JPH10104794A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material excellent in resistance to the remaining of fingerprints, giving a processed print sample less liable to scratch, excellent in curl resistance and excellent also in writability. SOLUTION: At least one photosensitive silver halide emulsion layer and at least one nonphotosensitive hydrophilic colloidal layer are formed on a substrate by coating to obtain the objective silver halide photographic sensitive material. The at least one hydrophilic col1. oidal layer contains Z>=400mg/m<2> porous fine particl.es and Ziu40mg41m' latex and/or oil contg. a dispersed water- insoluble org. compd.

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, and more particularly to a halogenated photographic material which is excellent in fingerprint adhesion, hardly damages a processed print sample, has excellent curl resistance, and has excellent writing properties. It relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art A halogenated photographic light-sensitive material is prepared by coating a support with a hydrophilic colloid layer containing at least one silver halide emulsion layer, and a white opaque support is used as the support. Sometimes. In particular, color paper is used as a support for photographic support of polyolefin laminate,
So-called RC base paper is used.

[0003] In the case of color paper, in recent years, glossy printed photographs have been preferred by ordinary users.
Sometimes, if the gloss due to the light reflection is strong, the printed image may be difficult to observe. Further, this glossy print photo has a drawback that fingerprint-like stains may be caused by touching with a hand.

On the other hand, when a user who does not like gloss prints or wants a print having a profound feeling, a color paper using a so-called typed RC base paper such as a mat surface or a silk surface in which the surface of the RC base paper is processed in advance is used. Print.

[0005] However, color paper prints using these molded RC base papers have strong light reflection depending on the position of the observation light source, and a solid pattern has not yet been sufficiently obtained.

A method for improving the surface gloss by containing fine particles on the surface or inside of a photosensitive material to obtain a matting effect is disclosed in JP-A-61-147248 and JP-A-1-1426.
No. 30, JP-A-6-75331, JP-A-7-2613
No. 42, etc., the prints obtained by these methods can provide a profound pattern to some extent, but are disadvantageous in that the processed prints are easily damaged when transported and transported. When the print is left under low humidity, it has a disadvantage that the curl is easily formed.

[0007] Regarding fingerprint adhesion, printing of color paper using a molded RC base paper is excellent,
Not yet enough.

On the other hand, in the case of a silver halide photographic light-sensitive material using thin RC base paper, the resulting printed photograph is attached to a general commercially available postcard and then used as a post card. In particular, the demand has been increasing in recent years.

Conventionally, when a user's favorite photograph is used as a postcard, a print photograph obtained from a silver halide photographic light-sensitive material using a thick support is used as it is as a "postcard". Had been

[0010] However, such a method of use leaves a complaint that the "new year ball lottery" cannot be enjoyed, especially in the New Year's New Year season or the like, as compared with a postcard with a new year ball lottery like a new year's postcard.

[0011] Therefore, a print photograph obtained from a silver halide photosensitive material using thin RC base paper as described above is pasted on a postcard such as a New Year's postcard with a New Year's ticket, and a postcard is created. Your favorite photo becomes “Postcard” as it is, and “New Year lottery” of New Year's postcard
This type of postcard is the mainstream nowadays.

When a printed photograph is used as a post card in this way, there are various demands for the printed photograph.

For example, as long as it is used as a postcard, the user can write characters on the surface of the photo,
Alternatively, a stamp may be pressed, so that aptitude for such a thing (hereinafter referred to as writing) is required.

Even when writing characters, the writing utensils are quite various, such as pencils, fountain pens, ballpoint pens, water-based magic,
At present, oil-based magic, black ink, and the like are used, and there are many types of ink for stamps.

With respect to such writing properties, it is desired to have suitability for all kinds of writing tools.

[0016] However, with the above-mentioned post-cards, letters can be written with an oil-based pen, but it is very difficult to write with a ball-point pen, pencil or the like, and the user's requirements have not yet been satisfied.

Also, postcards have very many opportunities to touch prints from production to delivery, and have fingerprint adhesion,
Improvements in scratch resistance are more desired.

[0018]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material which is excellent in fingerprint adhesion, hardly damages a processed print sample, has excellent curl resistance, and has excellent writing properties. To provide.

[0019]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrocolloid layer provided on a support, at least one of the non-photosensitive hydrocolloid layers is provided. A silver halide photographic light-sensitive material, characterized in that the layer contains 400 mg or more of porous fine particle powder per m ² and 40 mg or more of a latex and / or a dispersion oil of a water-insoluble organic compound.

(2) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrocolloid layer provided on a support, at least one of the non-photosensitive hydrocolloid layers is provided. Gelatin containing 400 mg or more of porous fine particle powder per m ^{2 in the} layer, and 1 g or more and 10 g or less per m ² on the side of the support opposite to the side on which the photosensitive silver halide emulsion layer is coated. A silver halide photographic light-sensitive material comprising a layer.

(3) The silver halide photographic light-sensitive material as described in (1) above, wherein at least one of the non-photosensitive hydrocolloid layers contains at least 400 mg of porous fine particle powder and at least 40 mg of latex per m ^2. material.

(4) The silver halide photographic material as described in (1), (2) or (3) above, wherein the porous fine particle powder is an inorganic compound.

(5) The silver halide photographic material as described in (4) above, wherein the porous fine particle powder is silica.

(6) The surface of the resin layer on the side of the support on which the silver halide photosensitive layer is coated has a center plane average roughness (SRa) of 0.2 μm or more and represented by the following formula 1. 6. The silver halide photographic material as described in the above item 5, wherein

[0026]

(Equation 2)

[Where SRa represents the average roughness of the center plane,
Lx represents a length in the X-axis direction of the measurement surface area, Ly represents the length of the Y-axis direction of the measurement surface area, S _A represents the area of the measurement surface area, is S _A = Lx * Ly, At this time, Lx = 7.5 m
m and Ly = 21 mm, f (x, y) represents the surface unevenness, and x and y represent the position coordinates of the measurement point in the x and y directions, respectively. (7) The silver halide photographic material as described in (6) above, wherein the thickness of the support is from 100 μm to 160 μm.

Hereinafter, the present invention will be described in detail. The porous fine particle powder according to the present invention is a fine particle powder having pores.

The porous fine particle powder of the present invention is a powder of a substance which can be dispersed in a hydrophilic binder, and has an average particle diameter of 0.1.
1 μm to 10 μm is preferable, and 0.5 to 5 μm is more preferable.

The porous fine particle powder of the present invention may be used alone or in a mixture with other porous fine particle powder. Examples of the porous fine particle powder of an organic compound include natural and synthetic organic polymer compounds such as cellulose esters, polymethyl methacrylate, polystyrene, and polydivinylbenzene and copolymers thereof. Is preferred. Specific inorganic compounds include silica, alumina,
Examples include aluminum hydroxide, titanium oxide, barium sulfate, calcium carbonate, magnesium sulfate, glass beads, and synthetic mica. Among them, silica is most preferred.

The surface area of the porous fine particle powder of the present invention is 10
It is at least 0 m ² / g, preferably at least 200 m ² / g. The size of the pores is preferably 300 mm or less in average diameter,
Preferably it is 250 °. The surface area and pore diameter of the porous fine particle powder can be determined by a gas adsorption method.

The method for producing the porous fine particle powder of the present invention comprises:
U.S. Pat. Nos. 1,665,264 and 1,935,17
6, 2,071,987, 2,459,903
No. 2,462,798 and 2,469,314
No. 2,505,895 and 2,685,569
No. 3,066,092, 4,070,286, and the like. The field of utilizing such a large surface area of such porous fine particle powder is wide,
Since it is used for catalysts, chromatography, chemical sensors, filters, etc., it can be easily obtained on the market.

The porous fine particle powder of the present invention is contained in the silver halide photographic light-sensitive material in an amount of 400 mg / m ² or more. 500 to 1500 mg is preferred, and 600 to 12 mg.
00 mg is most preferred. The layer contained is a non-photosensitive hydrocolloid layer, preferably a non-photosensitive hydrocolloid layer furthest from the support, specifically a protective layer.

The porous fine particle powder of the present invention may be directly added as it is to the coating solution for forming the non-photosensitive hydrocolloid layer to be added. Is more preferably added to a coating solution that forms

As means for dispersing the porous fine particle powder of the present invention in water or an aqueous solution of gelatin, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used.

When the same layer contains a dispersion oil of a latex and / or a water-insoluble organic compound, the content is preferably at least 40 mg / m ^{2 in the} silver halide photographic material, and is preferably used. Is 50 mg or more, and preferably contains latex.

When gelatin is coated on the side of the support opposite to the side on which the photosensitive silver halide emulsion layer is coated, 1 g or more and 10 g or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. It is the amount of coating.

As the latex, any generally known polymer latex may be used. Examples of the polymer include a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, a styrene-butadiene copolymer, an active methylene group, a water-soluble polymer. A polymer or copolymer comprising a monomer having a functional group or a crosslinkable group with gelatin can be preferably used. Especially,
In order to increase affinity with gelatin which is a binder,
Most preferably, a copolymer with a monomer having a water-soluble group or a crosslinkable group with gelatin mainly containing a hydrophobic monomer such as an alkyl ester of acrylic acid or styrene is used.

Desirable examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-
Desirable examples of monomers having a crosslinkable group with gelatin, such as acrylamide-2-methylpropanesulfonic acid and styrenesulfonic acid, include glycidyl acrylate, glycidyl methacrylate, and N-methylolacrylamide.

The polymer latex and its synthesis method are described in detail in JP-A-2-41, US Pat.
2,386, 2,853,457, 3,41
1,911, 3,411,912, 4,19
7,127, JP-B-45-5331, JP-A-60-
No. 18,540, etc., for example, an emulsion polymerization method, a method of redispersing a polymer obtained by solution polymerization, and the like. As an example, in the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of the monomer and 0.1% of the monomer are used.
About 30 to 100 ° C., preferably 60 to 90%, using 0.5 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant.
It is obtained by polymerizing under stirring at a temperature of 3 to 8 hours.

Examples of the polymerization initiator include water-soluble peroxides and water-soluble azo compounds. Examples of the dispersant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant in addition to the water-soluble polymer. These may be used alone or in combination.

Hereinafter, specific examples of the polymer latex according to the present invention will be described, but the present invention is not limited thereto.

[0043]

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The Tg (glass transition temperature) of the polymer forming the polymer latex used in the present invention is preferably 40 ° C. or less. Tg of polymer is "Polymer Handbook (1966, Wiley &Sons)"
The Tg (、 K) of the copolymer is represented by the following equation.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂
+ · · · + V in _W Tg _{W type, v 1, v 2 ··· v} W represents the weight fraction of the monomer in the _{copolymer, Tg 1, Tg 2 ··· Tg} W each in the copolymer It represents the Tg (゜ K) of a monomer homopolymer. Tg calculated according to the above equation has an accuracy of ± 5 ° C.

Any polymer latex having an average particle size of 0.5 to 300 nm can be preferably used. The average particle size of the polymer latex is described in "Chemistry of Polymer Latex (1973,
Electron microscopy described in “Polymer Press Association”),
It can be measured by a soap titration method, a light scattering method, or a centrifugal sedimentation method, but the light scattering method is preferably used.

The molecular weight of the polymer is not specifically defined, but is preferably 1,000 to 1,000,000 in total molecular weight.
00.

Examples of the water-insoluble organic compound dispersion oil include phthalic acid esters, phosphoric acid esters, fatty acid esters, organic acid amides, ketones, and hydrocarbon compounds. In addition, hydroquinones, phenols, benzotriazoles and the like generally contained in photographic light-sensitive materials can also be mentioned. Preferably 15 carbon atoms
The above is an organic compound. Hereinafter, specific examples of the organic compound according to the present invention are shown, but the present invention is not limited thereto.

Compound Examples O-1 Di-n-octyl phthalate O-2 Di-i-decyl phthalate O-3 Tri-n-nonyl phosphate O-4 Di (ω-butyl-di (ethyleneoxy)) adipate O- 5 di-n-octyl sebatate O-6 glycerin triacetate O-7 di-n-octyl fumarate O-8 trioctyl trimellitate O-9 tridodecyl phosphate O-10 trioctyl phosphine oxide O-11 n-hexadecane O- 12 n-Icosan O-13 n-docosan O-14 n-tetracosane O-15 n-hexacosan O-16 Sansocizer E-200 (manufactured by Nippon Rika Co., Ltd.) O-17 Sansocizer P-1500A (new O-18 Liquid paraffin No. 150-S (manufactured by Nippon Rika Co., Ltd.) O-19 dibutyl phthalate O-20 dinonyl phthalate O-21 2,5-di-tert-octylhydroquinone O-22 2,5-di-sec-dodecylhydroquinone O-23 2, 5-di-sec-tetradecylhydroquinone O-24 2-sec-dodecyl-5-sec-tetradecylhydroquinone O-25 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone O-26 pt-octylphenol

[0050]

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[0051]

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The high boiling organic compounds according to the present invention may be used alone or in combination of two or more.

The high-boiling organic compound according to the present invention may be used in combination with a low-boiling organic solvent and / or a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, using a stirrer, a homogenizer, a colloid mill. After emulsification and dispersion using a dispersing means such as a flow jet mixer or an ultrasonic device, the resultant is added to the target hydrophilic colloid layer.
When the hydrophilic colloid is present in the non-photosensitive hydrophilic colloid layer on the side closer to the support from the gelatin aqueous solution-containing layer, gelatin is preferably used as the hydrophilic colloid.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper, and the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably at least 13% by weight in order to improve sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

The value of the center plane average roughness (SRa) of the support is preferably at least 0.2 μm, more preferably at least 0.5 μm. When used for postcards, thickness 1
Using a support of 00 to 160 μm, 120 to 150 μm
m is preferable. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoat layer (adhesion on the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties). Good.

The composition of the silver halide photographic emulsion used in the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide and the like. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 100 mol% of silver chloride is preferable.

In order to obtain the silver halide emulsion used in the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain a silver halide emulsion used in the present invention, it is advantageous to include a heavy metal ion. Heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt.
Examples thereof include Group 10 metals, Group 12 transition metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be a cyanide ion,
Thiocyanate ion, cyanate ion, chloride ion,
Examples thereof include bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to make the silver halide emulsion contain a heavy metal ion, the heavy metal compound is added to the silver halide emulsion during physical ripening before silver halide grain formation, during silver halide grain formation, and during physical ripening after silver halide grain formation. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly 1 mol
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

Any shape can be used for the silver halide grains. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci. ) 21, 39 (197)
Particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be prepared and used by methods described in documents such as 3). Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The particle size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. It is in the range of 2 to 1.0 μm.

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains preferably has a coefficient of variation of 0.22 or less, more preferably 0.15 or less.
The following monodispersed silver halide grains, particularly preferably, two or more monodispersed emulsions having a coefficient of variation of 0.15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the present invention is
A sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer can be used in combination.

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, and inorganic sulfur.

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like.
10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
A range of ^10-5 mol is desirable.

As a gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of a silver halide emulsion includes:
A reduction sensitization method may be used.

The silver halide emulsion may contain a known antifoggant for the purpose of preventing fog generated during the preparation of the light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Agents can be used. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower column on page 7 of JP-A-2-14636, and more preferred specific compounds include II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Molar amounts are preferred.

For the photosensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect the photographic characteristics of the photographic emulsion, and does not stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. The compound preferably used is a compound represented by the general formula [I] described in JP-A-2-232652.
I].

When the light-sensitive material of the present invention is used as a color light-sensitive material, 400 to 900 nm
Has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the wavelength range of The silver halide emulsion contains one or more sensitizing dyes in combination.

As the spectral sensitizing dye used in the present invention, any of the known compounds can be used. Examples of the blue-sensitizing dye include BS-1 to BS-1 described in JP-A-3-251840, page 28. BS-8 can be preferably used alone or in combination. Green photosensitive sensitizing dyes include:
GS-1 to GS-5 described on page 28 of the publication are preferable,
Further, as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye,
As the infrared-sensitive sensitizing dye, JP-A-4-285950
And the dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. These infrared, red, green, and blue light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 and JP-A-5-6 described in JP-A-4-285950, pp. 8-9.
No. 6515, pages 15 to 17, compounds S-1 to S-
It is preferable to use 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in water or a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water, or adding it as a solid dispersion. It may be added.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
Examples include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Preferable examples of cyan couplers that can be preferably used include couplers represented by general formulas [C-I] and [C-II] described in JP-A-4-114154, page 5, lower left column. As a specific compound, the publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of the magenta coupler which can be preferably used include couplers represented by general formulas [MI] and [M-II] described in the upper right column of page 4 of JP-A-4-114154. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column on page 5 of the publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

As a yellow coupler which can be preferably used, a coupler represented by the general formula [YI] described in the upper right column of page 3 of JP-A-4-114154 can be mentioned. YC on the lower left column of page 3
-1 to YC-9. Among them, a coupler of the formula [Y-I] in which R _Y1 is an alkoxy group or a coupler represented by the formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, YC-8 and YC-9 and JP-A-6-673881 described in the upper left column of page 4 of JP-A-4-114154 are particularly preferred.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be included.

Examples of the high boiling point organic solvent which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl phosphate. And the like are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferable compound as a surfactant used for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. More preferably, within 3 hours and within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas [I] and [II] described in JP-A-2-66541, page 3, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Amine compounds represented by the general formula [A] described in JP-A-64-90445;
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, A hydrophilic colloid such as a single or a synthetic hydrophilic polymer such as a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener, and a carboxyl group-active hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to use a preservative and an antifungal agent as described in No. 6 in combination.

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material of the present invention, an image recorded on a negative may be optically formed on a photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

The present invention is preferably applied to a light-sensitive material in which the developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display,
A light-sensitive material for color proof can be used. In particular, it is preferably applied to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-(Γ-hydroxypropyl) ethylaniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development in the present invention is 3
5-70 ° C is preferred. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

Conventionally, the color development time is generally 3 minutes 30 minutes.
Although it is performed in about seconds, in the present invention, it is preferably performed within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative, a chelating agent and the like are used.

After the color development, the photosensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed.

The developing apparatus used for processing the photosensitive material of the present invention is a roller transport type in which the photosensitive material is conveyed by sandwiching the photosensitive material between rollers disposed in a processing tank. An endless belt system for conveying may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and a photosensitive material is conveyed and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. When processing in large quantities, it is usual to run using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0115]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 10% by weight was laminated, and the reflective support A (thickness = 230)
μm, SRa = 0.12 μm). After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer is provided,
Further, each layer having the following constitution was applied thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as described below.

First Layer Coating Solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and high-boiling organic solvent (DNP)
To 1.67 g, 60 ml of ethyl acetate was added and dissolved, and this solution was dissolved in 1 ml containing 7 ml of 20% surfactant (SU-1).
It was emulsified and dispersed in 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 1 and 2.

(H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0120]

[Table 1]

[0121]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl ] Hydroquinone Image Stabilizer A: pt-octylph Enol

[0123]

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[0124]

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[0125]

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[0126]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the average particle size was 0.64 μm, and the particle size distribution was the same as in EMP-1 except that the addition time of (solution A) and (solution B) and the addition time of solution (C) and solution (D) were changed. Monodisperse cubic emulsion EMP- having a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol%
1B was obtained.

The above-mentioned EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, a monodisperse cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

[0136]

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[0137]

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The sample thus obtained was designated as 101. Further, with respect to Sample 101, the type of the fine particle powder is shown in Table 3, the content per 1 m ² , the content layer, and the latex and / or water-insoluble organic compound. The same samples 102 to 117 were prepared except that the content per 1 m ^{2 of the} dispersion oil was changed as shown in Table 4. However, samples 116, 1
In No. 17, after a gelatin undercoat layer of the reflective support A was provided, gelatin was further coated on the opposite side (BC side) of the reflective support so that the amount of gelatin was as shown in Table 5 per m ² , and as a hardening agent, 1 was used. The fine particle powder was added to the aqueous gelatin solution, dispersed by an ultrasonic disperser, and then added to the coating solution for the containing layer.

The samples thus prepared were exposed to a green light wedge by a conventional method, and then subjected to a developing process in the following developing process.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developing solution tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml Triethylenediamine 2 g 3 g Diethylene glycol 10 g 10 g Potassium bromide 0.01 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium acetate sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter, and the tank solution was pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water.

The treated samples were evaluated as follows.

<Fingerprint Adhesion> The treated sample was cut into a suitable size, left for 3 hours at a constant temperature of 23 ° C. and 55% RH, and kept at a constant temperature and humidity of 23 ° C. and 55% RH. Below,
A finger was pressed on the surface of the sample, and a five-step evaluation was made according to the state of adhesion of the fingerprint as follows.

1: Fingerprint does not adhere. 2: Careful observation shows barely adhering of fingerprint. 3: Careful observation reveals adherence of fingerprint. 4: Fingerprint adheres. 5: Fingerprint adheres strongly. If 1, 2, 3 is practically no problem level,
If it is 5, it is a level that does not endure practical use.

<Low-humidity curl> The treated sample was 10 cm ×
After cutting to 10 cm, the sample was allowed to stand at 23 ° C. and 20% RH for 24 hours at a constant temperature and humidity of 23 ° C., and then, at a constant temperature of 23 ° C. and 20% RH and constant humidity, the curl degree was determined by the reciprocal of the radius of curvature. The larger the + number, the stronger and worse the + curl (curving upward with the image side up).

Curl = 1 / radius of curvature (m) <Scratch resistance test of processed sample> A black background sample that was exposed to white light and processed and cut into a wedge size was measured by the following method. A sample is set on a continuous load type scratch strength tester (Haydon) type 18 (manufactured by Shinto Kagaku Co., Ltd.) according to a prescribed method, and when a continuous load of 0 to 100 g is applied, scratches start to be generated on the sample surface. The weight (g) applied at the time of the test was measured by a prescribed method, and the raw sample was evaluated for a scratch resistance test. The larger the value, the better the scratch resistance. The needle used was a 0.1 mm diamond needle.

<Surface Writability> Specific characters, symbols, and the like were written on a white background sample treated without exposure using a commercially available pencil, and the writability was evaluated as follows.

1: Smoothly writing possible, no fading of letters and symbols, no burrs on print surface, etc. 2: Slight resistance to writing, but fading of letters, symbols, etc., print surface No scratching etc. occurred 3: Resistance to writing was felt, fainting of letters and symbols, and digging of the print surface occurred in places. 4: Writing was impossible at all. However, if the level is 3 or 4, the level is not practical. Table 5 shows the results.

[0151]

[Table 3]

[0152]

[Table 4]

[0153]

[Table 5]

From the above results, the present invention is excellent for comparison.

Example 2 The same processing as in Example 1 was performed as described below.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 3. 5 g 6.0 g Triethanolamine 10.0 g 10.0 g Sodium salt of diethylenetriaminepentaacetic acid 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Add water to make the total volume 1 liter, The pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fixer tank solution and replenisher tank solution Replenisher diammonium ferric ammonium diacetate dihydrate 100 g 50 g 3 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, use potassium carbonate or glacial acetic acid to make the tank solution pH = 7.0, and make up the replenisher solution pH = 6.
Adjust to 5.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Aqueous ammonia (25% aqueous solution of ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention could be effectively obtained.

Example 3 In Example 1, an NPS manufactured by Konica Corporation was used as an automatic developing machine.
-868J, ECOJET-P was used as a processing chemical, and a running process was performed according to the process name CPK-2-J1. The sample of the present invention evaluated in the same manner as in Example 1,
It has been confirmed that the effects of the present invention can be obtained.

Example 4 Photographic paper supports BF were prepared in the following manner.

A corona discharge was applied to the front and back surfaces of a paper pulp having a basis weight of 180 g / m ² , and a resin coating layer of 22 μm thick made of polyethylene containing 10% anatase type titanium dioxide was formed on the surface by extrusion coating. ,
A polyethylene resin coating layer is formed on the back surface by a co-extrusion coating method, and the obtained laminated body is cooled using a cooling roll having irregularities on the surface, and the photographic printing paper supports B to F (thickness = 220 μm). In addition, different cooling rolls were used so that the surface center plane average roughness (SRa) became a value shown in Table 6.

After the support was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and the same material as that of Sample 108 of Example 1 was applied to prepare Samples 201 to 205, and the writability of the surface was evaluated. Table 6 shows the results.

[0165]

[Table 6]

From Table 6, it was confirmed that the use of a support having an SRa of 0.2 or more in the present invention can provide more effective writing performance.

Example 5 Instead of the support B used in Example 4, a basis weight of 90 g / m 2 was used.
Photographic paper support G (thickness = 135 μm, SRa = 1.04) in the same manner except that paper pulp of No. ² was used.
Was manufactured. This support is used for ordinary postcards. When the thickness of the support is 100
Except that the basis weight of the paper pulp was adjusted so as to be に な る 165 μm, the following photographic printing paper supports H to J were manufactured in the same manner as in the above-described photographic printing paper support G manufacturing method.

[0168] If the thickness of the support is less than 100 μm, the rigidity cannot be maintained, and it is not practical as a support for photographic printing paper.
If it exceeds μm, the support for postcard photographic printing paper may not be practical due to postage restrictions.

After these supports were subjected to a corona discharge treatment, a gelatin undercoat layer was provided, and then gelatin was coated on the BC side so that 3 g per 1 m ² was applied, and H-1 was used as a BC side hardening agent. Then, the same thing as the sample 108 of Example 1 was applied, and samples 301 to 304 were formed. For comparison, a sample 305 obtained by applying the same material as the sample 104 of Example 1 to the support G, and a sample 306 obtained by applying the same material as the sample 101 to the support G in the same manner were prepared. This sample 306 is a normal postcard sample. These were evaluated for writability, fingerprint adhesion, and low-humidity curl on the surface. Table 7 shows the results.

[0170]

[Table 7]

From Table 7, it was found that the use of the support for a post card in the present invention resulted in more effective writing. A post card having a curl of 20 or more is at a level that cannot be practically used. Thus, it was found that when the present invention was used as a support for a post card, a post card excellent in writing properties, fingerprint adhesion and low-humidity curl was obtained.

[0172]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is excellent in fingerprint adhesion, hardly damages a processed sample, has excellent curl resistance, and is excellent in writability.

Claims (7)

[Claims] 1. A silver halide photographic material comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrocolloid layer provided on a support, wherein at least one of said non-photosensitive hydrocolloid layers is provided. to, 1m ² per 400
A silver halide photographic light-sensitive material comprising at least mg of porous fine powder and at least 40 mg of a latex and / or a water-insoluble organic compound dispersion oil. 2. A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrocolloid layer provided on a support, wherein at least one of said non-photosensitive hydrocolloid layers is provided. to, 1m ² per 400
mg or more of fine porous powder, and 1 m on the side of the support opposite to the side on which the photosensitive silver halide emulsion layer is coated.
^A silver halide photographic light-sensitive material having a gelatin layer coated in an amount of 1 g to 10 g per ² pieces. 3. At least one of the non-photosensitive hydrocolloid layers
^{2. The} silver halide photographic material according to claim 1, wherein the layer contains at least 400 mg of porous fine particle powder and at least 40 mg of latex per m < ² >. 4. The silver halide photographic material according to claim 1, wherein the porous fine particle powder is an inorganic compound. 5. The silver halide photographic material according to claim 4, wherein the porous fine particle powder is silica. 6. The support according to claim 1, wherein the surface of the resin layer on the side on which the silver halide photosensitive layer is coated has a center plane average roughness (SRa) of 0.2 μm or more represented by the following formula 1. 6. The silver halide photographic light-sensitive material according to claim 5, wherein: (Equation 1) Wherein, SRa represents the center plane average roughness, Lx represents a length in the X-axis direction of the measurement surface area, Ly represents the length of the Y-axis direction of the measurement surface area, S _A measured surface area Where S _A = Lx
* Ly at this time, Lx = 7.5 mm, Ly = 21
mm, f (x, y) represents an uneven surface, and x and y represent the position coordinates of the measurement point in the x and y directions, respectively. ] 7. The thickness of the support is not less than 100 μm and not more than 160 μm.
7. The silver halide photographic light-sensitive material according to claim 6, wherein m is equal to or less than m.