JPS6214150A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sliding and the adhesive properties and the resistivity for reducing a pressure and a finger print sensitivities by incorporating a monodispersed silver halide particle to a silver halide emulsion layer positioned at the most far distance from a substrate, and by incorporating fine particles having a mean particle size of 1-10mum to a non-photosensitive layer positioned at the most far distance from a substrate. CONSTITUTION:The silver halide emulsion layer positioned at the most far distance from the substrate comprises the monodispersed silver halide particles contg. substantially silver chlorobromide particle having an outer mainly composed of {100} surface. The most outer layer (the protective layer) positioned at the most far distance from the substrate is the non-photosensitive layer. The prescribed protective layer is contained fine particles having the mean particle size of 1-10mum. Thus, the titled material having the improved physical resistivity such as the resistivity for reducing the pressure sensitivity and the sliding property, and the improved anti-finger print sensitivity is obtd.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material for printing which has excellent physical durability and is easy to handle. [The back of invention W! ] In general, silver halide color photographic light-sensitive materials have three types of silver halide color photographic emulsion layers coated on a support, which are selectively sensitized to have sensitivity to blue light, green light, and red light. has been done. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side. A bleachable yellow filter layer is provided to absorb the blue light that passes through the emulsion layer. Furthermore, between each emulsion layer, another intermediate layer is provided for a specific purpose, and a protective layer is provided as the outermost layer. Also, for example, photosensitive 0F for color photographic paper.
! In general, a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are coated in this order from the side to be exposed to light, and as in the case of color negative photosensitive materials, each layer has an intermediate layer such as an ultraviolet absorbing layer for a special purpose. layer, protective layer, etc. - It is also known that these emulsion layers are provided in a different arrangement from the above, and in addition, instead of using one layer of each emulsion layer with different photosensitive areas, it is known that each emulsion layer is sensitive to substantially the same photosensitive area for each color light. It is also known to use two types of photosensitive emulsion layers having different properties. In these silver halide color photographic materials, for example, an aromatic primary amine compound is used as a color developing agent, and a dye image is formed by reacting exposed silver halide grains with a developing force puller. Ru. In this method, phenolic or naphtholic cyan couplers, 5-virazolone, 5-virazolone,
Pyrazolinobenzimidazole, pyrazolotriazole, indacylon or cyanoacetyl magenta couplers and acylacetamide or benzoylmethane yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer. Among these silver halide color photographic materials, the demand for silver halide color photographic materials for printing is increasing year by year, and manufacturers are increasing coating speeds and introducing new equipment in order to maintain production levels. However, methods of increasing the coating speed are attracting attention as a method that does not require a large amount of cost. However, by increasing the coating speed, the band Nm of the photosensitive material increases and light emission fog (also called static fog) occurs.
This tends to occur and becomes a major hindrance to increasing the spreading speed. On the other hand, in laboratories, it is inevitable to improve productivity in order to meet customer demands, and for this purpose high-speed printers and rapid processing systems are being introduced. In high-speed printers, transportability suitable for the printing speed of the photosensitive material is an essential performance, and it is necessary to improve the slipperiness of the surface of the photosensitive material.
゛In addition, since aiIi temperature processing or high-speed processing is performed in rapid processing systems, it is desired to improve the scratch resistance of the surface of photosensitive materials, and also to improve adhesion and gloss due to high temperature and high speed drying. is needed. In other words, there is a need for a physically tough color photographic material for printing. Under these circumstances, fine particle powder is applied to the outermost layer (retention
It is well known among photosensitive material manufacturers that the above-mentioned problems of antistatic properties, slipperiness, and adhesiveness can be effectively improved by adding fi). These matters are described, for example, in JP-A-53-70426 and JP-A-53-70426.
No. 3-116.143, No. 54-94319, No. 55
-161.230, 57-14,835, 5
No. 8-66.937, No. 58-153,925, No. 5
No. 8-163,936, etc. However, it has been found that by adding these fine grain powders to the outermost layer (protective layer), undeveloped silver halide photographic materials become extremely susceptible to desensitization due to pressure. (Hereinafter referred to as pressure desensitization) This pressure desensitization is particularly remarkable in the uppermost silver halide emulsion layer. That is, in color photographic light-sensitive materials for printing, it is usually noticeable in red-sensitive emulsions. As a cause of pressure desensitization, in photosensitive material production factories,
Desensitization is likely to occur due to the tension when winding up the coated sample or the pressure on the cut end when cutting the photosensitive material.On the other hand, in the distribution route, desensitization occurs due to the shock during transportation of the photosensitive material, and in the laboratory, the photosensitive material inside the printer or automatic processor Desensitization is likely to occur due to contact with other objects such as guides while driving. Once this pressure desensitization occurs, the finished print will be a loss with no commercial value. Of course, this Although some improvement is achieved by reducing the speed of each process, it is not sufficient and productivity also decreases.In addition, as a countermeasure for this, the outermost layer (protective layer) of silver halide color photographic light-sensitive materials for printing is used. The boiling point is about 17
High boiling point solvents of 5° C. or higher, higher alkyl sodium sulfates, higher aliphatic higher alcohol esters, etc. described in U.S. Pat. Techniques for adding carboworks, higher alkyl phosphate esters, silicone compounds, etc. are also known, but they are not sufficiently effective, and when used in large quantities, they actually cause problems such as sweating and deterioration of gloss. Another problem with handling is that silver halide color photosensitive materials for printing are usually stored in refrigerators at temperatures below 10°C in laboratories, and must be taken out of the refrigerator several hours before use and brought to room temperature before use. ing. However, if the print is left at room temperature for several hours, especially when handled by hand under high temperature and high humidity conditions, a fingerprint-like desensitization occurs, and the finished print loses its commercial value. This phenomenon is also remarkable, especially in the uppermost silver halide emulsion layer.
Furthermore, it is particularly noticeable in silver chlorobromide emulsions which have an outer surface consisting mainly of (100) planes. As a countermeasure for this problem, strangely enough, ordinary means effective for pressure desensitization did not improve the problem at all. As a result of intensive studies regarding the above-mentioned problems, the present inventors have found that, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive layer on a support, The silver halide emulsion layer located far away contains specific silver halide grains, and the outermost layer located farthest from the support is a non-photosensitive layer, and the non-photosensitive layer contains a specific fine grain powder. The present inventors have discovered that by including the above-mentioned pressure desensitization resistance, physical resistance such as slip property is improved, and surprisingly, fingerprint-like desensitization is improved, and the present invention has been achieved. . [Object of the Invention 1 Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for printing which has excellent physical durability. More specifically, it is an object of the present invention to provide a silver halide photographic light-sensitive material for printing, which has excellent antistatic effect, slipperiness, adhesiveness, resistance to pressure desensitization and fingerprint desensitization, and is easy to handle.

Structure 3 of the Invention The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer and at least 111 non-photosensitive layers on a support. The disposed silver halide emulsion layer contains monodisperse silver halide grains containing substantially silver chlorobromide grains having an outer surface mainly consisting of (100) planes, and
The outermost layer located farthest from the support is a non-photosensitive layer, which is achieved by a silver halide photographic light-sensitive material containing fine particle powder with an average particle size of 1 to 10 μm in the non-photosensitive layer. [Specific Structure of the Invention] In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer located farthest from the support mainly has (10
The outermost layer located farthest from the support (hereinafter referred to as the protective layer) is non-photosensitive. The layer structure may be a combination of a silver halide emulsion layer and a non-photosensitive layer as long as the protective layer contains fine grain powder with an average grain size of 1 to 1C1+a. For example, if a silver halide emulsion layer with arbitrary color sensitivity is
It may be a ψ color of the layer, or it may be a commonly used multicolor color photosensitive material. When the silver halide photographic light-sensitive material according to the present invention is a multicolor light-sensitive material, the layer structure of the silver halide emulsion layer,
That is, the layer order of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive emulsion layer is arbitrary, but preferably the silver halide emulsion located farthest from the support is It is a red-sensitive emulsion. In addition, the protection 5 of the present invention
Non-photosensitive layers (for example, an intermediate layer, a single filter layer, an irradiation prevention layer, etc.) may be optionally provided, but a preferred specific layer structure is to sequentially form them on the support from the support side. , a yellow dye image forming layer, a first intermediate layer, a magenta dye image forming layer, a second intermediate layer, a cyan dye image forming layer,
A third intermediate layer is arranged with a protective layer of the present invention containing fine particle powder with an average particle size of 1 to 10 μm. Next, regarding the monodisperse silver halide grains (hereinafter referred to as silver halide grains according to the present invention) that are used in the present invention and include substantially silver chlorobromide grains having an outer surface that is mainly truncated from the (100) plane. explain. In the silver halide grains according to the present invention, mainly (1
Having an outer surface consisting of a (100) plane may mean having a cubic crystal habit consisting of only a (100) plane, or having an outer surface consisting of a (100) plane.
This means that it may have a tetradecahedral crystal habit consisting of a plane and a (111) plane. Preferably, JP-A-59-
Measured by the X-ray analysis method described in No. 29243 - (diffraction ray intensity attributed to the (200) plane)/
The effects of the present invention are particularly remarkable when the silver halide grains are tetradecahedral, satisfying 0.5≦≦so, ooo when expressed as (diffraction line intensity attributed to the (222) plane). Become. The silver halide grains according to the present invention are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution of the silver halide grains. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is expressed by the following formula, where ri is the particle size of each particle, n
i represents the number. In the case of spherical silver halide grains, the grain size here refers to the diameter, or in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. . The average grain size of the silver halide grains according to the present invention is not particularly limited to υ1 in the present invention, but it is preferably 0.1 to 2.0 μm, more preferably 0.2 to 0.8 μm1.
More preferably (in the range of 1.35 to 0.55 μm). The silver halide composition of the silver halide grains according to the present invention is
It is essentially a silver chlorobromide emulsion. Here, a silver chlorobromide emulsion essentially means that the silver halide composition of the silver halide grains contained in the silver halide emulsion is less than 1 mol% of silver iodide, with the remainder consisting of silver chloride and silver bromide. That's true. The silver chloride content of the silver halide grains according to the present invention is preferably 5 mol% or more, more preferably 15 mol% or more. The composition of the silver halide grains according to the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously. The silver halide grains according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. The method for reacting the soluble silver salt with the soluble halogen salt may be a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but a simultaneous mixing method is preferred. Furthermore, for the production of monodispersed silver halide grains, it is also possible to use the pAg-chondrold double-jet method, which is described in JP-A-54-48521, etc., as a type of simultaneous mixing method. Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used. The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Metallic ions can be added using lead salts, thallium salts, iridium salts or complex salts, rhodium salts or n-salts, iron salts or fil salts, and can be included inside the particles and/or on the particle surfaces. By placing the particles in a reducing atmosphere, reduction-sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, use Research Disclosure 7764.
This can be carried out based on the method described in No. 34. In the silver halide emulsion layer containing the silver halide grains according to the invention, the monodisperse silver halide grains according to the invention may be used alone or in combination. Further, silver halide grains different from the silver halide grains according to the present invention, such as grains that do not have (100) planes (for example, octahedral grains, etc.), may be mixed and used, but in this case, (100) The ratio of grains without faces is preferably 50% or less of the projected area occupied by all silver halide grains. The silver halide grains according to the present invention are chemically sensitized by conventional methods. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a reduced coral sensitization method using a reducing substance,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. The silver halide grains according to the present invention are used in the photographic industry.
Using a dye known as a sensitizing dye, it is possible to optically sensitize to a desired wavelength range. ! ! The sensitive dye may be used alone, but 212. <The above may be used in combination. Along with sensitizing dyes, dyes that do not themselves have a spectral sensitizing effect,
Or a compound that does not substantially absorb visible light,
A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the emulsion. The silver halide grains according to the invention are preferably spectrally sensitized so that they are sensitive to green light. The silver halide grains according to the present invention are useful for preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials.
Or, for the purpose of keeping photographic performance stable, anti-capri agents or Compounds known as stabilizers can be added. A hydrophilic colloid is used in the protective layer of the present invention, and examples of the hydrophilic colloid used include gelatin, gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, etc.), albumin, collodion, etc.
Particularly preferred is gelatin. In addition, the average particle size contained in the protective layer of the present invention is 1 to 1.
The 0 μm fine particle powder is generally referred to as a matting agent in the art, and therefore will be referred to hereinafter as a matting agent unless otherwise specified. Examples of the matting agent according to the present invention include crystalline or amorphous silica, titanium dioxide, magnesium oxide, calcium carbonate, barium oxide, magnesium alumina silicate, acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl acrylate, etc. Methacrylate copolymer, itaconic acid
Styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-styrene copolymer, acrylic acid-7-functional acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid-ethyl + V methacrylate copolymer, Examples include polystyrene, starch, cellulose acetate propionate, and others such as U.S. Patent Nos. 1,221,980 and 2.992,
Examples include the compounds described in No. 101, etc., and these can be used alone or in combination of two or more. The particle size of the above-mentioned matting agent may be as long as the average particle diameter is 1 to 10 μm, but preferably 2 to 7 μm. The average particle size here refers to the diameter in the case of spherical particles, and the average value of the diameter when the projected image is converted into a circular image of the same area in the case of particles with shapes other than cubic or spherical. When the individual particle size is 1 and the number is ni, it is defined by the following formula.The method described in Japanese Patent Application Laid-Open No. 59-29243 is used for the single particle measurement method. The matting agent according to the present invention can be dispersed and contained in the 4 parts of Kamutamen, but the method for dispersing it may include a nonionic, cationic or anionic surfactant as required. Add other additives as necessary to the hydrophilic binder, use a high-speed rotation mixer, homogenizer, ultrasonic dispersion,
It can be formed by dispersing it by an emulsification dispersion method using shear stress using a ball mill or the like, and coating it as the outermost layer of a photosensitive material by any method used in the photographic field. As the coating stone for the matting agent according to the present invention, Honcho 4+/1
It is preferable to contain 0.5 to 50110 per 112 in 4KB. More preferably 1 to 2 per 1f
0m (l). Cough, the content group of the matting agent is 0 for hydrophilic colloid.
．． 1 to 2 weight Q% is preferred. In order to further reduce sliding friction, a high boiling point solvent or lubricant having a boiling point of about 175° C. or higher may be used in the protective layer of the present invention containing the matting agent of the present invention. However, if the amount is increased, serious defects such as deterioration of gloss and sweating will occur, so care must be taken when adding it. Examples of high-boiling solvents that can be used include acid amides, carbamates, esters, ketones, urea derivatives, and especially dimethyl phthalate, diethyl phthalate, di-
Phthalate esters such as propyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, cyamyl phthalate, dinonyl phthalate, diisodecyl phthalate, tricresyl phosphate, triphenyl phosphate, tri(2-ethylhexyl) ) phosphate,
Phosphate esters such as triisononyl phosphate, sepacylate esters such as dioctyl sebacate, di(2-ethylhexyl) sebacate, diisodecyl sebacate, glycerin esters such as glycerol tripropionate, glycerol dilib+late, etc. Examples include one or more of adipic acid esters, geltaric acid esters, succinic acid esters, maleic acid esters, phthalic acid esters, and citric acid esters. Also, examples of lubricants that can be used include higher alkyl sodium sulfate,
Higher fatty acid higher alcohol ester, power-bowax,
There are higher alkyl phosphate esters, silicone compounds, etc., among which U.S. Patent Nos. 2,882.157 and 3,1
Examples include compounds described in No. 21,060 and No. 3,850,640. Further, any surface quality can be used as the surface quality of the support according to the present invention, but a reflective support is preferable.For example, a white pigment such as titanium oxide is added to a polymer such as polyethylene, and paper is laminated. A support is preferred. The coupler for forming the dye image used in the present invention is not limited and various couplers can be used. However, as the coupler for forming the yellow dye image, a coupler represented by the following general formula [A] is used. be able to. General formula [A] In the formula, R1 represents an alkyl group or an aryl group, and R
2 represents an aryl group, and X represents a hydrogen atom or a group that removes M during the color development reaction process. R1 is a chain-linked or branched alkyl group (for example, butyl group) or aryl! (for example, a phenyl group), but preferably tt, < is an alkyl group (particularly a 1-butyl group), R2 represents an aryl group (preferably a phenyl group), and the alkyl group represented by these R1 and R2 ,
The aryl group includes those having a substituent, and it is preferable that the aryl group of R2 has a halogen atom, an alkyl group, etc. substituted with M, and X is represented by the following general formula [3] or [C]. The groups shown are preferable, and of the general formula 1B], the groups represented by the general formula [D] are particularly preferable. General formula [B] In the formula, 71C represents a group of nonmetallic atoms that can form a 14- to 7-membered structure. General formula [C] -O-R11 In the formula, R1+ represents an aryl group, a heterocyclic group or an acyl group, and an aryful group is preferable. General formula [D] represents a nonmetallic atomic group that can be formed. A preferred yellow coupler according to the present invention in the general formula [Δ] is represented by the following general formula [A']. General Formula [A'] In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable. In addition, R15, Rls and R17 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulf7-myl group, an alkylsulf7-onamide group, It represents an acylamido group, a ureido group, or a 7-mino group, R+s and R+s are each a hydrogen atom, and RI7 is preferably an alkoxycarbonyl group, an acylamido group, or an alkylsulfonamide group. Further, X represents a group having the same meaning as that represented by the general formula [Al, and preferably the general formula ET33 or [
CLt or a group represented by the above-mentioned general formula [8'] is more preferred among [8]. In addition, another preferable yellow coupler according to the present invention in the general formula 7!0 [Al] is the following general formula % general formula [A″] where R+a has the same meaning as R14 in the above general formula [A′] R19, R20 and R21 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxyl group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfonyl group, a sulfonamide group. group, an acylamide group, a ureido group, or an amino group, and X represents a group having the same meaning as that shown in the general formula [A']. It may be an emulsion layer, but preferably 11.. (is a blue-sensitive halogenated dFL agent layer and is added) is 2X10-3 to 10-3 per mole of fB.
5X10-' mole is preferable, more preferable 11, < is lX1
0-' to 5X10-' moles. Specific examples of the yellow coupler according to the iE invention are listed below, but the invention is not limited thereto. Margin below (Y-1) (Y-23 b (Y-3) (IJ. ff-4) (L (Y-5) (Y-6) (f cutting-7] L (Y-8) L ( Y-9) a3 (Y-10) (j (Y-123 L (Y-/3) d (Y-7+) I ■ Below margin (Y-75-) (Y-/6) (Y-/7 ) Self (Y-/8) L (Seecy-l'i') C Shiku Y-pan) L (Y-ZZ) (YJ3) CL (y-74-) CL Below margin (Y-25) C ( Y-263 (j (Y-2g) CL (Y-29) (Y-303 Q -L -I-r13 (Y-33) (Y-hold) (Y-Q) (Y-3b) (Y -3Y) (Y-97) (Y-Sho) (Y-4-1) (Y-斡) (Y-44) (Y-Special) (Y-Paddy) (Y-%] H0H3 (Y-4 '?) t (Y-48) L (Y-49) (Y-5; 0> (Y-5ノ) (Y-,!i2) t (Y-53) (Y-review) t Tsuriri Cyan Picture 4 is full of pleasure. ' in the general formula [E] represents an aryl group, a cycloalkyl group, or a cycloalkyl group. ' 1% represents an alkyl group or a phenyl group. R1 is a hydrogen atom, Represents a halogen atom, an alkyl group, or an alkoxy group. The group represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. General formula [F Co/'IIJ In the formula, R4 represents an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.).
j represents an alkyl group (eg, methyl group, ethyl group, etc.). Bird represents a hydrogen atom, a halogen atom (e.g., 27 atoms, chlorine, bromine, etc.) or an alkyl group (e.g., a methyl group, an ethyl group, etc.).A represents a hydrogen atom, a halogen atom, or an aromatic primary amine color developing agent. In the present invention, the aryl group represented by the general formula [E] is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. The cycloalkyl group represented by R8 is, for example, a pyridyl group or a 7-ran group.The cycloalkyl group represented by R1 is, for example, a cyclopropyl group or a cyclohexyl group. It may contain single or multiple substituents (for example, typical substituents introduced into phenyl groups include halogen atoms (e.g., chlorine, bromine, etc.), alkyl groups (e.g., methyl), group, ethyl group, propyl group, butyl group, dodecyl group, etc., hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, thoxy group)
, alkylsulfo/amide groups (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfone 7°mide group (e.g. phenylsulfo/amide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g. butylsulfonamide group, etc.), famoyl group, etc.), arylsulfamoyl MC, e.g. phenylsulfamoyl group, etc.],
Alkyloxycarbonyl group (e.g. methyloxycarbonyl group, etc.), monooxycarbonyl group (e.g. phenyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group,
Examples include sulfinyl group, sulfoxy group, sulfo group, aryloxy group, alkoxy group, carboxyl group, alkylcarbonyl group, arylcarbonyl wave, and aminocarbonyl group. Two or more of these ft substituents may be substituted with a phenyl group. Preferred groups represented by R8 include a phenyl group, a halogen atom, an alkylsulfonamide group, an arylsulfonamide group, a purkylphur7-amoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an alkylcarbonyl group. , an arylcarbonyl group, or a phenyl group having one or more cyano groups as substituents. The alkyl group represented by the island is linear or branched, and includes, for example, a methyl group, ethyl group, propyl group, butyl group, and octyl group. In the present invention, the cyan coupler represented by the general formula [E] is preferably a compound represented by the following general formula [E']. General formula [E'] H This phenyl group may have a single or multiple substituents, and typical It substituents to be introduced include halogen atoms (e.g. fluorine, chlorine, bromine, etc.). ), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group,
ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide M (e.g. 7-enylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group ( For example, butylsulfamoyl i),
Examples include an arylsulfamoyl group (eg, evaphenylsulfamoyl group, etc.), 'y#alkyloxycarbonyl group (eg, methyloxycarbonyl group, etc.), and an aryloxycarbonyl group (eg, phenyloxycarbonyl group, etc.). Two or more of these substituents may be substituted with a phenyl group. group represented by R1, p-octylsulfonamide group, 0-dodecylsulfonamide group], arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group), Arylsulfamoyl group (preferably L < haphenylsul7 amoyl group),
It is a phenyl group having one or more substituents of an alkyl group (preferably a methyl group or a trifluoromethyl group) or an alkoxy group (preferably a methoxy group or an ethoxy group). R is an alkyl group or an aryl group. An alkyl group or an alkyl group may have a single substituent or a multiplicity of substituents such as halogen atoms (e.g. fluorine, chlorine, etc.). , bromine, etc.) hydroxyl group, carboxyl group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group,
dodecyl group, etc.), aralkyl group, cyano group, nitro group,
Alkoxy group (e.g. methoxy group, ethoxy group) Aryloxy group, purkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.) Arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.) Alkyl sulfonamide group Famoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group C example, t
% aminosulfonamide group (e.g. dimethylaminosulfonamide group, etc.),
Examples include an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonylamide group, a carbamoyl group, and a sulfinyl group. Two or more types of these substituents may be introduced. Preferred groups for all groups are an alkyl group when n '' o and an aryl group when n = 1 or more. A more preferable group represented by a crow is n
= o = carbon number] to 22 alkyl groups (preferably methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group), and when n = 1 or more, phenyl group, or Alkyl group (preferably t-butyl group, 1-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecylsulfo/amide group), arylsulfonamide group (preferably a phenyl group having one or more substituents such as a phenylsulfonamide group), an aminosulfonamide group (preferably a dimethylaminosulfonamide group), or an alkyloxycarbonyl group (preferably a methyloxycarbonyl group or a butyloxycarbonyl group); Rdi represents an alkylene group. A linear or branched alkylene group having ~20 carbon atoms, and furthermore an alkylene group having 1 to 12 carbon atoms. Rlo represents a hydrogen atom or a hydrogen atom (fluorine atom). , chlorine, bromine or iodine), preferably a hydrogen atom. n is 0 or a positive integer, preferably 0 or ]. xt-z-o-, -co-1-COO-1 →αto, -8
O2N#, -NR'5O2NR"-, -S-, -5o
- or -Sow- represents a divalent group. Here, R'
, R' represents a substituted or llB-substituted alkyl group. X
Preferably ÷. -C-5O-1-SO,- group. Z3Ii Represents a group that can be separated by reaction with a hydrogen atom, a halogen atom, or an oxidized product of an aromatic primary amine color developing agent. Preferred are a chlorine atom and a chlorine atom. Typical specific examples of the cyan coupler represented by formula [E] are shown below in the margins, but the invention is not limited to these. OH (Engineering 44) CI-45) Cx-41) (Engineering and Shinji Cs; H++ (t) The cyan coupler used in RJ preferably has the following general formula (%), where R7 and Rlf are the same or different and represent a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group,
represents a propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, etc.).However, the total number of carbon atoms of R11 and Rlf is 8 to 16. Preferably, R1 and R1 are a hydrogen atom or an alkyl group (for example, a methyl group, a methyl group, or an amyl group).
(ethyl group, propyl group, butyl group, octyl group, etc.). D I'10''''2! represents a number. 24 is a hydrogen atom,
In the formula [E), LFI LE'), 21
．． 21.2, and 2. The group which can be separated by reaction with the oxidized product of the aromatic primary amine color developing agent represented by is well known to those skilled in the art, and can be used to modify the reactivity of the coupler, or 1. Separated from the coupler and used in a coating layer or other coating layer containing the coupler in a silver halide color photographic light-sensitive material. It works advantageously by fulfilling functions such as development inhibition, bleaching inhibition, and color correction. Typical examples include alkoxy groups, aryloxy groups, arylazo groups, thioethers, carbamoyloxy groups, acyloxy groups, imido groups, sulfonamide groups, thiocyano groups, or heterocyclic groups (e.g., oxacylyl, diazolyl, dorialyl, Tetrazolyl, etc. λ, etc. Particularly preferred examples of 2 are a hydrogen atom or a chlorine atom. Representative specific examples of cyan couplers represented by the formula [FJ are shown below, but the invention is not limited to these. (J-6) CI!-11) Day, C mouth 19) (t) c, H. The following is a blank space for 8 pages.
1” Wood gamma child l2”t)? , No" upper / 9th leaf Yuko elephant shape cuff
“2 clothes, 3 powers, 2 layers, 1 chamber, 11J mihi”?
"J-Ar 1 In the formula, Ar represents an aryl group, R1 represents a hydrogen atom or M substituent, R2 represents a MkJ3, Y is a hydrogen atom or W is -NH-1-NHCO-(
N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NH
CONH- is represented, and m is the U number of 1 or 2. ) The following margin is next! 2 General formula [represented by al. ) J Puller Nitsui'C details. Examples of the 7-reel ink represented by "A" include phenyl groups and naphthyl!!, preferably phenyl groups, and particularly preferably M-substituted phenyl groups. atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a sulfamoyl group, a sulfonyl group, a sulfonamide group, an acylamino group, and has two or more flMI in the phenyl group represented by A. Specific examples of rILl!km are listed below.Halogen atom: chlorine, JA compound, fluorine alkyl M: methyl.211ethyl, iso-propyl group, butyl group, t-butyl group, t-pentyl groups, but particularly preferred are furkyl groups having carbon f# atoms v11 to 5.Alkoxy groups: methoxy group, ethoxy group, butoxy group,
Among them, 5ec-butoxy group and 1so-pentyloxy octyloxy group are particularly preferred, and tsuba # and an alkoxy group having 1 to 5 atoms are particularly preferred. Aryloxy: Fuyunoxy group, β-naphthoxy group, etc., but this aryl moiety may further have an r:l base similar to that of the phenyl group represented by Ar. Alfkidicarbonyl M: As described above, it is a carbonyl group with an alkoxy group attached, and those having 1 to 5 atoms in the alkyl moiety, such as methoxycarbonyl and pentyloxycarbonyl groups, are IEat. Carbamoyl M: Carhamoyl group, alkylcarbamoyl base of dimethylcarbamoyl mW Sulfamoyl group: Sulfamoyl B, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, etc. Sulfonyl group: methanesulfoyl group Nyl ink, ethanesulfonyl, butanesulfonyl II, alkylsulfonyl base sulfonamide N: methanesulfonamide, toluenesulfonamide M, etc., furkylsulfonamide B, arylsulfonamide! Primary acylamino: acetamim L pivaloylamino is particularly preferably a halogen atom such as a benzamide group, among which chlorine is most preferred. The group ft represented by R1 is a halogen atom, an alkyl group, an alkoxy group, or the like. Specific examples are listed below. Halogen atoms: chlorine, bromine, fluorine alkoxy groups: methoxy, ethoxy, butoxy,
p such as 5ec-butoxy group, 1so-pentyloxy group, etc.
! #, an alkoxy group having 1 to 5 atoms is preferred. Alkyl group: A furkyl group having 1 to 5 atoms such as a methyl group, an ethyl group, a 1so-propyl group, a butyl group, a -butyl group, and a t-pentyl group is preferable. Particularly preferred is a halogen atom, with chlorine being particularly preferred. The substituent represented by R2 is a hegen atom, alkyl M5
An amide group, an imide group, an N-alkylcarbamoyllkoxycarbonyl group, or a urethane 51 group. Among these containers, amide groups (e.g., tetradecane amide group, 3-1
-4-human Ooxyphenoxytetradecanamide group, etc.), imide groups (e.g., dodecylsulfonamide group, octadecenylsuccinimide!-V), and sulfonamide groups (e.g., butylsulfonamide group, dodecylsulfonamide group, etc.) can be preferably used. \he'1-N+-, -Nl-IGO-11 atom is bonded to the atom of the pyrazolone nucleus) or -NHCONH-, but W is particularly preferably 1NH-. Examples of B that can be described by a coupling reaction with an oxidized product of an aromatic primary amine color-forming image agent represented by Y include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a 7/- ``-, <22 represents an atomic group that forms a 5- or 6-membered spot with atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms together with the chlorine atom. Specific examples are listed below: Halogen atom: chlorine, bromine, fluorine alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxyaryloxy group: phenoxy group, 4-methoxyaryloxy group. 1-kisif I
Noxy group, 4-nitrophenoxy long acyloxy group:
7 Setoxy group, myristoyloxy group, benzoyloxy M @ arylthio group; phenylthio group, 2-butoxy-5-
Octylphenylthio group, 2.5-dihexyloxyphenylthio group, etc. Alkylthio M: methylthio group, octylthio group, bexabucilthio group, benzylthio group, 2-(di1thyl7mino)ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phtriazolyl group, tetrazolyl group, etc. Next, the general formula [aJ? Hereinafter, the present invention is not limited to these representative examples of the magenta coupler represented by ``. ” ct ct a 18 ct l a 22 (J. C6 -24cL α t A 29CHs C2 a-35ct a -40CL These are, for example, , No. 432, No. 3.062.653
@, Same No. 3,127゜269, Same No. 3,311,47
6 @, same No. 3.1!12,896, same No. 3.419,
No. 391, No. 3.519.429, No. 3.555
．． No. 318, No. 3,684,514, I'P+1
No. 3,888,680, No. 3.907,571, No. 3.928,044@, No. 3,930.861
No. 3,930.866, No. 3,933,50
0@ etc. Mei Fii 1 Japanese Patent Publication No. 49-29639, 49
-111631, 49-129538, 50-
No. 130,111, No. 52-58922, No. 55-6
24b4@, Zhou 55-118034, IBJ56-
No. 38043, No. 57-35858, No. 60-238
55M publications, Arrow Patent No. 1.247,493M, Hellky rFR769,116@, Arrow Patent No. 792.52+
M, West German patent 2,156. C1 each Ming 1L Tokkosho, 1
16-60479@publication etc. The following margin The ultraviolet absorber used in the silver halide photographic photosensitive material of the present invention may be any compound that absorbs ultraviolet rays of 400111 or less, but preferably a benzotriazole compound represented by the following general formula [I]. be. h In the above general formula [I], R1, R1 and R3 are
Each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nido O group, or a hydroxyl group. Next, typical examples of the ultraviolet absorbent represented by the above general formula [I] will be shown. (Z) -1 l-1 (cho) -,2 0■ CI(. (1) -g H CH(υ ■-taH CH(tl (T-) /. O'B H C,H,, (υ [en - 7.2 H C,H, (υ (en -73 H (:L) -/Hiro0yoC,Hl, (υ (I) -/ j H (en - 76 H 01N"2S■ (Y) -/ 7 H (F-/♂ ('L) -/ 9H Similarly to the method for adding a hydrophobic compound that serves as a margin, solid dispersion method,
Latex dispersion method, oil in water? Various methods can be used for the type II emulsion dispersion method, and these methods can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic compounds such as Huplar can be applied, and the boiling point is usually about 1.
Dissolve in a V1 solvent with a high boiling point of 50°C or higher, using a low boiling point and/or water-soluble organic solvent as necessary, and use a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a stirrer or a homogenizer. After emulsifying and dispersing using a dispersion means such as a colloid mill, a 0-jit mixer, or an ultrasonic BH, it can be added to the desired hydrophilic colloid layer. A step of removing the organic solvent may be included. Examples of high boiling point organic solvents include phenol derivatives, phthalate ester phosphates, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. that do not react with the oxidized form of the image-carrying herbal medicine.
An organic liquid with a temperature of 50° C. or higher is used. The margins below indicate that these searchable FB media are generally 10 to 05 couplers used in the present invention. ! It is used at a rate of 150% heavy invasion. Preferably 20 to 100≦% excitation for the coupler. Hydrophobized substances such as couplers are dissolved in Fg(lI) in combination with iiL boiling point FfI medium or low point melt and dispersed in water using probes or ultrasonic waves as a dispersion aid for tsuba.
Anionic surfactants, nonionic surfactants, and cationic surfactants can be used. The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but in particular, it can be applied to color negative and positive films, color photographic paper, etc.
The effects of the present invention are effectively exhibited when applied to over 5J images. As a binder (or protective colloid) for silver halide emulsions, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymer substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable that the hardening agent be added to the processing solution to the extent that it is possible to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add a hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention. In the photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention, a backing containing a dispersion (latex) of a water-insoluble or Ii-soluble synthetic polymer is added for the purpose of improving dimensional stability. I can do it. Emulsion H of the silver halide photographic photosensitive t1n of the present invention has coloring gla! During processing, a dye-forming coupler that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine fJI imager (e.g., p-phenylenediamine derivatives, aminophenol derivatives, etc.) is used. The dye-forming couplers are typically selected to form a dye for each emulsion layer that absorbs light in the emulsion layer's light-sensitive spectrum; As the dye-forming coupler, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer.However, depending on the purpose, halogen You can also use a silver copy (1 x 58 light material n). The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion may contain dyes that flow out from the color light-sensitive material during development or are bleached. , an antistatic agent can be added for the purpose of preventing static electricity.Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, and can also be added to the emulsion layer and/or the support. It may also be used in protective colloid layers other than the emulsion layer on the side on which the emulsion layer is laminated.The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
(or other hydrophilic) Ooid layer has properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and (promoting development,
Various surfactants are used for the purpose of improving photographic properties (such as increasing contrast and sensitization). The photographic emulsion of the silver halide photographic light-sensitive material of the present invention will be described in the margins below.The support to which other layers are coated is a baryta layer or a laminated set of α-olefin polymer, etc., and flexible reflective material such as a composite material. Supports include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and rigid bodies such as glass, metal, and ceramics. The silver halide photographic light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., as required, to improve the adhesion, antistatic properties, and dimensional stability of the surface of the support. The coating may be coated via one or more subbing layers (to improve properties such as hardness, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties). When coating the silver halide photographic light-sensitive material of the present invention, a thickener may be used to improve coating properties.Coating methods include exdolsion coating, which allows two or more layers to be coated simultaneously; Curtain coatings are particularly useful. The silver halide photographic light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. As a light source, natural light (sunlight)
Excited by , tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, X-ray, γ-ray, α-ray, etc. Any known light source can be used, such as light emitted from a phosphor. The exposure time for FR is not only the exposure time of 1 millisecond to 1 second normally used in cameras, but also the exposure time shorter than 1 microsecond, such as 100 microseconds to 100 microseconds using a cathode ray tube or xenon flash lamp.
Exposures of 1 microsecond can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently. The silver halide photographic material of the present invention can be used to form color images by color development known in the art. In the present invention, the aromatic primary amine color developing agent used in the color developing solution includes known ones that are widely used in various color photocopying processes. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable than in the free state, they are generally used in the form of salts, such as the salt M salt or the sulfur 15 salt. Additionally, these compounds generally have a concentration of about 0.1 g to about 3017 g per color developer 11, preferably color developer 1f! of about 1 g to about 1517 g. In addition to the M1-class aromatic amine color developer, the color developer used in the present invention further contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, and potassium carbonate. alkaline agents such as
Alkali metal subsulfite 1i 111f salt, alkali metal bisulfite l
S! It is also possible to optionally contain salts, alkali metal thiocyanate M salts, alkali metal halides, benzyl alcohols, water/softeners, il thickening agents, and the like. This colored mem. The pH value is usually above 7, most commonly between 7 and 10.
It is about 13. In the present invention, after color-forming image processing, processing is performed with a processing solution having a fixed fixing ability, but if the processing solution having a fixing ability is a fixing solution, a bleaching 5B treatment is performed before that. As the bleaching agent used in the bleaching process, a metal oric acid is used. It has the effect of coloring and fading, and its a component is aminopolycarboxylic acid or Citric M, etc. ! It is made by coordinating metal ions such as iron cobalt and copper with acid. The most preferred organic acids used to form such FMH-containing metal n- include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic or aminopolycarboxylic acids may be alkali metal tin, ammonium or aqueous amine salts. The following are specific representative examples of these: [1] Ethylenedi7minetetraacetic acid E2conitri0triacetic acid [3] Iminodiacetic acid [4] Engineered ethylenediaminetetra (trimethylammonium) salt [6] Engineered ethylenediamine Tetrasodium Tetraacetate Store 17) Sodium Nitrilotriacetate Store The bleaching agent used contains the above-mentioned t1M metal n store as a bleaching agent and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium pallite, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. 8M again! ! %蓚1E vinegar 1L pH of carbonated salts, phosphates, etc.!
! Those known to be added to ordinary bleaching solutions, such as li agents, Z-ruxamines, and polyethylene oxides, can be added as appropriate. Furthermore, the fixing solution and the bleach-fixing solution contain ammonium sulfite layer,
TAN potassium, binitrous MIM7 ammonium. Shigeya ii! ! Potassium acid, sodium bisulfite, ammonium metabioxide, potassium metabioxide, metabioxide li! Sulfites such as 1M sodium, L borax,
*Sodium oxide, potassium hydroxide, sodium tawaromi,
A p)I buffer consisting of various salts such as potassium sulfate, sodium FAvi, heavy sodium M, sodium chloride, sodium hydroxide, sodium acetate, and ammonium hydroxide may be used alone or may contain 2N or more. Bleach fixing? ! ! Bleach fixation in (bath)? ! When processing the silver halide photographic light-sensitive material of the present invention while replenishing the filler, the bleach-fixing solution (bath) may contain thiosulfur [E thiocyanate or Azuki M salt, etc.] The bleach-fixing replenisher may contain these ingredients and be added to the 51Q bath. Bleach constant @ Use bleach constant to increase the activity of the solution! Rakuchu and bleach-fix replenisher lEr1! In the tank as desired! 2
Air blowing or 11 element blowing may be carried out, or a suitable oxidizing agent, such as pernitrogenated water source, odor 1L
Persulfuric acid and the like may be added as appropriate. Below is a margin [Specific effects of the present invention] The present invention has excellent antistatic effects during high-speed coating during the production of silver halide photographic materials, is less prone to static fog, and has good resistance to pressure desensitization. can be,
Furthermore, during printing, static fog is also less likely to occur, and because of its good slip properties, it has excellent conveyance and is less likely to suffer from pressure desensitization. Furthermore, as a secondary effect, it was also possible to improve the fingerprint-like desensitization that tends to occur when handling silver halide photographic materials. That is, it is possible to obtain a silver halide color photographic light-sensitive material for printing, which meets the recent demand for high productivity, has comprehensively excellent physical properties of the film and pressure resistance, and is easy to handle. [Specific Examples of the Invention] The present inventors conducted various experiments to confirm the effects of the present invention, and representative examples thereof are shown below. Example 1 A total of 13 types of samples were prepared by coating the following 1st to 7th layers on a reflective support made of polyethylene-coated paper. First layer: Blue-sensitive silver chlorobromide emulsion layer Silver chlorobromide emulsion containing 5 mol% of silver chloride, and exemplary yellow coupler (Y-7) and 2.5-G(1)-
An emulsified dispersion prepared by dissolving octylhydroquinone in dioctyl phthalate was used for coating. Second layer: First intermediate layer 2. An emulsified dispersion prepared by dissolving 5-di(1)-octylhydroquinone in dioctyl phthalate was coated. Third plate... Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 30 mol% of silver chloride, and exemplary magenta couplers (a-19> and 2°5-G(1
)-octylhydroquinone dissolved in dioctyl phthalate was used for coating. 4th layer...Second intermediate layer The following ultraviolet absorbers (LJV-1> and 2.5-G (
1) Coating was carried out using an emulsified dispersion prepared by dissolving -octylhydroquinone in dioctyl phthalate and using 2,4-di-chloro-S-triazine sodium salt as a hardening agent. No. 511... Red-sensitive silver chlorobromide emulsion layer Silver chlorobromide emulsion shown in Table 2 below (however, for comparison, it contains 0 mol% of silver chloride, that is, 100 mol% of silver bromide) coupler (II- 3> and 2,5-di([)-octylhydroquinone were dissolved in dioctyl phthalate to create an emulsified dispersion. Sixth layer...Third intermediate layer The following ultraviolet absorber (UV-1 ) and 2,5-G (1
)-octylhydroquinone was dissolved in dioctyl phthalate and an emulsified dispersion was prepared. 7th Layer...Protective layer A dispersion of gelatin and the matting agent shown in Table 2 dispersed in water and 2,4-di-chloro-8-triazine sodium salt as a hardening agent were used to coat the protective layer. Main ingredients of each layer! (mgω per 100Q, +)
are shown in Table-1. Use the blank space below 1) Take! 7 to the mouth and the moon z1-1 cumulative pressure E ↓λ-7
- Indication -0 (LIV-υ The margin below is a total of 21 types of samples created in this way (sample numbers 1 to 2
1) was evaluated for each performance using the methods shown below, and the results are summarized in Table 3. ■Pressure desensitization resistance An unexposed sample was scratched in the dark using a Hayton scratch meter with a needle of diameter O and Inv at varying loads, and then exposed to imagewise red light. I did it. Pressure desensitization resistance was evaluated based on the minimum load 1) at which pressure desensitization occurred in the image. Practical problems will arise if pressure desensitization is less than 30g. M semi-processing process (processing temperature and processing time) [1] Bleach development 38°C 3 minutes 30 seconds [2] Bleach tube 33°C 1 minute 30 seconds [3] Washing process
25-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes processing solution composition (color developing tank solution) Benzyl alcohol 151i ethylene glycol 1512 potassium sulfite
2.0g potassium bromide
0.7g sodium chloride
0.2g potassium carbonate 30
．． 09 Hydroxylamine til1m 3
．． O. Polyrin la (TPPS) 2.5
(13-methyl-4-amino-N-ethyl-N-(β-
Methanesulfonamidoethyl)-aniline sulfate
5.5g optical brightener (4,4=-diaminostilbenzsulfone M derivative)
1. OQ potassium hydroxide 2.
Add 0g of water to bring the total to 11 and adjust the pi (10, 20). Ammonium sulfate (40% solution) 27.51 fl Potassium carbonate or ice acid resistant pf-1? , adjust to 1 and add water to make the whole day 12. ■ Fingerprinting resistant Unexposed samples should be kept in the refrigerator (at least 24°C at about 10°C).
After leaving it for 8 minutes, immediately move it to a dark place at 23°C and 80% RH. After 60 seconds, touch the surface of the sample-coated side with your finger. Then, perform imagewise white light exposure and the standard treatment process shown in ■. The degree of desensitization was visually evaluated. O...No desensitization occurs △...Slight desensitization occurs (acceptable as a product) ×...
Causes desensitization (not acceptable as a product) ■Slip property (coefficient of static friction) Undeveloped !!
(manufactured by), load 5fJ/Cf, movement speed 50c
The static friction coefficient was measured under the conditions of m/min. This still J! ! A friction coefficient of 0.2 or more poses a practical problem. From the results in Table 3, the samples of the present invention (No. 6 to 10, 12, 13, 15
~18.20>. More specifically, the odor of the silver chloride bromide emulsion must be above a certain level, the coefficient of variation of the dispersion must be below a certain value, and the crystal habit must be within a certain range. It can be seen that the average particle size of the matting agent also needs to be within the range of the present invention. Example 2 In Example 1, the magenta coupler was an exemplary magenta coupler (a-52), the coating amount of the green-sensitive silver chlorobromide emulsion was 2ff1g per 100 C12, and the cyan coupler was an exemplary cyan coupler (It-3>). and (I-48)
The red-sensitive silver chlorobromide emulsion and the matting agent in the seventh layer were changed as shown in Table 4 to prepare a total of 10 FI samples. A total of 10 types of samples were created in this way (sample numbers 22-
31) was evaluated for performance using the method evaluated in Example 1, and the results are summarized in Table 5. Only the samples of the present invention (sample numbers 25.27 to 31) are
Pressure desensitization resistance ■Fingerprinting #4 included ■
It was confirmed that both properties, including smoothness, were satisfied and that it was overall excellent. Furthermore, in sample number 25, the 51st! The average grain size of red-sensitive silver chlorobromide of i is 0.45 μm to 0.2 μm10.7
Samples (Nos. 32, 33, and 34) were prepared in the same manner except that μm and 1.2 μm were changed, and in addition, among the sample numbers 32 to 34, a sample (No. 35. 36°37) was created.The results are shown in the table below.
6. From the results shown in Margin Table 6 below, it can be seen that the average grain size of silver halide has no direct effect on the present invention. Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural amendment (voluntary) December 10, 1985 Commissioner of the Japan Patent Office Academic award Mr. Dobe'-Sho, 1
, Incident Display 1985 Patent 'I! i No. 152806 2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship to the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Keio Benko, Representative Director of Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer and at least one light-insensitive layer on a support, the silver halide emulsion layer located farthest from the support is mainly composed of { the outermost layer containing monodisperse silver halide grains substantially including silver chlorobromide grains having an outer surface consisting of a 100} plane, and the outermost layer located farthest from the support is a non-photosensitive layer; A silver halide photographic material characterized in that the non-photosensitive layer contains fine particle powder having an average particle size of 1 to 10 μm.