JPH0619523B2 - A silver halide photographic light-sensitive material in which the occurrence of static marks and bending fog are prevented. - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material in which static marks and bending fog are prevented.

BACKGROUND OF THE INVENTION It is known that a support having an electrically insulating property used in a photographic light-sensitive material is easily charged by friction or peeling and causes various troubles such as suction of dust, electric shock and ignition. Further, also in a silver halide photographic light-sensitive material using such a support, various steps in its production, that is, winding, rewinding, coating of various coating layers including a photosensitive layer, and drying are performed. It is charged by friction or peeling with other substances during the process of transportation, and when it is discharged, the photographic light-sensitive material coated with the light-sensitive layer is exposed, and after development, it is called static mark. Irregular uneven light exposure due to static electricity occurs. Furthermore, when the manufactured photographic light-sensitive material is used or processed, static mark failure similarly occurs and various obstacles due to adhesion of dust and the like occur. The higher the sensitivity of the photosensitive material, the more remarkable the generation of these static marks. With the recent increase in the sensitivity of the photosensitive material, not only is the demand for a technology for suppressing the generation of static marks increasing, Acceleration of coating in material manufacturing process,
With the increase in the speed of drying and the increasing number of opportunities for severe mechanical handling due to high-speed automatic development processing, there is an increasing need for a technique for suppressing the occurrence of various failures due to electrostatic charging.

Especially in recent years, an ultra-compact high-speed automatic development processor called a minilab has been rapidly popularized, but most of them have a silver halide photographic light-sensitive material sandwiched by two rubber rollers from both sides and pressure-bonded to a development rack. Since it is designed to be transported, the generation of static marks that occur during transportation and the occurrence of bending fog in the compact processing machine will increase as the sensitivity of silver halide photosensitive materials increases. It's a problem.

In order to solve such a problem, various methods have been tried so far. A well-known and used method is to provide a conductive layer using a hydrophobic polymer as a binder on the back surface of the photographic light-sensitive material (the surface without the photographic light-sensitive layer, hereinafter referred to as BC layer). is there. However, a hydrophobic polymer has a small volume change with humidity, whereas a hydrophilic colloid coating film containing a silver halide emulsion such as a gelatin coating film has a large volume change with humidity.

Therefore, in a silver halide photographic light-sensitive material having a silver halide emulsion layer on the front surface and a conductive layer with a hydrophobic polymer as a binder on the back surface, the curl change due to humidity is large and It was difficult to apply to a light-sensitive material having a large area. Therefore, at the expense of antistatic performance,
It has been practiced to make the BC layer a hydrophilic colloid layer such as gelatin to suppress the curl change.

On the other hand, by improving the hydrophilic colloid layer itself,
Attempts have also been made to improve antistatic performance. For example, British Patent No. 861,134, German Patent No. 1,422,809,
Japanese Patent Publication No. 47-8742, Japanese Publication No. 57-19406, Japanese Publication No. 58-4329
Nonionic surfactants having a polyoxyethylene chain in the molecule shown in JP-A No. 58-208743, JP-A No. 58-203435, etc. are known to have excellent antistatic properties. .

It is also known to incorporate a fluorine-containing compound in a hydrophilic colloid to reduce the generation of static electricity.

For example, British Patent Nos. 1,330,356 and 1,524,631, US Patents 3,666,478 and 3,589,906, and Japanese Patent Publication No. 52-26687.
Nos. 4,352,975 and 1,497,256, and fluorine-containing surfactants disclosed in JP-A-49-46733 and JP-A-51-32322.
U.S. Pat.Nos. 3,753,716, 4,087,394, JP-A-54
-158222, JP-A-60-44973, and other fluorine-containing polymers.

However, when these compounds are contained in the hydrophilic colloid layer of a silver halide photographic light-sensitive material, the antistatic performance is somewhat improved, but the antistatic performance is not sufficient only by the individual techniques. In the case of a hydrophilic colloid layer such as, a static mark is generated and dust is more likely to be adsorbed to a dry film after development, as compared with the above-described silver halide photographic light-sensitive material in which a conductive layer is provided on the BC layer. It was a thing.

Therefore, when the gelatin BC layer contains a matting agent having a particle size of 3 μm or more, and the protective layer of the silver halide emulsion layer contains a polyoxyethylene-based surfactant and a silicone-based sliding agent, static marks are generated. A technique for preventing this is disclosed in JP-A-61-42653. Similarly, the emulsion layer and the protective layer contain a matting agent having a particle size of 3 μm or more, and the gelatin BC layer contains a fluorine-containing surfactant, a polyoxyethylene-based surfactant and a silicone-based slipping agent. A technique for preventing the occurrence of tick marks is disclosed in Japanese Patent Laid-Open No. 61-4.
It is shown in No. 25653.

In these techniques, a matting agent having a particle size of 3 μm or more is contained on one of the surfaces of two hydrophilic colloid layers sandwiching a support, and an antistatic agent and a lubricating sliding agent are used on the other side to make a static The mark is prevented from occurring. According to this method, it is possible to prevent the transfer of the silicone-based slipping agent, and to prevent the increase of the generation of static marks in the silver halide light-sensitive material stored in a rolled state for a long time to some extent, In the light-sensitive material, it is still not sufficient, and devitrification is caused by the use of a matting agent having a larger particle diameter, and the level of antistatic performance is the same as that of the above-described silver halide photographic light-sensitive material having a conductive layer on the back surface. However, it was difficult to apply it to a light-sensitive material having a low sensitivity and a high sensitivity.

[Object of the Invention] Accordingly, an object of the present invention is to suppress the generation of static marks, and particularly to suppress the generation of static marks when the both sides are strongly sandwiched by rubber rollers and conveyed. Further, it is to prevent the occurrence of fog on bending, and further to prevent the deterioration of the static mark generation preventing performance of the photosensitive material which has been wound and stored for a long period of time.

[Structure of the Invention] The present inventors have found that rather than using the surface modifier as described above on only one surface of the two hydrophilic colloid layers sandwiching the support, the hydrophilic colloid layer on both surfaces of the hydrophilic colloid layer is not It was found that excellent effects can be obtained by properly using the above surface modifiers, and the present invention has been completed.

That is, the object of the present invention is to provide a silver halide photographic light-sensitive layer having photographic constituent layers on both sides of a support, wherein the uppermost layers of the two photographic constituent layers are each represented by the following general formula [I]. Organopolysiloxane having a constitutional unit having a terminal group represented by the following general formula [II], a fluorine-containing compound represented by the following general formula [III], and a nonionic having a polyoxyethylene unit. Characterized in that it contains at least one compound selected from three compounds of surfactants, and that all of the three compounds are contained in either of the uppermost layers of the two photographic constitutional layers. And a silver halide photographic light-sensitive material.

General formula [I] [Wherein R ₁ represents a hydrogen atom, a hydroxy group or an organic group, R ₂ represents an organic group, and when R ₁ and R ₂ are organic groups, they may be the same or different. ] General formula [II] [Wherein R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom,
It represents a hydroxy group or an organic group, and R ₃ , R ₄ and R ₅ may be the same or different from each other. ] General formula [III] [In the formula, Rf represents an alkyl group, an alkyloxy group, an alkenyl group, an aryl group or an aryloxy group having at least 3 fluorine atoms.

A represents a divalent linking group, and X represents a hydrophilic group.

m represents 0 or 1. [Specific Structure of the Invention] In the present invention, the photographic constituent layers are a photosensitive silver halide emulsion layer, non-photosensitive layers such as an antihalation layer, an intermediate layer, a filter layer and a protective layer, and a back coat layer, It means all layers coated on a support, such as an overcoat layer.

Preferred as the silver halide photographic light-sensitive material of the present invention is one having a silver halide emulsion layer on one side of the support and a back coat layer on the other side.

Next, the organopolysiloxane, the fluorine-containing compound and the nonionic surfactant having a polyoxyethylene unit according to the present invention will be described.

Examples of the organopolysiloxane according to the present invention include U.S. Patents 3,042,522, 3,080,317, 2,694,637, Japanese Patent Publication No. 39-15714, British Patent 1,030,811, and 1,143,118.
Issue, 1,528,656, 1,275,657, 1,278,402,
No. 1,313,384, Japanese Patent Publication No. 51-15740, Japanese Patent Publication No. 45-34230
No. 4, JP-B-46-27428, JP-A-49-62128, JP-A-49-6
2127, JP-B-53-272, JP-B-55-47294, JP-A-60
-140341, 60-140342, 60-140343, 60-1889
No. 45, No. 60-231704, No. 60-231720, No. 60-240761
No. 60, No. 60-243167, No. 60-240732, No. 60-245638,
The compounds described in No. 61-216, No. 61-232, No. 61-260, etc. can be used.

Among the organopolysiloxanes according to the present invention, preferred compounds are those having a structural unit represented by the following general formula [I] in the compound, and the terminal of the compound having a terminal represented by the following general formula [II]. The thing having a group is mentioned. Further, although there are at least two terminals, these terminals may be the same group or different groups as long as they are represented by the general formula [II].

General formula [I] In the general formula [I], R ₁ represents a hydrogen atom, a hydroxy group or an organic group, R ₂ represents an organic group, and when R ₁ and R ₂ are organic groups, they may be the same or different. Examples of the organic group represented by R ₁ and R ₂ include alkyl groups, alkenyl groups, alkoxy groups, oxyalkylene groups, aryl groups and groups containing these groups.

General formula [II] In the general formula [II], R ₃ , R ₄ and R ₅ represent a hydrogen atom, a halogen atom, a hydroxy group or an organic group, and R ₃ , R ₄ and R ₅ may be the same or different from each other. good. Examples of the organic group include an alkyl group,
Examples thereof include alkenyl groups, alkoxy groups, oxyalkylene groups, aryl groups and groups containing these groups.

In the general formula [II], examples of the halogen atom represented by R ₃ , R ₄ and R ₅ include a fluorine atom and a chlorine atom.

In the general formulas [I] and [II], R ₁ , R ₂ , R ₃ ,
Examples of the alkyl group that can be mentioned as an example of the organic group represented by R ₄ and R ₅ include a methyl group, an ethyl group, a propyl group, an i-propyl group, a t-butyl group, a hexyl group,
Dodecyl group, tetradecyl group, heptadecyl group, octadecyl group and the like, alkenyl group, for example, vinyl group, butenyl group and the like, further alkoxy group, for example, methoxy group, ethoxy group, butoxy group and the like. Examples of the oxyalkylene group include an oxyethylene group, oxypropylene group and polyoxyethylene group, and examples of the aryl group include a phenyl group.

Examples of the group containing an alkyl group which is mentioned as an example of the organic group represented by R ₁ , R ₂ , R ₃ , R ₄ and R ₅ include —CH ₂ CH ₂ CF ₃ , —CH ₂ CH ₂ CH ₂ Cl, _{-CH 2 CH 2 COOH, -CH 2} CH 2 CH 2 COOH, -CH 2 CH 2 CH 2 NH 2, -CH 2 CH 2 CH 2 NHCH 2 CH 2 NH 2, The group comprises _{-CH 2 CH 2 SH, -CH 2} CH 2 CH 2 CN, -OOCC 17 H 35 and the like, also the alkenyl groups mentioned as examples of organic groups, for example CH ₂ CH ₂ SO ₂ CH═CH ₂ , and the like, and examples of the group containing an alkoxy group include —CH ₂ CH ₂ —O—C ₄ H ₉ (n) and —OCH ₂ CH ₂ OH. As the group containing an oxyalkylene group, for example, Etc., and examples of the group containing an aryl group include Etc.

The viscosity of the organopolysiloxane according to the present invention is not particularly limited, but normally, the viscosity measured at 25 ° C. is about 20.
Those showing ~ 100,000 centistokes are suitable.

The molecular weight of the organopolysiloxane according to the present invention can be used in the range of 1,000 to 1,000,000 according to the purpose, but is preferably 2,000 to 50,000.

Next, specific compounds of the organopolysiloxane according to the present invention will be listed, but the present invention is not limited thereto.

S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10 S-11 S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 S-20 S-21 S-22 S-23 S-24 S-25 S-26 S-27 S-28 S-29 S-30 S-31 S-32 S-33 S-34 S-35 S-36 S-37 S-38 S-39 S-40 S-41 S-42 S-43 S-44 S-45 S-46 S-47 S-48 Examples of the fluorine-containing compound according to the present invention include British Patent Nos. 1,293,189, 1,259,398, and U.S. Pat.
No. 6, No. 3,666,478, No. 3,754,924, No. 3,775,236,
3,850,640, JP 54-48520, 56-114944,
50-161236, 51-151127, 50-59025, 50-113
No. 221, No. 50-99525, Japanese Patent Publication No. 48-43130, Japanese Patent Publication No. 56-44
No. 411, No. 57-6577, JP-A No. 58-200235, No. 58-196544
JP-A-53-84712, JP-A-57-64228, JP-A-60-25854
Issue 2, I & EC Product Research and Development
and Development) 1 (3) (1962, 9), Oil Chemistry 12
(12) Fluorine-containing surfactants described in (1963) p653 to 622, etc., or JP-A Nos. 54-158222 and 52-12.
9520, JP-A-49-23828, British Patent No. 1,352,975,
1,497,256, U.S. Pat.No. 4,087,394, 4,016,125
No., No. 3,240,604, No. 3,679,411, No. 3,340,216,
3,632,534, JP-A-48-30940, JP-A-52-129520
No. 60-44973, No. 60-210613, No. 57-11342
No. 54-158222, No. 60-76742, No. 60-80849, US Pat. No. 3,753,716, and the like, and the fluorine-containing polymers are used.

A particularly preferred fluorine-containing compound is a fluorine-containing surfactant represented by the following general formula.

Rf- (A) _m -X In the formula, Rf is an alkyl group having at least three fluorine atoms (including those having a substituent, for example, dodecafluorohexyl group, heptadecafluorooctyl group, etc.),
Alkyloxy group (octylfluorooxy group), alkenyl group (including those having a substituent, for example, heptafluorobutylene group, tetradecafluorooctyl group, etc.),
An aryl group (including those having a substituent, for example, a trifluorophenyl group, a pentafluorophenyl group, etc.) or an aryloxy group (octylfluorophenyloxy group, etc.) is represented. A represents a divalent linking group, X represents a hydrophilic group, and m represents 0 or 1.

A is preferably an alkylene group (including those having a substituent, such as an ethylene group and a trimethylene group), an arylene group (including those having a substituent, such as a phenylene group), an alkylarylene group (having a substituent It also includes those having, for example, propylphenylene group, etc.) or arylalkylene groups (including those having a substituent, such as phenylethylene group, etc.), and these groups include oxygen atom, ester group, amide group, Also included are sulfonyl groups, heteroatoms such as sulfur atoms, or divalent linking groups interrupted by heterologous groups.

X is a hydrophilic group, for exampleA polyoxyalkylene group of (where B isRepresents the average degree of polymerization of the polyoxyalkylene group
Is an integer of 1 to 50. Also R₁Is a hydrogen atom,
Having an alkyl group or a substituent, including those having a substituent
Represents an aryl group including those including )
A nonion group, for example(In the formula, R_FourIs an alkylene group having 1 to 5 carbon atoms, for example
Represents methylene, ethylene, propylene, butylene
And R₂, R₃Has a substituent having 1 to 8 carbon atoms
Alkyl groups that also include, aryls that also have substituents
Represents a group such as a methyl group, an ethyl group, a benzyl group, etc.
You ) A hydrophilic betaine group represented by(In the formula, R₂, R₃, R_FiveIs the R₂Is synonymous with Y Is
Represents an anion, for example, a hydroxy group, a halogen group,
Sulfate group, carbonate group, perchlorate group, organic carboxylic acid group, organic
It represents a sulfonic acid group, an organic sulfuric acid group, or the like. )
Hydrophilic cation groups, eg -SO₃M-, -OSO₃M
-, -COOM,M represents an inorganic or organic cation, preferably water.
Elementary atoms, alkali metals, alkaline earth metals, ammoniu
And alkylamines having 1 to 3 carbon atoms. A
And Rf are as defined above. ) Hydrophilicity
An example is a nonion group. Hydrophilic group represented by X
Of these, a hydrophilic anion group and a hydrophilic base are particularly preferred.
It is a tine group.

Specific examples of typical fluorine-containing compounds of the present invention are shown below.

F-1 C ₇ F ₁₅ COOH F-2 F-3 C ₈ F ₁₇ SO ₃ K F-4 F-5 F-6 F-7 F-8 F-9 F-10 F-11 F-12 F-13 F-14 F-15 F-16 F-17 F-18 F-19 F-20 F-21 F-22 F-23 F-24 F-25 F-26 F-27 F-28 F-29 F-30 F-31 F-32 F-33 F-34 F-35 F-36 F-37 F-38 F-39 F-40 F-41 F-42 F-43 F-44 F-45 F-46 F-47 F-48 F-49 F-50 F-51 F-52 F-53 F-54 F-55 Next, the nonionic surfactant having a polyoxyethylene unit according to the present invention will be described (hereinafter abbreviated as nonionic surfactant).

The nonionic surfactants preferably used in the present invention include the following general formulas [NI], [N-II] and [N-].
III] can be mentioned.

General formula [NI] General formula [N-II] General formula [N-III] In the above general formula [N-I], R ₁ represents a hydrogen atom or an alkyl group, an alkenyl group or an aryl group having 1 to 30 carbon atoms, preferably 4 to 24 carbon atoms, and these groups have a substituent. Things are also included.

Examples of the alkyl group represented by R ₁ include a methyl group,
Examples thereof include an ethyl group, an octyl group, a dodecyl group, a tridecyl group, a hexadecyl group, and a docosyl group. Of these, an octyl group, a dodecyl group, a tridecyl group, and a hexadecyl group are preferable examples.

Examples of the substituent of the alkyl group represented by R ₁ include a hydroxy group, a halogen atom, an alkoxy group, an alkylthio group and the like.

The alkenyl group represented by R ₁ is an alkenyl group having 1 to 30 carbon atoms, preferably an alkenyl group having 4 to 24 carbon atoms, and specifically, a vinyl group, an allyl group, an isopropenyl group, a heptadecenyl group, an octadecenyl group. Etc.

Examples of the aryl group represented by R ₁ include a phenyl group and a naphthyl group.

When the aryl group has a substituent, examples of the substituent include an alkyl group such as a butyl group, a pentyl group, an octyl group, a nonyl group, an undecyl group, and a pentadecyl group.

The aryl group may have two or more substituents, preferably two substituents, which may be the same or different, and the mutual bonding positions of the substituents are, for example, When there are two, 1 for the phenyl group
The 3-position or 4-position is preferable, and the case where the 1-position and the 3-position respectively have a substituent is more preferable.

A represents a divalent linking group. As the linking group represented by A, for example, -O-, -S-, (Here, R ₁₂ represents a hydrogen atom or an alkyl group including those having a substituent, and 1 represents a number of 1 to 20) and the like.

n ₁ is the average number of moles of ethylene oxide added and is 2
It is a number of -50, preferably a number of 5-30, and particularly preferably a number of 7-25.

In the above general formula [N-II], R ₂ and R ₃ represent a hydrogen atom, an alkyl group, an alkoxy group or an acyl group.

Examples of the alkyl group represented by R ₂ and R ₃ include a methyl group, an ethyl group, an octyl group and a nonyl group, and an octyl group and a nonyl group are preferable.

Examples of the alkoxy group represented by R ₂ and R ₃ include a methoxy group, an ethoxy group and an octoxy group.
It is preferably an octoxy group.

Examples of the acyl group represented by R ₂ and R ₃ include a butyryl group, an isobutyryl group, a valeryl group and the like, and a valeryl group is preferable.

R ₄ and R ₅ represent a hydrogen atom or an alkyl group.

Examples of the alkyl group represented by R ₄ and R ₅ include a methyl group, an ethyl group and a propyl group, and a methyl group is preferable.

m is an integer of 2 to 50, preferably 3 to 20.

n ₂ has the same meaning as n ₁ .

In the above general formula [N-III], R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of the alkyl group represented by R ₆ and R ₇ include a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group or an ethyl group is preferable.

Examples of the aryl group represented by R ₆ and R ₇ include a phenyl group and a naphthyl group, and a phenyl group is preferable.

Examples of the heterocyclic group represented by R ₆ and R ₇ include a furyl group and a thienyl group, and a furyl group is preferable.

R ₈ and R ₁₀ represent a halogen atom or an alkyl group.

Examples of the halogen atom represented by R ₈ and R ₁₀ include a fluorine atom, a chlorine atom and a bromine atom, and a chlorine atom is preferable.

Examples of the alkyl group represented by R ₈ and R ₁₀ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group,
t-pentyl group, t-hexyl group, t-heptyl group, t
-Octyl group, nonyl group, decyl group, dodecyl group, octadecyl group and the like, preferably methyl group, ethyl group, isopropyl group, t-butyl group, t-pentyl group,
It is a t-hexyl group, a t-octyl group or a nonyl group.

R ₉ is a hydrogen atom or an alkyl group (for example, a methyl group,
(Ethyl group, propyl group, etc.) and the like, but preferably a hydrogen atom.

R ₁₁ represents a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom or an alkoxy group, particularly preferably a hydrogen atom.

Examples of the alkyl group represented by R ₁₁ include a methyl group, an ethyl group, a propyl group and the like.

Examples of the alkoxy group represented by R ₁₁ include a methoxy group, an ethoxy group and a propoxy group, and a methoxy group is preferable.

n ₃ and n ₄ may be the same or different and have the same meaning as n ₁ . Preferably n ₃ and n ₄ are the same.

These compounds are described in, for example, U.S. Patent Nos. 2,982,651 and 3,4.
28,456, 3,457,076, 3,454,625, 3,552,97
No. 2, No. 3,655,387, Japanese Patent Publication No. 51-9610, JP-A No. 53-2971
No. 5, No. 54-89626, No. 58-203435, No. 58-208743,
It is described in “New Surfactants” by Hiroshi Horiguchi (Sankyo Publishing Co., Ltd., 1975).

Next, specific examples of the nonionic surfactant preferably used in the present invention will be shown.

N-1 N-2 N-3 N-4 N-5 N-6 N-7 N-8 N-9 N-10 N-11 N-12 N-13 N-14 N-15 N-16 N-17 N-18 N-19 N-20 N-21 N-22 N-23 N-24 N-25 N-26 N-27 N-28 N-29 N-30 N-31 N-32 N-33 N-34 N-35 N-36 N-37 N-38 N-39 N-40 N-41 N-42 N-43 N-44 N-45 N-46 N-47 The amount of the organopolysiloxane according to the present invention is preferably used in a weight ratio of 0.3 to 30% with respect to a water-soluble binder such as gelatin.

The amounts of the fluorine-containing compound according to the present invention and the nonionic surfactant according to the present invention are preferably used in a weight ratio of 0.5 to 10% with respect to a water-soluble binder such as gelatin.

In the present invention, a preferable embodiment of the silver halide photographic light-sensitive material is that the uppermost photographic constituent layer on one side of the support is
Contains an organopolysiloxane and a fluorine-containing compound or an organopolysiloxane and a nonionic surfactant,
By containing a nonionic surfactant or a fluorine-containing compound in the uppermost layer of the photographic constituent layer on the other side of the support, the static friction coefficient of the outermost surface of one photographic constituent layer is 0.2 or less, and The absolute value of the peeling charge amount of the uppermost one of the photographic constituent layers was adjusted to 200 pico coulombs / cm ² or less.

Further, the organopolysiloxane, the fluorine-containing compound and the nonionic surfactant may be contained in both uppermost layers, but may be contained in either one of the uppermost layers.

Generally, the uppermost layer of a silver halide photographic light-sensitive material is a protective layer,
This is a back layer, an overcoat layer, or the like, and the present invention can be applied when the uppermost layer is any of these layers. Further, the present invention can be applied when the uppermost layer is a silver halide emulsion layer or the like.

In the present invention, the coefficient of static friction is the uppermost layer of the photographic constituent layer having a surface of 0.2 or less, in addition to the organopolysiloxane,
A wax, a matting agent or the like which has been conventionally used for improving the slipperiness may be used. Of course, a fluorine-containing compound or a polyoxyethylene-based compound may be used.

Further, an organopolysiloxane, a matting agent or the like may be used as the uppermost layer of the photographic constituent layer having a surface with an absolute value of the peeling charge amount of 200 pico coulombs / cm ² or less.

The silver halide emulsion used in the present invention includes silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any of those used for can be used.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. It may also be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAq in the mixing vessel, while taking into consideration the critical growth rate of silver halide crystals. By this method,
Silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The conversion may be used at any step in the formation of the silver halide to change the halogen composition of the grains.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

Silver halide grains include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt in the process of forming and / or growing the grain. By adding a metal ion using at least one selected from (including complex salts), these metal elements can be contained inside the particle and / or on the surface of the particle, and by placing in a suitable reducing atmosphere. , Reduction sensitizing nuclei can be provided inside the grain and / or on the surface of the grain.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (hereinafter R)
Abbreviated as D. ) It can be performed based on the method described in 17643, item II.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The size of silver halide grains may be 0.03 to 30 μ, preferably 0.05 to 10 μ.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown).
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye.

The silver halide emulsion includes fog prevention during the manufacturing process, storage or photographic processing of the silver halide photographic light-sensitive material.
Or during the chemical ripening for the purpose of keeping the photographic performance stable, at the end of the chemical ripening, and / or after the end of the chemical ripening,
By the time the silver halide emulsion is coated, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5- Triacryloyl-hexahydro-s-triazine, 1,3
-Vinylsulfonyl-2-propanol etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s
-Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.) and the like can be used alone or in combination.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of enhancing flexibility. A preferred plasticizer is A of RD17643 XII.
The compound described in 1.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color development processing, the emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) to form a dye. Dye forming couplers are used. The dye-forming couplers are usually selected so that for each emulsion layer a dye is formed which absorbs the light in the light-sensitive spectrum of the emulsion layer, and in the blue-sensitive silver halide emulsion layer a yellow dye-forming coupler is formed. A coupler, a magenta dye-forming coupler is used in the green light-sensitive silver halide emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive silver halide emulsion layer. However, the silver halide color photographic light-sensitive material may be produced by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Further, these dye-forming couplers need only reduce four silver ions in order to form one molecule of dye, but even if they are four-equivalent, only two silver ions need to be reduced. Either equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used are those in which the inhibitor is directly bonded to the coupling position and those in which the inhibitor is 2
Those linked to the coupling position via a valent group so that the inhibitor is released by an intramolecular nucleophilic reaction in the group that has left due to the coupling reaction or an intramolecular electron transfer reaction ( Timing DIR couplers, and timing DIR compounds). Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Yellow color couplers that can be used include, for example, U.S. Patent No. 2,875,057.
No. 3,265,506, No. 3,408,194, No. 3,551,15
No. 5, No. 3,582,322, No. 3,725,072, No. 3,891,4
45, West German Patent 1,547,868, West German Application Publication 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,425,
No. 020, Japanese Patent Publication No. 51-10783, JP-A Nos. 47-26133 and 48-73.
No. 147, No. 50-6341, No. 50-87650, No. 50-123342,
50-130442, 51-21827, 51-102636, 52-8
2424, 52-115219, 58-95346 and the like.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used. Examples of magenta color couplers that can be used include U.S. Pat. Nos. 2,600,788 and 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German Patent 1,810,464, West German Patent Application (OLS) 2,408,665, 2,417,945, 2,
No. 418,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, JP-A No. 4
9-74027, 49-74028, 49-129538, 50-60233
No. 50, No. 50-159336, No. 51-20826, No. 51-26541, No. 5
2-42121, 52-58922, 53-55122, Japanese Patent Application No. 55-11
Examples include those described in 0943.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used. Cyan color couplers that can be used include, for example, U.S. Pat.
No. 0, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044, JP-A-47-37425,
50-10135, 50-25228, 50-112038, 50-1174
No. 22, No. 50-130441, etc.,
The couplers described in JP-A-58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIRs that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, antifoggants, UV absorbers,
Among the fluorescent whitening agents and the like, various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method can be used for the hydrophobic compound, which is the chemical structure of the hydrophobic compound such as the coupler. It can be selected as appropriate. The oil-in-water emulsification dispersion method can be a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. Emulsify by using a dispersing agent such as a stirrer, homogenizer colloid mill, flowgit mixer, ultrasonic device, etc. using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After dispersion, it may be added to the desired hydrophilic colloid solution. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As the high boiling point solvent, a phenol derivative that does not react with an oxidized product of a developing agent, a phthalic acid alkyl ester (for example, dibutyl phthalate), a phosphoric acid ester (for example, tricresyl phosphate), a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester An organic solvent having a boiling point of 150 ° C. or higher, such as trimesic acid ester, is used.

A low boiling or water soluble organic solvent can be used with or in place of the high boiling solvent. Examples of the organic solvent having a low boiling point which is substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

When the dye-forming coupler, the DIR coupler, the colored coupler, the DIR compound, the image stabilizer, the antifoggant, the ultraviolet absorber, the optical brightener, etc. have an acid group such as carboxylic acid or sulfonic acid, they are treated as an alkaline aqueous solution. It can also be incorporated into a hydrophilic colloid.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

Between the emulsion layers (the same color-sensitive layer and / or different color-sensitive layers) of the light-sensitive material of the present invention, the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness. Alternatively, a color antifoggant can be used to prevent the graininess from being conspicuous.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer which prevents deterioration of a dye image can be used in the light-sensitive material of the present invention. Compounds which can be preferably used are those described in Item VII, J of RD17643.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer, an ultraviolet absorber to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and to prevent deterioration of the image by ultraviolet light. It may be contained.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. A compound which can be preferably used as a development accelerator is RD1764.
No. 3, Item XXI, B to D, and the development retarder is the compound, No. 17643, Item XXI, Item E. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The emulsion layer of the photographic light-sensitive material of the present invention comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound, for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may include a urethane derivative, a urea derivative, an imidazole derivative, and the like.

A fluorescent whitening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of a white background and making the white background less noticeable. The compound which can be preferably used as the optical brightening agent is described in the item V of RD17643.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

Reduction of gloss of the light-sensitive material, improvement of writing property on the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other. Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonate and styrene. And the copolymers thereof. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property improvement, antistatic property, slipperiness improvement, emulsion dispersion,
Various surfactants can be used for the purpose of preventing adhesion, improving photographic properties (acceleration of development, hardening, sensitization, etc.).

The support used in the light-sensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
Flexible reflection support such as paper laminated with ethylene / butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide. And a flexible support in which a reflective layer is provided on these films, glass, metal, pottery, and the like.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as required, and then directly or on the support surface, adhesiveness, antistatic property, dimensional stability, abrasion resistance, hardness,
It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful, but packet coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. The color development processing of the light-sensitive material of the present invention comprises, for example, a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilizing processing step which is carried out if necessary, and a processing step using a bleaching solution and a fixing step. Instead of the processing process using a solution, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or color development, bleaching and fixing can be carried out in one bath. It is also possible to perform a one-bath treatment step using the treatment liquid.

Further, in combination with these processing steps, a pre-hardening processing step, a neutralizing step thereof, a stop fixing processing step, a post-hardening processing step and the like may be performed. In these treatments, instead of the color development treatment step, a color developing agent or its precursor may be contained in the material and the development treatment may be performed by an activator treatment step, or an activator treatment step may be carried out. Beta processing can also be applied.
Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as a final step.) ・ Color development step-bleaching step-fixing step-Generating step-bleach-fixing step Process-Pre-hardening process-Color development process-Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplement Color development processing step-stop processing step-bleaching processing step-fixing processing step-activator processing step-bleach fixing processing step-activator processing step-bleaching processing step-fixing processing step-one-bath processing step The processing temperature is usually 10 Is selected in the range of ℃ ~ 65 ℃,
The temperature may exceed 65 ° C. Preferably from 25 ° C
Treated at 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds generally account for about 0.1 for Color Developer 1.
It is used at a concentration of -30 g, more preferably at a concentration of about 1-15 g for color developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-Oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are contained.

Particularly useful primary aromatic amino color developing agents are N, N '.
It is a -dialkyl-p-phenylenediamine compound, and the alkyl group and the phenyl group may be substituted or may not be substituted. Among them, particularly useful compounds are N, N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-methoxyethyl)-
Examples thereof include N-ethyl-3-methylaniline-p-toluenesulfonate.

Further, the above color developing agent may be used alone, and 2
You may use it in combination of 2 or more types. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be treated with an alkali solution (activator solution) instead of the color developing solution, and the bleach-fixing process is carried out immediately after the alkali solution treatment.

The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, and a preservative such as hydroxylamine or sulfite. You may. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, and the like can be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or more, preferably about 9 to 13.

In the color developing solution used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. Hexose, Porogalol-1,
It may contain 3-dimethyl ether or the like.

In the color developing solution used in the present invention, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminopentaacetic acid, 1
-Organophosphonic acid such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane-1 , 2,4-tricarboxylic acid and other phosphonocarboxylic acids, tripolyphosphoric acid, hexametaphosphoric acid and other polyphosphoric acids, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether amine tetraacetic acid,
Examples thereof include glycol ether diamine tetraacetic acid, ethylene diamine tetrapropionic acid, and phenylenediamine tetraacetic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are 5-450 g /, more preferably 20-250 g /
Used in.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative is applied if necessary.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B-45-8506, 46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

As the fixer, one having a generally used composition can be used as it is. What is used as a fixing agent is a compound which reacts with silver halide to form a water-soluble complex salt as used in a general fixing process, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, Representative examples thereof include thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount within the range of 5 g / mol or more, and generally 70-
Use at 250g /. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethyl sulfamide or dimethyl sulfoxide can be appropriately contained.

The pH of the fixer used is 3.0 or higher, but generally 4.5 to 1
0, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halogenating agent such as ammonium bromide is used. Bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a large amount of a halide such as ammonium bromide. be able to. Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the fixing processing step. The concentration of the fixing agent, the pH buffer that can be contained in the bleach-fixing solution, and other additives are the same as those in the fixing processing step.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.5-8.5.

[Effect of the Invention] In the silver halide photographic light-sensitive material of the present invention, even in the case of a high-sensitivity silver halide photographic light-sensitive material, occurrence of various failures due to electrostatic charging such as generation of static marks is sufficiently suppressed. To be done. Even when a high-speed automatic development processor is used, static marks are hardly generated.

Further, in the silver halide photographic light-sensitive material of the present invention,
For example, the occurrence of bending fog that occurs in a high-speed automatic development processor is suppressed.

Furthermore, in the silver halide photographic light-sensitive material of the present invention,
The performance of preventing static mark generation is sufficiently maintained when the film is wound and stored for a long period of time.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

The fluorine-containing compound (F-4) according to the present invention and the nonionic surfactant (N-6) according to the present invention are added to a gelatin binder, and a coating aid (sodium p-dodecylbenzenesulfonate) is further added. Thickener (potassium polystyrene sulfonate) and hardener (2-hydroxy-4,
6-dichloro 1,3,5-triazine) was added. The backing solution thus prepared had a gelatin coating amount of 3.0 g / m ² and a fluorine-containing compound coating amount of the present invention.
0.02 g / m ^2, the coating amount of the nonionic surfactant according to the present invention is 0.05 g / m ^2, an average particle diameter of 2.7 as a matting agent
The content of μ polymethylmethacrylate particles is 0.05g / m
^It was applied to one side of the triacetyl cellulose film support so that it would be ² .

Next, on the other surface of the triacetyl cellulose film support, layers having the compositions shown below were sequentially formed from the support side to prepare a silver halide photographic light-sensitive material sample A of this example.

First layer: antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

(Gelatin amount: 2.2 g / m ² ) Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

(Gelatin amount 1.2 g / m ² ) Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) (Gelatin amount 1.4 g / m ² ) Average particle size () 0.30 μm, AgB containing 6 mol% AgI
Monodisperse emulsion consisting of rI (Emulsion I): Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ⁻⁵ mol Cyan coupler (C-1) …… 0.06 mol to 1 mol of silver Colored cyan coupler (CC-1) …… 0.003 mol to 1 mol of silver DIR compound (D-1) …… 0.0015 mol to 1 mol of silver DIR compound (D-2) ... 0.002 mol to 1 mol of silver Fourth layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) (gelatin amount 1.0 g / m ² ) AgB with average particle size () 0.5μm and AgI 7.0mol%
Monodisperse emulsion consisting of rI (Emulsion II): Silver coating amount 1.3 g / m ² Sensitizing dye I: 3 × 10 ^-5 mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ⁻⁵ mol Cyan coupler (C-1) …… 0.02 mol for 1 mol of silver Colored cyan coupler (CC-1) …… 0.0015 mol for 1 mol of silver DIR compound (D-2) …… 0.001 mol per mol of silver Fifth layer; intermediate layer (IL) Same as the second layer, gelatin layer. (Gelatin amount 1.0 g / m ² ) Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) (Gelatin amount 2.0 g / m ² ) Emulsion-I ... coating silver amount increased by 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1.2 × 10 ^-5 mol per mol of silver Magenta coupler (M-1): Per mol of silver 0.050 mol Colored magenta coupler (CM-1) ...... 0.009 mol to 1 mol silver DIR compound (D-1) ...... 0.0010 mol to 1 mol silver DIR compound (D-3) ...... to 1 mol silver On the other hand, 0.0030 mol seventh layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) (gelatin amount 1.8 g / m ² ) Emulsion-II …… coating silver amount 1.4 g / m ² sensitizing dye III …… 1.0 × 10 ^-5 mol magenta coupler relative to 1.5 × 10 ^-5 mol sensitizing dye IV ...... silver mole per silver mole (M-1) 0.020 mol mosquito respect ...... silver mole Demagenta coupler (CM-1): 0.002 mol per mol of silver DIR compound (D-3): 0.0010 mol per mol of silver Eighth layer: Yellow filter layer (YC-1) (gelatin) Layer 1.5 g / m ² ) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Layer 9: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) (gelatin amount 1.9 g / m ² ) Monodisperse emulsion (Emulsion III) consisting of AgBrI containing 0.48 μm average grain size and 6 mol% AgI. Silver coating amount 0.9 g / m ² Sensitizing dye V …… 1.3 × 10 ^-5 mol for 1 mol of silver Yellow coupler (Y-1) …… 0.29 mol for 1 mol of silver 10th layer; high sensitivity blue Sensitive emulsion layer (BH-1) (gelatin amount: 1.6 g / m ² ) AgBrI containing an average particle size of 0.8 μm and AgI of 15 mol%.
Monodisperse emulsion (Emulsion IV) ...... Silver coating amount 0.5g / m ² Sensitizing dye V …… 1.0 × 10 ^-5 moles per 1 mole silver Yellow coupler (Y-1) …… 1 mole silver In contrast, 0.08 mol DIR compound (D-2) ... 0.0015 mol per 1 mol of silver 11th layer; 1st protective layer (Pro-1) (gelatin amount 1.2 g
/ M ² ) Silver iodobromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount
Gelatin layer containing 0.5 g / m ² UV absorbers UV-1 and UV-2.

12th layer; 2nd protective layer (Pro-2) (gelatin amount 1.2g
/ M ² ) Organopolysiloxane S-10.06 g / m according to the present invention
^2. A gelatin layer containing ethylmethacrylate-methylmethacrylate-methacrylic acid copolymer particles (average particle size 2.5 μm) and formalin scavenger (HS-1).

In addition to the above composition, a high boiling point organic solvent (HBS-1) and a surfactant were added to each layer, if necessary.

Further, H-1 was added to the twelfth layer as a hardening agent, and after coating, it was diffused into each layer to harden each layer.

The compounds contained in each layer of Sample A are as follows.

Sensitizing dye I; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'- The-
(3-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-
Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing Dye IV; Anhydro 9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5 ′ -Methoxythiacyanine C-1 CC-1 D-1 D-2 D-3 M-1 CM-1 Y-1 UV-1 UV-2 HS-1 H-1 HBS-1 The sample A thus prepared was prepared in the same manner as the sample A except that the kinds and the places of use of the fluorine-containing compound, the nonionic surfactant and the organopolysiloxane according to the present invention were changed as shown in Table 1. Samples B to V and A to D of the silver halide photographic light-sensitive material according to the present invention. The addition amounts of the fluorine-containing compound, the nonionic surfactant and the organopolysiloxane according to the present invention are used for either layer. Also in the case, the same as the sample A was used.

With respect to these samples A to V and A to D, the occurrence of bending fog and the occurrence of static marks were examined according to the following methods.

[Folding Fog] After folding the sample with a folding tester having a slit interval of 2 mm, the following developing process was performed to measure the folding fog of the green photosensitive layer.

[Static mark generation rate] ・ Immediately after the sample was conditioned for 12 hours in an atmosphere of 23 ° C and 25% RH, the width was 70 mm and the diameter was 10 mm in a dark room under the same conditions.
Two rollers, the surfaces of which were covered with neoprene rubber, were pressed with a force of 8 kg, and the rubber roller was rotated by sandwiching the sample between them to convey the sample at a speed of 50 mm / sec. Immediately after that, the following development processing is performed,
The degree of occurrence of static marks was examined.

-Wind sample A sample with a width of 65 mm was wound, left for 6 hours in an atmosphere of 45 ° C and 80% RH, then withdrawn, and the degree of generation of static marks was examined by the same method as above.

The static marks were evaluated as follows.

A: No static mark was observed.

B: Generation of static marks is slightly observed.

C: Generation of static marks is considerably recognized.

D: Generation of static marks is recognized almost all over the surface.

Processing step (38 ° C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the treatment liquid is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

[Bleaching liquid] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 m Water is added to adjust to pH = 6.0 using ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 m Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 m Add water to make 1.

As is apparent from Table 1, the fluorine-containing compound according to the present invention, the nonionic surfactant, and the three surface modifiers of the organopolysiloxane were used as the uppermost layers of both the supports of the silver halide color photographic light-sensitive material. The samples of the present invention, which are properly used, have a small bending fog and suppress the generation of static marks in the samples immediately on the same day, and also have less static marks generation in the wound samples that have been left for a long time in high humidity.

In particular, using organopolysiloxane for one of the uppermost layers,
When a nonionic surfactant and a fluorine-containing compound are used for the other uppermost layer, the occurrence of bending fog is small.
Further, when the organopolysiloxane and the nonionic surfactant are used for one uppermost layer and the fluorine-containing compound is used for the other uppermost layer, the generation of static marks in the wound and stored sample is not observed at all.

In addition, when organopolysiloxane and a fluorine-containing compound are used for one uppermost layer and a nonionic surfactant is used for the other uppermost layer, no static mark is observed in the wound and stored sample.

Example 2 A silver halide emulsion layer containing high-sensitivity silver halide grains consisting of 98.5 mol% silver bromide and 1.5 mol% silver iodide and having an average grain size of 1.2 μ, was formed on both sides of a polyethylene terephthalate support having an undercoat. And a protective layer were coated to obtain a silver halide photographic light-sensitive material for X-ray.

The following additives were added to the silver halide emulsion per mol of silver halide.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.2g Diethylene glycol 11.0g Cryoxal 1.2g Diethylhexyl succinate sodium sulfonate 1.5g Paranitriphenyltriphenyl phosphide chloride 0.2g Coating liquid is silver 4g / m ² , gelatin 1.7g / m ²
Was applied.

The protective layer was coated with a coating solution having the following composition so that the amount of gelatin would be 1.2 g / m ² .

[Protective layer composition] Gelatin 80 g Diethylhexyl succinate potassium sulfonate 1 g Mucochloric acid Polymethylmethacrylate having an average particle size of 3 to 4 µg 2 g Polyethylene-di-nonylphenol ether sodium sulfate 2 g [Treatment step] Current image 30 ° C 45 "Adhesion 25 ° C. 35 ″ water wash 15 ° C. 35 ″ dry 45 ° C. 20 ″ Developer composition is as follows.

Phenidone 0.4 g Metol 5 g Hydroquinone 1 g Anhydrous sodium sulfite 60 g Hydrous sodium carbonate 54 g 5-Nitroimidazole 100 mg Potassium bromide 2.5 g Water is added to 1000 m and pH is 10.20.

Further, in addition to the above, organopolysiloxane, nonionic surfactant and fluorine-containing compound were contained in the protective layer as shown in Table 2.

With respect to these samples, the occurrence of bending fog and static marks was examined in the same manner as in Example 1.

As is clear from Table 2, the three kinds of surface modifiers of the fluorine-containing compound, the nonionic surfactant and the organopolysiloxane according to the present invention were applied to both surface layers of the silver halide photographic light-sensitive material for X-ray. The samples of the present invention, which are properly used, have a small bending fog, and not only suppress the generation of static marks in the samples on the same day, but also generate less static marks even in the wound sample placed under high humidity.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Ichiro Oi No. 1 Sakuramachi, Hino City, Tokyo Photograph by Konishi Roku Photo Industry Co., Ltd. (72) Hideo Ota No. 1, Sakuracho, Hino City, Tokyo Photograph by Konishi Roku Photo Industry Co., Ltd. (56) Reference JP 54-38110 (JP, A) JP 59-74554 (JP, A) JP 60-140341 (JP, A) JP 56-78834 (JP, A) JP 54-89626 (JP, A)

Claims (1)

[Claims] 1. In a silver halide photographic light-sensitive layer having photographic constituent layers on both sides of a support, the uppermost layers of the two photographic constituent layers are structural units represented by the following general formula [I]. An organopolysiloxane having a terminal group represented by the following general formula [II]
[I] containing at least one compound selected from the three compounds of a fluorine-containing compound and a nonionic surfactant having a polyoxyethylene unit, and all of the three compounds are A silver halide photographic light-sensitive material, characterized in that it is contained in any one of the uppermost two photographic constituent layers. General formula [I] [Wherein R ₁ represents a hydrogen atom, a hydroxy group or an organic group, R ₂ represents an organic group, and when R ₁ and R ₂ are organic groups, they may be the same or different. ] General formula [II] [Wherein R ₃ , R ₄ and R ₅ are a hydrogen atom, a halogen atom,
It represents a hydroxy group or an organic group, and R ₃ , R ₄ and R ₅ may be the same or different from each other. ] General formula [III] [In the formula, Rf represents an alkyl group, an alkyloxy group, an alkenyl group, an aryl group or an aryloxy group having at least 3 fluorine atoms. A represents a divalent linking group, and X represents a hydrophilic group. m represents 0 or 1. ]