JPH1195359A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic sensitive material superior in rapid film hardening aptitude and the fog restraint of the long stored photosensitive material and resistance to blocking between the materials by hardening it with a specified film hardener and controlling the film pH in a specified range. SOLUTION: This photographic sensitive material is provided with at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer formed on one side of a paper support formed by coating both sides of a paper base with a resin, and the photosensitive material is hardened with at least one kind of hardener represented by formulae I and II and the like, and the film pH is controlled in 4-7. In formula I and II, each of R1 -R3 is an H atom or a substituent and R1 and R2 may combine with each other to form a hetero ring; (m) is an integer of 0-8; (n) is an integer of 0-5: and X<-> is an anion. It is preferred that the silver halide emulsion to be added here has a silver chloride content of >=95 mol.% and this photosensitive material contains a betaine type surfactant.

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 silver halide excellent in rapid hardening property, excellent in fog resistance of a sample stored for a long time, and excellent in sticking resistance between samples. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In recent years, with the spread of silver halide photographic light-sensitive materials (hereinafter, also simply referred to as "light-sensitive materials"), improvements in sample preservability, sample handling, and productivity have been increasing. .

[0003] Particularly, in the case of color paper, it is mainly used in developing laboratories, photo shops, etc.
In order not to impair the performance, it is preferable to store in a refrigerator or the like. However, the actual situation is that it is often left in a place that is not refrigerated for a long time in the distribution process, used labs, photo shops, etc. It is often left unattended. When such a sample is used, there is a drawback that yellow fog occurs on a completed white background, and improvement has been desired.

In the case of a silver halide photographic light-sensitive material, if the drying temperature after the development processing is lowered for some reason, the processed sample rarely sticks to another sample.
For this reason, a loss occurs, workability is reduced, and the like, and a silver halide photographic light-sensitive material excellent in sticking resistance has been desired.

[0005] On the other hand, silver halide photographic materials require several days after coating in order to obtain proper film properties after coating. For this reason, it may be stored in a factory for several days from application to shipment. But,
A silver halide photographic light-sensitive material having rapid hardening aptitude can be shipped immediately after being coated, leading to an improvement in productivity.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having excellent suitability for rapid hardening, excellent fog resistance of a sample stored for a long time, and excellent sticking resistance between samples. To provide.

[0007]

The above object of the present invention is attained by the following constitutions.

[0008] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper, General formula [HI],
A silver halide photographic light-sensitive material which is hardened by at least one hardening agent represented by [H-II] or [H-III] and has a coating pH of 4 to 7. material.

[0009]

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In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ may combine with each other to form a heterocyclic ring together with a nitrogen atom. m represents an integer of 0 to 8;
Represents an integer of 0 to 5, and X ⁻ represents an anion.

[0011]

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In the formula, R ₄ represents an alkyl group, R ₅ represents a substituent, and Y represents an atom or an atomic group capable of reacting with an N atom bonded to R ₄ to form a covalent bond. Represent
When Y reacts with a nitrogen atom, Z represents the remaining linking group for forming a 3- to 8-membered ring, n represents an integer of 0 to 5, and X represents
^- represents an anion.

2. 2. The silver halide photographic material as described in 1 above, wherein the silver halide emulsion contained in the photosensitive silver halide emulsion layer has a silver chloride content of 95 mol% or more.

3. 3. The silver halide photographic light-sensitive material according to the above item 1 or 2, further comprising a betaine-based surfactant.

4. 4. The silver halide photographic material as described in any one of the above items 1 to 3, wherein the coating has a pH of 4 to 6.

5. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper, The general formula [H-
A halogen hardened by at least one hardening agent represented by the formula [I], [H-II] or [H-III] and containing a compound which lowers the coating pH; Silver halide photographic material.

6. When the silver halide emulsion contained in the photosensitive silver halide emulsion layer has a silver chloride content of 95 mol%
6. The silver halide photographic material as described in 5 above, wherein

[7] 7. The silver halide photographic material as described in the above item 5 or 6, further comprising a betaine surfactant.

8. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper, The general formula [H-
I], a hardening agent hardened by at least one hardening agent represented by [H-II] or [H-III], and halogenation contained in the photosensitive silver halide emulsion layer. The silver emulsion has a silver chloride content of 95 mol% or more and contains at least one non-photosensitive hydrophilic colloid layer between the light-sensitive silver halide emulsion layer closest to the support and the support. Characteristic silver halide photographic material.

9. 9. The silver halide photographic material as described in 8 above, comprising a betaine surfactant.

10. The total gelatin content of the photosensitive silver halide emulsion layer closest to the support and the non-photosensitive hydrophilic colloid layer between the support is silver halide photographic material 1
10. The silver halide photographic light-sensitive material as described in 8 or 9, wherein the amount is 0.1 g to ³ g per m ² .

Hereinafter, the present invention will be described in detail.

The hardener of the present invention has the general formula [H-
At least one hardening agent selected from the group consisting of I], [H-II] and [H-III].

In the general formula [HI], R ₁ and R ₃ each represent a hydrogen atom or a substituent, and the substituent is not particularly limited, and examples thereof include an alkyl group and an aryl group. R ₁ is preferably a hydrogen atom. R ₃ is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfooxy group, a sulfoamino group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and a dialkylamino having 2 to 20 carbon atoms. And a substituent such as an N-alkylcarbamoyl group. When R ₃ is an alkoxy group, an alkyl group, a dialkylamino group, or an N-alkylcarbamoyl group, these groups may further have a substituent, and examples of such a substituent include a halogen atom, a carbamoyl group, and a sulfo group. Group, sulfooxy group, sulfoamino group and ureido group.

[0025] X ^over denotes an anion, a counter ion of N- carbamoyl pyridinium salts.

When a substituent of R ₃ contains a sulfo group, a sulfooxy group or a sulfoamino group, an internal salt is formed and X ⁻ may not be present. Preferred examples of the anion include a halide ion, a sulfate ion, a sulfonate ion, ClO ₄ ⁻ , BF ₄ ⁻ , and PF ₆ ⁻ . Preferred among this is given Cl ^- is. m represents an integer of 0 to 8, and m is preferably 0. n represents an integer of 0 to 5, and n is preferably 1.

The hardener represented by the general formula [HI] is described in detail in JP-B-56-12853 and JP-B-58-12853.
No. 32699, JP-A-49-51945, and 51-
Nos. 59625 and 61-9641.

In the general formula [H-II], R ₁ , R ₂ , R
₃ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group and an aryl group. R ₁ and R ₂ may be the same or different. R ₁ and R ₂ may be bonded to each other to form a heterocyclic ring together with the nitrogen atom. Examples of the ring include a pyrrolidine ring, a piperazine ring, and a morpholine ring. The definitions of R ₃ , X and n are the same as those in the general formula [HI].

A detailed description of the hardener represented by the general formula [H-II] can be found in JP-A-50-120616.

In the general formula [H-III], R ₄ represents an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms. R ₅ represents a substituent, preferably -SO ₃ ^- or -C
OO ^- number of carbon atoms which is substituted alkylene group having 1 to 4 or a -SO _3, a ^- represents a ^- or -COO. Y represents an atom or an atomic group capable of forming a covalent bond by reacting with an N atom bonded to R ₄ , and is preferably an ester group, a vinyl sulfone group, Br, Cl, CN, or an electron-withdrawing group. Activated double bond group. When Y reacts with a nitrogen atom, Z represents the remaining linking group for forming a 3- to 8-membered ring, preferably the remaining linking group for forming a 5- to 7-membered ring. X and n are defined by the general formula [HI]
Is the same as the definition in

A detailed description of the hardener represented by the general formula [H-III] can be found in JP-A-9-185144.

Specific examples of the hardener represented by the general formula [HI], [H-II] or [H-III] are shown below, but the hardener of the present invention is not limited to these. Not something.

[0033]

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[0034]

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[0035]

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The hardener in the present invention may be used alone, in combination with another hardener of the present invention, or in combination with a hardener not included in the present invention.

The first invention of the present invention is characterized in that the coating pH is 4-7.
Between. More preferably, it is between 4 and 6. The coating pH mentioned here is the pH of the raw sample, and the pH of the coating can be measured by dropping a few drops of water on the raw sample and usually using an electrode for pH measurement.

It is essential that the second invention of the present invention contains an additive for lowering the coating pH. Examples of the additive that lowers the coating pH include acidic compounds such as hydrochloric acid, sulfuric acid, acetic acid, citric acid, sulfurous acid, phthalic acid, and benzoic acid. The contained layer is not particularly limited.

The third invention of the present invention contains at least one non-light-sensitive hydrophilic colloid layer between the light-sensitive silver halide emulsion layer closest to the support and the support. The total gelatin content of the non-photosensitive hydrophilic colloid layer is preferably from 0.1 g to 3 g, more preferably from 0.4 g to 2.5 g, per m ^{2 of} the light-sensitive material. The non-photosensitive hydrophilic colloid layer may contain latex, oil, titanium oxide, barium sulfate, calcium carbonate, colloidal silver and the like.

In the present invention, it is highly preferable that a betaine-based activator is contained in the light-sensitive material of the present invention. Examples of betaine-based activators include carboxybetaine type, sulfobetaine type, imidazolium betaine type and the like. Here, specific examples of betaine-based activators are shown, but those used in the present invention are not limited to these.

[0041]

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[0042]

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[0043]

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The use amount of the betaine-based activator is
It is preferably 0.0001 to 1.0 g, more preferably 0.0005 to 0.5 g, and still more preferably 0.001 to 0.2 g per m ² . The layer containing the betaine-based activator is not particularly limited, but it is preferably contained in the layer furthest from the support and / or the layer adjacent to the support when applied by multi-layer simultaneous coating.

As the support for use 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, chloride support. A vinyl sheet, a polypropylene that may contain a white pigment, a polyethylene terephthalate support, baryta paper, or 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 13% by weight or more, more preferably 15% by weight, for improving sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support relating 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 as a variation coefficient described in
More preferably, it is 5 or less.

Ultramarine blue, oil-soluble dyes, etc. to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflection support or in the applied hydrophilic colloid layer to improve the whiteness. It is preferred to add a trace amount of a bluing agent or a reddish agent.

The composition of the silver halide photographic emulsion of the present invention is as follows:
Silver halide, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide, etc. may have any halogen composition, but contain 95 mol% or more of silver chloride. Silver chlorobromide 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 of 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 the silver halide emulsion of the present invention, it is advantageous to include a heavy metal ion. Examples of heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group ions 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 cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl ion. , Ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order for the silver halide emulsion of the present invention to contain heavy metal ions, the heavy metal compound is physically ripened before silver halide grains are formed, during silver halide grains, and after silver halide grains are formed. What is necessary is just to add in the arbitrary places of each process inside. 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 to 1 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ mol.
Mol to 5.times.10.sup.- ⁵ mol is preferred.

The silver halide grains of the present invention may have any shape. One preferred example is (1
It is a cube having the (00) plane as the crystal surface. Also,
U.S. Pat. Nos. 4,183,756 and 4,225,666
No., JP-A-55-26589, JP-B-55-4273.
No. 7 and The Journal of Photographic
Science (J. Photogr. Sci.) 21, 3
9 (1973) and the like, particles having an octahedral, tetradecahedral, dodecahedral, etc. shape can be produced and used. Further, particles having a twin plane may be used.

The silver halide grains used in the present invention are:
Although grains having a single shape are preferably used, it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer.

The grain size of the silver halide grains of the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, and more preferably, in consideration of other photographic properties such as rapid processing property and sensitivity. , 0.2 to 1.0 μm.

The particle size can be measured using the projected area of the particle or the approximate 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 of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 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 of the present invention may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time,
The seed particles may be grown after they are 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.

Further, JP-A-57-92523 and JP-A-57-92523 describe the same.
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 German Offenlegungsschrift 2,921,164, etc. 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 of the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

The chalcogen sensitizer applied to the silver halide emulsion of the present invention includes a sulfur sensitizer, a selenium sensitizer,
A tellurium sensitizer can be used, but 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 addition amount of the sulfur sensitizer used in the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect. The range is preferably from × 10 ^{-10 to} 5 × 10 ^-5 mol, and more preferably from 5 × 10 ^{-8 to} 3 × 10 ^-5 mol.

As the gold sensitizer used in the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. As the ligand compound used, dimethyl rhodanine, thiocyanic acid, mercaptotetrazole,
Mercaptotriazole and the like can be mentioned. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound used, the ripening conditions, etc., but is usually from 1 × 10 ^-4 mol to 1 × 1 per mol of silver halide.
It is preferably ^0-8 mol. More preferably, 1 × 1
It is 0 ^-5 mol to 1 × 10 ^-8 mol.

The chemical sensitization of the silver halide emulsion of the present invention may be a reduction sensitization.

The silver halide emulsion of the present invention is used for the purpose of preventing fog occurring during the process of preparing a silver halide photographic material, reducing performance fluctuation during storage, and preventing fog occurring during development. Known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in JP-A-2-14603.
General formula (II) described in the lower column on page 7 of Japanese Patent Publication No. 6
And more preferred specific compounds are (IIa-1) to (IIa-8), (IIb-1) to (IIb-) described on page 8 of the publication.
7) or 1- (3-methoxyphenyl) -5-
Compounds such as mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds, depending on their purpose,
It is added in the steps of preparing the silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the coating liquid preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide is used.
It is preferably used in an amount of about ^-4 mol. When added at the end of chemical sensitization, 1 × 10
^-6 mol to 1 × 10 ^-2 mol is preferable, and 1 × 10
^-5 mol to 5 × 10 ^-3 mol is more preferred. In the coating solution preparation step, when adding to the silver halide emulsion layer,
The amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, more preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × / m ^2.
An amount of about 10 ⁻⁹ mol to 1 × 10 ⁻³ mol is preferable.

The silver halide photographic light-sensitive material of the present invention includes
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, dyes having absorption in the visible region include AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared absorbing dyes include general formulas (I) and (II) described in the lower left column of page 2 of JP-A-1-280750. , (III) have preferred spectral characteristics, have no effect on the photographic characteristics of the silver halide photographic emulsion, and are free from contamination by residual color.
As specific examples of preferred compounds, the exemplified compounds (1) to (4) listed in the lower left column of page 3 to the lower left column of page 5 of the publication are referred to.
5).

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention since whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

As the spectral sensitizing dye used in the silver halide emulsion of the present invention, any of known compounds can be used.
BS-1 to 8 described in page 1 of JP 1840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Issue 1
It is preferable to use the compounds S-1 to S-17 described on pages 5 to 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 a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like 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. Can also be used, but a typical example is a wavelength band of 3
Known as a yellow dye-forming coupler having a spectral absorption maximum wavelength at 50 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength at a wavelength range of 500 to 600 nm, and a cyan dye-forming coupler having a spectral absorption maximum wavelength at a wavelength range of 600 to 750 nm. Are typical.

Examples of the cyan coupler which can be preferably used include couplers represented by formulas (CI) and (C-II) described in the lower left column of page 5 of JP-A-4-114154. As specific examples of the compounds, CC-1 to CC described in the lower right column of page 5 to the lower left column of page 6 of the same publication
-9.

Examples of the magenta coupler which can be preferably used include those represented by formulas (MI) and (M-II) described in JP-A-4-114154, upper right column on page 4. As specific examples of the compounds, MC-1 to MC described in the lower right column on page 4 to the upper right column on page 5 of the same publication.
C-11. Among the above magenta couplers, more preferred are couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, and among them, the RM of the general formula (MI) is 3 A coupler which is a lower alkyl group is particularly preferable because of its excellent light resistance. MC-8 to MC-11 described in the upper column on page 5 of the same publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction, and are therefore preferable.

Examples of the yellow coupler which can be preferably used include a coupler represented by the general formula (Y-I) described in the upper right column of page 3 of JP-A-4-114154. YC-1 to YC-9 described in the lower left column on page 3 of the publication.
Above all, a coupler in which R _{Y1 in} the general formula [Y-1] of the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone, and is preferable. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in JP-A-4-114154, lower left column of page 4, and JP-A-6-67388.
No., pages 13-14. Compounds represented by (1) to (47) are mentioned. 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 the couplers and other organic compounds used in the silver halide photographic light-sensitive material of the present invention, the boiling point is usually 15 points.
It is dissolved in a water-insoluble high-boiling organic solvent of 0 ° C. or more, if necessary, in combination with a low-boiling and / or water-soluble organic solvent, and emulsified and dispersed 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 at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phosphate; Is 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 compound preferable as a surfactant used for dispersing a photographic additive or adjusting the 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- described in JP-A-64-26854 is described.
1 to A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

The coupler of the present invention is preferably used in combination with a discoloration inhibitor to prevent discoloration 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 on page 3 of JP-A-2-66541 and general formula IIIB described in JP-A-3-174150.
A phenolic compound represented by
Amine compounds represented by the general formula A described in JP-A-62-182741, JP-A-6-182741
Metal complexes represented by IV and XV are particularly preferred for magenta dyes.

Further, the compound represented by formula I 'described in JP-A-1-19649 and JP-A-5-1141
The compound represented by the general formula II described in JP-A No. 7 is particularly preferable for yellow and cyan dyes.

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

In the silver halide light-sensitive material of the present invention, 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. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication. .

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula described in JP-A-1-250944.
A compound represented by the formula III-3, a compound represented by the general formula III described in JP-A-64-66646,
UV-1L to UV-27L described in 187240,
Examples include compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

The silver halide photographic light-sensitive material of the present invention includes
It is advantageous to use gelatin as a binder, but if necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, a homopolymer or a copolymer A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

Further, in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability, JP-A-3-13-1
It is preferable to add a preservative and an antifungal agent as described in JP-A-57646. Further, in order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in
It is preferable to add a slipping agent described in JP-A-8543 and JP-A-2-73250.

In coating a photographic 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 silver halide photographic light-sensitive material of the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be converted into digital information, then formed into an image on a CRT (cathode ray tube), and the image may be formed on a silver halide photographic material to be printed. The printing may be performed, or the printing may be performed by changing the intensity of the laser beam based on the digital information and scanning.

The present invention is preferably applied to a light-sensitive material in which a 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, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention 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-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N-ethyl-N-
(Β- (methanesulfonamido) ethyl) -aniline 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
-([Gamma] -hydroxypropyl) aniline In the present invention, the above color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.3.
0, more preferably pH 9.8-
Used in the range of 12.0.

The processing temperature of color development used in the present invention is preferably 35 ° C. to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high.

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

To the color developing solution, a known developer component compound can be added in addition to the above color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, or a belt. An endless belt system that fixes and transports the photosensitive material may be used,
A processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and a photosensitive material is transported. A spray method is used to spray the processing liquid. A web method is used to contact a carrier impregnated with the processing liquid. Alternatively, a method using a viscous treatment liquid may be used.

In the case of processing a large amount, it is usual to carry out a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. The method is to add a processing agent in the form of a tablet, and the method described in Published Japanese Patent Application No. 94-16935 is most preferable.

[0105]

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 produced by laminating 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 surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After corona discharge treatment of this reflective support,
A gelatin undercoat layer was provided, and each layer having the following constitution was further provided to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as described below.

First layer coating solution 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), 3.34 of (ST-2)
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 (DN)
P) Ethyl acetate (60 ml) was added and dissolved in 1.67 g, and this solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to disperse the yellow coupler. A liquid was prepared. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

Each of the coating solutions for the second to seventh layers was 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.

[0110]

[Table 1]

[0111]

[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-octyl Phenol

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

(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, 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-1B having an average particle size of 0.64 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained in the same manner as in P-1.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization 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, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a thickness of 0.08 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-mentioned 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 SS-1 was added in an amount of 2.0 × 10 ^-3 per mol of silver halide.

[0126]

Embedded image

[0127]

Embedded image

The sample thus obtained was designated as 101. Further, Samples 102 to 107 were prepared in the same manner as Sample 101 except that the hardeners shown in Table 3 were used. Further, the betaine-based activity shown in Table 3 was applied to 10 m of the first layer per m ² of the photosensitive material.
g and the seventh layer except that 20 mg was added to the seventh layer.
Samples 108 to 112 similar to 107 were prepared. The hardener amounts of Samples 102 to 115 were the amounts shown in Table 3 in terms of molar ratio with respect to the hardening material of Sample 101, and the coating pH values of Samples 101 to 112 are shown in Table 3. It was.

The thus prepared sample was exposed to light wedges by a conventional method, and then subjected to a developing process in the following developing process.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 45 seconds 800 cc Bleach Fix 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Drying 60 ８０80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid 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 Pentaacetic acid pentasodium 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. When pH = 10.10, replenisher is pH Adjusted to 10.60.

Bleach-fixing solution tank replenisher 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 is added to make a total volume of 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

These treated samples were evaluated as follows.

(Quick durable suitability evaluation)
The sample was allowed to stand at 55 ° C. and 55% RH for 1 day, and then the swelling ratio specified was measured.

The swelling ratio as used herein means that a raw sample of a silver halide photographic light-sensitive material is immersed for 45 seconds in a color developing solution adjusted to a temperature of 35 ° C. And the weight ratio of the swelled sample after swelling.

Swelling ratio = [(weight of swollen sample after swelling) −
(Weight of raw sample before swelling)] / [(weight of raw sample before swelling)-(weight of support)] × 100 If the measured swelling ratio reaches the range of 120% to 140%, rapid It has a hardening property.

(Evaluation of long-term storage fog resistance) A wedge-size sample was stored at 40 ° C. and 40% RH for 4 months.
The emerging sample was processed unexposed. X-
The yellow fog density was measured using Rite 310 (manufactured by X-Rite). The smaller the value, the lower the fog and the better.

(Evaluation of Sticking Resistance) The wedge-size-treated samples were stuck together on the emulsion-coated surfaces, respectively.
It was bundled. After fixing it, 40 ℃, 80%
Stored under RH conditions for 15 hours.

Thereafter, the samples in a state where the samples were adhered to each other were peeled off, and the sense of resistance at that time was evaluated based on the following 1 to 5 five-level evaluation. The closer to 1, the better, 5
The closer to, the more deteriorated.

1 ... the sample is not attached, 2 ... between 1 and 3, 3 ... there is enough resistance to make a sound when peeled off, 4 ... 3 and 5 Middle, 5 ... The sample is stuck and cannot be peeled off.

Table 3 shows the results.

[0143]

[Table 3]

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

(Example 2) The processing in Example 1 was changed as follows.

Processing step Processing temperature Time Replenishment amount 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 liquid and replenisher tank liquid 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) hydroxyamine 3 5.5 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g potassium carbonate 30g 30g Add water to make the total volume 1 liter, Click solution to pH = 10.10, replenishing solution is adjusted to pH = 10.60.

Bleach-fix solution tank solution and replenisher tank solution Replenisher diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 50 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 adjust the tank solution to pH = 7.0, Adjust to pH = 6.5.

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 ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Add water to make the total volume 1 liter, and adjust the pH 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, NPS-868J manufactured by Konica Corporation was used as an automatic developing machine and ECOJET-P was used as a processing chemical.
A running process was performed according to -2-J1. Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention were obtained.

Example 4 Sample 10 used in Example 1
Samples 201 to 206 were prepared in the same manner as in Sample No. 1 except that the hardeners shown in Table 4 and the compounds shown in Table 4 as acidic compounds for lowering the coating pH were added to the seventh layer in an amount of 5 mg per m ² of the photographic material. It was created. Further, Samples 202 to 206 were prepared except that a betaine-based activator shown in Table 4 was added to 10 mg of the first layer and 20 mg to the seventh layer per 1 m ² of the light-sensitive material.
Samples 207 to 211 similar to were prepared. Sample 20
The amounts of the hardeners of 1 to 211 were the amounts shown in Table 4 in terms of molar ratio with respect to the hardening material of Sample 101.

The sample thus prepared was subjected to the same processing as in Example 1, and evaluated in the same manner as in Example 1.

Table 4 shows the results.

[0155]

[Table 4]

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

(Embodiment 5) In Embodiment 4, Embodiment 2
The same processing as in Example 4 was performed, and the evaluation was performed in the same manner as in Example 4, and it was confirmed that the effects of the present invention were obtained.

(Embodiment 6) In Embodiment 4, Embodiment 3
The same processing as in Example 4 was performed, and the evaluation was performed in the same manner as in Example 4, and it was confirmed that the effects of the present invention were obtained.

(Example 7) Sample 10 used in Example 1
In contrast to 1, the hardeners shown in Table 5 were added to the seventh layer. The same samples 301 to 306 were prepared except that the S layer was provided between the first layer and the support. In addition, samples 301 to 30
Table 5 shows the amount of gelatin per m ² of the photographic material in the S layer of No. 6. 2 further betaine active agent shown in Table 5 the light-sensitive material 1 m ² per the S layer 10mg and seventh layer
Samples 307 to 311 similar to Samples 302 to 306 were prepared except that 0 mg was added. In addition, samples 301 to 311
The amount of the hardener was the amount shown in Table 5 in terms of the molar ratio with respect to the hardening material of Sample 101.

The sample thus prepared was subjected to the same processing as in Example 1, and evaluated as in Example 1.

Table 5 shows the results.

[0162]

[Table 5]

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

(Embodiment 8) In Embodiment 7, Embodiment 2
The same processing as in Example 7 was performed, and evaluation was performed in the same manner as in Example 7, and it was confirmed that the effects of the present invention were obtained.

(Embodiment 9) In Embodiment 7, Embodiment 3
The same processing as in Example 7 was performed, and evaluation was performed in the same manner as in Example 7, and it was confirmed that the effects of the present invention were obtained.

[0166]

As demonstrated in the examples, the silver halide photographic light-sensitive material of the present invention is excellent in rapid hardening aptitude, excellent in fog resistance of samples stored for a long period of time, and also excellent in sticking resistance between samples. Having.

Claims (10)

[Claims] 1. A silver halide having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In photographic light-sensitive materials, the general formulas [HI], [H
-II] or at least one hardening agent represented by [H-III], and has a coating pH of 4 to
7. A silver halide photographic light-sensitive material, Embedded image [Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ may combine with each other to form a heterocyclic ring together with a nitrogen atom. m represents an integer of 0 to 8;
And X ⁻ represents an anion. [Chemical formula 2] [Wherein, R ₄ represents an alkyl group, R ₅ represents a substituent,
Y represents an atom or an atomic group capable of forming a covalent bond by reacting with an N atom bonded to R _{4, and} when Y reacts with a nitrogen atom, Z represents a remaining group for forming a 3- to 8-membered ring. And n represents an integer of 0 to 5, and X ⁻ represents an anion. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion contained in the light-sensitive silver halide emulsion layer has a silver chloride content of 95 mol% or more. . 3. The silver halide photographic light-sensitive material according to claim 1, further comprising a betaine-based surfactant. 4. The silver halide photographic material according to claim 1, wherein the coating has a pH of 4 to 6. 5. A silver halide having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In a photographic light-sensitive material, the general formula [HI],
A silver halide photograph characterized by being hardened by at least one hardening agent represented by [H-II] or [H-III] and containing a compound which lowers the coating pH. Photosensitive material. 6. The silver halide photographic light-sensitive material according to claim 5, wherein the silver halide emulsion contained in the light-sensitive silver halide emulsion layer has a silver chloride content of 95 mol% or more. material. 7. The silver halide photographic material according to claim 5, which comprises a betaine surfactant. 8. A silver halide having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In a photographic light-sensitive material, the general formula [HI],
A silver halide emulsion hardened by at least one hardener represented by [H-II] or [H-III], and contained in the photosensitive silver halide emulsion layer; ,
A halogen having a silver chloride content of 95 mol% or more and containing at least one non-light-sensitive hydrophilic colloid layer between the light-sensitive silver halide emulsion layer closest to the support and the support; Silver halide photographic material. 9. The silver halide photographic material according to claim 8, further comprising a betaine surfactant. 10. A silver halide photographic light-sensitive material having a total gelatin content of a photosensitive silver halide emulsion layer closest to the support and a non-photosensitive hydrophilic colloid layer between the support and 1 m of a silver halide photographic material.
10. The silver halide photographic light-sensitive material according to claim 8, wherein the weight of the silver halide photographic material is 0.1 g to ³ g.