JP2003270760A - Fluorine compound and silver halide photographic sensitive material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stably manufacturable silver halide photographic sensitive material provided with antistatic performance. <P>SOLUTION: In the silver halide photographic sensitive material having on a support one or more layers including a photosensitive silver halide emulsion layer, any one of the layers contains a compound represented by formula (1) wherein each R is H or F; m and n are each an integer of 3-16; each Y is a single bond, -S-, -SO<SB>2</SB>-, -SO- or -O-; L<SP>1</SP>and L<SP>3</SP>are each independently a ≥4C divalent group; L<SP>2</SP>is a di- or higher valent group; p is an integer of 1-6; R<SP>1</SP>-R<SP>4</SP>are each independently H or a substituted or unsubstituted alkyl; and each X<SP>-</SP>is a counter anion but may be absent when an inner salt is formed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[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, since many of these materials are perfluorooctane sulfonic acid and its derivatives, and perfluorohexanoic acid and its derivatives, there is concern about accumulation and the like, so the development of another fluorosurfactant is desired. . Generally, if the chain length of the perfluoroalkyl chain is shortened, the decomposability (decomposability of the compound after use) is improved, which is considered to be advantageous from the viewpoint of safety. The orientation of is significantly reduced. Therefore, it is strongly desired to develop a fluorosurfactant having a shorter fluoroalkyl chain and having both surface orientation (related to antistatic property) and homogeneity of the coating film.

An object of the present invention is to provide a novel fluorine compound which is excellent in surface orientation and can form a uniform coating film when used for forming a coating film. Further, the present invention is
It is an object of the present invention to provide a silver halide photographic light-sensitive material which is capable of stable production and has antistatic properties.

[0007]

Means for solving the problems Means for solving the above problems are as follows. That is, <1> In a silver halide photographic light-sensitive material having one or more layers including a photosensitive silver halide emulsion layer on a support, one of the layers contains a compound represented by the following general formula (1). A silver halide photographic light-sensitive material characterized by being

[0008]

[Chemical 3]

In the formula, R represents a hydrogen atom or a fluorine atom, m and n each represent an integer of 3 to 16, and Y represents a single bond, --S--, --SO _2- , --SO-- or Represents --O--, L ¹ and L ³ each independently represent a divalent group having 4 or more carbon atoms, and L ² represents (p +
1) represents a valent group, p represents an integer of 1 to 6, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. , X ⁻ represent a counter anion, but may not be present when forming an intramolecular salt.

<2> The above-mentioned <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> At least one of the silver halide emulsions contained in the silver halide emulsion layer is an emulsion in which 50% or more of the total projected area of silver halide grains is occupied by grains having an aspect ratio of 3 or more. <2> The silver halide photographic light-sensitive material as described in <1> or <2> above.

<4> A fluorine compound represented by the following general formula (1).

[0012]

[Chemical 4]

In the formula, R represents a hydrogen atom or a fluorine atom, m and n each represent an integer of 3 to 16, and Y represents a single bond, --S--, --SO _2- , --SO-- or Represents --O--, L ¹ and L ³ each independently represent a divalent group having 4 or more carbon atoms, and L ² represents (p +
1) represents a valent group, p represents an integer of 1 to 6, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. , X ⁻ represent a counter anion, but may not be present when forming an intramolecular salt.

<5> The above <4>, which is a compound obtained by reacting compounds represented by the following general formula (3), the following general formula (2) and the following general formula (2) ′. The fluorine compound described in 1.

[0015]

[Chemical 5]

In the formula, R represents a hydrogen atom or a fluorine atom, m and n each represent an integer of 3 to 16, and Y represents a single bond, --S--, --SO _2- , --SO-- or Represents --O--, L ¹ and L ³ each independently represent a divalent group having 4 or more carbon atoms, and L ² represents (p + 1)
Represents a valent group, p represents an integer of 1 to 6, and R
¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X represents a group which can be a counter anion after the reaction.

<6> Fluorine represented by the general formula (1) including a step of reacting compounds represented by the general formula (3), the general formula (2) and the general formula (2) ′, respectively. Method for producing compound. <7> A surfactant containing a fluorine compound represented by the general formula (1). <8> An aqueous coating composition containing the fluorine compound represented by the general formula (1).

[0018]

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] First, the fluorine compound of the present invention will be described in detail. The fluorine compound of the present invention is represented by the following general formula (1).

[0019]

[Chemical 6]

In the formula, R represents a hydrogen atom or a fluorine atom, m and n each represent an integer of 3 to 16, and Y represents a single bond, --S--, --SO _2- , --SO-- or Represents -O-, L ¹ and L ³ each independently represents a divalent group having 4 or more carbon atoms, L ² represents a divalent or higher group, and p is any of 1 to 6 Represents an integer,
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X ⁻ represents a counter anion, but is not necessary when forming an intramolecular salt. Good.

In the above general formula (1), R represents a hydrogen atom or a fluorine atom, and a fluorine atom is preferable from the viewpoint of surface tension lowering ability, coating suitability, and antistatic property of silver halide photographic light-sensitive material. In the general formula (1), m and n each represent an integer of 3 to 16, and from the viewpoint of degradability, 3 to 8 are preferable, 3 to 6 are more preferable, and 3 or 4 are particularly preferable.

In the general formula (1), Y is a single bond and -S.
_{-, - SO 2 -, -} SO- or an -O-. In particular,
When representing the m and n are small integers (specifically, 3-10), Y is a single bond, -S -, - SO ₂ - or -S
It is preferably O-, a single bond, -S- or -SO.
More preferably, it represents _2-, more preferably represents a single bond or -S-, and particularly preferably represents -S-.
When m and n are small integers, the hydrophilicity of Y is preferably low because the water solubility of the hydrophobic site is reduced and the surface tension lowering ability is improved.

In the general formula (1), L¹And L³Are each
Independently represents a divalent group having 4 or more carbon atoms constituting the group.
You Preferably, a substituted or unsubstituted alkylene group,
A substituted or unsubstituted cycloalkylene group, substituted or
Is an unsubstituted bicycloalkylene group, substituted or unsubstituted
An arylene group or a substituted or unsubstituted heteroaryl
It represents a divalent group containing at least one alkylene group. L¹Oh
And L³Are those groups (substituted or unsubstituted alkyl).
Ren group, substituted or unsubstituted cycloalkylene group,
A substituted or unsubstituted arylene group and a substituted or unsubstituted
Substituted heteroarylene groups) as well as
Linking one or the other, or with one of these groups and Y
May contain a linking group for linking. As the linking group
Is-(covalent bond), -O-, -S-, -CO-, -C
OO-, -CONR^Ten-, -OCO-, -OCONR¹¹
-, -NR¹²CO-, -NR¹³COO-, -NR¹⁴CO
NR¹⁵-, -SO-, -SO₂-, -SO₂NR¹⁶-,-
NR¹⁷SO₂-, -SiR¹⁸R^{1 9}-,-PR²⁰-, -P
O (OR^{twenty one}) O-, -OPO (OR^{twenty two})-, -PO (O
R^{twenty three}) NR^{twenty four}-, -NR^{twenty five}PO (OR²⁶)-, -NR²⁷
PO (NR²⁸R²⁹) NR ³⁰-, -NR³¹− Is good
Good R^Ten~ R³⁰Are each independently a hydrogen atom or
It represents a substituted or unsubstituted alkyl group.

L ¹ and L ³ are a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, or these groups (substituted or unsubstituted alkylene group, substituted or unsubstituted It is preferable to represent a divalent group containing any one of an unsubstituted cycloalkylene group and a substituted or unsubstituted arylene group) and the above-mentioned linking group, and the constituent carbon atoms are 3 to 12
Or a substituted or unsubstituted alkylene group, a constituent carbon atom thereof is a substituted or unsubstituted 3 to 8 cycloalkylene group, a constituent carbon atom thereof is a substituted or unsubstituted 6 to 10 arylene group, or these groups (substituted Or an unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group and a substituted or unsubstituted arylene group), and the total number of carbon atoms containing the linking group is 6 to 20.
It is more preferable to represent the divalent group of, a substituted or unsubstituted alkylene group having 3 to 12 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, or a group thereof. It is further preferred that the carbon atom containing any one of the (substituted or unsubstituted alkylene group and the substituted or unsubstituted arylene group) and the linking group represents a divalent group of 6 to 20 in total, and the carbon atoms constituting the group are It is particularly preferred that the carbon atom containing 3 to 12 unsubstituted alkylene groups, or any of the unsubstituted alkylene groups and unsubstituted arylene groups and the linking group represents a divalent group of 6 to 20 in total.

Especially when m and n are small (specifically,
3 to 10) or when there is a linking group near Y,
L¹And L³Each of the linking groups contained in
Combined), -O-, -S-, -CO-, -COO-, -CO
NR^Ten-, -OCO-, -OCONR¹¹-, -NR¹²C
O-, -NR¹³COO-, -NR¹⁴CONR¹⁵-, -S
O-, -SO₂-, -SO₂NR¹⁶-, -NR¹⁷SO
₂-, -NR³¹− Is preferred, and − (shared binding
Combined), -O-, -S-, -CO-, -COO-, -CO
NR^Ten-, -OCO-, -NR¹²CO-, -NR¹³CO
O-, -NR¹⁴CONR ¹⁵-, -SO₂NR¹⁶-, -N
R³¹It is more preferable that it is-, (covalent bond), and -O.
-, -COO-, -CONR^Ten-, -OCO-, -NR
¹³COO-, -SO₂NR¹⁶-More preferred
,-(Covalent bond), -COO-, -OCO-, -O-
Is particularly preferable. If m and n are small,
L¹And L³The hydrophilicity of the linking group contained in each is low
In this case, the function of the hydrophobic part becomes more remarkable, and the surface tension lowering ability is improved.
It is preferable because the above properties are improved.

The preferred ranges of L ¹ and L ³ differ depending on the values of m and n, respectively. Generally, m and n
When L is small (specifically, 3 to 10), the hydrophobicity of L is increased, the water solubility is decreased, and it is easily oriented on the surface, so that even if added at a low concentration, a sufficient effect is exhibited. It will be easier. On the other hand, when m and n are large (specifically, 11
In (16) to (16), the desired solubility and surface activity can be obtained by reducing the number of carbon atoms constituting each of L ¹ and L ³ or introducing a hydrophilic linking group.

In the general formula (1), L²Is (p + 1) value
Represents the group of. Preferably, a substituted or unsubstituted alkyl
Ren group, substituted or unsubstituted cycloalkylene group,
A substituted or unsubstituted bicycloalkylene group, substituted or not
Is an unsubstituted arylene group, substituted or unsubstituted hetero
Arylene groups, or these groups (substituted or unsubstituted
An alkylene group, substituted or unsubstituted cycloalkyl
Group, a substituted or unsubstituted bicycloalkylene group,
A substituted or unsubstituted arylene group and a substituted or unsubstituted
A substituted heteroarylene group) by a linking group
Represents a bonded divalent or higher valent group. The linking group is-(covalent bond
Combined), -O-, -S-, -CO-, -COO-, -CO
NR^Ten-, -OCO-, -OCONR¹¹-, -NR¹²C
O-, -NR¹³COO-, -NR¹⁴CONR¹⁵-, -S
O-, -SO₂-, -SO₂NR¹⁶-, -NR¹⁷SO
₂-, -SiR¹⁸R¹⁹-,-PR²⁰-, -PO (O
R^{twenty one}) O-, -OPO (OR^{twenty two})-, -PO (OR^{twenty three})
NR^{twenty four}-, -NR^{twenty five}PO (OR²⁶)-, -NR²⁷PO
(NR²⁸R²⁹) NR³⁰-, -NR³¹− Is preferred
Yes. R ^Ten~ R³⁰Is a hydrogen atom or a substituted or unsubstituted
Represents an alkyl group.

The higher the hydrophilicity of L ² is, the higher the performance of the surfactant is. Therefore, L ² is --O--, --S--, --CO--, --COO.
^{-, - CONR 10 -, -} OCO -, - OCONR 11 -,
-NR ¹² CO-, -NR ¹³ COO-, -NR ¹⁴ CONR
^{15 -, - SO -, -} SO 2 -, - SO 2 NR 16 -, - NR
_{^{17 SO 2 -, - PR 20}} -, - PO (OR 21) O -, - O
PO (OR ²² )-, -PO (OR ²³ ) NR ^24- , -NR
²⁵ PO (OR ²⁶ )-, -NR ²⁷ PO (NR ²⁸ R ²⁹ ) NR
³⁰ - and -NR ³¹ - is preferably any one or more group containing a linking group, -O -, - COO -, - CO
^{NR 10 -, - OCO -,} - OCONR 11 -, - NR 12 C
^{O -, - NR 13 COO -} , - NR 14 CONR 15 -, - S
_{O -, - SO 2 -,} - SO 2 NR 16 -, - NR 17 SO
^{_{2 -, - PO (OR 21}} ) O -, - OPO (OR 22) -,
^{-PO (OR 23) NR 24 -} , - NR 25 PO (OR 26)
^{-, - NR 27 PO (NR} 28 R 29) NR 30 - and -NR
³¹ - is one or more group containing any of the linking group and even more preferably ^{-O -, - CONR 10 -,} - OCO -, - O
^{CONR 11 -, - NR 12 CO} -, - NR 13 COO -, -
NR ¹⁴ CONR ¹⁵ −, −SO ₂ NR ¹⁶ −, −NR ¹⁷ SO ₂
A group containing at least one linking group selected from — and —NR ³¹ — is particularly preferred.

In the general formula (1), p represents an integer of 1-6. It is preferably 1 to 3, and more preferably 1 or 2.

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. It is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, and 1 to 1 carbon atoms.
More preferably, it represents an alkyl group of 6 or an aralkyl group having 7 to 10 carbon atoms, and particularly preferably a methyl group.

In the general formula (1), X ⁻ represents a counter anion. Specifically, halide ions, organic carboxylates, organic sulfonates, inorganic sulfonates, and the like, halide ions, organic sulfonates are preferred, chloride ions, bromide ions, iodide ions,
Aryl sulfonates are preferred and aryl sulfonates are especially preferred.

Specific preferred examples of the fluorine compound represented by the general formula (1) are shown below, but the present invention is not limited to the following specific examples. In addition,
In the following specific examples wherein X ^- is omitted, X ^- as can be any of the above exemplified counter anion.

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

Fluorine compound represented by the above general formula (1) (hereinafter sometimes referred to as "fluorine compound of the present invention")
Are obtained by reacting the compounds represented by the following general formula (3), the following general formula (2) and the following general formula (2) ′, respectively.

[0038]

[Chemical 11]

In the above formula, R, m, n, Y, L ¹ , L ³ , L
Each of ² , p, R ¹ , R ² , R ³ and R ⁴ has the same meaning as in the general formula (1). X represents a group which can be a counter anion after the reaction.

One example of the method for producing a fluorine compound of the present invention is a solution in which equimolar amounts of the compounds represented by the general formulas (2), (2) 'and (3) are dissolved in a solvent such as methanol. Is maintained at room temperature or higher and each compound is reacted. Then, the reaction solution may be concentrated to obtain the desired product.

The fluorine compound of the present invention is used as a surfactant in various recording materials (especially silver halide photographic light-sensitive materials).
It is preferably used in an aqueous coating composition for forming the layers constituting the. Among them, it is particularly preferable to use it for forming the hydrophilic colloid layer as the uppermost layer of the photographic light-sensitive material, since it is possible to obtain effective antistatic ability and coating uniformity.
Hereinafter, the aqueous coating composition containing the fluorine compound of the present invention as a surfactant will be described.

The aqueous coating composition contains the fluorine compound of the present invention and a medium in which the fluorine compound is dissolved and / or dispersed. In addition, other components may be appropriately contained depending on the purpose. In the aqueous coating composition,
The medium is preferably an aqueous medium. The aqueous medium is
Water and organic solvents other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol,
(Methyl cellosolve, dimethylformamide, acetone, etc.) and water. 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, one type of the fluorine compound of the present invention may be used alone, or two or more types may be mixed and used. Further, other surfactant may be used together with the fluorine 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,
A fluorine-based surfactant other than the surfactant of the present invention may be used. 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 (pages 649 to 706), Research Disclosure (RD) Item 17643, pages 26 to 27 (December 1978).
18) 16650 (November 1979),
307105, pages 875-876 (November 1989)
Mon) and the like.

Typical examples of the other components which may be contained in the aqueous coating composition 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. Derivative, methacrylate derivative, acrylamide derivative,
A methacrylamide derivative, a styrene derivative, a conjugated diene derivative, an N-vinyl compound, an O-vinyl compound, vinyl nitrile, another vinyl compound (for example, ethylene, vinylidene chloride)], a homopolymer or a copolymer, and a dispersion of a condensation polymer ( For example, polyester, polyurethane, polycarbonate, polyamide) can be mentioned.
For specific examples of this type of polymer compound, for example,
JP-A-62-215272 (707-763)
Page), Research Disclosure (RD) Item 1764
3,651 (Dec. 1978), id 18716, 6
50 pages (November, 1979), ibid., 307105, 873.
Up to page 874 (November 1989) and the like.

The aqueous coating composition may contain various other compounds, and they may be dissolved or dispersed in a medium. For example, when used for forming a constituent layer of a photographic light-sensitive material, various couplers,
Examples thereof include an ultraviolet absorber, a color mixing inhibitor, a static inhibitor, a scavenger, an antifoggant, a hardener, a dye, and an antifungal agent. Further, as described above, the aqueous coating composition of the present invention is preferably used for forming the hydrophilic colloid layer of the uppermost layer of the photographic light-sensitive material, but in this case, the coating composition contains a hydrophilic colloid. In addition to (for example, gelatin) and the fluorine compound of the present invention, other surfactants, matting agents, sliding agents, colloidal silica, gelatin plasticizers and the like can be contained.

The amount of the fluorine compound used in the present invention 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 raw material contained in the aqueous composition, the constitution of the medium and the like. The amount can be arbitrarily determined. For example, when the aqueous coating composition 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 fluorine compound of the present invention in the coating composition is 0. It is preferably from 0.003 to 0.5% by mass, and is 0.1% with respect to the gelatin solid content.
It is preferably from 03 to 5 mass%.

[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 fluorine 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 fluorine 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 more preferable the photographic performance is obtained, so that the tabular grain emulsion preferably has 50% or more of the total projected area 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 circle equivalent 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 for changing the side index 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 in the process for producing a silver halide emulsion. 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.

In the case of 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)₂PdC
l₆, Na₂PdCl_Four, (NH_Four)₂PdCl_Four, Li₂Pd
Cl_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, "Photoemulsion 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.

Preferred sensitization method for silver halide emulsions
There is selenium sensitization. Known for selenium sensitization
The unstable selenium compound of
Metal selenium, selenoureas (for example, N, N-dimethyl
Tilselenourea, N, N-diethylselenourea, etc.),
Uses selenium compounds such as renoketones and selenoamides
Can be Selenium sensitization is sulfur sensitization or precious gold
Better to use in combination with genus sensitization or both
There may be better cases. For example, thiocyanate is described above
Added before adding the spectral sensitizing dye and chemical sensitizer
Is preferred. More preferably, even more preferably after forming particles.
More preferably, it is added after the desalting step is completed. Even during chemical sensitization
It is preferable to add cyanate, ie chemical sensitization
It is preferable to add thiocyanate more than once in the process
Good As thiocyanate, potassium thiocyanate is used.
, Sodium thiocyanate, ammonium thiocyanate
Are used. Thiocyanate is usually an aqueous solution.
Alternatively, it is dissolved in a water-soluble solvent and added. Addition amount is halo
1 × 10 per mol of silver genide^-Fivemol ~ 1 x 10 ^-2
mol, more preferably 5 × 10^-Fivemol-5 × 10^-3
mol.

Gelatin is advantageously used as the protective colloid used in the preparation of the silver halide emulsion and as the binder of the other hydrophilic colloid layers, 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 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.

Desalting during preparation of emulsion, for example, during grain formation
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. It is also possible to add a water-soluble silver salt (eg AgNO ₃ ) or an alkali halide water-soluble (eg NaCl, KBr, KI) and continuously add it 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 thiosulfonates 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 manufacturing 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. The treatment is described in European Patent No. 0565096A1 (published October 13, 1993) 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.

[0081] 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 fluorine compound of the present invention, or may be used in combination. It doesn't matter. ) 13 Static Page 27 Page 650 Right column 876-877 page     Preventive agent 14 Matting agent 878-879 page

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.

[0083]

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. <Synthesis Example Synthesis of Exemplified Compound FS-3> N- (3-Dimethylaminopropyl) -6- (3,3,4,4,5,
5,6,6,6-Nonafluorohexylthio) -hexanamide 4.07 g (8.5 mmol), methanol 5
mL and triethylene glycol di-p-toluenesulfonate (1.95 g, 4.25 mmol) were mixed, and the mixture was reacted at room temperature for 1 hour and then at 40 ° C. for 1 hour. The reaction solution is concentrated and dried, and 1,8-bis [3- [8- (3,3,
4,4,5,5,6,6,6-Nonafluorohexylthio) -hexanecarbamoyl] -propyl-dimethylammonium] -3,6-dioxaoctane = p-toluenesulfonate (FS-3: X = para Toluene sulfonate) was obtained in an amount of 6.1 g. ¹ H-NMR of the obtained compound
The data are as follows. ¹ H-NMR (heavy DMSO): δ1.15-1.40
(M, 8H), 1.50-1.65 (m, 8H), 1.7
5-1.88 (m, 4H), 2.05 (t, 4H), 2.
30 (s, 6H), 2.58 (t, 4H), 2.65-
2.80 (m, 4H), 3.00-3.15 (m, 16
H), 3.30-3.48 (m, 8H), 3.50-3.
65 (m, 4H), 3.75-3.90 (s, 4H),
7.11 (d, 4H), 7.50 (d, 4H), 7.85
−7.95 (m, 2H)

<Example 1: Measurement of surface tension lowering ability of fluorine compound> The fluorine compound of the present invention shown in Table 1 below and a fluorine-containing surfactant for comparison (comparative compounds FC-1 to FC-1).
3) A 0.0001 to 1.0 mass% aqueous solution of 3) is prepared,
Kyowa Interface Science Co., Ltd. automatic surface tension meter (CBVP-
Z type).

[0085]

[Table 1]

[0086]

[Chemical 12]

From the results shown in Table 1, the fluorine compounds of the present invention are FC-2 and 3 which are conventional cationic surfactants.
It was found that the micelle forming ability was superior to that of the perfluorooctanesulfonic acid derivative FC-1 and that the performance was equal to or higher than that of the perfluorooctanesulfonic acid derivative FC-1.

<Example 2: 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 (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary particle 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 by a bar coating method at 10 mL / The coating amount was 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: 77.1 Am ^{2 /} kg, σr: 37.4 Am ²
/ Kg) 1100 parts by mass, water 220 parts by mass and a silane coupling agent [3- (poly (degree of polymerization of 10) oxyethynyl) oxypropyltrimethoxysilane] 165 parts by mass, and well kneaded in an open kneader for 3 hours. did. The roughly dispersed viscous liquid was dried at 70 ° C. for one day and night to remove water, and then heat-treated 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 substance-containing intermediate liquid was prepared according to 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, 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% solids, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion liquid b] 128 g (solid content 30%) AA-1.5 dispersion liquid [Dispersion liquid a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industry Co., Ltd.) diluent 203 g (solid content 20%, diluted) Solvent: Methyl ethyl ketone / cyclohexanone = 1/1) Methyl ethyl ketone 170 g Cyclohexanone 170 g A 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 Layer of Higher Fatty Acid Ester Lubricant) Preparation of Dispersion Stock Solution of Sliding Agent The following solution (a) was dissolved by heating at 100 ° C., added to solution (i) and dispersed by a high-pressure homogenizer to prepare a slip agent. A dispersion stock solution of was prepared. Solution A 399 parts by mass of the following compound C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H ₁₀₁ 171 parts by mass of the following compound n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 parts by mass a 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

[0095]

[Chemical 13]

[0096]   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 with the above formulation, the following was additionally added. 252.93 parts by mass of diacetone alcohol 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.

[0101]   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

[0102]   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

[0103]   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

[0104]   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

[0105]   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

[0106]   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

[0107]   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. Wet cake of ExF-2 (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 0.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) A slurry of the above composition was stirred with a dissolver to roughly disperse, and then an 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.

[0110]

[Table 2]

In Table 2, the emulsions Em-A to C were optimally added with 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.

[0112]

[Table 3]

The sensitizing dyes listed in Table 3 are shown below.

[0114]

[Chemical 14]

[0115]

[Chemical 15]

[0116]

[Chemical 16]

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.

[0118]

[Chemical 17]

[0119]

[Chemical 18]

[0120]

[Chemical 19]

[0121]

[Chemical 20]

[0122]

[Chemical 21]

[0123]

[Chemical formula 22]

[0124]

[Chemical formula 23]

[0125]

[Chemical formula 24]

[0126]

[Chemical 25]

[0127]

[Chemical formula 26]

[0128]

[Chemical 27]

[0129]

[Chemical 28]

The above silver halide color photographic light-sensitive material was used as a sample 100. 16th with respect to the above sample 100
Sample 101 was prepared in the same manner as Sample 100, except that the fluorine compound FS-7 of the present invention was added to the layer at 0.008 g / m ² as a surfactant. 16th in Sample 101
To the FS-7 of the layer, the fluorine compound and the comparative compound shown in Table 4 were added as surfactants in place of FS-7 so that the addition amount for each layer would be an equal mass in terms of the amount of fluorine. Samples 102-104 and Comparative Sample 1
05-107 were produced respectively.

<Evaluation> (1) Charge Adjustment Ability Test The charge adjustment ability of the manufactured samples 100 to 107 was evaluated. After charging the surface of the sample of 35 mm x 120 mm opposite to the emulsion-coated surface with a double-sided tape in an environment of a temperature of 25 ° C and a relative humidity of 10%, after carrying out a nip between opposing rubber rollers grounded, , Faraday cage. The measurement results of the charge amount are shown by the charge series index. The charge train index is 1 obtained by subtracting the charge amount of each of the samples 101 to 110 from the charge amount of the sample 100.
It is a value multiplied by ⁰⁹ . Those having a charge train index smaller than -0.5 were judged to have sufficient charge train adjusting ability. The results are shown in Table 4.

[0132]

[Table 4]

From the results shown in Table 4, the surfactant containing no fluorine has no charge adjusting ability, whereas the conventional fluorine-containing surfactant exhibits the charge adjusting ability when the perfluoroalkyl group has a long chain. It was found that the compound having a short-chain fluorinated alkyl group having 4 carbon atoms (Comparative Compound FC-2) had a reduced charge adjusting ability. On the other hand, it was revealed that the fluorine compound of the present invention has a sufficient charge controllability even when the fluorinated alkyl group has a short chain. The surface of the sample of the present invention is treated with XPS (X-ray photoelec).
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 fluorine compound of the present invention effectively contained the fluorine atom on the sample surface. I realized that

(2) Repelling property evaluation In the samples 101 to 107, the constitutional components were the same except that the particle size of B-1 in the 16th layer was 3 μm and all the fluorine compounds to be added had the same mass as the sample 101. Samples 201 to 207 shown in Table 5 were prepared. Further, a sample 208 was prepared in the same manner as the sample 201, except that the fluorine compound to be added was replaced with potassium 2- (N-propyl-perfluorooctane sulfamoyl) ethanoate. In the preparation of Samples 201 to 208, the slide bead coating method was used to form the 16th layer at 1 m / s.
After applying the coating solution with ec, it is immediately dried, and the number of craters (where the coating film is repelled in spots) on the surface of the coating film is visually counted, and the repellency frequency is calculated based on the counted value. Was calculated. Here, 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 is 100 or less, the repelling effect was determined to be effective. The results are shown in Table 5.

[0135]

[Table 5]

From the results shown in Table 5, it was found that when the coating liquid containing the fluorine compound of the present invention as a surfactant was used, the cissing number was reduced in all cases. That is, it was found that the fluorine compound of the present invention is excellent in the ability to reduce the occurrence of cissing. Further, together with the results in Table 4, it was revealed that the fluorine compound 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 107 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 of 24 sheets) 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 treatment 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

[0140]   (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

[0141]   (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

[0143]

As described above, according to the present invention,
Even when it has a perfluoroalkyl group that is not a perfluorooctane sulfonic acid derivative or a perfluorohexanoic acid derivative, it has excellent surface orientation and enables the formation of a uniform coating film when used for coating formation. It is possible to provide a different fluorine compound. Further according to the invention,
It is possible to provide a silver halide photographic light-sensitive material which is capable of stable production and has antistatic properties. Particularly, even with a compound having a short perfluoroalkyl chain, a uniform and excellent coating film can be formed, and a silver halide photographic light-sensitive material excellent in antistatic property can be provided.

Claims (2)

[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 represents a hydrogen atom or a fluorine atom, m and n each represent an integer of 3 to 16, and Y represents a single bond, —S—, —SO ₂ —, —SO—, or —O. Represents-, L ¹ and L ³ each independently represent a divalent group having 4 or more carbon atoms, L ² represents a (p + 1) -valent group, and p is any of 1 to 6 Represents an integer of R ¹ , R ² ,
R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X ⁻ represents a counter anion, but may not be present when forming an intramolecular salt. ) 2. A fluorine compound represented by the following general formula (1). [Chemical 2] (In the formula, R represents a hydrogen atom or a fluorine atom, m and n each represent an integer of 3 to 16, and Y represents a single bond, —S—, —SO ₂ —, —SO—, or —O. Represents-, L ¹ and L ³ each independently represent a divalent group having 4 or more carbon atoms, L ² represents a (p + 1) -valent group, and p is any of 1 to 6 Represents an integer of R ¹ , R ² ,
R ³ and R ⁴ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X ⁻ represents a counter anion, but may not be present when forming an intramolecular salt. )