g / m ² Binder: Gelatin 2 g / m ² Sensitizing dye: Dye-1 2.1 mg / Ag 1 g Additive: C ₁₈ H ₃₅ OCH ₂ CH ₂ O ₂₀ H 5.8 mg / Ag 1 g Coating aid: Poly p-styrene sulfonate potassium salt 50 mg
/ m ² Hardener: 1,2-bis (vinylsulfonylacetamide) ethane 45 mg / m ² (emulsion layer-2) Coating silver amount: Emulsion A 4 g / m ² Binder: Gelatin 6.8 g / m ² Sensitizing dye: Dye-1 2.1mg / Ag1g _{additives: C 18 H 35 OCH 2 CH} 2 O 20 H 5.8mg / Ag1g trimethylolpropane 420 mg / m ² coating aid: potassium poly p- styrene sulfonate 170m
g / m ² Sensitizing dye: Dye-1 is the following structural formula (Surface protection layer) Binder: Gelatin 0.7 g / m ² Coating aid: N-oleoyl-N-methyl taurate sodium salt 0.2 mg / m ² Matting agent: Polymethylmethacrylate fine particles (average particle size 3 μ) 0.13 mg / m ² (3) Measurement of Sensitivity Each sample was exposed to 400 lux tungsten light for 1/10 seconds through an optical wedge, and then subjected to the following automatic processor processing.

Processing liquid temperature x time development HPD (Fuji Photo Film Co., Ltd.) 26.5 ° C x 1 minute Fixing Super Fujitsuku DP (Fuji Photo Film Co., Ltd.) 26.5 ° C x 1 minute Rinse water 16 ° C x 1 minute Dry 50 ° C × 1 minute Fixed, higher than fog density (0.2 optical density) using the same method for each sample fixed, washed with water and dried
Was measured for photographic sensitivity.

 The results are summarized in Table 1.

(4) Evaluation of residual color Each sample was subjected to the automatic processor processing described above ((3) Sensitivity measurement section) in an unexposed state. The residual color at this time was measured with a spectrophotometer. The residual color was composed of mordanting dyes II-1 and II-6 and sensitizing dye Dye-1.
Each contribution is summarized in 1 according to the acceptance level.

(5) Adhesion evaluation between layers For each sample, make 50 squares of 1 cm square on the coated surface with a knife, attach a commercially available polyester adhesive tape made by Nitto Electric Industry Co., Ltd., and attach it At the time of peeling, the area of the coated surface peeled off with an adhesive tape was measured to evaluate the adhesiveness.

From the results in Table 1, it is understood that the compound of the present invention has a high mordant property of the dye, and thus has good sensitivity and is also excellent in terms of residual color. It is also clear that the adhesiveness between the layers is at the same excellent level as that of the conventional cross-linked latex type mordant.

Example 2 A biaxially stretched 175 μm-thick polyethylene terephthalate film was subjected to corona discharge treatment, and a first undercoating liquid having the following composition was applied by a wire bar coater to a coating amount of 5.1 cc / m ^2. And dried at 175 ° C for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface.

On the first undercoat layer on both sides of the above, a second
The undercoating liquid was applied on both sides one by one so that the coating amount was 8.5 cc / m ^2, and dried to complete an undercoated film.

Second undercoat liquid Preparation of Emulsion Layer Coating Solution In water 1, potassium bromide 5 g, potassium iodide 0.05 g, gelatin 30
g, 5 of the thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and maintained at 73 ° C. While stirring, add an aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide in 45 seconds by the double jet method. did. Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of the addition was twice that at the start of the addition. Subsequently, an aqueous solution of 153.34 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 25 minutes by the control double jet method while maintaining the potential at pAg8.1. The flow rate at this time was accelerated so that the flow rate at the end of the addition was eight times the flow rate at the start of the addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and 50 cc of 1% potassium iodide aqueous solution was added to 30 cc.
It was added over seconds. After that, the temperature was lowered to 35 ° C and soluble salts were removed by the precipitation method, then the temperature was raised to 40 ° C and 68 g of gelatin, 2 g of phenol and 7.5 g of trimethylolpropane were added.
PH 6.55, pAg8.1 with caustic soda and potassium bromide.
Adjusted to 0.

After the temperature was raised to 56 ° C., 175 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 625 mg of a sensitizing dye having the following structure were added. After 10 minutes, 5.5 mg of sodium thiosulfate pentahydrate, 163 mg of potassium thiocyanate, 3.chloroauric acid.
6 mg was added and quenched after 5 minutes to solidify. The resulting emulsion had an aspect ratio of 3 with 93% of the total projected area of all grains.
The average projected area diameter of all grains consisting of the above grains and having an aspect ratio of 2 or more is 0.95 μm, standard deviation
23%, the average thickness was 0.155 μm, and the aspect ratio was 6.1.

The following chemicals were added to this emulsion per mole of silver halide to prepare a coating solution.

2,6-Bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80mg Sodium polyacrylate (average molecular weight 41,000) 4.0g Ethyl acrylate / acrylic acid / methacrylic acid =
Copolymer plasticizer with composition ratio of 95/2/3 20.0 g Nitron 50 mg The emulsion layer coating solution thus obtained was similarly coated on both surfaces of the above-mentioned support by coextrusion with the surface protective layer solution. At this time, the coating amount per one side of the emulsion layer and the surface protective layer was as follows.

<Emulsion layer> Silver coating amount 1.9 g / m ² Gelatin coating amount 1.5 g / m ² <Surface protective layer> Gelatin 0.81 g / m ² Dextran (average molecular weight 39,000) 0.81 g / m ² matting agent (average particle size 3.5 μm) Polymethyl methacrylate / methacrylic acid = 9/1 copolymer 0.06 g / m ² 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 15.5 mg / m ² sodium polyacrylate (average molecular weight 41,000) 70 mg /
As the m ² hardener, 1,2-bis (sulfonylacetamido) ethane was applied so as to be 56 mg / m ² per side. Thus,
Photographic materials 10 to 17 of the present invention were obtained.

Evaluation of photographic performance X-ray sensitometry was performed on photographic materials 10 to 17 by making GRENEX Orthoscreen HR-4 of Fuji Photo Film Co., Ltd. in close contact with both sides using a cassette. The adjustment of the exposure amount was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the automatic processor processing was carried out by distributing the following time.

The used developer and fixer had the following compositions.

(Developer) potassium hydroxide 29 g potassium sulfite 44.2 g sodium hydrogen carbonate 7.5 g boric acid 1.0 g diethylene glycol 12 g ethylenediaminetetraacetic acid 1.7 g 5-methylbenzotriazole 0.06 g hydroquinone 25 g glacial acetic acid 18 g triethylene glycol 12 g 5 -Nitroindazole 0.25 g 1-phenyl-3-pyrazolidone 2.8 g glutaraldehyde (50 wt / wt%) 9.86 g sodium metabisulfite 12.6 g potassium bromide 3.7 g Water added 1.0 (fixer) ammonium thiosulfate (70 wt / 200% Ethylenediaminetetraacetic acid disodium salt dihydrate 0.02g Sodium sulfite 15 g Boric acid 10 g Sodium hydroxide 6.7 g Glacial acetic acid 15 g Aluminum sulfate 10 g Sulfuric acid (36N) 3.9 g Add water to bring the total volume to 1 ( The pH was adjusted to 4.25) Sensitivity was expressed as the specific sensitivity with photographic material 14 as 100.

Measurement of Sharpness (MTF) The MTF of the combination of the HR-4 screen and the automatic processor processing was measured. The measurement was performed with an aperture of 30 μm × 500 μm, and the evaluation was performed at a portion where the optical density was 1.0 using an MTF value where the spatial frequency was 1.0 cycle / mm.

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

Regarding the adhesiveness between layers, a sensory test was conducted to see if the coated surface was peeled off when the above-mentioned polyester adhesive tape was attached to the coated sample and peeled off (○ mark: substantially The coated surface is not peeled off. × mark: The film peeled off partially or entirely).

 The above results are summarized in Table 2.

From the results in Table 2, it is clear that the compound of the present invention is capable of significantly improving the residual color without impairing the levels of sensitivity and sharpness, and has excellent adhesiveness between layers. Is.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one mordant layer composed of a polymer dispersion represented by the following general formula [I] having a protonated ammonium structure. General formula [I] In the formula, X ¹ and X ² each represent a hydrogen atom or a fluorine atom. X ³ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. X ⁴ represents a monovalent group containing an alkyl group composed of a hydrocarbon having 9 or more carbon atoms. A represents a repeating unit having a protonated ammonium structure. B represents a repeating unit obtained by copolymerizing a copolymerizable monoethylenically unsaturated monomer other than the above. x, y, z represent the weight percentage of each component, x is 5-60,
The value of y is 40 to 95, and the value of z is 0 to 55.