JPH075616A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a photographic sensitive material free from the occurrence of uneven coating and poor adhesion at the time of applying emulsion and small in bleeding due to coating and with the lapse of time and the deterioration of slidability with time after development processing. CONSTITUTION:The photographic sensitive material contains at least each of one kind of aqueous dispersion represented by formulae [4]; R17-X(ZO)nR18, and [5]; R19-X(Z0)mR20, and/or at least one kind of aqueous dispersion selected among formulae[1]: R11-COO-R12, [2]: R13-OCO-X-COOR14, and [3]: R15-COO-X- OCOR16 in at least one layer. In formulae [1]-[5], each of R11-R19 is a long-chain hydrocarbon group or the like; R20 is-COOM or the like polar group; X is a bonding group; Z is alkylene group or the like; and each of m and n is an integer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as photographic light-sensitive material, which has at least one light-sensitive silver halide emulsion layer on one side of a support and is excellent in slipperiness). A photosensitive material, a photographic light-sensitive material, or a light-sensitive material).

[0002]

BACKGROUND OF THE INVENTION Photographic light-sensitive materials are generally provided on one or both sides of a support such as cellulose triacetate, polyethylene terephthalate, paper or paper coated on both sides with polyethylene, either directly or through an undercoat layer. A silver halide photographic emulsion layer and, if necessary, various layers such as an intermediate layer, a protective layer, a filter layer, an antistatic layer and an antihalation layer are combined and coated. These layers generally have a hydrophilic binder such as gelatin as a constituent component. A photographic light-sensitive material having a photographic emulsion layer on both sides of a support includes, for example, a direct X-ray film, but most other photographic light-sensitive materials have a photographic emulsion layer on only one surface of the support. . Therefore, in the latter case, there is a surface on which the photographic emulsion layer is not coated, that is, the surface of the support, which is generally referred to in the art as the "back surface" of the photographic light-sensitive material.

A photographic light-sensitive material is processed in various manufacturing processes such as coating, drying and processing, and is also used in various devices, machines, during handling such as taking-up, rewinding or conveying in photographing, development, printing, projection and the like. Contact friction between a contact portion with a photosensitive material such as a camera or an adhered matter such as dust or fiber waste is often seriously adversely affected.
In particular, since the back surface often comes into direct contact with various equipment, for example, scratches and abrasions are likely to occur, the drivability of the photosensitive material in the camera and other machines is deteriorated, and film scraps are likely to occur. These scratches appear on the image surface at the time of printing or projection, and are serious defects in practical use. Recently, photosensitive materials have been treated conventionally due to the expansion of use and processing methods for photosensitive materials such as high-speed coating, rapid photography and rapid processing, and diversification of environments during use such as high temperature and high humidity atmosphere. As a result of severe handling, scratches and deterioration of driveability are more likely to occur. Therefore, there is a demand for a light-sensitive material having a surface quality with high slipperiness and scratch resistance that can sufficiently withstand such severe conditions.

Conventionally, as a means for improving the slipperiness and scratch resistance of a photographic light-sensitive material, a method of providing a surface layer containing a slipping agent has been used. As a slip agent, for example, Japanese Patent Publication No. 53
-292, polyorganosiloxanes such as those disclosed in U.S. Pat. No. 4,275,146, higher fatty acid amides such as those disclosed in U.S. Pat. No. 4,275,146;
3541, British Patent No. 927,446, or Japanese Patent Laid-Open Nos. 55-126238 and 58-9063.
Higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in U.S. Pat.
Higher fatty acid metal salts as disclosed in Japanese Patent No. 516, polyester compounds comprising a dicarboxylic acid having up to 10 carbon atoms and an aliphatic or cycloaliphatic diol as disclosed in JP-A-51-37217. It has been known.

By adding such a slip agent to the surface layer, the slip property and scratch resistance of the photographic light-sensitive material are improved,
Furthermore, the following points become problems. For example, when silicone is applied to the back layer, the added silicone migrates to the surface of the support on the side on which the photographic emulsion is coated, which significantly repels coating properties such as repellency and deterioration of wettability during coating of the photographic emulsion. It causes deterioration and uneven coating of the emulsion. Further, when higher fatty acids, polyhydric alcohol esters of higher fatty acids, higher fatty acid amides, higher alcohol esters of higher fatty acids, higher fatty acid metal salts, etc. are used, white powder may be produced by bleeding of the slip agent during application or over time. The developing process causes the slipping agent to be eluted or fall off, resulting in the loss of its effect or contamination of the processing solution.

Such problems have been considerably solved by using higher fatty acids and their derivatives.
However, as a problem, higher fatty acids, higher fatty acid amides, and higher fatty acid metal salts cause white powder due to bleeding of the sliding agent during or after application of the coating solution, or due to the high melting point thereof, or when the developing agent causes a slipping agent. The effect may be lost or the processing solution may be contaminated by elution or loss. In addition, a binder layer is generally provided on the surface of the back layer of the support for the purpose of protecting the lower layer, providing a mat layer, an antistatic layer, or the like.
Therefore, it is desirable that the above slipping agent is contained in the binder in order to reduce the number of coating layers. When the above slip agent is used with a binder, it is used as a solution or dispersion. When it is applied by being dissolved in the coating liquid, there arises a problem that the slip agent is not dissolved in the coating liquid. When the lubricant is dispersed and applied, the haze is increased, the slip / scratch resistance is deteriorated, and the dispersion stability of the lubricant in the coating liquid is not sufficient, and the lubricant during the coating step or during coating is Agglomeration, sedimentation, etc. became a problem, and sufficient satisfactory performance could not be obtained. Further, from the viewpoint of environmental pollution, it is not preferable to dissolve it in an organic solvent, apply a hydrophobic lubricant, and dry it, and its improvement is important. From this point of view, a method of applying a hydrophobic slip agent in an aqueous system instead of an organic solvent system will be an essential technique for environmental protection in the future. However, in order to achieve sufficient sliding performance and coated surface condition, the slip agent is dispersed in the presence of a conventionally used surfactant, and even if an organic solvent is coexistent, the dispersed particles cannot be made smaller and The dispersion stabilization could not be achieved either. Therefore, the slip property of the emulsion surface provided by an aqueous system is generally insufficient, and scratches due to poor slippage are likely to occur during handling or processing. Further, in the system in which the slip agent on the back surface is coated with an aqueous system, gelatin or latex is used as the binder, but the surface state is poor as in the emulsion side and sufficient performance cannot be obtained.

[0007]

Therefore, a first object of the present invention is to provide a photographic light-sensitive material which is improved in stability of a dispersion containing a slip agent and which is uniformly applied during application. A second object of the present invention is that there are no problems such as coating unevenness and adhesion failure during coating, less bleeding during coating or over time, and less deterioration of slipperiness over time after development processing or under various use conditions. It is intended to provide a photographic light-sensitive material having a surface layer.

[0008]

These problems are solved in a silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a support and at least one layer of the following general formula [4 ] And / or one of general formula [5] and / or at least one selected from [1], [2] and [3], and the total content thereof is 0.0005 to Achieved by a silver halide photographic light-sensitive material characterized by being 0.7 g / m ² . Formula (1) R ₁₁ -COO-R ₁₂ Formula (2) R ₁₃ -OCO-X-COOR ₁₄ Formula (3) R ₁₅ -COO-X-OCOR ₁₆ Formula (4) R ₁₇ -X ( ZO) _n R ₁₈ general formula [5] R ₁₉ —X (ZO) _m R _{20 In the} formula, R _{11 to} R ₁₇ represent an aliphatic hydrocarbon group having 1 to 100 carbon atoms, and total carbon atoms of R ₁₁ and R ₁₂ The number of carbon atoms, the total number of carbon atoms of R ₁₃ and R _14, the total number of carbon atoms of R ₁₅ and R ₁₆ , and the total number of carbon atoms of R ₁₇ and R ₁₈ are 36 to 150, respectively. R ₁₈ is a hydrogen atom and has 1 carbon atom
~ 100 alkyl groups, alkenyl groups, aralkyl groups,
Represents an alkylcarbonyl group. R ₁₉ has 8 to 100 carbon atoms
Represents an aliphatic hydrocarbon group, and R ₂₀ is —COOM, SO ₃
M, -OSO ₃ M, a -PO ₃ M _2, M is H, alkali metal salts (lithium, sodium, potassium, rubidium), alkaline earth metals (magnesium, calcium), total alkyl having 1 to 20 carbon atoms It represents an ammonium group or an ammonium group. X represents a divalent linking group having 2 to 50 carbon atoms, and Z represents an alkylene group, an arylene group or an aralkylene group having 2 to 12 carbon atoms. n is 2 to 100, m is 0
Represents an integer of 100.

First, the slip agent in the present invention will be described in detail. R _{11 to} R ₁₇ are preferably linear or branched aliphatic hydrocarbon groups having 3 to 70 carbon atoms, more preferably 8 to 60 linear aliphatic hydrocarbon groups, and particularly preferably undecyl. , Dodecyl, oleyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl.
Also, the total carbon number of R ₁₁ and R ₁₂ , the total carbon number of R ₁₃ and R ₁₄ ,
The total carbon number of R ₁₅ and R _{16 and} the total carbon number of R ₁₇ and R ₁₈ are preferably 40 to 100, and more preferably 50 to 100, respectively. Also, the preferred R
₁₈ is a hydrogen group, a linear or branched aliphatic alkyl group having 1 to 70 carbon atoms, an alkenyl group, an aralkyl group or 1 carbon atom
~ 70 linear or branched alkylcarbonyl groups,
Particularly preferred is a hydrogen group, a linear or branched alkyl group having 1 to 50 carbon atoms, or a linear or branched alkylcarbonyl group having 1 to 10 carbon atoms.

Preferred alkyl groups having 1 to 50 carbon atoms for R ₁₈ are methyl, ethyl, propyl, butyl and octyl, alkenyl groups are aryl, ethylenyl and crotonyl, and aralkyl groups are xylyl and phenyl. Examples of the alkylcarbonyl group include acetyl, ethylcarbonyloxy, butylcarbonyloxy, hexylcarbonyloxy and phenylcarbonyl. Among the divalent linking groups for X, preferred are alkylene having 0 to 40 carbon atoms, arylene,
Aralkylene, particularly preferably, - (CH ₂₎ a
-, Phenylene, -CH = CH-, and a is 0 to 10
Represents 0. Further, Z is preferably ethylene, propylene, butylene, glycerin or phenethylene, and particularly preferably ethylene, propylene or glycerin. n is preferably 2 to 50, and more preferably an integer of 2 to 30. R ₁₉ preferably represents an aliphatic hydrocarbon group having 10 to 60 carbon atoms, and more preferably 12 to 50 carbon atoms.
Is an aliphatic hydrocarbon group of C _n H _{2n + 1-}
(N = 12-40) is preferable. Preferred for R ₂₀ is
SO ₃ M, —OSO ₃ M, and —PO ₃ M ₂ are preferable, and M is preferably H, an alkali metal salt (lithium, sodium, potassium), an alkaline earth metal (magnesium,
Calcium), an alkyl ammonium group having 1 to 8 total carbon atoms, and an ammonium group. Furthermore, the melting point of the lubricant of the general formula [1] to the general formula [4] is preferably 40 ° C to 250 ° C, more preferably 50 ° C to 220 ° C, and further preferably 60 ° C to 200 ° C. If the melting point is too low, the lubricant tends to become oily at high temperatures, causing deterioration of the sliding performance such as transfer. If the melting point is too high, dispersibility in water will be poor.

Specific examples of the compounds represented by the general formulas [1], [2] and [3] which can be preferably used in the photographic light-sensitive material of the present invention are described below. _{(1-1) n-C 15 H} 31 COOC 30 H 61 -n (1-2) n-C 17 H 35 COOC 30 H 61 -n (1-3) n-C 15 H 31 COOC 30 H 61 - n (1-4) n-C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ -n (1-5) n-C ₁₅ H ₃₁ COOC ₅₀ H ₁₀₁ -n (1-6) n-C ₂₇ H ₄₃ COOC ₂₈ H _{57 -n (1-7) n-C 21} H 43 COO- (CH 2) 7 CH (CH 3) -
_{C 9 H 19 (1-8) n} -C 21 H 43 COOCH 2 CH (CH 3) -C 9
H ₁₉ (1-9) n-C ₂₁ H ₄₃ COOC ₂₄ H ₄₉ -iso (1-10) CH ₃ COOC ₅₀ H ₁₀₁ -n (1-11) C ₁₁ H ₂₃ COOC ₅₀ H ₁₀₁ -n (1- 12) C ₁₇ H ₃₃ COOC ₅₀ H ₁₀₁ -n

(2-1) n-C ₂₉ H ₄₉ OCO (CH ₂ ) ₂ C
_{OOC 24 H 49 -n (2-2)} n-C 18 H 37 OCO (CH 2) 4 COOC 40 H 81 -
_{n (2-3) n-C 18} H 37 OCO (CH 2) 18 COOC 18 H 37 -
n (2-4) iso-C ₂₄ H ₄₉ OCO (CH ₂ ) ₄ COOC ₂₄ H
₄₉ -n (2-5) n-C ₄₀ H ₈₁ OCO (CH ₂ ) 2 COOC ₅₀ H _{101
-n (3-1) n-C 17} H 35 COO (CH 2) 6 OCOC 17 H 35 -
_{n (3-2) n-C 21} H 43 COO (CH 2) 18 OCOC 21 H 43 -
n (3-3) iso-C ₂₃ H ₄₇ COO (CH ₂ ) ₂ OCOC ₂₃ H
₄₇ -n (3-3) iso-C ₁₅ H ₃₁ COO (CH ₂ ) ₆ OCOC ₂₁ H
₄₃ -n

Specific examples of the compound represented by the general formula [4] which can be preferably used in the photographic light-sensitive material of the present invention are described below. (4-1) n-C ₃₀ H ₆₁ O (CH ₂ CH ₂ O) ₁₀ H (4-2) n-C ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₅ H (4-3) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₅ H (4-4) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₃₀ H (4-5) n-C ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₀ H (4-6) n-C ₅₀ H ₁₀₁ (CH ₂ CH ₂ O) ₁₆ H (4-7) n-C ₅₀ H _101- (CH (CH ₃ ) CH ₂ O)
₃ (CH ₂ CH ₂ O) ₁₆ H (4-8) n-C ₅₀ H _101- (CH ₂ CH (OH) CH ₂ O) <sub>3
- (CH (OH) CH 2</sub> O) 3 - (CH 2 CH 2 O) 15
H (4-9) n-C ₄₀ H ₈₁ OCOCH ₂ CH ₂ COO (CH ₂
CH ₂ O) ₁₆ H (4-10) n-C ₅₀ H ₁₀₁ OCOCH = CHCOO (CH ₂
CH ₂ O) ₁₆ H (4-11) n-C ₅₀ H ₁₀₁ OCOCH ₂ CH ₂ COO- (C
_{H 2 CH (OH) CH 2} O) 3 - (CH 2 CH 2 O) 15
H (4-12) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₅ COCH ₃ (4-13) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₅ COCH
= CHCOOH (4-14) n-C ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₅ CH ₃ (4-15) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₅ COCH ₃ (4-16 ) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₃₀ COC ₃
H ₇

(4-17) n-C ₅₀ H _101- (CH ₂ CH (O
_{H) CH 2 O) 3 -} (CH (OH) CH 2 O) 3 - (C
H ₂ CH ₂ O) ₁₅ COCH ₃ (4-18) n-C ₅₀ H ₁₀₁ -OC ₆ H _4- COO (CH ₂ CH ₂
O) ₁₅ H (4-19) n-C ₅₀ H ₁₀₁ -OCOC ₆ H _4- O (CH ₂ CH ₂
O) ₁₅ H Hereinafter, specific examples of the compound represented by the general formula [5] which can be preferably used in the photographic light-sensitive material of the present invention will be described. (5-1) n-C ₁₄ H ₂₉ OSO ₃ Na (5-2) n-C ₁₆ H ₃₃ OSO ₃ Na (5-3) n-C ₁₈ H ₃₇ OSO ₃ Na (5-3) n-C ₁₈ H ₃₇ OSO ₃ NH ₄ (5-3) n-C ₁₈ H ₃₅ OSO ₃ N (CH ₃ ) ₃ (5-4) n-C ₂₂ H ₄₅ OSO ₃ Na (5-5) n-C ₃₀ H ₇₁ OSO ₃ Na (5-6) n-C ₄₀ H ₈₁ OSO ₃ Na (5-7) n-C ₅₀ H ₁₀₁ -OSO ₃ Na (5-8) n-C ₁₄ H ₂₉ O (CH ₂ CH _{2 O) 2 SO 3 Na (5-9} ) n-C 18 H 37 O (CH 2 CH 2 O) 4 SO 3 Na (5-10) n-C 50 H 101 O (CH 2 CH 2 O) 10 SO ₃ N
a

(5-11) n-C ₅₀ H _101- (CH ₂ CH (O
H) CH ₂ O) ₃ SO ₃ Na (5-12) n-C ₁₄ H ₂₉ SO ₃ Na (5-13) n-C ₁₈ H ₃₇ SO ₃ Na (5-14) n-C ₃₀ H ₇₁ OCH ₂ CH ₂ SO ₃ Na (5-15) n-C ₁₄ H ₂₉ COONa (5-16) n-C ₁₈ H ₃₇ COONa (5-17) n-C ₁₈ H ₃₇ OPO ₃ Na ₂ (5-18) n-C ₃₀ H ₇₁ OPO ₃ Na ₂ (5-19) n-C ₅₀ H ₁₀₁ -OPO ₃ K ₂ (5-20) n-C ₃₀ H ₇₁ O (CH ₂ CH ₂ O) ₄ OPO ₃ N
a ₂ (5-21) pn-C ₁₅ H ₃₁ -C ₆ H ₄ SO ₃ Na (5-22) n-C ₅₀ H ₁₀₁ OCOCH = CHCOO (CH ₂
CH ₂ O) ₁₆ -OSO ₃ Na

In the present invention, at least one layer of the photographic light-sensitive material is selected from the following general formulas [4] and [5], and / or [1], [2] and [3]. It is characterized in that it contains an aqueous dispersion of at least one kind, and the total content thereof is 0.0005 to 0.7 g / m ² . Preferably the total content is 0.001-0.5
g / m ² , more preferably 0.002-0.2 g
/ M ² . Further, the content (weight ratio) of the lubricant represented by the general formula [4] and the lubricant represented by the general formula [5] is 97:
It is preferably 3 to 30:70, more preferably 95: 5.
50:50, more preferably 90: 10-6
It is 0:40. Further, the total content of the lubricant represented by the general formula [4] and the lubricant represented by the general formula [5] of the present invention, and the lubricant selected from [1], [2] and [3] The content ratio (weight ratio) is preferably 100: 0 to 30:70, and more preferably 100: 0 to 40 :.
60, more preferably 100: 0 to 50:50
Is. The average particle size of the aqueous dispersion of the present invention is 0.5 to
0.0001 μm is preferable, and 0.2 to 10 is more preferable.
0.0001 μm, more preferably 0.15 to 0.00
It is 01 μm.

As a method for dispersing the slip agent in an aqueous system, a generally known emulsification / dispersion method can be used.
Furthermore, a finely dispersed slip agent can be prepared by adding the mixture of the slip agent of the present invention to a water-based solution, heating the solution to dissolve the slip agent, and cooling with stirring and dispersing. The preferred method of preparation is to melt and dissolve in the presence of an organic solvent at a temperature equal to or higher than the melting point of the slipping agent, and then cool or add or disperse in a poor solvent while stirring and dispersing. Examples of the disperser used at that time include ultrasonic waves, a homogenizer, a dissolver, a high-pressure jet mixer, a vibration mill, and a polytron. Further, there is a method of dissolving in an organic solvent and emulsifying in water. The organic solvent that can be used has a boiling point of about 30.
Organic solvents having a temperature of ℃ or more, preferably 50 ℃ or more and about 160 ℃ or less can be used, and typical examples are methanol, ethanol, propanol, isopropanol, butanol,
Acetone, methylene chloride, chloroform, dioxane, ethylene glycol, ethylene glycol monobutyl ether, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-
Examples include ethoxyethyl acetate and dimethylformamide. Such emulsification / dispersion methods are described in textbooks such as "Karimai, Pebble, Hidaka" and "Handbook for Emulsification / Dispersion Technology Application" (Science Forum Edition).

When applying the lubricant compound to the surface layer, it may be coated on a binder capable of forming a film, or may be used together with the binder. As such a polymer, those which form an aqueous hydrophilic colloidal liquid are generally preferable. Examples of these hydrophilic binders include Research Disclosure No. 176
43, 26, and ibid. 18716, page 651, and examples include water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, and the like. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like, and cellulose ester includes carboxymethyl cellulose and hydroxyethyl cellulose. Is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Of these, gelatin and latex polymers are most preferable. Further, a gelatin derivative or the like may be used in combination with gelatin. The protective layer containing the hydrophilic binder can be hardened. Examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-
Hydroxy-4,6-dichloro-1,3,5-triazine, other reactive halogen-containing compounds, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, Examples thereof include compounds having a reactive olefin, N-hydroxymethylphthalimide, N-methylol compound, isocyanates, aziridine compounds, acid derivatives, epoxy compounds, and halogen carboxaldehydes such as mucochloric acid. . Alternatively, as the inorganic compound hardening agent, chromium alum, zirconium sulfate and the like can be mentioned. Further, a carboxyl group-activating type hardener and the like can also be used.

The method for applying the slip agent is a liquid dipping method, a spray method, a dip coating method, a bar coating method, a spin coating method,
Application by an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294. Is preferred. The lubricant of the present invention uses heat or air for drying after its application, but it is particularly preferable to convey it by heated air or a conveying roll, for example, 25
-300 degreeC is preferable, More preferably, it is 30-250 degreeC.
And particularly preferably 30 to 200 ° C. At that time, the entire drying zone may be heated, and if different zones are provided, the respective zones may have different temperatures. Generally, the transportation in the drying zone in this photographic industry is
The coating surface is handled immediately after coating so that the coating surface and the roller do not come into contact with each other. Further, even when the coating solution of the slip agent is not completely dried, the opposite surface is often brought into contact with a roller having a melting point or higher and conveyed. Therefore, in the drying zone, it is common sense that the lubricant is exposed to a temperature equal to or higher than its melting point, and the transport roller is equal to or higher than the melting point and may come into contact with it. Furthermore, in order to improve the surface state of the lubricant after the solvent is volatilized and dried at a temperature equal to or lower than the melting point of the lubricant,
It is also preferable to pass through a high-heat zone having a melting point or higher or a roller again.

The slip agents of the present invention include polyorganosiloxanes as disclosed in JP-B-53-292, higher fatty acid amides described in US Pat. No. 4,275,146, and US Pat. , 933,516, and higher fatty acid metal circles may be used in combination. Further, an oily compound such as liquid paraffin generally known as a slippery compound can also be used. The sliding performance obtained by the present invention has a friction coefficient of preferably 0.25 to 0.01, more preferably 0.16 to 0.01, and the sample was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours. Later, the value was measured with a friction coefficient measuring device using a 5 mmφ stainless steel ball. The smaller the value, the better the slipperiness. Reducing the coefficient of friction not only improves transportability in manufacturing, cameras and laboratories, but also prevents film scratches.

The sensitive material prepared by using the slip agent of the present invention is evaluated not only for its sliding property by the specific coefficient of static friction as described above but also for the sliding property with both sides of the sensitive material. However, the friction coefficient between the emulsion surface and the back surface of the slip agent of the present invention is 0.25 or less, and further, 0.16 or less. Also, the friction coefficient can be reduced by using the present slipping agent even in the case of contact with other materials, and the coefficient is generally 0.25 or less. In this case, the mating material may be iron, aluminum plate, zinc plate, stainless steel, plastic (for example, nylon, vinyl chloride, rubber, polyethylene, polyethylene terephthalate, polymethylmethacrylate, polypropylene, etc.).

Next, antistatic used in the light-sensitive material of the present invention
The agent will be described. As an antistatic agent used in the present invention
Is not particularly limited, for example, an anionic polyelectrolyte
As, carboxylic acids and carboxylates, sulfonates
Electrolytes containing, for example, JP-A-48-22017, Japanese Patent Publication
JP-A-46-24159, JP-A-51-30725,
JP-A-51-129216, JP-A-55-95942
Are macromolecules as described in. Cationic high content
As the child, for example, JP-A-49-121523 and JP-A-
Recorded in Sho 48-91165 and Japanese Patent Sho 49-24582
Some are listed. Also, depending on the processing
As an antistatic agent that does not lose its conductivity, ZnO, Ti
O₂, SnO₂, Al₂O₃, In₂O₃, SiO₂,
MgO, BaO, MoO ₃, V₂O_FiveChosen from
At least one crystalline metal oxide or these
Fine particles of complex oxides are mentioned, and it is special to use them.
Is preferred. Among these, SnO is particularly preferable.₂The Lord
About 5 to 20% of antimony oxide is contained as a component and / or
Further contains other components (eg silicon oxide, boron, phosphorus, etc.)
It is a conductive material contained. These conductive crystalline
Fine particles of oxides or their composite oxides have volume resistivity
Is 10⁷Ω-cm or less, more preferably 10^FiveΩ-cm or less
Is. The particle size is 0.002-0.7μ.
m, particularly preferably 0.005 to 0.3 μm.

These antistatic agents may be present in at least one layer of the light-sensitive material layer, for example, a back side undercoat layer, a back layer or a back outermost layer, an emulsion side undercoat layer, an emulsion layer, an intermediate layer or an emulsion. The outermost layer on the side can be mentioned.
The binder used in that case is not particularly limited, and may be a water-soluble binder, an organic solvent-based binder, or may be crosslinked like a latex. The volume resistance of the obtained antistatic layer is 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω.
Ω or less, more preferably 10 ⁹ Ω or less. Examples of the binder include gelatin, SBR latex, vinylidene chloride latex, polyacrylic acid ester, diacetyl cellulose, triacetyl cellulose, urethane and the like. In the present invention, the incorporation of a matting agent in the outermost layer is effective for enhancing the effect of the slip agent of the present invention. It is preferable in terms of suppressing blocking between the surface and the emulsion surface of the light-sensitive material and the back surface. The matting agent that can be used in the present invention is not particularly limited, but it is an inorganic compound or a polymer compound having a glass transition temperature Tg of 50 ° C. or higher. Two or more kinds of these matting agents can be mixed and used. Examples of inorganic compounds used as these matting agents include barium sulfate and
Fine powders of inorganic substances such as manganese colloid, titanium dioxide, strontium barium sulfate, silicon dioxide, and aluminum oxide, and further, for example, silicon dioxide such as synthetic silica obtained by a wet method or gelation of silicic acid, titanium slag, and sulfuric acid. Examples thereof include titanium dioxide (rutile type and anatase type). In addition, the particle size is relatively large,
For example, it can also be obtained by pulverizing from an inorganic substance of 20 μm or more and then classifying (vibrating filtration, air classification, etc.).

Further, as the polymer compound matting agent,
Polytetrafluoroethylene, cellulose acetate,
There are polystyrene, polymethylmethacrylate, polypropylmethacrylate, polymethylacrylate, polyethylene carbonate, starch and the like, and also pulverized and classified products thereof. In addition, acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, phthalic acid diester, styrene derivative, vinyl ester, acrylamides, vinyl ethers, allyl compounds, vinyl ketones, vinyl heterocyclic compounds , Allyl compounds, acrylonitrile, methacrylonitrile, polyfunctional monomers, and the like, a high molecular compound which is a polymer of one or more kinds of monomers, and various means such as suspension polymerization, spray drying, or The particles may be formed by a dispersion method or the like. The average particle size of these matting agents is 0.01 to
15.0 μm, preferably 0.02 to 7.0 μm
m, more preferably 0.05 to 5 μm. Their content is 0.1 to 10 ³ mg / m ^2, preferably in the 0.2~500mg / m ^2, more preferably 0.
4 to 250 mg / m ² . When a matting agent is applied, it is preferable to use a binder capable of forming a film. In that case, it is desirable that the surface of the back surface can be provided with a roughness by the matting agent, and it is preferable that the matting agent is applied to the outermost layer of the back surface or the outermost layer of the emulsion. It is also preferable to add the matting agent to the sliding layer or the magnet layer. Furthermore, it is desirable to have a form in which a slip agent is applied on the matting agent layer.

Next, the support used in the present invention will be described. The film support in the present invention is not particularly limited, but various plastic films can be used, and preferred are cellulose derivatives (for example, diacetyl-, triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate, etc.). Polyamide, U.S. Pat. No. 3,023,101.
Polycarbonate described in Japanese Patent Publication No. 4840414 and the like (polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene 1,2-diphenoxyethane-4,4'-dicarboxy). Rate, polybutylene terephthalate, polyethylene naphthalate), polystyrene, polypropylene, polyethylene, polymethylpentene, polysulfone, polyether sulfone, polyarylate, polyetherimide, etc., and particularly preferably triacetyl cellulose, polyethylene terephthalate, polyethylene na. It is phthalate. Some of these films have polar groups (epoxy, COO ₂ M, OH, NR
₂ , NR ₃ X, SO ₃ M, OSO ₃ M, PO ₃ M ₂ , O
P ₃ M ₂ , where M is H, an alkali metal, or ammonia and R is H, or may have an alkyl group having 1 to 20 carbon atoms).

Of these supports, various methods can be used for the polyester film in order to reduce the curl. For example, as described in JP-A-51-16358, the glass transition point of a polyester film is set to 3
There is a method of heat treatment at a temperature lower than 0 ° C to 5 ° C. Further, there is a method disclosed in JP-A-1-131550, and in the successive biaxial stretching step, a difference in crystallinity and orientation is obtained by applying a temperature gradient to the front and back surfaces of the film between longitudinal stretching and transverse stretching. It is to put on a permanent curl. There is also a method in which the curl is wound in the opposite direction to the curl when wound as a product to cancel the curl over time that occurs when the product is stored. A method such as heat treatment at a temperature can be used. A glass transition temperature of 9 can be used as a support that exhibits an effect of preventing curling during heat treatment.
Polyesters of 0 ° C or higher and 200 ° C or lower are particularly effective. This is because the effect of this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so when used by general users, the temperature that is exposed to the highest temperature (the temperature in the car in the summer, exceeding 80 ° C) is This is because it is necessary to have a glass transition temperature of 90 ° C. or higher. In addition, a general-purpose polyester film having transparency and a glass transition temperature exceeding 200 ° C. has not existed until now. There are various kinds of such polyester films, and particularly preferable supports are polyethylene naphthalate, polyarylate, and copolymers and polymer blends using these as raw materials. These supports are preferably subjected to a heat setting treatment after biaxial stretching, and may be heat relaxed if necessary.

In this case, the heat treatment needs to be performed at a temperature of 50 ° C. or higher and a glass transition temperature or lower for 0.1 hour or more and 1500 hours or less. Of these, a particularly preferable heat treatment method is illustrated below. For example, in the case of polyethylene naphthalate, it has a Tg of about 120 ° C. Therefore, heat treatment at a temperature of 119 ° C. or lower for 0.2 to 72 hours is preferable, and heat treatment at 115 ° C. for 24 hours is more preferable. In particular, in order to perform the heat treatment in a short time, it is preferable to raise the temperature once to Tg or more and gradually cool it in the vicinity of Tg because the efficiency is greatly improved. In the case of polyethylene naphthalate, once maintain a temperature between 130 ° C and 200 ° C, cool it to 125 ° C, then 1
By gradually cooling to 00 ° C. for 40 minutes, the heat treatment temperature can be significantly shortened. When the support subjected to such heat treatment is measured by a differential thermal analysis diameter, an endothermic peak appears in the vicinity of Tg, and the larger the endothermic peak, the harder the winding tendency becomes.
And 100 mcal / g or more, more preferably 200
It is preferable that the heat treatment is performed so that the heat resistance is not less than mcal / g.

A plasticizer may be added to these supports for the purpose of imparting flexibility. Particularly for cellulose esters, plasticizer-containing substances such as triphenyl phosphate, biphenyl diphenyl phosphate, and dimethyl ethyl phosphate are usually used. The support may contain a dye for the purpose of neutralizing the base tint, preventing light piping, preventing halation and the like. A part of the light-sensitive material is exposed to light during shooting and development processing, and a light piping failure occurs in which light reaches a portion that should not be covered. Therefore, in the present invention, it is preferable that a dye is contained in the support to prevent light piping. The dye is not particularly limited, and various conventionally used dyes for photographic supports can be used. These supports of the present invention have a thickness of 40 μm.
m or more and 300 μm, more preferably 60 μm to 2
It is 00 μm. If the thickness is less than 40 μm, the toy-like curl generated by the shrinkage stress of the emulsion layer during drying becomes remarkable and the flatness is apt to deteriorate, and if it is more than 300 μm, the film strength becomes strong, but the film was stored in a film cartridge for a long time. It is easy to get fired when you need it. The molecular weight of these support polymers is preferably 10,000 or more, more preferably 20,000 to 100,000.

In order to firmly adhere a photographic layer (eg, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, a magnetic recording layer, a conductive layer) on these supports, chemical treatment (acid, alkali, Surface treatment such as oxidant liquid treatment), mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc. After that, the photographic emulsion may be directly applied to obtain the adhesive force, or after the surface treatment of these, an undercoat layer may be provided and the photographic emulsion layer may be applied thereon. Among these, corona discharge treatment, flame treatment, ultraviolet treatment, and glow discharge treatment are particularly preferable, and the treatment is performed at a high temperature during the treatment (for example, 50 ° C. or higher, preferably 70 ° C. or higher, for several seconds to several seconds). (Several minutes are preferable)
Is. For the cellulose derivative, a single layer of gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent is applied to provide an undercoat layer.

For the polyester-based support, a layer that adheres well to the support (hereinafter abbreviated as the first undercoat layer) is provided as the first layer, and a hydrophilic layer that adheres well to the photographic layer as the second layer is further provided. There are a so-called multi-layer method in which a resin layer (hereinafter abbreviated as a second undercoat layer) is applied, and a single-layer method in which only one resin layer containing both a hydrophobic group and a hydrophilic group is applied. In the first undercoat layer in the multilayer method, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid,
Polymers such as polyethyleneimine, epoxy resin, gelatin, grafted gelatin, nitrocellulose, etc., alone or mixed, including copolymers starting from monomers selected from itaconic acid, maleic anhydride, etc. Can be used. Further, in the second undercoat layer, gelatin is mainly studied. In the single layer method, a method is often used in which the support is swollen and interfacially mixed with the hydrophilic undercoating polymer to achieve good adhesiveness. Examples of the hydrophilic undercoating polymer include water-soluble polymers such as gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers and maleic anhydride copolymers, carboxymethyl cellulose, hydroxyethyl cellulose and the like. Latex polymers such as cellulose ester, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer, acrylic acid ester-containing copolymer, vinyl acetate-containing copolymer, vinyl acetate-containing copolymer and the like are used. Of these, gelatin is preferred. Further, as the compound for swelling the support used in the present invention, resorcin, chlorresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol,
Trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, chloral hydrate and the like are used. Of these, preferred are resorcin and p-chlorophenol.

The above-mentioned hydrophilic undercoat polymer can use the above-mentioned hydrophilic polymer hardener as a curing agent. If desired, the undercoat liquid may contain various additives. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. The undercoat layer of the present invention includes SiO ₂ , Ti
Inorganic fine particles such as O ₂ or polymethylmethacrylate copolymer fine particles (0.05 to 10 μm) can be contained as a matting agent, and the addition amount thereof is 0.05 to 50.
mg / m ² is preferred. The undercoating liquid relating to the present invention is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. No. 2,681. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 294,294. US Pat. No. 2,76, as required
1,791, 3,508,947, 2,941,8
No. 98 and No. 3,526,528, Yuji Harazaki, “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) and the like can be used to simultaneously coat two or more layers. Furthermore, the undercoating liquid of the present invention has a polyester support (polyethylene phthalate,
Polyethylene naphthalate, etc.) may be uniaxially stretched and then coated with an undercoating liquid, and then biaxially stretched to prepare an undercoated support.

Next, the silver halide photographic light-sensitive layer of the present invention will be described in detail. The light-sensitive material of the present invention comprises a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly used in the hydrophilic colloid layer. In that case, the binder of the hydrophilic colloid layer includes, for example, proteins such as gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic colloids such as Polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives and partial hydrolysates thereof, dextran, polyvinyl acetate, polyacrylic acid ester, rosin and the like can be mentioned, if necessary. Mixtures of two or more of these colloids may be used. The most used of these is gelatin or its derivatives, and the gelatin referred to here is so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. The compounds contained therein are also not particularly limited, and include alkali metals, alkaline earth metals (for example, barium, magnesium, cesium, strongtium, etc.), heavy metals (iron, silver, copper, lead, tin, zinc, titanium, Silicon, Al, etc.), the content of which is 0.
It may be 1 to 20000 ppm and is not particularly limited.

In the present invention, anion, nonion,
A cation and a betaine fluorine-containing surfactant can be used in combination. These fluorine-containing surfactants are disclosed in JP-A-49-
No. 10722, British Patent No. 1,330,356, JP-A Nos. 53-84712, 54-14224, and 50.
-113221, U.S. Pat. No. 4,335,201,
U.S. Pat. No. 4,347,308, British Patent No. 1,417,91.
No. 5, Japanese Examined Patent Publication No. 52-26687, No. 57-26719
No. 59-38573, JP-A-55-149938.
No. 54, No. 54-48520, No. 54-14224, No. 58-200235, No. 57-146248, No. 5
8-196544, British Patent No. 1,439,402
No., etc. In the present invention, a nonionic surfactant may be used. Specific examples of these surfactants preferably used in the present invention are described below.

[0034]

[Chemical 1]

[0035]

[Chemical 2]

[0036]

[Chemical 3]

The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material. For example, a surface protective layer, an emulsion layer, an intermediate layer Examples thereof include an undercoat layer and a back layer. The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may be 0.0001 g to 1 g per 1 square meter of the photographic light-sensitive material, more preferably 0.0005 to 0.5 g, Particularly preferred is 0.0005 g to 0.2 g. Further, two or more kinds of these surfactants of the present invention may be mixed.
Also, ethylene glycol, propylene glycol, 1,
1,1-trimethylolpropane etc. JP-A-54-896
A polyol compound as shown in No. 26 can be added to the protective layer or another layer of the present invention. Other known surfactants may be added to the photographic constituent layers of the present invention alone or in combination. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics.

The photographic light-sensitive material of the present invention contains US Pat. Nos. 3,411,911 and 3,411,912 in the photographic constituent layers.
And polymer latexes described in JP-B-45-5331 and the like. The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardeners (alone or in combination). The light-sensitive material of the present invention will be described below. Preferred in the present invention are black-and-white light-sensitive materials, roentgen light-sensitive materials, graphic light-sensitive materials and color photographic light-sensitive materials, color papers, either negative light-sensitive materials or positive light-sensitive materials, in either roll form or sheet form. Good. Among them, color photographic light-sensitive materials are preferable, and typical examples thereof include a color reversal film and a color negative film.

A general color negative film will be described below. The light-sensitive material of the present invention has a blue-sensitive layer on a support,
It suffices that at least one of the silver halide emulsion layers of the green color sensitive layer and the red color sensitive layer is provided, and the number of silver halide emulsion layers and the non-photosensitive layer and the layer order are not particularly limited.
As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light. In a multilayer silver halide color photographic light-sensitive material,
In general, the unit photosensitive layers are arranged in order from the support side in the order of red color sensitive layer, green color sensitive layer, and blue color sensitive layer. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers, DIR compounds, etc. as described in the specifications of 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-1127.
No. 51, No. 62-200350, No. 62-20654.
No. 1, No. 62-206543, No. 56-25738.
No. 62-63936, 59-202464,
It is described in JP-B-55-34932 and JP-B-49-15495. Silver halide grains have regular crystal shapes such as cubes, octahedra and tetradecahedrons, irregular crystal shapes such as spheres and plates, and crystal defects such as twin planes. It may have one or a combination thereof. The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types",
And No. 18716 (November 1979), 648.
P. Glafkides, Chemicet Phisique Photographi, "Physics and Chemistry of Photography" by Graphide
que, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogr
aphic Emulsion Chemistry (Focal Press, 196
6)), "Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making a
nd Coating Photographic Emulsion, Focal Press, 19
64) and the like. U.S. Pat. Nos. 3,574,628 and 3,65
The monodisperse emulsions described in, for example, 5,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Pho
tographic Science and Engineering), Volume 14, 24
8-257 (1970); U.S. Pat. No. 4,434,434.
No. 226, No. 4,414, 310, No. 4,433, 0
48, 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in No. 112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure No. 17643 and No. 1871.
6 and the relevant portions are listed later.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4, whitening agent 24 Page 5 antifoggant page 24-25 page 649 right column-and stabilizer 6 light absorber, page 649 right column-filter dye, page 25-26 page 650 left column UV absorber 7 stain inhibitor page 25 right column 650 Page left to right column 8 dye image stabilizer page 25 9 hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizer page 27 page 650 page left column 12 coating aid, page 26-27 page 650 right column surface Activator

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound which can be immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII mentioned above.
-C-G. Yellow couplers include, for example, U.S. Pat. No. 3,933,50.
No. 1, No. 4,022,620, No. 4,326,0
No. 24, No. 4,401,752, No. 4,248,
961, Japanese Patent Publication No. 58-10739, British Patent No. 1,
425,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023.
No. 4,511,649, European Patent 249,4.
Nos. 73A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, W.
Those described in O (PCT) 88/04795 and the like are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308,
No. 4,334,011, No. 4,327,173
West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, US Pat. Nos. 3,446,622, and 4,333,999.
No. 4,753,871, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,163,67
No. 0, Japanese Examined Patent Publication No. 57-39413, US Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has excessive diffusibility include U.S. Pat. No. 4,366,237 and British Patent 2,125,57.
No. 0, European Patent No. 96,570, and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of the polymerized dye-forming couplers are U.S. Pat.
U.S. Pat. No. 4,576,910, British Patent 2,102,13.
No. 7, etc. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the aforementioned RD17643, VII to F patents, JP-A-57-151944, and JP-A-57-15423.
No. 4, No. 60-184248, No. 63-37346.
And U.S. Pat. No. 4,248,962 are preferred.

As couplers which release a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252 and the like, and after separation as described in EP 173,302A Couplers that release dyes that recolor, R.I. D. No. 11449, 24
No. 241, a bleaching accelerator releasing coupler described in JP-A No. 61-201247, a ligand-releasing coupler described in U.S. Pat. No. 4,553,477 and the like, JP-A-63-7.
Examples thereof include couplers releasing the leuco dye described in No. 5747.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives, hydrocarbons and the like. The auxiliary solvent has a boiling point of about 30.
Organic solvents having a temperature of not less than 50 ° C., preferably not less than 50 ° C. and not more than about 160 ° C. can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. .

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less, and the film swelling speed T _1/2 is preferably 30 seconds or less. The film thickness is 25
℃ means a film thickness measured at a relative humidity of 55% (2 days), the film swelling rate T _1/2 can be measured in accordance with a known method in the art. For example, A. Green et al. Photographic Science and Engineering (Photogr. Sci. Eng.),
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 19, No. 2, pp. 124-129, T
_1/2 is the saturation film thickness which is 90% of the maximum swelling film thickness reached when processed with a color developer at 30 ° C. for 3 minutes and 15 seconds.
_It is defined as the time to reach a film thickness of _1/2 .

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness. The color photographic light-sensitive material according to the present invention has the RD. No.
Development can be carried out by a usual method described on pages 28 to 29 of 17643 and 615 left column to right column of No. 18716. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, the Schiff base type compounds described in U.S. Pat. No. listed.

Next, the photosensitive material of the present invention is preferably a roll-shaped film when the film is conveyed by a camera or a printer. The cartridge used may be mainly composed of metallic or synthetic plastic.
When molding plastics, a plasticizer is mixed with plastics as needed. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene, and butyl palmitate. It is something. Specific examples of the plastic material are shown below, but the invention is not limited thereto.

Specific examples include polystyrene, polyethylene,
Polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methyl methacryl resin, vinyl formal resin, vinyl butyral resin, polyethylene terephthalate, Teflon , Nylon, phenol resin, melamine resin, etc. Particularly preferred plastic materials are polystyrene, polyethylene, polypropylene and the like. Further, the cartridge may contain various antistatic agents. The antistatic agent is not particularly limited, but carbon black, metal oxide particles, nonion, anion,
Cations, betaine-based surfactants, nonions, anions, cations, betaine polymers and the like can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. Preferably, its electrical resistance is 25 ° C
It is 10 ¹² Ω or less at / 10% RH. Usually, the cartridge is manufactured by using plastic in which carbon black, a pigment, etc. are kneaded in order to impart a light shielding property. Furthermore, the form may be the same as the current size, but currently 25
The diameter of the m / m cartridge is 22 m / m or less, preferably 20
Setting it to m / m or less and 14 m / m or more is effective for downsizing the camera.

The ratio of the internal volume of the cartridge case to the plastic used in the cartridge and the cartridge case is 4 to 0.7, preferably 3 to 1. In the case of the cartridge containing the 135 color sensitive material of the present invention, the total weight of the plastic used in the cartridge and the cartridge case is usually 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less.

[0054]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 1-1) Preparation of Support On one side (back layer) of cellulose triacetate having a thickness of 115 μm, the following coating composition for antistatic layer was applied.
5 ml / m ² was applied and dried at 120 ° C. for 3 minutes to form an antistatic layer (at this time, the temperature inside the casing of the drying system and the substantial temperature of the transport roller were 120 ° C.). confirmed). (Cationic polymer content in antistatic layer: 50 mg / m ² ) (Coating composition for antistatic layer) Diacetyl cellulose 1.0 g Cationic polymer below 3.5 g Needle-shaped vanadium pentoxide 0.50 g SnO ₂ / Sb ₂ O ₃ (9/1 weight ratio) 7.0 g Ethylene glycol 27 ml Methanol 600 ml Acetone 400 ml

[0055]

[Chemical 4]

The above polymer was dissolved in 1% by weight of saline solution in an amount of 0.1% by weight, and η _{SP / C} (viscosity number) measured at 30 ° C. was 0.12. Next, on the above antistatic layer,
Apply the following coating composition to 25 ml / m ² and
It was dried at 00 ° C. for 3 minutes to form an auxiliary layer (binder layer). (At this time, it was confirmed that the temperature inside the casing of the drying system and the substantial temperature of the conveying roller were 100 ° C.) (Coating composition) Methylene chloride 100 ml Methanol 150 ml Acetone 750 ml Diacetyl cellulose 6 g SiO ₂ fine particles 0.7 g ( Average particle size 0.1 μm) C ₈ F ₁₇ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₁₀ H 0.1 g C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ H 0.1 g On this auxiliary layer In addition, the slip agent (the slip agent of the present invention (1-
4) / lubricant (4-3) of the present invention, 12/3 mg / m ² ) xylene / toluene / cyclohexane / methyl ethyl ketone / cyclohexanone / acetone (equal weight each)
A sample was prepared by dispersing (0.003 μm) with a mixed solvent, coating with a bar coater at a coating amount of 7 ml / m ² , and drying at 110 ° C. for 5 minutes. (At this time, it was confirmed that the temperature inside the casing of the drying system and the substantial temperature of the transfer roller were 110 ° C.)

1-2) Preparation of Photosensitive Material (Preparation of Emulsion Undercoat Layer) The surface opposite to the back surface was subjected to corona discharge treatment and ultraviolet irradiation treatment to obtain gelatin (0.
1 g / m ² ), formalin (0.01 g / m ² ) applied,
It was used as an emulsion surface undercoat layer. Then, the following photosensitive layer was applied. (Photosensitive layer composition) 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 Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1.5 × 10 ^-5 ExS-3 4.5 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0.020 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.11 ExC-7 0.0010 ExC-8 0.025 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8.0 × 10 ^-4 ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.35 Gelatin 1.30

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.38 ExS-7 3.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Thirteenth layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

14th layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Sliding agent Dispersion Listed in Table 2

Here, a method for preparing the lubricant dispersion will be described. The slip agent of the present invention shown in Table 2 was added to water at a ratio (weight ratio) of the addition amount shown in the table to a concentration of 2% by weight, heated to 100 ° C., melted and dissolved naturally. Cooled. At this time, it was cooled while being dispersed by ultrasonic waves. The aqueous dispersion of the obtained slip agent was added and applied to the 14th layer (second protective layer) so as to have the content shown in the table. Further, in order to improve the storage stability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property of each layer, W-1 to W-3, B-
4 to B-6, F-1 to F-17, and iron salt, lead salt, gold salt, platinum salt, iridium salt, palladium salt, and rhodium salt.

[0073]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope.

[0075]

[Chemical 5]

[0076]

[Chemical 6]

[0077]

[Chemical 7]

[0078]

[Chemical 8]

[0079]

[Chemical 9]

[0080]

[Chemical 10]

[0081]

[Chemical 11]

[0082]

[Chemical 12]

[0083]

[Chemical 13]

[0084]

[Chemical 14]

[0085]

[Chemical 15]

[0086]

[Chemical 16]

[0087]

[Chemical 17]

[0088]

[Chemical 18]

[0089]

[Chemical 19]

Development of these samples was carried out as follows. Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step was as follows. Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 g Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Add water 1.0 liter pH 10.0

Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to 1.0 liter pH 6.0 Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sulfurous acid Sodium 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added to 1.0 liter pH 6.6 Stabilized solution Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 liter Add water to 1.0 liter

1-3) Evaluation of Characteristics Next, evaluation of these samples will be described. Evaluation of sliding characteristics (1) Measurement of dynamic friction coefficient After the sample was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, a HEIDON-14 dynamic friction coefficient measuring device was used to measure 5 mm.
φ stainless steel ball, load 100g, friction speed 6
It was measured at 0 cm / min. The smaller the value, the better the slipperiness. (2) Scratch strength After conditioning the sample for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, the tip of the sample was 0.5 mmR on the evaluation surface of the sample before development processing.
Applying a sapphire needle vertically, applying a continuous load, 60
Scratch at a speed of cm / min. The scratched sample was developed and printed at 45 times magnification, and the load at which scratches began to be seen was taken as the scratching strength. The larger the value, the better.

(3) Evaluation of surface state The number of cissings per 1 m ^{2 of the} obtained sample was evaluated. The larger the number, the worse the coated surface. (4) Evaluation of coating liquid stability (Evaluation of particle size of lubricant dispersion) The particle size of the dispersion solution was measured by Coulter submicron particle analyzer N4.
It was measured by. The measurement was carried out by appropriately diluting the dispersion liquid with water to a measured concentration. (Evaluation of Dispersion Stability) A slip agent dispersion liquid was used as a Poic integrating sphere turbidimeter SEP-PT-501D (Mitsubishi Kasei Co., Ltd.).
The turbidity was measured with. The smaller the value, the better the dispersion stability.

1-4) Results Table 2 shows the results of evaluation on the emulsion side of the above samples. The control sample (1-1) has poor slipperiness and scratch strength before and after the treatment. On the other hand, comparative samples (1-2) to (1-) using only one kind of the lubricant of the present invention.
In the case of 4), it was not possible to satisfy all of the dispersion stability, the sliding property, the scratch strength and the surface state at the same time. Further, comparative samples (1-18) to (1-
Regarding 19), it was not possible to satisfy all of the stability of the dispersion liquid, the sliding property, the scratch strength and the surface state at the same time. Further, Comparative Samples (1-20) to (1-22) using Comparative Samples other than the present invention as the slip agent cannot satisfy all of the dispersion stability, the sliding property, the scratch strength and the surface condition at the same time. It was On the other hand, the samples (1-5) to (1-17) of the present invention satisfied all of the dispersion stability, the sliding property, the scratch strength and the surface state at the same time. It should be noted that the sample of the present invention (1-7) to which the addition amount of the slipping agent is within the scope of the present invention but is not optimum
(1-9) tended to be slightly inferior in terms of slip characteristics and scratch strength. But it wasn't a big deal. The sample of the present invention was processed into a 135 film form and loaded into a current metal cartridge, loaded into a travel mini of a Fuji Photo Film camera, photographed, developed and examined for scratches on the image. The sample of the invention showed almost no scratches and excellent photographs were obtained. On the other hand, the samples other than the present invention were found to have some scratches on the film, impairing its commercial value.

[0095]

[Table 2]

[0096]

[Table 3]

Example 2 2-1) Preparation of Support (Coating of Undercoat Layer) Polyethylene naphthalate chips (glass transition point: 120 ° C.) were melt extruded, and then 3.4 times in the longitudinal direction and horizontally. It was stretched 4 times to produce a biaxially stretched polyester having a thickness of 85 μm. At this time, an extrusion temperature of 300 ° C., a longitudinal stretching temperature of 140 ° C., and a transverse stretching temperature of 130
A film was formed at a temperature of 250 ° C for 6 seconds at 250 ° C. Further, at the time of this longitudinal stretching, one side was heated and the temperature difference between the front and the back was set to 20 ° C. and the stretching was performed. Wrap this support around a stainless steel core, 1
Heat treatment was performed at 10 ° C. for 72 hours to prepare a support. (This support was wound around a 7 mm core, and then heat treated at 80 ° C. for 2 hrs, and the core set value was 40 in ANSI Curl value.) As a measure against light piping, yellow, magenta and cyan dyes were mixed. molten polyethylene naphthalate chip Te, each color density ^{(D B, D G, D} R)
It is stained with 0.05, 0.05, 0.05.

After corona discharge treatment, ultraviolet ray irradiation treatment and glow discharge treatment on both sides of each of them, an undercoat solution having the following composition was applied by a bar coater at 10 cc / m ² . For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. At this time,
From the current and voltage readings, the object to be processed is 0.375kV ・ A ・
Min / m ² was processed. The discharge frequency during processing is 9.6
kHz, gap clearance between electrode and dielectric roll is 1.6
It was mm. Also, the ultraviolet irradiation treatment is performed at 115 ° C. for 1
Irradiation was carried out at 50 mJ / cm ² . Further, glow discharge treatment is performed at 90 ° C., vacuum degree of 0.1 mmHg, 2.5 Kw, 27
It was carried out at KHz for 10 seconds. For drying, a sample was prepared by drying at 110 ° C. for 5 minutes (at this time, it was confirmed that the temperature inside the casing of the transport system and the substantial temperature of the transport roller, and the film temperature were also 110 ° C.).

Water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Acetone 50 parts by weight Sodium salicylate 0.1 parts by weight Ethylene dichloride 50 parts by weight Diacetyl cellulose 1 part by weight Gelatin 2 parts by weight p-Chlorophenol 4 parts by weight Resorcin 0. 5 parts by weight Cresol 0.5 parts by weight (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.3 parts by weight Glutaraldehyde 0.05 parts by weight Formaldehyde 0.05 parts by weight Dichlorotriazine sodium salt 0.05 Parts by weight trimethylolpropane triaziridine 0.05 parts by weight trimethylolpropane tritoluene diisocyanate 0.05 parts by weight triglycidyl trimethylolpropane 0.05 parts by weight

(Coating of Back Layer) For each of the above-mentioned surface-treated supports, the following composition was applied to the surface of the support after the undercoating on the side opposite to the side on which the undercoating layer was provided. A back layer was applied to prepare a sample. (1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. An aqueous 1N sodium hydroxide solution was added dropwise to this solution until the solution had a pH of 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The average particle size was 0.05 μm. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions have been removed is redispersed in 1500 parts by weight of water and sprayed in a firing furnace heated to 500 ° C.
Fine particles of a stannic oxide-antimony monoxide composite having a bluish average particle size of 0.005 μm were obtained. The resistivity of this fine particle powder was 25 Ω · cm. A mixed solution of 40 parts by weight of the above fine powder and 60 parts by weight of water was adjusted to pH 7.0, and roughly dispersed by a stirrer, and then a horizontal sand mill (Dynomill, Willy A. B).
ackfen AG) and dispersed until the residence time reached 30 minutes. The average particle size of the secondary aggregate is 0.15μ
It was m.

(2) Coating of Antistatic Layer The following formulation [A] was applied to a dry film thickness of 0.2 μm and dried at 110 ° C. for 1 minute (at this time, the temperature inside the casing of the transport system and Substantial temperature of the transport roller is 11
It was confirmed to be 0 ° C). [Formulation A] 10 parts by weight of conductive fine particle dispersion liquid (SnO ₂ / Sb ₂ O ₃ , 0.10 μm) Gelatin 1 〃 ・ Water 27 〃 ・ Methanol 60 〃 ・ p-Chlorophenol 0.1 〃 ・ Resorcin 2 〃 ・ Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.01 〃 ・ Toluene diisocyanate 0.2 〃 ・ (CH ₂ ═CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH-OH 0.1 〃 ・ Poly ( Degree of polymerization 10) Oxyethylene paranonylphenol ether 0.03 〃 ・ Sodium dodecylbenzene sulfonate 0.01 〃

(3) Coating of Back Layer Further, a back dispersion coating liquid was prepared with the following formulation using diacetyl cellulose as a binder.・ Silicon dioxide (average particle size 0.3 μm) 3 g ・ Aluminum oxide 10 g ・ Diacetyl cellulose 320 g ・ Poly (degree of polymerization 10) oxyethylene paranonylphenol ether 20 g ・ Sodium p-stearylbenzenesulfonate 1.8 g ・ Toluene diisocyanate 10 g Colloidal silica (aerosil average particle size 0.02 μm) 5 g C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ CH ₂ O) ₆ H 1 g Poly (vinylidene difluoride / vinylidene tetrafluoride) (Molar ratio 9: 1) 2 g

Poly (methyl methacrylate / divinylbenzene) (molar ratio 9: 1, average particle size 1.0 μm) 3 g, (CH ₂ ═CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH—OH 0.3 g, methyl ethyl ketone 3000 g -Cyclohexanone 3000 g-Acetone 500 g-Methyl methacrylate / sodium vinyl sulfonate copolymer (molar ratio 95: 5, molecular weight 14000) 10 g Dispersion was carried out at 2000 rpm for 2 hours using a sand grinder. Glass beads were used as the dispersion medium. After adding 30% of the toluene diisocyanate compound to the obtained liquid with a binder, the coating amount of solid diacetyl cellulose was 0.3 g /
Applied on top of the antistatic layer previously applied to give m ² , 1
It was dried at 10 ° C for 3 minutes (at this time, it was confirmed that the temperature inside the casing of the conveying system and the substantial temperature of the conveying roller were 110 ° C).

(4) Coating of Sliding Layer (Preparation of Sliding Agent Dispersion Liquid) Sliding Agent (The sliding agent of the present invention (1-
4) / The sliding agent (4-3) of the present invention, 12/3 g / m ² ) is heated and melted at 100 ° C. with an equal weight of xylene, and 10 times amount of isopropanol of room temperature is stirred in this liquid and ultrasonicated. While being added all at once, a dispersion liquid (4.5% by weight) was prepared. Further, the obtained primary dispersion was added to xylene / cyclohexanone / isopropanol (= 70/25/5 weight ratio).
High pressure homogenizer (25 ℃, 300kg / c)
It was prepared by finely dispersing with m ² ) so that the concentration of the slipping agent would be 0.2% by weight. The application was performed by a slide coating method. Then, it was dried at 110 ° C. for 1 minute to form a sliding layer to prepare a sample (at this time, it was confirmed that the temperature inside the casing of the drying system, the transport roller and the film was substantially 110 ° C.). .

2-2) Preparation of Photosensitive Material A support having the back surface prepared above was coated with a photosensitive layer and processed into a sample in the same manner as in Example 1 to prepare a sample. Development processing was carried out using Example 1 of the present invention. 2-3) Results Table 3 shows the results of evaluation of the above samples. The control sample (2-1) has poor slidability and scratch strength before and after the treatment. On the other hand, Comparative Samples (2-2) to (2-4) using only one kind of the slip agent of the present invention simultaneously satisfy all of the dispersion stability, the slip characteristics, the scratch strength and the surface state. I couldn't do that. In addition, comparative samples (2-18) to (2-1) outside the addition amount range of the present invention.
Regarding 9) as well, it was not possible to satisfy all of the dispersion stability, the sliding property, the scratch strength and the surface state at the same time. Comparative samples (2-20) to (2-22) using comparative samples other than the present invention as a slip agent were not able to satisfy all of the dispersion stability, the sliding property, the scratch strength and the surface condition at the same time. . On the other hand, the sample (2
-5) to (2-17) satisfied all of the dispersion stability, the sliding property, the scratch strength, and the surface condition at the same time. It should be noted that the sample of the present invention (2-7) to (2-
9) tended to be slightly inferior in terms of slip characteristics and scratch strength. But it wasn't a big deal.

Further, it was processed into a 135 film form and loaded into a current metal cartridge, loaded into a Travel Mini made by Fuji Photo Film, photographed, developed and examined for scratches in the image. The sample showed almost no scratches and excellent photographs were obtained. On the other hand, the samples other than the present invention were found to have some scratches on the film, impairing its commercial value. The dispersion of the present invention was applied by water, and there were no problems with odor and explosion protection. Furthermore, the sample of the present invention was wound around a winding core of 7 mm core and subjected to core setting at 80 ° C. for 2 hours. As a result of evaluation of curl, a sample having almost no curl and no trouble during development processing was obtained. On the other hand, a sample using a support which was not heat-treated at 110 ° C./72 hours was prepared in the same manner, wound around a core of a 7 mm core, and subjected to core setting at 80 ° C. for 2 hours. As a result of the evaluation of the habit, the winding habit was strong and troubles (development unevenness and rear edge fold in the drying zone) occurred during the development processing. In the sample of the present invention, even if the scotch tape was attached to the back side and peeled off vigorously, no peeling of the back surface was observed. On the other hand, when the sample which was not subjected to the surface treatment of the present invention was similarly adhered to the back surface by scotch tape and peeled off vigorously, peeling of the entire back surface was easily observed.
Therefore, in the present invention, it was found that the surface treatment is very effective in terms of adhesion. In addition, Sample 2-6 of the present invention
Comparative sample 2-6 ′ containing no antistatic agent (volume resistance 1 × 10 ¹⁵ Ω or more) had low humidity (25
The antistatic property at 10 ° C., 10% RH) was poor, and static marks were inferior to those of Sample 2-6 of the present invention (volume resistance of about 1 × 10 ⁹ Ω) when rubbed violently. That is, it was found that the combination of the slip agent of the present invention and the antistatic agent has excellent performance.

[0107]

[Table 4]

[0108]

[Table 5]

[0109]

As a result of the above, by carrying out the present invention, a light-sensitive material having good sliding characteristics, scratching strength, and surface condition can be produced. Further, the stability of the dispersion liquid containing the slipping agent was further improved, and a photographic light-sensitive material coated uniformly and uniformly during coating could be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08J 7/00 7310-4F G03C 1/38 1/795 1/81 1/85 // C08L 1: 00 67:00

Claims (13)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a support, wherein at least one layer of the photographic light-sensitive material is represented by the following general formula [4] or general formula [5]. It contains an aqueous dispersion of one kind and / or at least one kind selected from [1], [2] and [3], and its total content is 0.0005 to 0.7 g / m ^2. A silver halide photographic light-sensitive material characterized by: Formula (1) R ₁₁ -COO-R ₁₂ Formula (2) R ₁₃ -OCO-X-COOR ₁₄ Formula (3) R ₁₅ -COO-X-OCOR ₁₆ Formula (4) R ₁₇ -X ( ZO) _n R ₁₈ general formula [5] R ₁₉ —X (ZO) _m R _{20 In the} formula, R _{11 to} R ₁₇ represent an aliphatic hydrocarbon group having 1 to 100 carbon atoms, and total carbon atoms of R ₁₁ and R ₁₂ The number of carbon atoms, the total number of carbon atoms of R ₁₃ and R _14, the total number of carbon atoms of R ₁₅ and R ₁₆ , and the total number of carbon atoms of R ₁₇ and R ₁₈ are 36 to 150, respectively. R ₁₈ is a hydrogen atom and has 1 carbon atom
~ 100 alkyl groups, alkenyl groups, aralkyl groups,
Represents an alkylcarbonyl group. R ₁₉ has 8 to 100 carbon atoms
Represents an aliphatic hydrocarbon group, and R ₂₀ is —COOM, SO ₃
M, -OSO ₃ M, a -PO ₃ M _2, M is H, alkali metal salts (lithium, sodium, potassium, rubidium), alkaline earth metals (magnesium, calcium), total alkyl having 1 to 20 carbon atoms It represents an ammonium group or an ammonium group. X represents a divalent linking group having 0 to 50 carbon atoms, and Z represents an alkylene group, arylene group or aralkylene group having 2 to 12 carbon atoms. n is 2 to 100, m is 0
Represents an integer of 100. 2. The silver halide photographic light-sensitive material according to claim 1, wherein Z is ethylene, propylene, butylene, glycerin or phenethylene. 3. The content (weight ratio) of the lubricant represented by the general formula [4] and the lubricant represented by the general formula [5] is 97:
3. The silver halide photographic light-sensitive material according to claim 1, which is 3 to 30:70. 4. The total content of the lubricant represented by the general formula [4] and the lubricant represented by the general formula [5], and [1] and [2].
4. The silver halide photographic light-sensitive material according to claim 1, wherein the content ratio (weight ratio) of the lubricant selected from [3] is 100: 0 to 30:70. 5. The average particle size of the water dispersion is 0.5 to 0.0.
The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is dispersed in 001 μm. 6. The melting point of the sliding agent represented by the general formula [1], [2], [3] or [4] is 40 ° C. to 250 ° C., which is characterized in that Silver halide photographic light-sensitive material. 7. At least one layer contains a conductive metal oxide or / and an ionic polymer as an antistatic agent, and has a volume resistance of 10 ¹² Ω or less (25 ° C./10% RH). The silver halide photographic light-sensitive material according to claim 1. 8. A matting agent and / or a fluorine-containing surfactant having an average particle diameter of 0.01 to 7 μm is contained in at least one of the photographic constituent layers.
The silver halide photographic light-sensitive material described in. 9. A support is made of a cellulose derivative or a polyester derivative having a thickness of 50 to 300 μm, and the surface thereof is subjected to at least one treatment of ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment, and flame treatment. The silver halide photographic light-sensitive material according to any one of claims 1 to 7, wherein 10. The cellulose derivative of the support is cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyacetyl cellulose phthalate, cellulose long chain alkyl ester, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate. 8. The silver halide photographic light-sensitive material according to claim 7, wherein the rate or the polyester derivative is polyethylene terephthalate or polyethylene naphthalate. 11. The support is heat-treated at Tg or less in advance, or when the support has a curl, the heat treatment at Tg or more is performed with a silver halide photographic material. The silver halide photographic light-sensitive material according to claim 8 or 9. 12. A polyester support having a glass transition temperature of 60 ° C. or higher and 200 ° C. or lower, and the polyester support has a glass transition temperature of 50 ° C. or higher between the time of film formation and the coating of the photosensitive layer. The silver halide photographic light-sensitive material according to claim 8, which is heat-treated at a temperature not higher than the glass transition point of the polyester support for 0.1 to 1500 hours. 13. A polyester support having a glass transition temperature of 60 ° C. or higher and 200 ° C. or lower, which is uniaxially stretched, then undercoated and biaxially stretched.
11. The silver halide photographic light-sensitive material according to item 11.