JP2003114504A - Fluorine compound, surfactant, water-based coating composition containing the same and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stably producible silver halide photographic sensitive material provided with antistatic performance. SOLUTION: In the silver halide photographic sensitive material having one or more layers including a photosensitive silver halide emulsion layer on the base, one of the layers contains a compound of formula (1) wherein R<1> and R<2> are each substituted or unsubstituted alkyl but at least one of R<1> and R<2> is fluorine substituted alkyl; R<3> -R<5> are each H or a substituent; X<1> , X<2> and Z are each a divalent linking group or a single bond; M<+> is a cationic substituent; and m is 0 or 1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine compound and a surfactant capable of imparting surface functions such as water / oil repellency, antifouling property and antistatic property, and an aqueous coating composition using the same. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, a compound having a fluorinated alkyl chain has been known as a surfactant. Such surfactants have unique properties of the fluoroalkyl chain (water and oil repellency,
Various surface modifications can be carried out due to its lubricity, antistatic property, etc., and it is used for the surface treatment of a wide range of base materials such as fibers, cloth, carpets, resins and the like. Further, when a surfactant having a fluorinated alkyl chain (hereinafter referred to as a fluorine-containing surfactant) is added to an aqueous medium solution of various substrates, a uniform film can be formed without cissing during the film formation. Not only that, the adsorption layer of the surfactant can be formed on the surface of the substrate, and the above-mentioned unique property of the fluorinated alkyl chain can be brought to the surface of the coating film.

Various surfactants are used in photographic light-sensitive materials and play an important role. The photographic light-sensitive material is usually prepared by individually coating a plurality of coating solutions containing an aqueous solution of a hydrophilic colloid binder (eg gelatin) on a support to form a plurality of layers. Often, simultaneous multilayer coating of multiple hydrophilic colloid layers is also performed. These layers include an antistatic layer, an undercoat layer, an antihalation layer, a silver halide emulsion layer, an intermediate layer, a filter layer, a protective layer, etc., and various materials for expressing each function are contained in each layer. Is added. Further, a polymer latex may be contained in the hydrophilic colloid layer to improve the physical properties of the film. In addition, color couplers, UV absorbers,
In order to contain a water-insoluble functional compound such as a fluorescent whitening agent or a sliding agent in the hydrophilic colloid layer, these materials are used as they are or high-boiling organic compounds such as phosphate ester compounds and phthalate ester compounds. It may be used for preparing a coating solution by emulsifying and dispersing in a hydrophilic colloid solution in a state of being dissolved in a solvent. As described above, generally, the photographic light-sensitive material is composed of various hydrophilic colloid layers, and at the time of its production, the coating liquid containing various materials is uniformly applied at high speed without defects such as cissing and coating unevenness. Is required. In order to meet such a demand, a surfactant is often added to a coating solution as a coating aid.

On the other hand, photographic light-sensitive materials are manufactured, photographed,
Contact with various substances during the development process. For example, in the processing step, when the photosensitive material is in a wound state,
The back layer formed on the back surface of the support may come into contact with the surface layer. Further, it may come into contact with stainless steel, a rubber roller, or the like when it is conveyed in the processing step. When contacted with these materials, the surface of the light-sensitive material (gelatin layer) is likely to be positively charged, and in some cases causes unnecessary discharge, leaving an undesired exposure mark (called static mark) on the light-sensitive material. It will be. A compound having a fluorine atom is effective for reducing the chargeability of gelatin, and a fluorine-based surfactant is often added.

[0005]

As described above, the surfactant, especially the fluorine-based surfactant is a coating aid for imparting the homogeneity of the coating film, or an antistatic property for the photographic light-sensitive material. It is used as a material that plays a role in, for example, JP-A-49-46733, JP-A-51-33222, JP-A-57-64228, JP-A-64-536, JP-A-2-141739, and JP-A-2-141739. -95550
Specific examples thereof are disclosed in Japanese Laid-Open Patent Publication No. 4-248543 and the like. However, these materials do not always have satisfactory performance in response to the recent demand for higher sensitivity and higher speed coating of photographic light-sensitive materials, and further improvements in fluorine-based surfactants are desired. Generally, shortening the chain length of the perfluoroalkyl chain is considered to be advantageous in terms of decomposability (decomposability of the compound after use), but the orientation of the fluorinated alkyl chain on the surface of the coating is significantly reduced. To do. Thus, having a shorter fluoroalkyl chain,
Further, there is a strong demand for the development of a fluorosurfactant capable of satisfying both the surface orientation (related to antistatic property) and the homogeneity of the coating film.

The present invention provides a novel fluorine compound having a short perfluoroalkyl group and excellent in surface orientation and capable of forming a uniform coating film when used for forming a coating film, and a novel fluorine compound and an interface containing the same. It is an object to provide an activator. Another object of the present invention is to provide an aqueous coating composition capable of forming a coating film that is homogeneous and has antistatic properties. Further, it is an object of the present invention to provide a silver halide photographic light-sensitive material which can be stably produced and which has antistatic properties.

[0007]

In order to solve the above problems, the silver halide photographic light-sensitive material of the present invention has a silver halide photographic material having on a support one or more layers including a light-sensitive silver halide emulsion layer. In the light-sensitive material, one of the layers contains a compound represented by the following general formula (1).

[0008]

[Chemical 4]

In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, but at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom. R
³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, X ¹ , X ² and Z each independently represent a divalent linking group or a single bond, and M ⁺ represents a cationic substituent. Represent Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1.

In a preferred embodiment of the present invention, the outermost layer has a non-photosensitive hydrophilic colloid layer, and the outermost layer contains the compound represented by the general formula (1). A silver halide photographic light-sensitive material; the above-mentioned silver halide photographic light-sensitive material containing the compound represented by the general formula (1) and an anionic or nonionic surfactant in the outermost layer. Further, as a preferred embodiment of the present invention, the compound represented by the general formula (1) is represented by the following general formula (1-a), and a more preferred embodiment. The compound represented by the general formula (1) is represented by the following general formula (1-c)
The above silver halide photographic light-sensitive material is provided.

[0011]

[Chemical 5]

Where R¹¹And R^{twenty one}Respectively replace or
Represents an unsubstituted alkyl group, but R ¹¹And R^{twenty one}Little
At least one represents an alkyl group substituted with a fluorine atom.
And R ¹¹And R^{twenty one}Has a total carbon number of 19 or less.
R¹³, R¹⁴And R¹⁵Are independently replaced or absent
Represents a substituted alkyl group and is bonded to each other to form a ring.
May be. X¹¹And X^{twenty one}Are independently -O-,-
S- or -NR³¹Represents-, R³¹Is a hydrogen atom or
Represents a substituent, and Z represents a divalent linking group or a single bond. Y
^-Represents a counter anion, but when the charge is 0 in the molecule
For Y^-It does not have to be. m is 0 or 1.

[0013]

[Chemical 6]

In the formula, n ¹ is an integer of ¹ to 6 and n ² is 3 to 8
2 (n ¹ + n ² ) is 19 or less.
R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group, which may be bonded to each other to form a ring. X ¹¹ and X ²¹ are each independently -O-,-
S- or -NR ³¹ - represents, R ³¹ represents a hydrogen atom or a substituent, Z is represents a divalent linking group or a single bond. Y
^- represents a counter anion, when the intramolecular charge is 0 Y ^- may not be. m is 0 or 1.

In a preferred embodiment of the present invention, the photosensitive silver halide emulsion layer contains an emulsion in which tabular grains having an aspect ratio of 3 or more account for 50% or more of the total projected area. The above silver halide photographic light-sensitive material is provided.

In order to solve the above problems, the present invention provides a fluorine compound represented by the general formula (1-a), a surfactant containing a compound represented by the general formula (1-a), and the above. Provided is an aqueous coating composition containing a compound represented by formula (1-a).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In addition, in this specification, "-" shows the range which includes the numerical value described before and after that as a minimum value and a maximum value, respectively.

[Fluorine compound and surfactant] First,
The fluorine compound and the surfactant of the present invention will be described. The fluorine compound of the present invention is represented by the following general formula (1). The fluorine compound of the present invention can be used as a surfactant.

[0019]

[Chemical 7]

In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, and at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom. R
³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, X ¹ , X ² and Z each independently represent a divalent linking group or a single bond, and M ⁺ represents a cationic substituent. Represent Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1.

In the general formula (1), R ¹ and R ² each represent a substituted or unsubstituted alkyl group. The alkyl group has 1 or more carbon atoms and may be linear, branched or cyclic. As the substituent,
Examples thereof include a halogen atom, an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, and a phosphoric acid ester group. However, at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom (hereinafter, the alkyl group substituted with a fluorine atom is referred to as “Rf”).

Rf is an alkyl group having 1 or more carbon atoms and substituted with at least one fluorine atom, and Rf may be substituted with at least one fluorine atom, and may be linear, branched or cyclic. The structure may be.
Further, it may be further substituted with a substituent other than a fluorine atom, or may be substituted only with a fluorine atom. R
As the substituent of f other than the fluorine atom, an alkenyl group,
Examples thereof include an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group and a phosphoric acid ester group.

Rf is preferably a fluorine-substituted alkyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 4 to 10 carbon atoms. As a preferable example of Rf,

[0024]

[Chemical 8]

And the like.

More preferably, Rf has a tri-terminal.
Alky having 4 to 10 carbon atoms substituted with a fluoromethyl group
Group, particularly preferably-(CH₂)_n1-(CF₂)
_n2It is an alkyl group having 3 to 10 carbon atoms represented by F (n
¹Represents an integer of 1 to 6. n²Represents an integer of 3 to 8).
Specifically, -CH₂-(CF₂)₂F,-(CH₂)₆−
(CF₂)_FourF,-(CH₂)₃-(CF₂)_FourF, -CH₂
-(CF₂)₃F,-(CH₂)₂-(CF₂)_FourF,-(C
H₂)₃-(CF₂)_FourF,-(CH₂)₆-(CF ₂)_FourF,
-(CH₂)₂-(CF₂)₆F,-(CH₂)₃-(C
F₂)₆F,-(CH ₂)₂-(CF₂)₆F etc.
It Among these, in particular,-(CH₂)₂-(CF₂)_Four
F and-(CH₂)₂-(CF₂)₆F is most preferred.

In the general formula (1), it is preferable that both R ¹ and R ² represent Rf.

When R ¹ and R ² each represent an alkyl group other than Rf, that is, an alkyl group which is not substituted with a fluorine atom, the alkyl group is a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms. , And more preferably a substituted or unsubstituted alkyl group having 6 to 24 carbon atoms. Preferred examples of the unsubstituted alkyl group having 6 to 24 carbon atoms include:
n-hexyl group, n-heptyl group, n-octyl group, t
ert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-
Hexyldecyl group, octadecyl group, eicosyl group, 2
-Octyldodecyl group, docosyl group, tetracosyl group,
Examples thereof include 2-decyltetradecyl group, tricosyl group, cyclohexyl group, cycloheptyl group and the like. Further, preferred examples of the alkyl group having 6 to 24 total carbon atoms having a substituent include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, β-phenethyl group,
2-methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-
Phenyl dodecyl group, 18-phenyl octadecyl group,
Examples thereof include a 12- (p-chlorophenyl) dodecyl group and a 2- (diphenylphosphate) ethyl group.

The alkyl group other than Rf represented by R ¹ and R ² is more preferably C 6-18.
Is a substituted or unsubstituted alkyl group. 6 to 1 carbon atoms
Preferred examples of the unsubstituted alkyl group of 8 include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,
1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and the like can be mentioned. Preferred examples of the substituted alkyl group having a total carbon number of 6 to 18 having a substituent include a phenethyl group, a 6-phenoxyhexyl group, and a 12-
Examples thereof include a phenyldodecyl group, an oleyl group, a linoleyl group and a linolenyl group.

The alkyl group other than Rf represented by R ¹ and R ² is particularly preferably n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-hexyl group. Nonyl group, 1,1,3
-Trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, oleyl group, linoleyl group, linolenyl group, most preferably having 8 to 16 carbon atoms. It is a linear, cyclic or branched unsubstituted alkyl group.

In the general formula (1), R ³ , R ⁴ and R ⁵
Each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 carbon atom).
To 20, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, for example, methyl group, ethyl group, isopropyl group, tert-butyl group,
n-octyl group, n-decyl group, n-hexadecyl group,
A cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like), an alkenyl group (preferably having a carbon number of 2 to 20, more preferably a carbon number of 2 to 12, and particularly preferably a carbon number of 2 to 8). , Vinyl group, allyl group, 2-butenyl group, 3-pentenyl group and the like), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). An alkynyl group of, for example, a propargyl group, a 3-pentynyl group and the like), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms). An aryl group, for example, a phenyl group, a p-methylphenyl group, a naphthyl group and the like), a substituted or unsubstituted amino group ( It is preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, Examples include dibenzylamino group),

Alkoxy group (preferably having 1 to 2 carbon atoms)
0, more preferably a C1-C12, particularly preferably a C1-C8 alkoxy group, for example, a methoxy group, an ethoxy group, a butoxy group and the like), an aryloxy group (preferably a carbon number of 6). To 20, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as a phenyloxy group,
2-naphthyloxy group and the like), acyl group (preferably having a carbon number of 1 to 20, more preferably having a carbon number of 1).
To 16 and particularly preferably an acyl group having 1 to 12 carbon atoms, for example, an acetyl group, a benzoyl group, a formyl group,
Pivaloyl group and the like), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl group, Ethoxycarbonyl group and the like), aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 carbon atoms).
An aryloxycarbonyl group of 10 and, for example,
Phenyloxycarbonyl group and the like), acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetoxy group, benzoyl group). Oxy groups and the like),

Acylamino group (preferably having 2 to 2 carbon atoms)
0, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as an acylamino group, for example, an acetylamino group, a benzoylamino group and the like), an alkoxycarbonylamino group (preferably a carbon number of 2 to 2). Two
0, more preferably an alkoxycarbonylamino group having 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms,
For example, a methoxycarbonylamino group and the like, an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms) And, for example, a phenyloxycarbonylamino group and the like, a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms).
6, particularly preferably a sulfonylamino group having 1 to 12 carbon atoms, for example, a methanesulfonylamino group, a benzenesulfonylamino group and the like), a sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably a carbon number). 0 to 16, particularly preferably a sulfamoyl group having 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group and a phenylsulfamoyl group), a carbamoyl group (preferably Is a carbamoyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group and a phenylcarbamoyl group. ),

Alkylthio group (preferably having 1 to 2 carbon atoms)
0, more preferably an alkylthio group having 1 to 16 carbon atoms, and particularly preferably an alkylthio group having 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group. An arylthio group (preferably 6 to 20 carbon atoms) is more preferable. It is preferably an arylthio group having 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group and the like, and a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms). 16, particularly preferably 1 to 1 carbon atoms
A sulfonyl group having 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms). Group, for example, a methanesulfinyl group, a benzenesulfinyl group, etc.), a ureido group (preferably having a carbon number of 1 to 1).
20, more preferably a ureido group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include an unsubstituted ureido group, a methylureido group, a phenylureido group, and the like, and a phosphoramide group. (Preferably a phosphoric acid amide group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms;
Diethylphosphoric acid amide group, phenylphosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group Group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 12 heterocyclic groups, for example, heterocyclic groups having a hetero atom such as nitrogen atom, oxygen atom, sulfur atom, for example, imidazolyl group, pyridyl group, quinolyl group, furyl group. , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably, A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

R ³ , R ⁴ and R ⁵ are preferably an alkyl group or a hydrogen atom, more preferably a hydrogen atom.

In the above formula, X¹And X²Are each divalent
Represents a linking group or a single bond. Regarding the divalent linking group
Is not particularly limited, but is preferably an arylene group or -O.
-, -S- or -NR³¹-(R³¹Is a hydrogen atom or
Represents a substituent, and the substituent is R ³, R^FourAnd R^FiveIs that
The same as the examples of the substituents respectively represented,³¹As preferred
Is an alkyl group, the aforementioned Rf or hydrogen atom,
More preferably a hydrogen atom) or
Groups obtained in combination, more preferably -O-,-
S- or -NR³¹Is. X¹And X²Better as
More preferably, -O- or -NR³¹-And more preferred
Is -O- or -NH-, particularly preferably -O.
−

In the above formula, Z represents a divalent linking group or a single bond. The divalent linking group is not particularly limited,
Preferably an alkylene group, an arylene group, -C (= O)
-, -O-, -S-, -S (= O)-, -S (= O) ₂
—Or —NR ³² — (R ³² represents a hydrogen atom or a substituent, and the substituent is the same as the examples of the substituent represented by R ³ , R ⁴ and R ⁵ , and R ³² is preferably an alkyl group or hydrogen. Atom, and more preferably a hydrogen atom), or a group obtained by combining them, and more preferably an alkylene group having 1 to 12 carbon atoms and 6 to 1 carbon atoms.
2 arylene groups, -C (= O)-, -O-, -S-,
-S (= O) -, - it is a single or a group obtained by their combination - S (= O) ₂ - or -NR ^32. More preferably as Z, an alkylene group having 1 to 8 carbon atoms, -C
(= O)-, -O-, -S-, -S (= O)-, -S
(═O) ₂ — or —NR ³² — is a group obtained alone or in combination thereof, and includes, for example,

[0038]

[Chemical 9]

And the like.

In the above formula, M ⁺ represents a cationic substituent, and M ⁺ is preferably an organic cationic substituent, more preferably an organic cationic group containing a nitrogen or phosphorus atom. A pyridinium cation or an ammonium cation is more preferable, and a trialkylammonium cation represented by the following general formula (2) is more preferable.

[0041]

[Chemical 10]

In the above formula, R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group. As the substituent, those mentioned as the substituents of R ³ , R ⁴ and R ⁵ can be applied. If possible, R ¹³ , R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. R
¹³ , R ¹⁴ and R ¹⁵ preferably have 1 to 12 carbon atoms.
Is an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group, an ethyl group,
It is a methylcarboxyl group, and particularly preferably a methyl group.

In the above formula, Y ⁻ represents a counter anion, which may be an inorganic anion or an organic anion. Further, when the charge becomes 0 in the molecule, Y ⁻ may be omitted. The inorganic anion is preferably iodine ion, bromine ion, chlorine ion or the like, and the organic anion is preferably,
Examples thereof include p-toluenesulfonate ion, benzenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion and the like. More preferably as Y ⁻ , an iodine ion, a p-toluenesulfonate ion,
Benzenesulfonate ion, more preferably p-
It is toluene sulfonic acid.

In the above formula, m represents 0 or 1, preferably 0.

Among the compounds represented by the above general formula (1), the compound represented by the following general formula (1-a) is preferable.

[0046]

[Chemical 11]

Where R¹¹And R^{twenty one}Respectively replace or
Represents an unsubstituted alkyl group, but R ¹And R²Less
And one represents an alkyl group substituted with a fluorine atom,
R¹¹And R^{twenty one}Has a total carbon number of 19 or less. R¹³, R
¹⁴And R¹⁵Are independently substituted or unsubstituted
Represents a kill group, which may be bonded to each other to form a ring.
Yes. X¹¹And X^{twenty one}Are independently -O-, -S- or
Or-NR³¹Represents-, R³¹Is a hydrogen atom or a substituent
And Z represents a divalent linking group or a single bond. Y ^-Is a pair
Represents an anion, but when the charge in the molecule becomes 0, Y
^-It does not have to be. m is 0 or 1. In the formula, Z
And Y^-Are respectively those in the above general formula (1) and
It is synonymous and the preferable range is also the same. R¹³, R¹⁴,
R¹⁵For m and m, refer to the above general formula (1).
And the preferred range is also the same.
It

In the formula, X ¹¹ and X ¹² are respectively —O—,
-S- or -NR ³¹ - (R ³¹ represents a hydrogen atom or a substituent, as preferably as .R ³¹ can be applied, those exemplified as the substituent for the R ^3, R ⁴ and R ⁵ are the substituents An alkyl group, the aforementioned Rf, or a hydrogen atom,
More preferably, it is a hydrogen atom). X ¹¹ and X
²¹ is more preferably -O- or -NH-, and further preferably -O-.

In the above formula, R ¹¹ and R ²¹ have the same meanings as R ¹ and R ² in formula (1), respectively, and the preferred ranges are also the same. However, the total carbon number of R ¹¹ and R ²¹ is 19 or less. m is 0 or 1.

Among the compounds represented by the above general formula (1), the compounds represented by the following general formula (1-b) are preferable.

[0051]

[Chemical 12]

In the formula, R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group, which may be bonded to each other to form a ring. Z represents a divalent linking group, and A and B each represent a fluorine atom or a hydrogen atom. n ¹ represents an integer of ¹ to 6, and n ² represents an integer of 3 to 8. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. In the formula, Z and Y ⁻ have the same meanings as those in the above general formula (1), respectively, and the preferable ranges are also the same. R ¹³ , R ¹⁴ , R ¹⁵ and m have the same meanings as those in the general formula (1), respectively, and the preferred ranges are also the same. A and B are preferably fluorine atoms.

Among the compounds represented by the above general formula (1), the compounds represented by the following general formula (1-c) are more preferable.

[0054]

[Chemical 13]

In the formula, n ¹ is an integer of ¹ to 6 and n ² is 3 to 8.
2 (n ¹ + n ² ) is 19 or less.
R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a substituted or unsubstituted alkyl group, which may be bonded to each other to form a ring. X ¹¹ and X ²¹ are each independently -O-,-
S- or -NR ³¹ - represents a. R ³¹ represents a hydrogen atom or a substituent, and Z represents a divalent linking group or a single bond. Y
^- represents a counter anion, when the intramolecular charge is 0 Y ^- may not be. m is 0 or 1. In the formula, Z and Y ⁻ have the same meanings as those in the above general formula (1), respectively, and the preferable ranges are also the same.
R ¹³ , R ¹⁴ , R ¹⁵ and m have the same meanings as those in the general formula (1), respectively, and the preferred ranges are also the same.

N ¹ represents an integer of ¹ to 6, preferably 1
Represents an integer of 3 to 3, more preferably 2 or 3,
Most preferably it is 2. n ² represents an integer of 3 to 8,
It is more preferably 3 to 6, and even more preferably 4 to 6.
Is. A preferred combination of n ¹ and n ² is n ¹
Is preferably 2 or 3 and n ² is 4 or 6.

Specific examples of the compound represented by the above general formula (1) are shown below, but the present invention is not limited to the following specific examples. In the structural description of the exemplified compounds below, unless otherwise specified, an alkyl group and a perfluoroalkyl group mean a linear structure. Moreover, 2EH of the abbreviations in the notation means 2-ethylhexyl.

[0058]

[Chemical 14]

[0059]

[Chemical 15]

[0060]

[Chemical 16]

[0061]

[Chemical 17]

[0062]

[Chemical 18]

[0063]

[Chemical 19]

[0064]

[Chemical 20]

[0065]

[Chemical 21]

[0066]

[Chemical formula 22]

[0067]

[Chemical formula 23]

[0068]

[Chemical formula 24]

[0069]

[Chemical 25]

[0070]

[Chemical formula 26]

[0071]

[Chemical 27]

Next, the above general formulas (1) and (1-
An example of a general synthetic method for the compounds represented by a), (1-b) and (1-c) (hereinafter, these may be collectively referred to as “the compound of the present invention”) is shown. The invention is not limited to these. The compounds of the present invention are
It can be synthesized using a fumaric acid derivative, a maleic acid derivative, an itaconic acid derivative, a glutamic acid derivative, an aspartic acid derivative or the like as a raw material. For example, when a fumaric acid derivative, a maleic acid derivative or an itaconic acid derivative is used as a raw material, it can be synthesized by subjecting their double bond to a Michael addition reaction with a nucleophilic species and then cationization with an alkylating agent. .

[Aqueous Coating Composition] The fluorine compound of the present invention is preferably used as a surfactant in a coating composition for forming layers constituting various recording materials (in particular, silver halide photographic light-sensitive materials). To be Above all, it is particularly preferable to use it for forming the hydrophilic colloid layer of the uppermost layer (outermost layer) of the photographic light-sensitive material because it is possible to obtain effective antistatic ability and coating uniformity. Hereinafter, the coating composition containing the fluorine compound of the present invention as a surfactant will be described.

The aqueous coating composition of the present invention contains the surfactant of the present invention and a medium in which the surfactant is dissolved and / or dispersed. In addition, other components may be appropriately contained depending on the purpose. In the aqueous coating composition of the present invention, the medium is preferably an aqueous medium. The aqueous medium includes water and a mixed solvent of water and an organic solvent other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, etc.). In the present invention, the medium of the coating composition preferably contains water in an amount of 50% by mass or more.

In the aqueous coating composition of the present invention, one type of the compound of the present invention may be used alone, or two or more types may be mixed and used. Further, other surfactants may be used together with the compound of the present invention. Examples of the surfactant that can be used in combination include various anionic, cationic and nonionic surfactants. The surfactant used in combination may be a polymer surfactant or a fluorine-based surfactant other than the compound of the present invention. The surfactant used in combination is more preferably an anionic or nonionic surfactant. Examples of the surfactant that can be used in combination include, for example, JP-A-62-215272 (649-
706), Research Disclosure (RD) Item1
7643, pp. 26-27 (December 1978), id. 18
716, 650 (November 1979), ibid. 30710
5, 875-876 pages (November 1989) and the like.

Typical examples of the other components which may be contained in the aqueous coating composition of the present invention include polymer compounds. The polymer compound may be a polymer soluble in an aqueous medium (hereinafter referred to as “soluble polymer”) or an aqueous dispersion of polymer (so-called polymer latex). The soluble polymer is not particularly limited, and examples thereof include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the like. Polymer latex includes various vinyl monomers [eg, acrylates. Or a copolymer of a derivative, a methacrylate derivative, an acrylamide derivative, a methacrylamide derivative, a styrene derivative, a conjugated diene derivative, an N-vinyl compound, an O-vinyl compound, vinyl nitrile, and other vinyl compounds (eg ethylene, vinylidene chloride). , A dispersion of a condensation polymer (for example, polyester, polyurethane, polycarbonate, polyamide). Specific examples of this type of polymer compound are disclosed, for example, in JP-A-62-215272 (707 to 76).
Page 3), Research Disclosure (RD) Item 176
43, 651 (December 1978), id 18716.
650 pages (November 1979), 307105, 87.
Examples thereof include polymer compounds described on pages 3 to 874 (November 1989).

The aqueous coating composition of the present invention may contain various other compounds, and they may be dissolved or dispersed in a medium. For example, when it is used for forming a constituent layer of a photographic light-sensitive material, various couplers, ultraviolet absorbers, color mixture preventing agents, antistatic agents, scavengers, antifoggants, hardening agents, dyes, antifungal agents, etc. You can Further, as described above, the aqueous coating composition of the present invention is preferably used for forming the hydrophilic colloid layer which is the uppermost layer of the photographic light-sensitive material. (E.g. gelatin) and other than the fluorine compound of the present invention, other surfactants and matting agents,
A sliding agent, colloidal silica, gelatin plasticizer and the like can be contained.

The amount of the compound of the present invention to be used is not particularly limited, and it may be used depending on the structure of the compound to be used, its use, the kind and amount of the material contained in the aqueous composition, the constitution of the medium and the like. Can be arbitrarily determined. For example, when the aqueous coating composition of the present invention is used as a coating liquid for the hydrophilic colloid (gelatin) layer of the uppermost layer of a silver halide photographic light-sensitive material, the concentration of the compound of the present invention in the coating composition is 0. It is preferably 003 to 0.5% by mass, and is preferably 0.03 to 5% by mass based on the gelatin solid content.

[Silver Halide Photosensitive Material] The silver halide photographic material of the present invention has one or more layers containing a photosensitive silver halide emulsion layer on a support, and any one layer of the present invention It is characterized by containing the compound of. A preferred embodiment of the silver halide photographic light-sensitive material of the present invention is an outermost layer having a non-photosensitive hydrophilic colloid layer, and the outermost layer containing the compound of the present invention.

The silver halide photographic light-sensitive material of the present invention can be prepared by coating one or more aqueous coating compositions of the present invention on a support. The coating system of the coating composition is not particularly limited, and may be any of a slide bead coating system, a slide curtain coating system, an extrusion curtain coating system and an extrusion bead coating system. Of these, the slide bead coating method is preferable.

Various materials used in the silver halide photographic light-sensitive material of the present invention will be described below by taking a silver halide color photographic light-sensitive material as an example. The shape of the silver halide grain emulsion that can be used in the silver halide photographic light-sensitive material of the present invention is one having a regular crystal such as a cube, octahedron or tetradecahedron, spherical or tabular. Those having such irregular crystals, those having crystal defects such as twin planes, or a composite form thereof. In particular, tabular grains are more preferable.

In the tabular grain emulsion, 50% or more of the total projected area is preferably occupied by grains having an aspect ratio of 3 or more. Here, the projected area and aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method in which a shadow is cast together with a latex sphere for reference. When viewed in a direction perpendicular to the principal plane, tabular grains usually have a hexagonal, triangular or circular shape, but have a diameter (circular equivalent diameter) corresponding to a circle having an area equal to the projected area. The aspect ratio is the value divided by the thickness. The shape of tabular grains is more preferable as the ratio of hexagons is higher, and
The ratio of the lengths of adjacent sides of the hexagon is preferably 1: 2 or less.

The higher the aspect ratio, the better the photographic performance of the effect of the present invention is. Therefore, it is preferable that 50% or more of the total projected area of the tabular grain emulsion is occupied by grains having an aspect ratio of 8 or more. More preferably, the aspect ratio is 1
It is 2 or more. If the aspect ratio becomes too large, the coefficient of variation of the particle size distribution described above tends to increase, so the aspect ratio is usually preferably 50 or less.

The average grain diameter of the silver halide grains is preferably 0.2 to 10.0 μm, more preferably 0.5 to 5.0 μm, as the average equivalent circle diameter. The equivalent circle diameter is the diameter of a circle having an area equal to the projected area of the parallel principal planes of the particles. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification. The average equivalent sphere diameter is 0.1
To 5.0 μm, preferably 0.6 to 2.0 μm
More preferably m. These ranges have the best sensitivity / granularity relationship for photographic emulsions. In the case of tabular grains, the average thickness is preferably 0.05 to 1.0 μm. Here, the average equivalent circle diameter means an average value of equivalent circle diameters of 1000 or more grains arbitrarily sampled from a uniform emulsion. The same applies to the average thickness. The silver halide grains may be monodisperse or polydisperse.

The tabular grain emulsion preferably comprises (111) main planes facing each other and side faces connecting the main planes. It is preferable that at least one twin plane is provided between the main planes. In the tabular grain emulsion used in the present invention, it is preferable that normally two twin planes are observed. This 2
The spacing of the twin planes can be less than 0.012 μm as described in US Pat. No. 5,219,720. Further, as described in JP-A-5-249585, the value obtained by dividing the distance between (111) principal planes by the twin plane spacing can be 15 or more. In the present invention, it is preferable that 75% or less of all the side faces connecting the opposing (111) main planes of the tabular grain emulsion be composed of the (111) faces. Here, 75% or less of all side surfaces are composed of (111) planes, and 25% of all side surfaces.
This means that crystallographic planes other than the (111) plane are present at a higher ratio. Usually, the plane can be understood as a (100) plane, but the other plane, that is, (1
10) Faces and faces with higher indices can also be included. In the present invention, the effect is remarkable when 70% or less of all the side faces are composed of (111) faces.

The silver halide solvent usable in the present invention is, for example, US Pat. Nos. 3,271,157 and 3,53.
1,289, 3,574,628, and JP-A-54-1019, JP-A-54-158917 and the like (a) organic thioethers, JP-A-5
3-82408, 55-77737, 55-2
(B) a thiourea derivative described in JP-A No. 982 and the like, and (c) a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent, JP-A-54
(D) imidazoles, (e) ammonia, (f) thiocyanate and the like described in Japanese Patent Application Laid-Open No. 100717.

Particularly preferred solvents are thiocyanate, ammonia and tetramethylthiourea. The amount of solvent used varies depending on the type, but in the case of thiocyanate, the preferred amount is silver halide 1.
It is 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol.

As a method of changing the surface index of the side surface of the tabular grain emulsion, reference can be made to European Patent No. 515894A1. Further, the polyalkylene oxide compounds described in US Pat. No. 5,252,453 can also be used. U.S. Pat. No. 4,6 as an effective method
80,254, 4,680,255, 4,68
The surface index modifiers described in each specification such as No. 0,256 and No. 4,684,607 can be used. Ordinary photographic spectral sensitizing dyes can also be used as a modifier having the same surface index as above.

The silver halide emulsion can be prepared by various methods as long as the above requirements are satisfied. The preparation of a tabular grain emulsion usually consists of basically three steps of nucleation, ripening and growth. In the process of nucleation, US Pat. Nos. 4,713,320 and 4,9
No. 42,120, a gelatin having a low methionine content is used, and nucleation is performed at a high pBr, as described in JP-A No. 4,914,014.
Nucleation in a short time as described in JP-A-222940 is extremely effective in the nucleation step of the tabular grain emulsion used in the present invention. In the aging step, it is possible to perform in the presence of a low-concentration base described in US Pat. No. 5,254,453, and at a high pH described in US Pat. No. 5,013,641, tabular grains. It may be effective in the ripening step of the emulsion. In the growing step, the growth is carried out at a low temperature described in U.S. Pat. No. 45,248,587. 4,672,027 and 4,6
The use of silver iodide fine grains described in Japanese Patent No. 93,964 is particularly effective in the step of growing a tabular grain emulsion.
Further, it is also preferable to grow by adding silver bromide, silver iodobromide or silver chloroiodobromide fine grain emulsion and ripening. It is also possible to supply the above-mentioned fine grain emulsion by using the stirring device described in JP-A-10-43570.

The silver halide emulsion includes silver iodobromide, silver iodochloride,
It is preferably silver bromochloride or silver iodochlorobromide. Further, it is more preferably composed of silver iodobromide or silver iodochlorobromide. Silver iodochlorobromide may contain silver chloride, but the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less or 0 mol%. Regarding the silver iodide content, the variation coefficient of the grain size distribution is preferably 25% or less, so that the silver iodide content is 20 mo.
It is preferably 1% or less. By reducing the silver iodide content, it becomes easy to reduce the variation coefficient of the grain size distribution of the tabular grain emulsion. In particular, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less. Regardless of the silver iodide content, the variation coefficient of the distribution of silver iodide content between grains is preferably 20% or less, and particularly preferably 10% or less.

The silver halide emulsion preferably has a structure within the grain with respect to the silver iodide distribution. In this case, the silver iodide distribution structure may have a double structure, a triple structure, a quadruple structure, or a structure of more than that.

The structure of the silver halide emulsion is preferably, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide and a higher-order structure having a higher structure. The boundary of the silver iodide content between the structures may be clear or may have a continuous and gradual change. Usually powder X
The measurement of the silver iodide content using the line diffraction method does not show two distinct peaks having different silver iodide contents, and the X-axis which is tailed toward the high silver iodide content is observed. The line diffraction profile is shown.

The silver iodide content of the phase inside the surface is preferably higher than the silver iodide content of the surface, and the silver iodide content of the phase inside the surface is preferably 5 mol%.
Or more, more preferably 7 mol% or more.

When the silver halide emulsion is tabular grains,
It is preferable to use tabular grains having dislocation lines. The dislocation lines of tabular grains are described in, for example, J. F. Hamilton, Ph
ot. Sci. Eng. , 11, 57, (1967) and T.W. Shiozawa, J .; Soc. Photo. Sc
i. It can be observed by a direct method using a transmission electron microscope at low temperature described in Japan, 35, 213, (1972). That is, the silver halide grains taken out carefully so that dislocation lines are not applied to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. The sample is cooled and observed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly by using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). it can. From the photograph of the grain obtained by such a method, the position and number of dislocation lines for each grain when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more on average per grain. More preferably 20 on average per particle
More than a book. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 lines, and it is possible to clearly distinguish from the case where there are only a few lines. The average number of dislocation lines per grain is 10
The number of dislocation lines is counted for 0 grains or more and the number average is obtained.

The silver halide grains may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization and noble metal sensitization at any timing during the silver halide emulsion production process. it can. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on the timing of chemical sensitization. There are a type in which chemically sensitized nuclei are embedded in a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. Depending on the purpose, the chemically sensitized nuclei can be formed at a desired position depending on the preparation conditions of the emulsion, but it is preferable to form at least one type of chemically sensitized nuclei near the surface.

As one of the chemical sensitizations that can be preferably carried out, chalcogenide sensitization and noble metal sensitization may be used alone or in combination. These chemical sensitizations are reported by James (T.
H. James), The Photographic Process, 4th
Edition, published by Macmillan, 1977, (TH James, The Th
eory of the Photographic Process, 4th ed, Macmilla
n, 1977) 67-76 and using active gelatin, and Research Disclosure, Vol. 120, April 1974, 1200.
8; Research Disclosure, Volume 34, 1975
June, 13452, U.S. Pat. No. 2,642,361
No. 3,297,446, No. 3,772,031
Issue No. 3,857,711 Issue No. 3,901,714
No. 4,266,018, and 3,904,4.
No. 15, as well as British Patent No. 1,315,75
PAg 5-10, pH as described in specification No. 5
5 to 8 and a temperature of 30 to 80 ° C., sulfur, selenium,
It can be tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable.

For gold sensitization, chloroauric acid and potassium chloride are used.
Loloaurate, potassium aurithiocyanate, sulfurized
Known compounds such as gold and gold selenide can be used.
It For palladium sensitization, palladium divalent salt or tetravalent
Salts can be used. Preferred for palladium sensitization
As a new palladium compound, R₂PdX₆Or R ₂
PdX_FourThe compound represented by Where R is water
Represents an elementary atom, an alkali metal atom or an ammonium group
You X is a halogen atom (chlorine, bromine or iodine atom)
Represents Specifically, K₂PdCl_Four  , (NH_Four)₂Pd
Cl₆, Na₂PdCl_Four, (NH_Four)₂PdCl_Four, Li₂P
dCl_Four, Na₂PdCl₆Or K₂PdBr _FourIs preferred
Yes. Thiocyanates for gold and palladium compounds
Alternatively, it is preferably used in combination with selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,05
The sulfur-containing compound described in each specification of 4,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038.
Nos. 3,411,914 and 3,554,757, JP-A-58-126526, and Duffin, "Photographic Emulsion Chemistry", pages 138-143.

The silver halide emulsion is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol per mol of silver halide.
Is. The preferable amount of the palladium compound is 1 × 10 ^{−3 to} 5 × 10 ⁻⁷ mol per mol of silver halide. The preferable amount of thiocyan compound or selenocyan compound is 5 × 1 per mol of silver halide.
It is 0 ⁻² to 1 × 10 ⁻⁶ mol. The preferred amount of the sulfur sensitizer used for the silver halide grains is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 mol, per mol of silver halide. × 10 ^-7 mo
It is l.

Selenium sensitization is a preferred sensitizing method for silver halide emulsions. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. Selenium sensitization may be more preferably used in combination with sulfur sensitization, precious metal sensitization, or both. For example, it is preferable to add thiocyanate before adding the above-mentioned spectral sensitizing dye and chemical sensitizer. More preferably, it is added after the particle formation, and more preferably after the desalting step is completed. It is preferable to add thiocyanate even during chemical sensitization, that is, it is preferable to add thiocyanate twice or more in the step of chemical sensitization. As thiocyanates, potassium thiocyanate,
Sodium thiocyanate, ammonium thiocyanate and the like are used. The thiocyanate is usually added after being dissolved in an aqueous solution or a water-soluble solvent. The addition amount is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mo per mol of silver halide.
1, more preferably 5 × 10 ⁻⁵ mol to ⁵ × 10 ⁻³ mo.
It is l.

As the protective colloid used in the preparation of the silver halide emulsion and as the binder for the other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Use various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. be able to.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan.No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The obtained emulsion was washed with water for desalting,
It is preferable to newly disperse the protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but
The range of 10 is preferable, and the range of 3 to 8 is more preferable. The pAg at the time of washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 to 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.

During emulsion preparation, for example during grain formation, desalting
About the time of chemical sensitization, the salt of metal ions is present before coating.
This is preferable depending on the purpose. When doping particles
Is a chemical sensitizer or a modifier on the surface of grains during grain formation.
When used as a product, it should be added after grain formation and before the end of chemical sensitization.
And are preferred. You can dope the whole particle,
Alternatively, only the core part of the particle, only the shell part, the epitaxy
It is also possible to dope only the core part and only the base particles.
It Examples of the metal ions include Mg, Ca, Sr, and B.
a, Al, Sc, Y, LaCr, Mn, Fe, Co, N
i, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
n, Pb, Bi, etc. can be used. These gold
Genus is ammonium salt, acetate, nitrate, sulfate, phosphoric acid
Particle shape such as salt, hydroxide or hexacoordinated complex salt, tetracoordinated complex salt
It can be added if it is in the form of a salt that can be dissolved at the time of formation.
It For example, CdBr₂, CdCl₂, Cd (NO₃)₂, P
b (NO₃)₂, Pb (CH₃COO)₂, K₃[Fe (CN)
₆], (NH_Four)_Four[[Fe (CN)₆], K₃IrCl₆,
(NH_Four) ₃RhCl₆, K_FourRu (CN)₆Etc.
It Ligands for coordination compounds include halo, aco, and sia
No, cyanate, thiocyanate, nitrosyl, thioni
You can choose from trosyl, oxo, carbonyl
Wear. Although these may use only one type of metal compound,
You may use it in combination of 2 type or 3 or more types.

The metal compound is preferably added by dissolving in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
l, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. Alternatively, it may be added to a water-soluble silver salt (for example, AgNO3) or an alkali halide water-soluble (for example, NaCl, KBr, KI) and continuously added during the formation of silver halide grains. Furthermore, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. S, Se, Te
Besides, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

The emulsion preferably uses an oxidizing agent for silver during the manufacturing process. However, silver nuclei that contribute to the improvement in sensitivity obtained by reduction sensitization on the grain surface must remain to some extent. Particularly effective is a compound that can convert extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good.

Preferred oxidizing agents are the inorganic oxidizing agents of thiosulfonate and the organic oxidizing agents of quinones.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
Those described in each specification of No. 47 and Japanese Patent Publication No. 52-28660 can be used. One of preferred compounds is Japanese Patent Publication No. 07-78597 (Japanese Patent Application No. 62-4).
7225). Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Addition during emulsion preparation to exert the original antifoggant and stabilizing effect, control grain crystal wall, reduce grain size, reduce solubility of grain, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

Techniques such as layer arrangement which can be used for emulsions and photographic light-sensitive materials using the emulsions, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, and development. Regarding the treatment, European Patent No. 0565096A1 (October 1993)
(Published on March 13) and the patents cited therein. Below, each item and the corresponding description place are listed.

1. Layer structure: page 61, lines 23-35, page 61, line 41-page 62, line 2. Middle layer: p. 61, lines 36-40, 3. Multilayer effect imparting layer: p. 62, lines 15-18, 4. Silver halide halogen composition: p. 62, lines 21-25, 5. Crystal habit of silver halide grains: p. 62, lines 26-30, 6. Silver halide grain size: p. 62, lines 31-34, 7. Emulsion production method: Page 62, lines 35-40, 8. Silver halide grain size distribution: 62-page 41-42
Line, 9. Tabular grains: p. 62, lines 43-46, 10. Internal structure of particles: p. 62, lines 47-53, 11. Emulsion latent image forming type: page 62 line 54-page 63 5
Line, 12. Physical and chemical ripening of emulsion: page 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogging emulsion: p. 63, lines 14-31, 15. Non-photosensitive emulsion: page 63, lines 32-43, 16. Silver coating amount: Page 63, lines 49-50, 17. Photographic Additives: Research Disclosure (R
D) Item17643 (December 1978), Item18
716 (November 1979) and Item 307105.
(November, 1989), and each item and related description are shown below.

[0113] Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer Page 23 Page 648 Right column Page 866 2 Sensitivity enhancer, page 648, right column 3 Spectral sensitizers, pages 23 to 24, page 648, right column, pages 866 to 868     Supersensitizer: page 649, right column 4 Whitening agents Page 24 Page 647 Right column Page 868 5 Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870       Stabilizer 6 Light absorbers, pages 25-26, page 649, right column, page 873     Filter dye, page 650, left column     UV absorber 7 Anti-Staining Agent, page 25, right column, 650, left column to right column, page 872 8 Dye image stabilizer, page 25, page 650, left column, page 872 9 Hardener, page 26, page 651, left column, pages 874-875 10 Binder page 26 page 651 left column page 873-874 11 Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12 Coating aid, pages 26-27, page 650, right column, pages 875-876     Surfactant (These may be partially or wholly substituted with the compound of the present invention, or may be used in combination. I don't know. ) 13 Static Page 27 Page 650 Right column Page 876-877     Preventive agent 14 Matting agent pp. 878-879

18. Formaldehyde scavenger: 6
P. 4, lines 54-57, 19. Mercapto-based antifoggant: page 65, line 1-2, 20. Release agents such as fogging agents: Page 65, lines 3-7, 21. Dye: Page 65, lines 7-10, 22. Color couplers in general: Page 65, lines 11-13, 23. Yellow, magenta and cyan couplers: page 65, lines 14-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: p. 65, lines 29-31, 26. Colored coupler: p. 65, lines 32-38, 27. Functional couplers in general: Page 65, lines 39-44, 28. Bleach accelerator releasing coupler: page 65 lines 45-48, 29. Development accelerator releasing coupler: p. 65, lines 49-53, 30. Other DIR couplers: Page 65, Line 54-Page 66, 4
Line, 31. Coupler dispersion method: Page 66, lines 5-28, 32. Preservatives and fungicides: p. 66, lines 29-33, 33. Kind of sensitive material: page 66, lines 34-36, 34. Photosensitive layer film thickness and swelling speed: page 66 line 40-page 1
Line, 35. Back layer: Page 67, line 3-8, 36. General development processing: Page 67, lines 9-11, 37. Developer and developer: Page 67, lines 12-30, 38. Developer additive: Page 67, lines 31-44, 39. Inversion processing: Page 67, lines 45-56, 40. Treatment liquid aperture ratio: Page 67, line 57-Page 68, line 12, 41. Development time: Page 68, lines 13-15, 42. Bleach-fix, bleach-fix: page 68 line 16-69 31
Line, 43. Automatic processor: Page 69, lines 32-40, 44. Rinse, rinse, stabilize: p. 69 line 41-p. 70
Line, 45. Replenishment and reuse of processing liquid: p. 70, lines 19-23, 46. Built-in developer sensitive material: Page 70, lines 24-33, 47. Development processing temperature: p. 70, lines 34-38, 48. Use in a film with a lens: page 70, lines 39-41, and 2-ferric carboxylic acid or 2,6-pyridinedicarboxylic acid and ferric salts such as ferric nitrate described in EP 602600. And a bleaching solution containing persulfate can also be preferably used. In the use of this bleaching solution, it is preferable to interpose a stopping step and a water washing step between the color developing step and the bleaching step. Use an organic acid such as acetic acid, succinic acid or maleic acid as the stopping solution. Is preferred. Further, the bleaching solution contains an organic acid such as acetic acid, succinic acid, maleic acid, glutaric acid or adipic acid in an amount of 0.1 to 2 mol / L for the purpose of pH adjustment and bleaching fog.
It is preferable to contain in the range of.

[0115]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The materials, reagents, ratios, operations and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1: Synthesis of Exemplified Compound FS-1 1-1 2- (N, N-Dimethylaminoethanethionyl) maleic acid 1,4-di (3,3,4,4,5,5)
Synthesis of 5,6,6,6-nonafluorohexyl) Maleic acid 1,4-di (3,3,4,4,5,5,5)
25.1 g (4,6,6,6-nonafluorohexyl)
1 mmol), 6.4 g (45 mmol) of N, N-dimethylaminoethanethiol hydrochloride, and 5.7 g (41 mmol) of potassium carbonate were dissolved in 60 mL of N, N dimethylformamide, and the mixture was heated at 60 ° C. for 4 hours. It was stirred. Then, after adding 500 mL of chloroform and washing the organic phase with a saturated aqueous solution of sodium hydrogencarbonate, the organic layer is recovered, the organic solvent is distilled off under reduced pressure, and silica gel column chromatography (hexane / ethyl acetate: 8/2 to 0). / 10
(Volume ratio)) to carry out the purification operation to obtain the target compound at 15.8.
g (yield 54%) was obtained.

1-2 Synthesis of Exemplified Compound FS-1 2- (N, N-Dimethylaminoethanethionyl) maleic acid 1,4-di (3,3,4,4,5,5,6,6,6)
5.8 g (22 mmol) of 6-nonafluorohexyl), 1.5 mL (24 mmol) of iodomethane and 60 mL of methanol were added, and the mixture was heated under reflux for 10 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, and a recrystallization operation was performed with hexane-ethyl acetate (2/1 (volume ratio)) to obtain 18.9 g of the target compound (FS-1) as a colorless transparent solid ( Yield 100%). ¹ of the resulting compound
The 1 H-NMR data are as follows. ¹ H-NMR (DMSO-d ₆ ): δ2.66 (m, 4)
H), 2.85-2.92 (m, 2H), 3.09
(M, 11H), 3.54 (d, 2H), 3.86-
3.91 (m, 1H), 4.31-4.47 (m, 4
H)

Example 2: Synthesis of Exemplified Compound FS-7 2-
(2- (N, N-dimethylamino) ethanethionyl) succinic acid 1,4-di (3,3,4,4,5,5,6,6)
14.4 g (20 m of 6,6-nonafluorohexyl)
mol), 3.8 g of methyl p-toluenesulfonate
(20 mmol) and 60 mL of methanol were added, and the mixture was heated under reflux for 2 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, recrystallization operation was performed with ethyl acetate, and the obtained solid was dried under reduced pressure at 80 ° C. for 2 hours. As a colorless transparent solid, 15.3 g (yield: 85) of the target compound (FS-7) was obtained.
%)Obtained. The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ): δ2.51 (s, 3
H), 2.86 (br, 4H), 2.92 (m, 2)
H), 3.04 (m, 2H), 3.08 (s, 9H)
3.55 (m, 2H), 3.90 (dd, 1H), 4.
33-4.60 (m, 4H), 7.11 (d, 2H)
7.48 (d, 2H)

Example 3: Synthesis of Exemplified Compound FS-13 3-1 2- (2- (N, N-Dimethylamino) ethylamino) succinic acid 1,4-di (3,3,4,4,4) 5,
Synthesis of 5,6,6,6-nonafluorohexyl succinic acid 1,4-di (3,3,4,4,5,5,6,6)
12.0 g (20 m of 6,6-nonafluorohexyl)
mol), 1.N of N, N-dimethylaminoethylamine.
9 g (22 mmol), and 2.9 g of potassium carbonate
(22 mmol) is dissolved in 50 mL of acetonitrile,
The mixture was heated under reflux for 6 hours. After that, the reaction solution was transferred to a separating funnel, 500 mL of ethyl acetate was added, the organic phase was washed with a saturated aqueous solution of sodium hydrogen carbonate, and then the organic layer was recovered.
The organic solvent was distilled off under reduced pressure and silica gel column chromatography (chloroform / methanol: 100/3 to 10).
0/6 (volume ratio)) and then the target compound
0.7 g (54% yield) was obtained.

3-2 Synthesis of FS-13 10.7 g (15 mmol) of the above compound, 2.9 g (15 mmol) of methyl p-toluenesulfonate and 40 mL of methanol were added, and the mixture was heated under reflux for 2 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, recrystallization operation was performed with ethyl acetate, and the obtained solid was dried under reduced pressure at 80 ° C. for 2 hours. As a colorless transparent solid, the target compound (FS-1
10.0 g (yield 74%) of 3) was obtained. The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ): δ 2.50 (s, 3)
H), 2.61-2.73 (br, 8H), 3.07
(S, 9H) 3.33 (m, 2H), 3.66 (m, 1
H), 4.30-4.40 (m, 4H), 7.11.
(D, 2H) 7.48 (d, 2H)

Example 4: Synthesis of Exemplified Compound FS-16 4-1 2- (3- (N, N-dimethylamino) propylamino) succinic acid 1,4-di (3,3,4,4,4) 5,
Synthesis of 5,6,6,6-nonafluorohexyl) Maleic acid 1,4-di (3,3,4,4,5,5,5)
30.0 g (4,6,6,6-nonafluorohexyl)
9 mmol), 6.8 mL (54 mmol) of N, N-dimethylaminopropylamine, and 7.5 g (54 mmol) of potassium carbonate in 120 mL of acetonitrile.
And was heated to reflux for 6 hours. Then, the reaction solution was transferred to a separating funnel, 1000 mL of ethyl acetate was added, and the organic phase was washed with a saturated aqueous solution of sodium hydrogen carbonate, and then the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography ( Chloroform / methanol: 10
The purification operation was performed at 0/3 (volume ratio) to obtain 26.4 g (yield 75%) of the target compound as a brown oily compound.

4-2 Synthesis of FS-16 26.4 g (37 mmol) of the above compound, 6.92 g (37 mmol) of methyl p-toluenesulfonate and 100 mL of methanol were added, and the mixture was heated under reflux for 2 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, and the target compound (FS-16) was converted to 3 as a yellow tar-like compound.
3.3 g (yield 100%) was obtained. ¹ H of the obtained compound
-The NMR data are as follows. ¹ H-NMR (DMSO-d ₆ ): 1.82 (br. 2)
H), 2.50 (s, 3H), 2.62-2.76 (b
r, 8H), 3.04 (s, 9H) 3.33 (br, 2
H), 3.65 (br, 1H), 4.32-4.39.
(M, 4H), 7.11 (d, 2H) 7.48 (d, 2)
H)

Example 5: Synthesis of Exemplified Compound FS-47 Maleic acid 1-mono (2-ethylhexyl) 4-mono (3,3,4,4,5,5,6,6,6-nonafluorohexyl) 20.0 g (42 mmol) of N), 4.0 g (46 mmol) of N, N-dimethylaminoethylamine, and 5.8 g (42 mmol) of potassium carbonate.
It was dissolved in 60 mL of N dimethylformamide and stirred at 60 ° C. for 12 hours. After that, add 500 mL of chloroform
In addition, after washing the organic phase with a saturated aqueous solution of sodium hydrogencarbonate, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and purified by silica gel column chromatography (chloroform / methanol: 98/2 (volume ratio)). This was performed to obtain 15.9 g of an oily compound (yield 67%). Then, 60 mL of methanol and 1.9 mL (31 mmol) of iodomethane were added, and the mixture was heated under reflux for 8 hours. After that, the organic solvent was distilled off under reduced pressure with an evaporator to obtain 19.9 g (yield 67%) of a target compound (FS-47) as a yellow wax-like compound. The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ): δ 0.83 (m, 6)
H), 1.20 (m, 8H), 1.53 (m, 1H),
2.61-2.97 (m, 6H), 2.90 (br, 1
H), 3.09 (s, 9H), 3.17 (s, 1H),
3.30 (m, 2H) 3.66 (m, 1H), 4.02
(M, 2H), 4.35 (t, 2H)

Example 6: Synthesis of Exemplified Compound FS-64 Maleic acid 1-mono (2-ethylhexyl) 4-mono (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ) Of 35.5 g (75 mmol) and 11.7 g of N, N-dimethylaminoethanethiol hydrochloride (82
Mmol) and 10.4 g (75 mmol) of potassium carbonate were dissolved in 60 mL of N, N dimethylformamide, and the mixture was stirred at 60 ° C. for 4 hours. Then, 500 mL of chloroform was added, the organic phase was washed with a saturated aqueous solution of sodium hydrogen carbonate, the organic layer was recovered, and the organic solvent was distilled off under reduced pressure. Then, 100 mL of methanol and 4.7 mL (75 mmol) of iodomethane were added, and the mixture was heated under reflux for 8 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator, and recrystallization operation was performed with hexane-ethyl acetate (2/1 (volume ratio)) to obtain 49.7 g of the target compound as a yellow wax-like compound (yield 92%). )Obtained. The ¹ H-NMR data of the obtained compound are as follows. ¹ H-NMR (DMSO-d ₆ ): δ 0.83 (m, 6)
H), 1.29 (m, 8H), 1.52 (m, 1H),
2.64 (m, 2H), 2.84-2.91 (m, 2
H), 3.09 (s, 9H), 3.16 (d, 2H)
3.56 (m, 2H), 3.85 (dd, 1H), 4.
01 (m, 2H), 4.36 (br, 2H)

Example 7: Synthesis of Exemplified Compound FS-70 7-1 Aspartic acid 1,4-di (3,3,4)
Synthesis of 4,5,5,6,6,6-nonafluorohexyl) Aspartic acid 10.0 g (80 mmol), 3,3
Dissolve 44.3 g (163 mmol) of 4,4,5,5,6,6,6-nonafluorohexanol and 18.2 g (96 mmol) of p-toluenesulfonic acid monohydrate in 400 mL of toluene, and then dissolve at 120 ° C. It was stirred for 15 hours.
After that, it was cooled to room temperature, the precipitated crystals were collected by filtration,
After adding 500 mL of ethyl acetate and a saturated aqueous solution of sodium hydrogen carbonate to wash the organic phase, the organic layer is recovered, the organic solvent is distilled off under reduced pressure, and 35.5 g (yield: 76%) of the target compound as a yellow oily compound. )Obtained.

7-2 N- (N ', N'-dimethylaminomethylcarbonyl) aspartic acid 1,4-di (3,3,4,4,5,5,6,6,6-nonafluorohexyl) Synthesis of aspartic acid 1,4-di (3,3,4,4,5,5
8.2 g of 5,6,6,6-nonafluorohexyl)
(13.1 mmol), 1.35 g (13.1 mmol) of N, N-dimethylglycine, 1-ethyl-3 (3
2.76 g (1.43 mmol) of -dimethylaminopropyl) carbodiimide hydrochloride (hereinafter WSC) was dissolved in 50 mL of dimethylformamide, stirred at 50 ° C for 2 hours, ethyl acetate was added, and a saturated aqueous solution of sodium hydrogencarbonate was added. In addition, after washing the organic phase, the organic layer was recovered, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane / ethyl acetate: 2/8 (w /
The purification operation was performed in w)) to obtain 5.6 g (yield 60%) of the target compound as a yellow oily compound.

7-3 Synthesis of FS-70 5.6 g (7.9 mmol) of the above oily compound, p
-1.47 g (7.9 mm) of methyl toluenesulfonate
ol) and 25 mL of methanol were added, and the mixture was heated under reflux for 6 hours. Then, the organic solvent was distilled off under reduced pressure with an evaporator,
As a yellow tar-like compound, the target compound (FS-7
0) was obtained (6.9 g, yield 99%). Of the obtained compound
^{The 1} H-NMR data are as follows. ¹ H-NMR (DMSO-d ₆ ): δ 2.29 (s, 3
H), 2.56-2.78 (m, 4H), 2.85.
(D, 2H), 3.21 (s, 9H), 4.15 (s,
2H), 4.31-4.40 (m, 4H), 4.73.
(M, 1H), 7.10 (d, 2H), 7.48 (d,
2H) 9.11 (d, 1H)

Example 8: Synthesis of Exemplified Compound FS-71 8-1 Glutamic acid 1,5-di (3,3,4,4,4)
Synthesis of 5,5,6,6,6-nonafluorohexyl) -toluenesulfonate 14.7 g (0.1 mol) of glutamic acid, 3,3
Dissolve 58.2 g (0.22 mol) of 4,4,5,5,6,6,6-nonafluorohexanol and 22.8 g (0.12 mol) of p-toluenesulfonic acid monohydrate in 500 mL of toluene. Then, the mixture was stirred at 120 ° C. for 6 hours.
Then, the mixture was cooled to room temperature, and the precipitated crystals were separated by filtration and dried to give 69.6 g of the desired product as white crystals (yield 89
%)Obtained.

8-2 Glutamic acid 1,5-di (3,3
Synthesis of 3,4,4,5,5,6,6,6-nonafluorohexyl glutamic acid 1,5-di (3,3,4,4,5,5,5)
After adding 15.0 g (19.2 mmol) ethyl acetate of 6,6,6-nonafluorohexyl) p-toluenesulfonate and a saturated aqueous solution of sodium hydrogen carbonate to wash the organic phase, the organic layer was recovered and The solvent was distilled off under reduced pressure to obtain 15.0 g (yield 74%) of the target compound as a yellow oily compound.

8-3 N- (N ', N'-dimethylaminomethylcarbonyl) glutamic acid 1,5-di (3,3)
Synthesis of 3,4,4,5,5,6,6,6-nonafluorohexyl glutamic acid 1,5-di (3,3,4,4,5,5,5)
8.31 g (1 of 6,6,6-nonafluorohexyl)
3.0 mmol), 1.4 of N, N-dimethylglycine
0 g (13.7 mmol), 2.74 g (1.
(43 mmol) was dissolved in 50 mL of dimethylformamide, stirred at 50 ° C. for 3 hours, chloroform was added, saturated aqueous sodium hydrogen carbonate solution was added, and the organic phase was washed, and then the organic layer was recovered and the organic solvent was distilled under reduced pressure. After that, the residue was purified by silica gel column chromatography (chloroform) to obtain 7.48 g (yield 79%) of the target compound as a yellow oily compound.

8-4 Synthesis of FS-71 N- (2- (N ', N'-dimethylamino) ethyl) glutamic acid 1,5-di (3,3,4,4,5,5,5)
6,6,6-nonafluorohexyl) 3.4 g (4.8
mmol), 0.88 of methyl p-toluenesulfonate
g (4.8 mmol) and 27 mL of methanol were added 9
Heated to reflux for hours. Then, the mixture was filtered through Celite, the filtrate was collected, and the organic solvent was distilled off under reduced pressure with an evaporator to obtain 3.6 g (yield 83%) of the target compound (FS-71) as a yellow tar-like compound. ¹ H- of the obtained compound
The NMR data are as follows. ¹ H-NMR (DMSO-d ₆ ): δ1.92 (m, 1)
H), 2.09 (m, 1H), 2.30 (s, 3H),
2.50-2.83 (m, 6H), 3.24 (s, 9
H) 4.21 (s, 2H), 4.39 (m, 5H),
7.14 (d, 2H), 7.53 (d, 2H) 9.09
(D, 1H)

[Example 9: Measurement of surface tension lowering ability of fluorine-containing compound and surfactant] A 0.1% by mass aqueous solution of the fluorine-containing surfactant of the present invention and a comparative example shown in Table 1 was prepared,
The dynamic surface tension at 100 msec was measured by the maximum bubble pressure method using an automatic dynamic surface tension meter BP-DP3 manufactured by Kyowa Interface Science Co., Ltd. The measured dynamic surface tension is shown in Table 1 below. As can be seen from the results shown in Table 1, the compounds of the present invention are excellent in the ability to lower the dynamic surface tension.

[0133]

[Table 1]

[0134]

[Chemical 28]

[Example 10: Preparation and evaluation of silver halide color photographic light-sensitive material] (1) Support A support was prepared as follows. 1) First layer and subbing layer For a polyethylene naphthalate support having a thickness of 90 μm, the treatment atmosphere pressure was 2.66 × 10 on both sides of each.
Pa, H ₂ O partial pressure in atmospheric gas 75%, discharge frequency 3
0 kHz, output 2500 W, processing intensity 0.5 kV ・ A ・
Glow discharge treatment was performed at min / m ² . On this support,
A coating solution having the following composition was used as the first layer in Japanese Patent Publication No. 58-4589.
The bar coating method described in Japanese Patent Laid-Open Publication No. 2003-242242 was used to coat at a coating amount of 5 mL / m ² . Conductive fine particle dispersion liquid (SnO ₂ / Sb ₂ O ₅ particle concentration 50 mass parts 10% aqueous dispersion liquid. Secondary particle aggregate with primary particle diameter 0.005 μm and average particle diameter 0.05 μm) Gelatin 0. 5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 parts by mass Sorbitan monolaurate

After coating the first layer, it was wound on a stainless steel core having a diameter of 20 cm and heated at 110 ° C. (Tg of PEN support: 1
After heat treatment at 19 ° C. for 48 hours for heat history and annealing, a support is sandwiched between the first layer side and a coating solution having the following composition as an undercoat layer for emulsion on the side opposite to the first layer side, using a bar coating method. The coating amount was 10 mL / m ² . Gelatin 1.01 parts by mass Salicylic acid 0.30 parts by mass Resorcin 0.40 parts by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n-Propanol 10 0.08 parts by mass

Further, the following second and third layers were sequentially coated on the first layer. 2) Dispersion Co of second layer magnetic substance Co-deposited γ-Fe ₂ O ₃ magnetic substance (average major axis length: 0.25 μ)
m, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A /
^{m, σs: 77.1Am 2 /kg,σr:37.4Am 2} /
kg) 1100 parts by mass, water 220 parts by mass, and a silane coupling agent [3- (poly (degree of polymerization: 10) oxyethynyl) oxypropyltrimethoxysilane] 165 parts by mass were added, and the mixture was well kneaded in an open kneader for 3 hours. .
The roughly dispersed viscous liquid is dried at 70 ° C for one day,
After removing water, heat treatment was performed at 110 ° C. for 1 hour to prepare surface-treated magnetic particles. Further, the following formulation was kneaded again in the open kneader for 4 hours. Surface-treated magnetic particles 855 g Diacetylcellulose 25.3 g Methylethylketone 136.3 g Cyclohexanone 136.3 g Further, finely dispersed at 2000 rpm for 4 hours with a sand mill (1/4 G sand mill) according to the following formulation. As the media, glass beads of 1 mmΦ were used. The above kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g

Further, a magnetic material-containing intermediate liquid was prepared with the following formulation. Preparation of magnetic substance-containing intermediate liquid Fine magnetic substance dispersion liquid 674 g Diacetyl cellulose solution 24280 g (solid content 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, disperse to a disperser And stirred to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion was prepared according to the following formulation. (A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shin-Etsu) 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ceramic-coated sand mill (1 /
It was finely dispersed at 800 rpm for 4 hours using a 4G sand mill). As the media, 1 mmΦ zirconia beads were used. (B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Kagaku Co., Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm with methyl ethyl ketone as a dispersion medium,
The solid content is 30%.

Preparation of Second Layer Coating Liquid 19053 g of the above magnetic substance-containing intermediate liquid 264 g of diacetyl cellulose solution (4.5% solid content, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion liquid “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [Dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluting solution 203 g (solid content 20%, dilution) Solvent: Methyl ethyl ketone / cyclohexanone = 1/1) Methyl ethyl ketone 170 g Cyclohexanone 170 g The coating solution prepared by mixing and stirring the above was applied with a wire bar to a coating amount of 29.3 mL / m ² . Dry 1
It was carried out at 10 ° C. The thickness of the magnetic layer after drying is 1.0
was μm.

3) Third Layer (Layer Containing Higher Fatty Acid Ester Lubricant) Preparation of Dispersion Stock Solution of Lubricant The following solution (a) was dissolved by heating at 100 ° C., added to solution (i) and dispersed with a high pressure homogenizer to prepare a slip agent. A dispersion stock solution of was prepared. A liquid following compounds 399 parts by weight _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 parts by Lee Liquid Cyclohexanone 8600 parts by mass Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation. Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (Shin-Etsu silicone - down Corp.) Compound _{1-1: (CH 3 O) 3} Si- (CH 2) 3 -NH 2) 5.53 parts by weight Compound 1 2 .93 parts by mass

[0142]

[Chemical 29]

[0143]   Sea host KEP50 88.00 parts by mass (Amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.)

After stirring for 10 minutes according to the above formulation, the following was further added. Diacetone alcohol 252.93 parts by mass While cooling and stirring the above liquid with ice, an ultrasonic homogenizer "SONIFIER450 (BRANSON Co., Ltd.)
3) for 3 hours to disperse the spherical inorganic particle dispersion liquid c1.
Was prepared. Preparation of spherical organic polymer particle dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass methyl ethyl ketone 120 parts by mass cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1 ) While cooling with ice and stirring, ultrasonic homogenizer "SONI
FIER450 (manufactured by BRANSON Co., Ltd.) was used for dispersion for 2 hours to prepare a spherical organic polymer particle dispersion liquid c2.

Preparation of Third Layer Coating Liquid The following was added to 542 g of the above lubricant dispersion stock solution to prepare a third layer coating liquid. Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The Seahosta KEP50 dispersion liquid [c1] 53.1 g The spherical organic polymer particle dispersion liquid [c2] 300 g Megafac F-178K 4.8 g (Dainippon Ink) Co., Ltd., solid content 30%) BYK310 5.3 g (BYK Chem Japan Co., Ltd., solid content 25%)

The coating solution for the third layer is placed on the second layer 10.3.
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

(2) Coating of Photosensitive Layer Next, each layer having the following composition was multilayer coated on the undercoat side of the support to prepare a color negative film. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening Agents (specific compounds are listed below, followed by a number, followed by a chemical formula). The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver.

[0148]   First layer (first antihalation layer)   Black colloidal silver 0.122   0.07 μm silver iodobromide emulsion silver 0.01   Gelatin 0.919   ExM-1 0.066   ExC-1 0.002   ExC-3 0.002   Cpd-2 0.001   F-8 0.010   HBS-1 0.005   HBS-2 0.002   Second layer (second antihalation layer)   Black colloidal silver 0.055   Gelatin 0.425   ExF-1 0.002   F-8 0.012   Solid Disperse Dye ExF-7 0.120   HBS-1 0.074   Third layer (middle layer)   ExC-2 0.050   Cpd-1 0.090   Polyethyl acrylate latex 0.200   HBS-1 0.100   Gelatin 0.700

[0149]   4th layer (low sensitivity red sensitive emulsion layer)   Em-D Silver 0.577   Em-C Silver 0.347   ExC-1 0.188   ExC-2 0.011   ExC-3 0.075   ExC-4 0.121   ExC-5 0.010   ExC-6 0.007   ExC-8 0.050   ExC-9 0.020   Cpd-2 0.025   Cpd-4 0.025   HBS-1 0.114   HBS-5 0.038   Gelatin 1.474   Fifth layer (medium speed red emulsion layer)   Em-B silver 0.431   Em-C Silver 0.432   ExC-1 0.154   ExC-2 0.068   ExC-3 0.018   ExC-4 0.103   ExC-5 0.023   ExC-6 0.010   ExC-8 0.016   ExC-9 0.005   Cpd-2 0.036   Cpd-4 0.028   HBS-1 0.129   Gelatin 1.086

[0150]   6th layer (high-sensitivity red-sensitive emulsion layer)   Em-A silver 1.108   ExC-1 0.180   ExC-3 0.035   ExC-6 0.029   ExC-8 0.110   ExC-9 0.020   Cpd-2 0.064   Cpd-4 0.077   HBS-1 0.329   HBS-2 0.120   Gelatin 1.245   7th layer (middle layer)   Cpd-1 0.094   Cpd-6 0.369   Solid disperse dye ExF-4 0.030   HBS-1 0.049   Polyethyl acrylate latex 0.088   Gelatin 0.886   Eighth layer (layer that gives a multilayer effect to the red sensitive layer)   Em-J silver 0.293   Em-K Silver 0.293   Cpd-4 0.030   ExM-2 0.120   ExM-3 0.016   ExM-4 0.026   ExY-1 0.016   ExY-4 0.036   ExC-7 0.026   HBS-1 0.090   HBS-3 0.003   HBS-5 0.030   Gelatin 0.610

[0151]   9th layer (low sensitivity green emulsion layer)   Em-H silver 0.329   Em-G silver 0.333   Em-I silver 0.088   ExM-2 0.378   ExM-3 0.047   ExY-1 0.017   ExC-7 0.007   HBS-1 0.098   HBS-3 0.010   HBS-4 0.077   HBS-5 0.548   Cpd-5 0.010   Gelatin 1.470   10th layer (medium-speed green emulsion layer)   Em-F silver 0.457   ExM-2 0.032   ExM-3 0.029   ExM-4 0.029   ExY-3 0.007   ExC-6 0.010   ExC-7 0.012   ExC-8 0.010   HBS-1 0.065   HBS-3 0.002   HBS-5 0.020   Cpd-5 0.004   Gelatin 0.446

[0152]   11th layer (high sensitivity green emulsion layer)   Em-E silver 0.794   ExC-6 0.002   ExC-8 0.010   ExM-1 0.013   ExM-2 0.011   ExM-3 0.030   ExM-4 0.017   ExY-3 0.003   Cpd-3 0.004   Cpd-4 0.007   Cpd-5 0.010   HBS-1 0.148   HBS-5 0.037   Polyethyl acrylate latex 0.099   Gelatin 0.939   12th layer (yellow filter layer)   Cpd-1 0.094   Solid disperse dye ExF-2 0.150   Solid disperse dye ExF-5 0.010   Oil-soluble dye ExF-6 0.010   HBS-1 0.049   Gelatin 0.630

[0153]   13th layer (low-sensitivity blue emulsion layer)   Em-O silver 0.112   Em-M Silver 0.320   Em-N silver 0.240   ExC-1 0.027   ExC-7 0.013   ExY-1 0.002   ExY-2 0.890   ExY-4 0.058   Cpd-2 0.100   Cpd-3 0.004   HBS-1 0.222   HBS-5 0.074   Gelatin 2.058   14th layer (high sensitivity blue emulsion layer)   Em-L silver 0.714   ExY-2 0.211   ExY-4 0.068   Cpd-2 0.075   Cpd-3 0.001   HBS-1 0.071   Gelatin 0.678

[0154]   Fifteenth layer (first protective layer)   0.07 μm silver iodobromide emulsion silver 0.301   UV-1 0.211   UV-2 0.132   UV-3 0.198   UV-4 0.026   F-11 0.009   S-1 0.086   HBS-1 0.175   HBS-4 0.050   Gelatin 1.984   16th layer (2nd protective layer)   H-1 0.400   B-1 (diameter 0.8 μm) 0.050   B-2 (diameter 3.0 μm) 0.150   B-3 (diameter 3.0 μm) 0.050   S-1 0.200   Gelatin 0.750   W-1 0.056

Further, W-1 to W-4 and B-4 to B are added to each layer in order to improve storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property. -6, F-1
.About.F-19, and lead salt, platinum salt, iridium salt, and rhodium salt.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the 12th layer was dispersed by the following method. ExF-2 wet cake (containing 17.6 mass% water) 2.800 kg sodium octylphenyldiethoxymethanesulfonate (31 mass% aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg Water 4.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) The slurry having the above composition was stirred with a dissolver to roughly disperse the mixture, and then agitator mill LMK-4 was used to rotate at a peripheral speed of 10 m /
s, discharge rate of 0.6 kg / min, filling rate of zirconia beads having a diameter of 0.3 mm is 80%, and the absorbance ratio of the dispersion is 0.29.
To obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm. Similarly, E
A solid dispersion of xF-4 and ExF-7 was obtained. The average particle size of the fine dye particles is 0.28 μm and 0.49 μm, respectively.
It was m. ExF-5 is a European Patent No. 549,489A.
Microprecipitation described in Example 1 of
Itation) The dispersion method was used. The average particle size was 0.06 μm.

[0157]

[Table 2]

In Table 2, the emulsions Em-A to Em had the optimum amounts of the spectral sensitizing dyes 1 to 3, and were optimally gold-sensitized, sulfur-sensitized, and selenium-sensitized. In the emulsion Em-J, the spectral sensitizing dyes 7 and 8 were added in an optimum amount, and gold sensitization, sulfur sensitization and selenium sensitization were optimally performed. In the emulsion Em-L, the spectral sensitizing dyes 9 to 11 were added in the optimum amounts, and the gold sensitization, the sulfur sensitization and the selenium sensitization were optimally performed. In the emulsion Em-O, the spectral sensitizing dyes 10 to 12 were added in the optimum amounts, and the gold sensitization and the sulfur sensitization were optimum. Emulsions Em-D, H, I, K, M and N were optimally gold-sensitized, sulfur-sensitized and selenium-sensitized with the spectral sensitizing dyes shown in Table 3 added optimally.

[0159]

[Table 3]

The sensitizing dyes listed in Table 3 are shown below.

[0161]

[Chemical 30]

[0162]

[Chemical 31]

[0163]

[Chemical 32]

Preparation of tabular grains is described in JP-A-1-158.
Low molecular weight gelatin was used according to the examples described in Japanese Patent No. 426. Emulsions Em-A to K contained Ir and Fe in optimum amounts. Emulsions Em-L to O were reduction-sensitized during grain preparation. When a high-voltage electron microscope was used for the tabular grains, dislocation lines as described in JP-A-3-237450 were observed. Emulsions Em-A to C and J were rearranged by using an iodine ion-releasing agent according to the example described in JP-A-6-11782. Emulsion Em-E is
Dislocations were introduced by using silver iodide fine particles prepared immediately before the addition in another chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570. The compounds used for each layer are shown below.

[0165]

[Chemical 33]

[0166]

[Chemical 34]

[0167]

[Chemical 35]

[0168]

[Chemical 36]

[0169]

[Chemical 37]

[0170]

[Chemical 38]

[0171]

[Chemical Formula 39]

[0172]

[Chemical 40]

[0173]

[Chemical 41]

[0174]

[Chemical 42]

[0175]

[Chemical 43]

[0176]

[Chemical 44]

[0177]

[Chemical formula 45]

The above silver halide color photographic light-sensitive material was used as sample 100. 16th with respect to the above sample 100
The layer contains the surfactant FS-1 of the present invention in an amount of 0.008 g / m ^2.
A sample 101 was prepared in the same manner as the sample 100 except that it was added. The surfactant shown in Table 4 was added in place of FS-1 to FS-1 of the 16th layer in Sample 101 so that the addition amount for each layer would be an equivalent mass in terms of fluorine amount. Samples 102-103 and 109-11
4 and comparative samples 104 to 108 were prepared.

<Evaluation> (1) Charge Adjusting Ability The charge adjusting ability of the test samples 100 to 114 was evaluated. The amount of charge is 35 m in an environment where the temperature is 25 ° C and the relative humidity is 10%.
The opposite side of the emulsion-coated side of the m × 120 mm sample was adhered with a double-sided tape, a nylon ribbon was wound around a grounded opposing roller, and the nip was conveyed between the rollers, and then the sample was placed in a Faraday cage. It was measured. The measurement results of the charge amount are shown by the charge series index. The charge train index is a value obtained by subtracting the charge amount of each of the samples 101 to 114 from the charge amount of the sample 100 by 10 ⁹ times. Those having a charge train index smaller than -1.0 were judged to have sufficient charge train adjusting ability for practical use. The results are shown in Table 4. As is clear from the results shown in Table 4, conventional fluorine-based surfactants exhibit charge controllability only with compounds having a long-chain perfluoroalkyl group, and a fluoroalkyl group having 6 or less carbon atoms ( The comparative compound FC-4) has insufficient charge controllability. On the other hand, it was found that the sample of the present invention has a sufficient charge controllability even though it has a short-chain fluorinated alkyl group.

Furthermore, the surface of the sample of the present invention was treated with XPS (X
-Ray photoelectron spectrum
As a result of quantifying the F atom / carbon atom ratio on the surface, a good correlation was observed between the charge controllability and the amount of surface fluorine, and the surfactant of the present invention effectively presents fluorine atoms on the sample surface. I realized that

[0181]

[Table 4]

(2) Repelling characteristic evaluation Further, B-1 of the 16th layer in Samples 101 to 108
Samples 201 to 208 shown in Table 5 were prepared with the same constituent components except that the particle diameter of 3 was 3 μm, and the fluorine-based surfactants added were all equal in mass to Sample 101. Samples 201 to 208 were coated by the slide bead coating method at 1 m / sec and then immediately dried, and the number of craters generated on the surface of the coating film was visually counted and indicated by the cratering frequency. The repelling frequency is a percentage of the repelling number of each sample with respect to the repelling number of the sample 208. When the repelling frequency was 100 or less, it was determined that the repelling effect was effective. The results are shown in Table 5 below.

[0183]

[Table 5]

Each of the surfactants of the present invention is excellent in the ability to reduce cissing, and as shown in Example 1, the value of the dynamic surface tension of the aqueous solution and the cissing frequency are well correlated. It has been shown. Further, together with the results in Table 4, it is clear that the surfactant of the present invention is superior to the comparative compound in terms of both charge controllability and reduction of cissing.

(3) Photographic properties Samples 101 to 108 were left under conditions of a temperature of 40 ° C. and a relative humidity of 70% for 14 hours, and then exposed through a continuous wedge at a color temperature of 4800 ° K for 1/100 seconds. Color development processing was performed. The photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The sensitivity was evaluated by the relative value of the logarithm of the reciprocal of the exposure amount expressed in lux · second which gives a fog density plus a yellow density of 0.2. All the materials had the same photographic characteristics such as sensitivity and color image density.

Development is performed by Fuji Photo Film Co., Ltd. automatic developing machine F.
It carried out by the following method using P-360B. The overflow solution of the bleaching bath was modified so that it was entirely discharged into the waste liquid tank without flowing into the post-bath. This FP-360B is equipped with the evaporation correction means described in Published Technical Report 94-4992 (published by the Institute of Invention and Innovation). The treatment process and the treatment liquid composition are shown below. (Treatment process) Process Treatment time Treatment temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C. 20 mL 11.5 L Bleach 50 seconds 38.0 ° C. 5 mL 5 L Fixing (1) 50 seconds 38.0 ° C. -5 L Fixing (2) 50 seconds 38.0 ° C 8mL 5L water washing 30 seconds 38.0 ° C 17mL 3L stable (1) 20 seconds 38.0 ° C -3L stable (2) 20 seconds 38.0 ° C 15mL 3L dry 1 minute 30 seconds 60.0 ° C * Replenishment amount: Replenishment amount per 1.1 m of 35 mm width of photosensitive material (equivalent to one shot for every 24 shots) Stabilizer and fixer are countercurrent method from (2) to (1), The overflow liquid of washing water was introduced into the fixing bath (2). The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the washing step were 2.5 mL and 2.0 mL, respectively, per 35 mm width of the photosensitive material of 1.1 m, and It was 2.0 mL.
The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm ^{2 for the} color developing solution and 120 for the bleaching solution.
cm ² , and other treatment liquids were about 100 cm ² .

The composition of the processing liquid is shown below.   (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3 mg-   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

[0188]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-Diaminopropanetetraacetic acid secondary     Ammonium iron monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with ammonia water] 4.6 4.0

[0189]   (Fixing (1) Tank liquid)   5:95 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution   (PH 6.8)   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240mL 720mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water) The tap water was washed with H-type strongly acidic cation exchange resin (Amberlite IR-1 manufactured by Rohm and Haas).
20B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / L or less, followed by 20 mg / L sodium diisocyanurate dichloride and 150 mg / L sodium sulfate
Was added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizer) Common to tank liquid and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-Benzisothiazoline-3 -On sodium 0.10 ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 water In addition 1.0 L pH 8.5

[0191]

Industrial Applicability As described above, the compound of the present invention is excellent in surface orientation and can form a uniform coating film when used for forming a coating film. Further, according to the present invention, it is possible to provide an aqueous coating composition capable of forming a coating film having a uniform and antistatic property. Furthermore, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is capable of stable production and has an antistatic property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) G03C 1/76 501 G03C 1/76 501 (72) Inventor Akira Ikeda 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film (72) Inventor Nobuo Hamamoto No. 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H023 FC03 GA04 4H006 AA01 AB76 BJ50 BT12 BU32 BU50 BV22 TA04 TB53 TB55

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material having one or more layers including a light-sensitive silver halide emulsion layer on a support, one of the layers containing a compound represented by the following general formula (1): A silver halide photographic light-sensitive material characterized by being [Chemical 1] (In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, but at least one of R ¹ and R ² represents an alkyl group substituted with a fluorine atom. R ³ , R ⁴ and R ⁵ independently represent a hydrogen atom or a substituent,
X ¹ , X ² and Z each independently represent a divalent linking group or a single bond, and M ⁺ represents a cationic substituent. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1. ) 2. The halogen according to claim 1, wherein the outermost layer has a non-photosensitive hydrophilic colloid layer, and the outermost layer contains the compound represented by the general formula (1). Silver halide photographic light-sensitive material. 3. The silver halide photograph according to claim 2, wherein the outermost layer further contains an anionic or nonionic surfactant other than the compound represented by the general formula (1). Photosensitive material. 4. The compound represented by the general formula (1) is
It is represented by the general formula (1-a).
The silver halide photographic light-sensitive material according to any one of 1 to 3
Fee. [Chemical 2] (In the formula, R¹¹And R^{twenty one}Are each substituted or unsubstituted
Represents an alkyl group, but R ¹¹And R^{twenty one}At least one of
Represents an alkyl group substituted with a fluorine atom, R ¹¹And R
^{twenty one}Has a total carbon number of 19 or less. R¹³, R¹⁴and
R¹⁵Are independently substituted or unsubstituted alkyl groups
And may be bonded to each other to form a ring. X¹¹Oh
And X^{twenty one}Are each independently -O-, -S- or -NR
³¹Represents-, R³¹Represents a hydrogen atom or a substituent, and Z represents
It represents a divalent linking group or a single bond. Y^-Is a counter anion
As shown, if the charge becomes 0 in the molecule, Y^-Not
Good. m is 0 or 1. ) 5. The silver halide according to claim 1, wherein the compound represented by the general formula (1) is represented by the following general formula (1-c). Photographic material. [Chemical 3] (In the formula, n ¹ represents an integer of ¹ to 6 and n ² represents an integer of 3 to 8, but 2 (n ¹ + n ² ) is 19 or less. R ¹³ , R ¹⁴ and R ¹⁵ are each independently. a substituted or unsubstituted alkyl group, optionally bonded to each other to form a ring .X ¹¹
And X ²¹ are each independently —O—, —S— or —N.
R ³¹ − represents, R ³¹ represents a hydrogen atom or a substituent, and Z
Represents a divalent linking group or a single bond. Y ⁻ represents a counter anion, but Y ⁻ may not be present when the charge becomes 0 in the molecule. m is 0 or 1. ) 6. A photosensitive silver halide emulsion layer containing an emulsion in which 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 3 or more. The silver halide photographic light-sensitive material according to any one of 1. 7. A fluorine compound represented by the general formula (1-a). 8. A surfactant containing a compound represented by the general formula (1-a). 9. An aqueous coating composition containing the compound represented by the general formula (1-a).