JP2000035640A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic sensitive material having excellent properties such as fast processing property and storage property of the raw material by hardening a specified silver halide emulsion layer or the like with a specified film hardening agent and incorporating a betaine-based surfactant into the uppermost layer of nonphotosensitive layers. SOLUTION: This silver halide photographic sensitive material used has at least one photosensitive silver halide emulsion layer containing >=95 mol.% silver chloride and at least one nonphotosensitive layer on at least one face of a supporting body. In this method, the total amt. of gelatin included in the silver halide emulsion layers and nonphotosensitive layers is controlled to <=6.5 g per 1 m2, and layers are hardened by using at least one kind of film hardening agent expressed by the formula. Moreover, the pH of the hardened film is controlled to >=5.3 and <=7, and the uppermost layer of nonphotosensitive layers contains a betaine-based surfactant. In the formula, R31, R34, R37 are alkylene groups or the like, R32, R33, R35, R36, R38, R39 are hydrogen atoms or the like, J1, J2 are -O- or the like, k, l, m are 0 or 1, but when at least one of k and l is 1, m is not 0.

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 a processing method therefor, and more particularly, it is excellent in rapid processing suitability, excellent in preservability of raw samples, excellent in sticking resistance between printed samples and samples, The present invention relates to a silver halide photographic light-sensitive material having a small reduction in sharpness of a print sample over time, excellent scratch resistance when wet, and excellent coloring properties of a yellow coloring dye, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, color development processing has been increasingly simplified and speeded up, and it has been desired that processing can be performed quickly and that the processing is stable.

[0003] From the viewpoint of speeding up the processing time, silver bromide, silver chlorobromide and silver chloride containing substantially no silver iodide are used as silver halide emulsions applied to color photographic paper. Have been. It is known that silver halide emulsions having a higher silver chloride content have higher developability and are advantageous for rapid processing.

[0004] In addition, the silver development is reduced by using a means such as speeding up silver development or increasing color development efficiency, or by reducing the amount of binder to reduce the thickness of the emulsion by reducing the amount of binder. There are ways to increase sex.

[0005] As a result, the ratio of the time of the drying step to the entire processing step is increasing as the color development processing time itself is being accelerated, and there is also a demand for faster drying after the development processing. Gelatin is used as a binder in each of the photographic constituent layers of the photographic light-sensitive material. However, if the amount of gelatin contained in the photographic light-sensitive material is large, a large amount of the light-sensitive material is brought into the drying process, and if the amount of gelatin is large, the light-sensitive material is brought into the drying process. There is a problem that it takes a long drying time due to an increase in the amount of water therein, or causes poor drying under high humidity conditions such as during the rainy season, and a reduction in the amount of gelatin is desired.

[0006] On the other hand, with the spread of silver halide photographic light-sensitive materials, improvements in the preservability of samples and in the handling of samples have been increasing.

[0007] In particular, in the case of color paper, it is mainly used in developing laboratories, photo shops, and the like.
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., and depending on the area, it may be used for a long time in a high temperature or high humidity environment. It is often left unattended. Such samples may have reduced sensitivity during long-term storage, require color correction at the time of printing, and are extremely laborious at the time of printing. Also, labs, photo shops,
If the user gets wet when handling the print for some reason, it rarely sticks to another sample. For these reasons, there is a demand for a silver halide photographic light-sensitive material having a small sensitivity fluctuation and excellent sticking resistance.

In the case of color paper, after exposure, development processing is performed, and an image as a print can be obtained. It is desirable that these prints do not fluctuate even when the user is left in various environments for a long period of time, but when stored under high humidity for a long period of time, the images blur and the sharpness of the images decreases. To be rare. Further, during a series of operations of development processing, the color paper is conveyed at a high speed in a swollen state containing water, and at that time, scratches sometimes occur. Further, the image of a silver halide photographic light-sensitive material contains a coupler in the light-sensitive material, and the coupler forms a dye by a development process. Research on silver halide photographic materials and processing methods is needed. Improvement of these drawbacks as described above has been desired very recently.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the first and second inventions of the present invention is to provide excellent suitability for rapid processing, excellent storage stability of raw samples, excellent sticking resistance between print samples, and excellent print samples. The object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in sharpness deterioration during storage with time.
An object of the third invention of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in rapid processing suitability, excellent in preservability of raw samples, excellent in sticking resistance between print samples and samples, and excellent in scratch resistance when wet. To provide. The object of the fourth invention of the present invention is to be excellent in rapid processing suitability, excellent in preservation of raw samples, excellent in sticking resistance between printed samples and samples,
An object of the present invention is to provide a silver halide photographic light-sensitive material excellent in the coloring property of a yellow coloring dye. An object of the fifth and sixth aspects of the present invention is to provide a silver halide photograph having excellent suitability for rapid processing, excellent storage stability of a raw sample, excellent sticking resistance between a printed sample and a sample, and excellent coloring property of a yellow coloring dye. An object of the present invention is to provide a method for processing a photosensitive material.

[0010]

The above object of the present invention is achieved by the following constitution.

1. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer containing 95 mol% or more of silver chloride and at least one non-photosensitive layer on one side of a support, The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 6.5 g or less per m ² and is hardened by at least one hardener represented by the following general formula [HI]. A silver halide photographic light-sensitive material having a coating pH of 5.3 or more and 7 or less and containing a betaine surfactant in the uppermost layer of the non-photosensitive layer.

[0012]

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Wherein R ₃₁ , R ₃₄ and R ₄₇ are an alkylene group,
Represents an arylene group. _R32 , _R33 , _R35 , _R36 , _R38 ,
R ₃₉ represents a hydrogen atom, an alkyl group, a hydroxyl group or a vinylsulfonyl group. J ₁ and J ₂ are -O-, -S-,-(C
= 0)-, -CH (OH)-, -NHCO-, -CON
Represents H-. k, l, and m represent 0 or 1. Where k,
When at least one of 1 is 1, m cannot be 0. ] 2. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer containing 95 mol% or more of silver chloride and at least one non-photosensitive layer on one side of a support, The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 6.5 g / m ^2.
Or less, which is hardened by at least one of the hardeners represented by the general formula [HI], has a coating pH of 5.3 or more and 7 or less, and is closest to the support. Silver halide containing at least one non-photosensitive hydrophilic colloid layer having a total gelatin content of 0.01 g or more and 1 g or less per m ² between a light-sensitive silver halide emulsion layer and the support. Photosensitive material.

3. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer containing 95 mol% or more of silver chloride and at least one non-photosensitive layer on one side of a support, The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 6.5 g or less per m ² , and the surface of the support is subjected to energy treatment, thereby forming a hardener-reactive group on the surface. And a film hardened by at least one hardening agent represented by the general formula [HI], and a film p
A silver halide photographic material, wherein H is 5.3 or more and 7 or less.

4. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer containing 95 mol% or more of silver chloride and at least one non-photosensitive layer on one side of a support, The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 6.5 g or less per 1 m ² and is hardened by at least one hardener represented by the aforementioned general formula [HI]. And a coating pH of 5.3 to 7 and the photosensitive silver halide emulsion layer contains at least one yellow coupler represented by the following general formula [I]. Photosensitive material.

[0016]

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[In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a diffusion-resistant aliphatic group or an aromatic group. R ₃ represents a hydrogen atom or a halogen atom, and X represents 5 or 6 which can be eliminated upon coupling with an oxidized developing agent.
Represents a nitrogen-containing heterocyclic group. ] 5. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer containing 95 mol% or more of silver chloride and at least one non-photosensitive layer on one side of a support, The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 6.5 g / m ^2.
A silver halide photographic material hardened by at least one of the hardeners represented by the general formula [HI] and having a coating pH of 5.3 or more and 7 or less,
A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed using an apparatus in which the thickness of a color development bath is 100 times or less the thickness of the silver halide photographic light-sensitive material during color development processing. .

6. In a silver halide photographic material having at least one photosensitive silver halide emulsion layer containing 95 mol% or more of silver chloride and at least one non-photosensitive layer on one side of a support, The total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive layer is 6.5 g or less per 1 m ² and is hardened by at least one hardener represented by the aforementioned general formula [HI]. A method for processing a silver halide photographic material, comprising applying a processing solution to a silver halide photographic material having a coating pH of 5.3 or more and 7 or less.

[7] At least one fluorine-containing surfactant
2. The silver halide photographic light-sensitive material according to 1, wherein the material is used as a seed.

8. A layer containing at least one non-photosensitive hydrophilic colloid layer having a total gelatin of 0.03 g or more and 0.8 g or less per m ² between the light-sensitive silver halide emulsion layer closest to the support and the support; 3. The silver halide photographic light-sensitive material according to item 2, wherein

9. The silver halide according to any one of items 1 to 4, 7, and 8, wherein the total silver halide contained in the silver halide emulsion layer is 0.6 g or less per m ^{2 in} terms of silver amount. Photosensitive material.

10. The coating pH is 5.8 or more to 6.5.
9. The silver halide photographic light-sensitive material according to item 9, wherein:

11. When the thickness of the color developing bath is not more than 100 times the thickness of the silver halide photographic light-sensitive material when the silver halide photographic light-sensitive material described in 1-4, 7-10 is subjected to color development processing. A method for processing a silver halide photographic material, wherein the processing is performed using a certain apparatus.

12. A processing method for a silver halide photographic light-sensitive material, which comprises applying a processing solution to the silver halide photographic light-sensitive material described in any one of 1 to 4 and 7 to 10 and processing.

Hereinafter, the present invention will be described in detail.

The gelatin used in the silver halide color photographic light-sensitive material of the present invention is hardened by a hardener represented by the following general formula [HI].

[0027]

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Wherein R ₃₁ , R ₃₄ and R ₃₇ are an alkylene group,
Represents an arylene group. _R32 , _R33 , _R35 , _R36 , _R38 ,
R ₃₉ represents a hydrogen atom, an alkyl group, a hydroxyl group or a vinylsulfonyl group. J ₁ and J ₂ are -O-, -S-,-(C
= 0)-, -CH (OH)-, -NHCO-, -CON
Represents H-. k, l, and m represent 0 or 1. Where k,
When at least one of 1 is 1, m cannot be 0. The hardener represented by the general formula [HI] useful in the present invention is shown below, but the present invention is not limited thereto.

[0029]

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[0030]

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The method of synthesizing these hardeners is described in US Pat.
029,542, JP-B-44-29622, 47
No. 24259, No. 47-25373 and the like.

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 silver halide photographic light-sensitive material of the present invention has a coating pH of 5.3 or more and 7 or less. More preferably, it is between 5.8 and 6.5. The coating pH mentioned here is the pH of a raw sample, and the coating pH is measured by measuring 10 μl of pure water in a micropipettor,
0 μl is dropped on a raw sample, and the pH can be measured using a pH measurement electrode on the water drop.

The total amount of gelatin contained in the silver halide photographic light-sensitive material of the present invention is preferably 1 g or more and 6.5 g or less per m ^{2 in} order to obtain a function as a binder from the viewpoint of rapid processing. .

The first invention of the present invention contains at least one type of betaine surfactant in the uppermost layer of the non-photosensitive layer. As the betaine-based surfactant, there are carboxybetaine type, sulfobetaine type, imidazolium betaine type and the like. Here, specific examples of the betaine-based surfactant are shown, but those used in the present invention are not limited to these.

[0036]

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[0037]

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[0038]

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The amount of the betaine-based surfactant used is 0.0001 to 1.0 g, preferably 0.0005 to 0.5 g, more preferably 0.001 to 0.2 g per m ² of the light-sensitive material. It is. When applied by multi-layer simultaneous coating, it is preferable that the compound is contained in the layer farthest from the support and the layer adjacent to the support. Further, it is preferable to use it in combination with a fluorinated surfactant. Specific examples of the fluorinated surfactant are shown below, but those used in the present invention are not limited to these.

The fluorine-containing anionic surfactant preferably used in the present invention includes those represented by the following general formula [FA].

Formula (FA) (Cf)-(Y) n wherein Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is -COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (O
M) ₂ wherein M represents a hydrogen atom, or an alkali metal atom or an ammonium group, and n is 1 or 2.

More preferably used fluorine-containing anionic surfactants include those represented by the following general formula [FA '].

Formula [FA '] Rf- (D) _t- Y In the formula, Rf represents a fluorine-substituted alkyl group or an aryl group having 3 to 30 carbon atoms, and D represents -O-, -COO-, -C
ON (R ₁₎ - or -SO ₂ N (R ₁₎ - comprising coupling a represents a divalent group having 1 to 12 carbon atoms containing at least one, wherein R ₁ is alkyl of 1 to 5 carbon atoms Represents t, t is 1 or 2, and Y is -COOM, -S
O ₃ M, —OSO ₃ M or —P (＝ O) (OM) ₂ , wherein M represents a hydrogen atom, an alkali metal atom, or an ammonium group. The following are specific examples of the compounds, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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It is particularly preferable to use a fluorine-containing anionic surfactant containing at least one bond of —SO ₂ N (R ₁ ) —.

The fluorine-containing cationic surfactant used in the present invention is a compound represented by the following general formula [FK].

[0052] Formula [FK] R'f-G-J ⁺ L ^- However, R'f is a 1-20C hydrocarbon group having a carbon, at least one hydrogen atom is substituted with a fluorine atom . G represents a chemical bond or a divalent group. J ⁺ is a cationic group, L ^- represents a counter anion.

An example of R'f is -C_kF_{2k + 1}(K = 1
-20, especially 3-12), HC_qF _2q-, -C_qF_2q-1
(Q = 2 to 20, especially 3 to 12),
As an example of G,

[0054]

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The following can be mentioned.

As an example of J ⁺ ,

[0057]

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The following can be mentioned.

R 'and R "represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, A' represents an alkylene group or an arylene group, p is 0 to 6, and q 'is 2 to 6. 20
Represents

[0060] In addition, L ^- as an example of

[0061]

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The following can be mentioned.

Specific examples of the fluorine-containing cationic surfactant preferably used in the present invention are described below.

[0064]

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[0065]

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[0066]

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In the present invention, particularly the hardly soluble -SO ₂ N
It is further preferred to use a fluorine-containing cationic surfactant having at least one bond of (R ′) —. Here, the term "poorly soluble" means that 2.0 g of the surfactant was added to 100 ml of pure water at 23 ° C., stirred for 1 hour, left at 23 ° C. for 24 hours, and then precipitates and suspended matters were visually observed. Sometimes poorly soluble. For example, FK-1, FK-8, FK-15,
FK-16 and the like correspond to, but are not limited to, these and can be separated by the above test.

Among these fluorinated surfactants according to the present invention, a certain one is a trade name of Megafac F from Dainippon Ink and Chemicals, and Fluorad (trade name) from Minnesota Mining and Manufacturing Company. Fluorad) under the trade name FC, from Imperial Chemical Industries, Inc. under the trade name Monflor, under the name EI Dupont Nemelas.
It is commercially available from And Company under the trade name Zonyls or from Farbeberke Hoechst under the trade name Licovet VPF.

In the present invention, it is particularly preferable to use a combination of a fluorinated cationic surfactant and a fluorinated anionic surfactant.

The total amount of the fluorinated cationic surfactant and the fluorinated anionic surfactant used in the present invention is 1.0 to 0.0001 g / m ² , preferably 0.3 to 0.0005 g. / M ² , more preferably 0.1
5 to 0.001 g / m ² is good. When used in combination, two or more kinds of fluorine-containing cationic surfactants and two or more kinds of fluorine-containing anionic surfactants may be used in combination. In addition, a fluorine-containing nonionic surfactant, a fluorine-containing betaine surfactant, and a hydrocarbon surfactant may be used in combination. Further, the addition ratio of the fluorinated anionic surfactant to the fluorinated cationic surfactant of the present invention is preferably 1:10 to 10: 1, more preferably 3: 7 to 7: 3 in terms of molar ratio.

The second invention of the present invention relates to a method for producing a silver halide emulsion comprising at least one layer having a total gelatin of 0.01 g or more and 1 g or less per m ² between the light-sensitive silver halide emulsion layer closest to the support and the support. It contains a non-photosensitive hydrophilic colloid layer.
If the total gelatin content of the non-photosensitive hydrophilic colloid layer between the photosensitive silver halide emulsion layer closest to the support and the support is too low, it is difficult to apply the coating. Since it is not preferable, the amount is preferably 0.03 g or more and 0.8 g or less, more preferably 0.04 g or more and 0.6 g or less, per m ^{2 of} the photosensitive material.
The non-photosensitive hydrophilic colloid layer may contain latex, oil, titanium oxide, barium sulfate, calcium carbonate, colloidal silver and the like.

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, a paper support made of natural pulp or synthetic pulp, 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.

The third invention of the present invention uses a support in which the surface of the above-mentioned support is subjected to energy treatment, and as a result, a hardener reactive group is formed on the surface. These energy treatments
JP-A-9-197618, JP-A-9-258376
, European Patent No. 785,466, JP-A-10-204
No. 43, etc., include glow discharge, plasma processing, burner heating processing, and the like.

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, and more preferably 15% 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 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. for adjusting 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 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. From the viewpoint of rapid processing property and processing stability, it is preferably 97 mol% or more, more preferably 9 mol% or more.
Silver halide emulsions containing from 8 to 100 mol% of silver chloride are preferred. The total silver halide contained in the silver halide emulsion layer is preferably 0.6 g or less per m ^{2 in} terms of silver amount from the viewpoint of rapid processing, and from 0.1 g to 0.6 g from the viewpoint of color development. The following is preferred.

For obtaining 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.

For obtaining the silver halide emulsion of the present invention, it is advantageous to contain heavy metal ions. 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; and twelfth metals such as cadmium, zinc, and mercury. 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, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, or the like. Examples include nitrate ion, carbonyl, 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. When the heavy metal ion is added to the silver halide emulsion, the amount is 1 to 1 mol per mol of silver halide.
More preferably from 10 ^-9 mol to 1 x 10 ^-2 mol, particularly preferably from 1 x 10 ^-8 mol to 5 x 10 ^-5 mol.

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.) Volume 21,
39 (1973), etc.
Particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains relating to the present invention, grains having a single shape are preferably used, but it is particularly preferred 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, more preferably 0.1 to 1.2 μm 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 monodisperse 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.
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 related to 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 10 ^{-10 to} 5 × 10 ^-5 mol, more preferably 5 × 10 ^{-8 to} 3 × 10 ^-5 mol.

As the gold sensitizer related to the present invention, 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, and mercaptotriazole. 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, ripening conditions, etc., but is usually from 1 × 10 ^-4 mol to 1 × 10 ⁴ mol per mol of silver halide.
Preferably it is ^-8 mol. More preferably 1 × 10
^-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 generated during the preparation process of the silver halide photographic material, reducing performance fluctuation during storage, and preventing fog generated 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 steps such as a step of preparing silver halide emulsion grains, a step of chemical sensitization, and a step of preparing a coating solution at the end of the step of chemical sensitization. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol / 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 it is 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.

In the silver halide photographic light-sensitive material of the present invention,
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 dye include general formulas (I) and (I) described in the lower left column of page 2 of JP-A-1-280750. The compounds represented by II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not cause contamination due to residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

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 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 silver halide photographic light-sensitive material relating to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. Any compound that can be formed can be used, and particularly typical ones are a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 5
Typical are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of 00 to 600 nm, and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers which can be preferably used in the silver halide photographic light-sensitive material relating to the present invention include the general formulas (C-I) and (C) described in the lower left column of page 5 of JP-A-4-114154. C-II). Specific compounds are described in the same publication, page 5, lower right column to page 6, lower left column, CC-1 to CC-1.
What is described as CC-9 can be mentioned.

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material relating to the present invention include those represented by the general formulas (MI) and (MI) described in the upper right column on page 4 of JP-A-4-114154. M-II). Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication, MC-1.
To MC-11. Among the above magenta couplers, more preferred are those represented by the general formula (M
-I), among which couplers of the above general formula (MI) in which RM is a tertiary alkyl group have excellent light resistance and are particularly preferred. MC-8 to MC-11 described in the upper column on page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction power, and thus are preferable.

The yellow couplers which can be preferably used in the silver halide photographic light-sensitive material relating to the present invention include those represented by the general formula (Y-I) described in the upper right column on page 3 of JP-A-4-114154. Couplers to be used. Specific compounds are disclosed in the specification 3 of the same publication.
Those described as YC-1 to YC-9 in the lower left column of the page can be mentioned. Above all, a coupler in which RY1 of 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. preferable. Among these, particularly preferred examples of the compounds are described in YC-8 and YC-9 described in the lower left column on page 4 of JP-A-4-114154, and on pages 13 to 14 of JP-A-6-67388. And compounds represented by Nos. (1) to (47). Further most preferred compounds are described in JP-A-4-818.
It is a compound represented by General Formula [Y-1] described in JP-A-47-47, page 1 and JP-A-47-175, page 11-17. However, the fourth invention of the present invention uses a yellow coupler represented by the following general formula [I].

[0111]

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[Wherein, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a diffusion-resistant aliphatic or aromatic group. R ₃ represents a hydrogen atom or a halogen atom, and X represents 5 or 6 which can be eliminated upon coupling with an oxidized developing agent.
Represents a nitrogen-containing heterocyclic group. As the aliphatic group represented by R ₁ in the general formula [I], a linear, branched, or cyclic alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an adamantyl group; n-dodecyl group, 1-hexylnonyl group and the like. The alkyl group represented by R1 may further have a substituent, for example, a halogen atom (for example, chlorine atom, bromine atom, etc.), an aryl group (for example, phenyl group, pt-octylphenyl) Group), an alkoxy group (such as a methoxy group), an aryloxy group (such as a 2,4-di-t-amylphenoxy group), a sulfonyl group (such as a methanesulfonyl group), an acylamino group (such as an acetyl group,
A benzoyl group), a sulfonylamino group (eg, an n-dodecanesulfonylamino group), and a hydroxy group.

In the general formula [I], examples of the aromatic group represented by R ₁ include an aryl group having 6 to 14 carbon atoms (for example, a phenyl group, a 1-naphthyl group, and a 9-anthranyl group). . The aryl group represented by R1 may further have a substituent, for example, a nitro group, a cyano group, an amino group (eg, a dimethylamino group, anilino group, etc.), an alkylthio group (eg, a methylthio group, etc.) A group having the same meaning as the alkyl group represented by R ₁ in the general formula [I], or the general formula [I]
And the same substituents as those described for the substituent of the alkyl group represented by R ₁ .

R ₁ is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

The non-diffusible aliphatic group represented by R ₂ in the general formula [I] is preferably a group having 8 carbon atoms.
To 21 straight-chain, branched or cyclic alkyl groups such as 2,6-dimethylcyclohexyl group, 2-ethylhexyl group, isotridecyl group, hexadecyl group, and octadecyl group. The diffusion-resistant alkyl group represented by R ₂ is, for example, a compound represented by the following general formula [I
It may have a structure via a functional group in the middle as represented by I).

[0116] Formula [II] in -J-X-R ₁₂ Formula, J represents a straight-chain or branched alkylene group of up to 20 from 1 carbon atoms, e.g., methylene, 1,2-ethylene group, 1, 1-dimethylmethylene group, 1-decyl represents a methylene group, R ₁₂ is a linear or branched alkyl group, such as alkyl groups represented by R ₁ in the general formula (I) up to 20 1 carbon atoms Represents the same group as

X represents —O—, —OCO—, —OSO ₂ —,
-CO -, - COO -, - CON (R 13) -, - CON
_{(R 13) SO 2 -,} - N (R 13) -, - N (R 13) CO
_{-, - N (R 13)} SO 2 -, - N (R 13) CON
_{(R 14) -, - N} (R 13) COO -, - S (O) n -,
-S (O) _n N (R ₁₃ )-or -S (O) _n N
(R ₁₃ ) CO— (wherein, R ₁₃ and R ₁₄ represent a hydrogen atom or a group having the same meaning as the alkyl group and the aryl group represented by R ₁ in formula (I). Represents a binding group such as Also, R ₁₂ and J
May combine with each other to form a cyclic structure.

The alkyl group represented by R ₂ may further have a substituent. In this case, examples of the substituent include those of the alkyl group represented by R ₁ in the general formula [I]. Represents a group having the same meaning as the substituent.

In the general formula [I], examples of the diffusion-resistant aromatic group represented by R ₂ include groups having the same meaning as the aryl group represented by R ₁ in the general formula [I]. . The aryl group represented by R ₂ may further have a substituent. In this case, the substituent includes
For example, a group having the same meaning as the substituent of the aryl group represented by R ₁ in the general formula [I] can be mentioned. Among the substituents of the aryl group represented by R ₂ , a linear or branched alkyl group having 4 to 10 carbon atoms is preferable. In the general formula [I], R ₂ is preferably a diffusion-resistant aromatic group.

In the general formula [I], R ₃ represents a hydrogen atom or a halogen atom, and examples of the halogen atom include a chlorine atom and a bromine atom. R ₃ is preferably a chlorine atom.

In the above general formula [I], X represents a nitrogen-containing heterocyclic group which can be eliminated at the time of coupling with an oxidized developing agent, and is represented by the following general formula [III].

[0122]

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In the above general formula [III], Z ₁ represents a group of nonmetal atoms necessary for forming a 5- or 6-membered ring in cooperation with a nitrogen atom. Here, the atomic groups required to form the nonmetallic atomic group include, for example, substituted and unsubstituted methylene and methine,> C = O,> NR ₁₅ (R ₁₅ is a hydrogen atom, an alkyl group, Represents an alkyl group, an aryl group, or a heterocyclic group), -N =, -O-, and -S
(O) _m- (m represents an integer from 0 to 2) and the like.

In the present invention, the nitrogen-containing heterocyclic group X represented by the general formula [III] is represented by the following general formulas [IV], [V], [V
It is preferably a group represented by I], [VII], [VIII] or [IX].

[0125]

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The above general formulas [IV], [V], [VI], [VI
In I] or [VIII], R ₁₆ , R ₁₇ and R ₁₈
Each represents a group that can be substituted on the nitrogen-containing heterocyclic ring, and has, for example, the same meaning as the groups exemplified as the substituents of the alkyl group, cycloalkyl group, and aryl group represented by R ₁ in the general formula [I]. And the group of
In the general formula [VIII], R ₁₉ represents, for example, a group having the same meaning as the alkyl group and the aryl group represented by R ₁ in the general formula [I], and further includes a carbonyl group (eg, an acetyl group, a trifluoroacetyl group). An alkylcarbonyl group such as a pivaloyl group, a benzoyl group, a pentafluorobenzoyl group, an arylcarbonyl group such as a 3,5-di-t-butyl-4-hydroxybenzoyl group, and the like; and a sulfonyl group (for example, a methanesulfonyl group, Alkylsulfonyl group such as trifluoromethanesulfonyl group, and arylsulfonyl group such as p-toluenesulfonyl group).

In the above general formulas [VII] and [VIII], Z ₂ is> NR ₂₀ (R ₂₀ is the same as R ₁₅ in group Z ₁ in the above general formula [III]), -O- , Or-
S (O) _k- (k represents an integer from 0 to 2).

In the above general formula [IX], Z ₃ is> NR.
₂₁ (R ₂₁ represents a group having the same meaning as R ₁₅ of group Z ₁ in formula [III]) or —O—.

In the above general formula [IX], Z ₄ is> NR.
₂₂ (R ₂₂ represents a group having the same meaning as R ₁₅ of group Z ₁ in formula [III]) or> C (R ₂₃ ) (R ₂₄ ) (R ₂₃
And R ₂₄ represent a hydrogen atom or a group having the same meaning as the group mentioned as a substituent of the alkyl group and the aryl group represented by R ₁ in the above general formula [I]). In the present invention, the nitrogen-containing heterocyclic group X represented by the general formula [III] is particularly preferably a group represented by the general formula [IX].

The yellow coupler represented by the above formula [I] may be bonded at any of the substituents to form a bis, tris, tetrakis or polymer.

Next, typical specific examples of the yellow coupler represented by the general formula [I] used in the present invention will be shown, but the present invention is not limited thereto.

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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The yellow coupler of the present invention represented by the general formula [I] can be easily synthesized by a conventionally known method.

When the oil-in-water emulsion dispersion method is used for adding 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. 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 phosphate 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 preferred compound 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 No. 5-5, and general formulas XII and XII described in JP-A-62-182741.
Metal complexes represented by I, XIV and XV are particularly preferred for magenta dyes. Further, a compound represented by the general formula I 'described in JP-A-1-19649 and JP-A-5-11
The compound represented by the general formula II described in JP-A-417 is particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the color-forming dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the 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, U.S. Pat.
The fluorescent dye-releasing compound described in No. 7 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,
Compounds II-1 to II-14 described on page 4 and compound 1 described on page 17 are exemplified.

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.

In the silver halide photographic light-sensitive material of the present invention,
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.

In order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability, the colloid layer is disclosed in
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 sample after processing, a protective layer is disclosed in JP-A-6-11.
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) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 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) aniline 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 of color development according to the present invention is 35
The temperature is preferably from 70 ° 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, the higher the temperature, the more preferable.

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, known developing component compounds can be added in addition to the above color developing agents. 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 according to 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, a water washing process is usually 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, and the photosensitive material may be transferred to a belt. An endless belt system that transports fixedly may be used, but 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 method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. In the form of adding a treating agent.
Are most preferred.

In the fifth invention of the present invention, the processing is carried out using an apparatus in which the thickness of the color developing bath is 100 times or less the thickness of the silver halide photographic material. This is because low replenishment of the processing solution is desired for environmental suitability, but from the viewpoint of transportability, it is preferably 10 times or more and 100 times or less.

In the sixth invention of the present invention, a silver halide photographic material is processed by applying a processing solution.

[0158]

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 Polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. 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 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 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.

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

Further, as a hardening agent, (HA) or (HB)
Was added. Surfactants (SU-
2) was added to adjust the surface tension.

[0163]

[Table 1]

[0164]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i -Decyl phthalate PVP: polyvinylpyrrolidone HA: tetrakis (vinylsulfonylmethyl) methane HB: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octyl Hydroquinone HQ-2: 2,5-di-sec-dodecyl hydroquinone HQ-3: 2,5-di-sec-tetradecyl hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl hydroquinone HQ-5 : 2,5-di [(1,1-dimethyi) 4-hexyloxycarbonyl) butyl] hydroquinone Image stabilizer A: Pt-octylphenol

[0166]

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[0167]

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[0168]

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[0169]

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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 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) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g 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, EMP was performed except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
In the same manner as in -1, a monodispersed 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.

The above 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 amount 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 mol was added.

[0179]

Embedded image

[0180]

Embedded image

The sample thus obtained was designated as 101, and the coating pH was measured by the following method and found to be 5.5.

Dilute hydrochloric acid was added to the seventh layer of Sample 101 to prepare Sample 102 in which the coating pH was adjusted to 5.2.

Further, Sample 103 was prepared in the same manner as in Sample 101 except that the hardeners shown in Table 3 were used, and the pH of the coating film of this sample was measured to be 5.6.

Further, a diluted hydrochloric acid solution was added to the seventh layer of the sample 103 to prepare a sample 104 whose pH was adjusted to 5.2, and a 10% aqueous solution of sodium carbonate was similarly added to the seventh layer of the sample 103. A sample 105 adjusted to have a coating pH of 7.1 was produced.

The total gelatin of Samples 101 to 105 was 1
Samples 106 to 110 in which the amount of gelatin applied to each layer was uniformly reduced to 6.5 g per m ² were prepared. Furthermore, the activator of the present invention was added to the seventh layer, and the hardening agent, the coating pH, the total gelatin per m ^{2 and} the total silver halide contained in the silver halide emulsion layer per m ² were determined by the silver content. Sample 10 was obtained except that the conversion was changed as shown in Table 3.
Samples 111 to 120 similar to 8 were produced.

The coating pH and total gelatin per 1 m ² were reduced by the above-mentioned method. The amount of the activator was as shown in Table 3. The hardener was changed so as to be equimolar to the hardening material of Sample 101, and the amount of silver was reduced such that the amount of silver applied to each layer was reduced uniformly to achieve the amount. .

(Measurement method of coating pH) 10 μl of pure water was measured with a micropipette, and a total volume of 10 μl was dropped on a raw sample. The pH was measured with a precision trace pH electrode manufactured by Toa Denpa Kogyo Co., Ltd. The pH was measured according to a conventional method.

After the thus prepared sample was exposed to light wedge by a conventional method, development processing was performed in the following development processing step A.

[Development Processing Step A] Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc drying 60-80 ° C. 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 Sodium pentaacetate 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 the total volume 1 liter. = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Tank solution and replenisher for bleach-fixing solution Diethylenetriaminepentaacetic acid ammonium ferric 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.

These treated samples were evaluated as follows.

(Fast processing suitability)
The sample is processed in the processing step B in which the time of the color development, bleach-fixing, and stabilization steps in the development processing step A is halved, and the obtained sample is reflected by a Konica Corporation PDA-65 densitometer with blue light. The density was measured, and each gradation (using the gradient (γ) of a straight line connecting the two points of the density 0.80 and 1.80 of the characteristic curve) was obtained. The suitability for rapid processing was determined by the following formula.

Rapid processing suitability = γB (gradation in development processing step B) / γA (gradation in development processing step A) The closer this value is to 1, the better the rapid processing suitability.

(Preservation property of raw sample) A wedge size sample was stored for one month in a refrigerator under the conditions of 40 ° C and 40% RH, and the sample was kept in an environment of 20 ° C and 50% RH. It was exposed to light and processed under the conditions of the development processing step A. S based on the sensitivity of the red photosensitive layer obtained from the refrigerator storage product
A, the sensitivity of the stored product was set to SB under the conditions of 40 ° C. and 40% RH, and the sensitivity variation was determined by the following equation.

Sensitivity variation = SB / SA The closer this value is to 1, the smaller the sensitivity variation and the better the preservability of the raw sample.

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

1 ... the sample is not stuck 2 ... between 1 and 3 3 ... there is enough resistance to make a sound when peeled off 4 ... between 3 and 5 5. ..Samples are stuck together and cannot be peeled off (Evaluation of sharpness deterioration over time) After the resolution test chart is printed on each sample with red light and the above-mentioned development processing step A is performed, it is obtained. The density of the obtained cyan image was measured with a microdensitometer PDM-5D (manufactured by Konica Corporation), and the value represented by the following equation was taken as the immediate sharpness. Immediate sharpness (%) = (Dmax-Dmin of dense line print image of 3 lines / mm) / (Dmax-Dm in large area part)
in) Here, Dmax: maximum density, Dmin: minimum density.

Next, the above sample for immediate sharpness evaluation was
After storing under high temperature and high humidity of 60 ° C. and a relative humidity of 60% for 14 days, sharpness was evaluated in the same manner as described above.

The degree of sharpness deterioration during storage over time was determined by the following equation.

Degree of sharpness deterioration = (Sharpness (%) on 14 days under high temperature and high humidity) / (immediate sharpness (%)) The closer this value is to 1, the smaller the sharpness deterioration with time.

Table 3 shows the results.

[0205]

[Table 3]

As is clear 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 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 ８０80 ° 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) hydroxyamine 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, Is pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fixing solution tank solution and replenisher solution Tank solution replenisher solution diethylenetriaminepentaacetate 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 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 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, Konica Corporation's N was used as an automatic developing machine.
PS-868J, ECOJET-P as processing chemical
And a running process was performed according to the process name CPK-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.

The first to third embodiments are embodiments relating to the first aspect of the present invention.

Example 4 A zeroth layer was provided under the first layer of each of the samples 101 to 110 used in Example 1, and gelatin was added in the amount shown in Table 4 so that the total gelatin became the amount shown in Table 4. Then, similar samples 201 to 210 were prepared except that the weight was uniformly reduced from each layer and the coating pH was changed to the value shown in Table 4. Also, except that the hardener, the coating pH, the total gelatin per m ^{2 and} the total silver halide contained in the silver halide emulsion layer per m ^{2 of} Sample 208 were changed as shown in Table 4 in terms of silver amount, , Sample 20
Samples 211 to 216 similar to No. 8 were produced. In addition, the coating p
The method for reducing the amount of H and the total gelatin per m ² was the same as in Example 1. The hardener was changed so as to be equimolar to the hardening material of Sample 101, and the amount of silver was reduced such that the amount of silver applied to each layer was reduced uniformly to achieve the amount. .

The sample thus obtained was treated in the same manner as in Example 1, and the suitability for rapid processing, the preservability of the raw sample, and the evaluation of sticking resistance were evaluated in the same manner as in Example 1. As a result, the present invention was It was excellent. Evaluation of sharpness deterioration over time was performed in the same manner as in Example 1.

Table 4 shows the results.

[0219]

[Table 4]

As is clear from the above results, the present invention is excellent for comparison.

Example 5 In Example 4, the same processing as in Example 2 was performed, and evaluation was performed in the same manner as in Example 4, and it was confirmed that the effects of the present invention could be obtained.

Example 6 In Example 4, the same processing as in Example 3 was performed, and evaluation was performed in the same manner as in Example 4, and it was confirmed that the effects of the present invention could be obtained.

Examples 4 to 6 are examples relating to the second aspect of the present invention.

Example 7 The supports of Samples 106 and 108 used in Example 1 were subjected to energy treatment on the surface of a white polyester support by the method described in JP-A No. 10-20443 to form an amino group. , And the same samples 301 and 302 were prepared except that the coating pH was adjusted to be the same. The sample thus obtained was subjected to the same treatment as in Example 1, and the suitability for rapid processing, the storage stability of the raw sample, and the evaluation of sticking resistance were evaluated in Example 1.
As a result, the present invention was excellent in comparison.
The wet scratch resistance was evaluated by the following method.

(Evaluation of scratch resistance when wet) Exposure with white light
Cut the treated black sample to wedge size and cut for 3 minutes
It was immersed in water at 5 ° C., and then measured by the following method. A sample was set on a continuous load type scratch strength tester (Haydon) type 18 (manufactured by Shinto Kagaku Co., Ltd.) according to the prescribed method, and when a continuous load of 0 to 50 g was applied to the sample surface, the sample surface was damaged. The load (g) applied when it began to be generated was measured by a prescribed method, and the wet-scratch resistance test was evaluated based on the measured load (g). The larger the value, the better the scratch resistance. The needle used was a 0.2 mm sapphire needle.

The results are shown below.

Sample Scratch resistance when wet Scratched load (g) 106 (comparison) 20 g 108 (comparison) 23 g 301 (comparison) 25 g 302 (present invention) 34 g As is apparent from the above results, the present invention Is excellent for comparison.

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

Example 9 In Example 7, the same processing as in Example 3 was performed and evaluated in the same manner as in Example 7, and it was confirmed that the effects of the present invention could be obtained.

Examples 7 to 9 are examples relating to the third aspect of the present invention.

Example 10 The yellow couplers of Samples 101 to 110 used in Example 1 were changed to those shown in Table 5 in equimolar amounts, and the coating p
Samples 401 to similar except that H was changed to the values shown in Table 5
410 was produced. The hardener and coating pH of sample 408
Samples 411 to 415 similar to Sample 408, except that the total gelatin per m ^{2 and} the total silver halide contained in the silver halide emulsion layer per m ² were changed as shown in Table 5 in terms of silver amount. Was prepared. The coating pH and total gelatin per 1 m ² were reduced in the same manner as in Example 1. The hardener was changed so as to be equimolar to the hardening material of Sample 101, and the amount of silver was reduced such that the amount of silver applied to each layer was reduced uniformly to achieve the amount. . The sample thus obtained was treated in the same manner as in Example 1, and the suitability for rapid processing, the preservability of the raw sample, and the evaluation of sticking resistance were evaluated in the same manner as in Example 1. As a result, the present invention was excellent in comparison. Was.
Further, the coloring property of the yellow coloring dye of the yellow coupler was evaluated by the following method.

(Evaluation of Chromogenic Property) The sample was exposed according to a conventional method and subjected to color developing processing. The obtained sample was used for PDA-6.
Using a 5 densitometer (manufactured by Konica Corporation), the maximum color density (Dmax) of the blue-sensitive emulsion layer was measured. The higher the value of Dmax, the better the color developability.

The results are shown in Table 5.

[0234]

[Table 5]

As is clear from the above results, the present invention is excellent for comparison.

Example 11 In Example 10, the same processing as in Example 2 was performed, and the evaluation was performed in the same manner as in Example 10, and it was confirmed that the effects of the present invention could be obtained.

Example 12 In Example 10, the same processing as in Example 3 was performed, and the evaluation was performed in the same manner as in Example 10, and it was confirmed that the effects of the present invention could be obtained.

The tenth to twelfth embodiments relate to the fourth aspect of the present invention.

Example 13 The samples shown in Table 6 were processed under the following processing conditions, and the suitability for rapid processing, the preservability of raw samples, and the evaluation of sticking resistance were evaluated in the same manner as in Example 1. As a result, the present invention And was excellent. In the same manner as in Example 10, the yellow coupler was evaluated for its coloring property.

The thickness of the section of the processing space of the processing apparatus is about 2.
The following processing steps were performed using a processing system designed so that the processing solution volume in the processing space was about 60% of the total volume of the processing solution used in this system.

Processing step Processing temperature Time Replenishment amount Color development 42.0 ± 0.3 ° C. 18 seconds 65 ml Bleaching and fixing 38.0 ± 0.5 ° C. 19 seconds 60 ml Stabilization 30-34 ° C. 16 seconds 120 ml Drying 60-80 ° C. The composition of the developing solution for 27 seconds is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml diethylene glycol 15 g 15 g potassium bromide 0.02 g 0.008 g potassium chloride 3 g 0.3 g potassium sulfite 5.0 × 10 ⁴ mol 7.0 × 10 ⁴ mol N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g 15.0 g N, N-bis (2-sulfoethyl) hydroxyamine 6.0 g 6 0.0 g sodium diethylenetriaminepentaacetate 5.0 g 7.5 g sodium p-toluenesulfonate 15.0 g 15.0 g potassium carbonate 33 g 30 g Water was added to make a total volume of 1 liter, and the tank solution was pH = 1.
At 0.10, the replenisher is adjusted to pH = 10.40.

Bleach-fixing solution tank solution and replenisher tank solution Replenisher Ferric ammonium ethylenediaminedisuccinate 0.20 mol 0.32 mol Ethylenediaminedisuccinate 0.02 mol 0.032 mol Ammonium thiosulfate 0.65 mol 1.04 mol ammonium sulfite 0.12 mol 0.192 mol Water was added to make the total volume 1 liter. The tank solution was adjusted to pH = 6.0 with potassium carbonate or glacial acetic acid, and the replenisher was adjusted to pH = 5.
Adjust to 0.

Stabilizing solution tank solution and replenisher o-phenylphenol 0.1 g Optical brightener (Tinopearl SFP) 1.0 g ZnSO4.7H2O 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g Ammonium sulfite (40% aqueous solution) 5.0 ml Water was added to make the total volume 1 liter, and the pH was adjusted to 7.8 with sulfuric acid or aqueous ammonia.

The results are shown in Table 6.

[0246]

[Table 6]

As is clear from the above results, the present invention is excellent for comparison.

The thirteenth embodiment is an embodiment according to the fifth aspect of the present invention.

Example 14 The sample of Example 13 was treated under the following processing conditions and evaluated in the same manner as in Example 13. It was confirmed that the present invention was excellent in comparison.

The fourteenth embodiment is an embodiment according to the sixth aspect of the present invention.

As a processing apparatus, a coating and developing system is used. The first constituent liquid (a) is supplied to the emulsion surface of the photosensitive material heated by the heating means of the processing apparatus, and then the second constituent liquid (a) is supplied. In the same manner as in b), a color development step was carried out by supplying the emulsion to the emulsion surface of the light-sensitive material. The second constituent liquid is supplied 0.5 seconds after the supply of the first constituent liquid.

The processing steps including the color developing step are described below.

Processing Step Processing Temperature Time Replenishment Color Development 80 ° C. 7 seconds 40 ml Bleaching and Fixing 38.0 ± 0.5 ° C. 7 seconds 60 ml Stabilization 30-34 ° C. 16 seconds 120 ml Drying 60-80 ° C. 15 seconds The composition is shown below.

Color developer: First constituent solution (a) 500 ml of pure water 1.0 g of sodium sulfite 1.0 g of pentasodium diethylenetriaminepentaacetate 3.0 g 20.0 g of p-toluenesulfonic acid N-ethyl-N- (β-methanesulfone Amidoethyl) -3-methyl-4-aminoaniline sulfate 43.0 g Water is added to make 1 l, and the pH is adjusted to 2.0 using potassium hydroxide or 50% sulfuric acid.

Color developer: Second component solution (b) Pure water 500 ml Potassium chloride 10.0 g Diethylenetriaminepentasodium pentasodium 3.0 g Potassium carbonate 82.0 g p-toluenesulfonic acid 15.0 g Water was added to make 1 liter. PH is adjusted to 13.5 with potassium hydroxide or 50% sulfuric acid.

Bleach-fixing / stabilizing treatment step Same as in Example 13.

Example 15 As a printer processor, QDP1 manufactured by Konica Corporation was used.
500A, Konica ECOJET-H as processing chemical
Examples 1, 2, 4, 7, and 7, except that QA-B was used and running processing was performed in accordance with the process name CPK-HQA-1.
Tested as for 10.

As a result, the effect of the present invention was obtained.

As is evident from the above, according to the constitutional requirements of the present invention, excellent suitability for rapid processing, excellent preservation of raw samples, excellent resistance to sticking between print samples, and decrease in sharpness of print samples over time. Thus, a silver halide photographic light-sensitive material excellent in wet scratch resistance, excellent in wet scratch resistance, and excellent in coloring property of a yellow coloring dye of a yellow coupler, and a processing method thereof can be provided.

[0260]

EFFECTS OF THE INVENTION According to the first and second aspects of the present invention, rapid processing suitability is excellent, raw sample storage stability is excellent, print sample sticking resistance is excellent, and sharpness of print sample during storage with time is reduced. Thus, a silver halide photographic light-sensitive material excellent in the above was provided. According to a third aspect of the present invention, there is provided a silver halide photographic material having excellent suitability for rapid processing, excellent storage stability of raw samples, excellent sticking resistance between print samples and samples, and excellent scratch resistance when wet. I was able to. According to a fourth aspect of the present invention, there is provided a silver halide photographic light-sensitive material which is excellent in rapid processing suitability, excellent in preservability of raw samples, excellent in sticking resistance between a printed sample and a sample, and excellent in coloring property of a yellow coloring dye. We were able to. Fifth and sixth aspects of the present invention
The present invention provides a method for processing a silver halide photographic light-sensitive material which is excellent in rapid processing suitability, excellent in preservability of a raw sample, excellent in sticking resistance between a print sample and a sample, and excellent in coloring property of a yellow coloring dye. Was completed.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03C 1/76 501 G03C 1/76 501 1/91 1/91 7/36 7/36 7/407 7/407

Claims (12)

[Claims] At least one layer of 9 on one side of a support
In a silver halide photographic material having a photosensitive silver halide emulsion layer containing 5 mol% or more of silver chloride and at least one non-photosensitive layer, the silver halide emulsion layer and the non-photosensitive layer The total amount of gelatin is 6.5 g or less per m ² , and is hardened by at least one hardening agent represented by the following general formula [HI], and the coating pH is 5.3 or more and 7 or less. And a betaine-based surfactant is contained in the uppermost layer of the non-photosensitive layer. Embedded image [Wherein R ₃₁ , R ₃₄ and R ₃₇ represent an alkylene group or an arylene group. R ₃₂ , R ₃₃ , R ₃₅ , R ₃₆ , R ₃₈ and R ₃₉ represent a hydrogen atom, an alkyl group, a hydroxyl group or a vinylsulfonyl group. J ₁ and J ₂ are -O-, -S-,-(C = O)-,-
Represents CH (OH)-, -NHCO-, -CONH-.
k, l, and m represent 0 or 1. However, m is never 0 when at least one of k and l is 1. ] 2. On one of the supports, at least one layer of 9
In a silver halide photographic material having a photosensitive silver halide emulsion layer containing 5 mol% or more of silver chloride and at least one non-light-sensitive layer, the silver halide emulsion layer and the non-light-sensitive layer contain the same. The total amount of gelatin is 6.5 g or less per m ² , and is hardened by at least one hardener represented by the above general formula [HI], and the coating pH is 5.3 or more and 7 or less. And between the photosensitive silver halide emulsion layer closest to the support and the support, at least one non-photosensitive hydrophilic colloid layer having a total gelatin of 0.01 g to 1 g per m ^2. A silver halide photographic light-sensitive material comprising: 3. On one of the supports, at least one layer of 9
In a silver halide photographic material having a photosensitive silver halide emulsion layer containing 5 mol% or more of silver chloride and at least one non-light-sensitive layer, the silver halide emulsion layer and the non-light-sensitive layer contain the same. The total amount of gelatin to be used is 6.5 g or less per 1 m ² , and the surface of the support is subjected to energy treatment, so that a hardener-reactive group is formed on the surface, and the general formula [ HI], and hardened with at least one hardening agent represented by the formula:
Is 5.3 or more and 7 or less. 4. On one side of the support, at least one layer of 9
In a silver halide photographic material having a photosensitive silver halide emulsion layer containing 5 mol% or more of silver chloride and at least one non-light-sensitive layer, the silver halide emulsion layer and the non-light-sensitive layer contain the same. The total amount of gelatin is 6.5 g or less per m ² , and is hardened by at least one hardener represented by the above general formula [HI], and the coating pH is 5.3 or more and 7 or less. Wherein the light-sensitive silver halide emulsion layer contains at least one yellow coupler represented by the following general formula [I]. Embedded image [Wherein, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a diffusion-resistant aliphatic group or an aromatic group. R ₃ represents a hydrogen atom or a halogen atom, and X represents a 5- or 6-membered nitrogen-containing heterocyclic group which can be eliminated upon coupling with an oxidized developing agent. ] 5. On one of the supports, at least one layer of 9
In a silver halide photographic material having a photosensitive silver halide emulsion layer containing 5 mol% or more of silver chloride and at least one non-light-sensitive layer, the silver halide emulsion layer and the non-light-sensitive layer contain the same. The total amount of gelatin is 6.5 g or less per m ² , and is hardened by at least one hardener represented by the above general formula [HI], and the coating pH is 5.3 or more and 7 or less. The silver halide photographic light-sensitive material is processed using an apparatus in which the thickness of a color developing bath when the color development processing is performed is 100 times or less the thickness of the silver halide photographic light-sensitive material. For processing silver halide photographic light-sensitive materials. 6. On one side of the support, at least one layer of 9
In a silver halide photographic material having a photosensitive silver halide emulsion layer containing 5 mol% or more of silver chloride and at least one non-light-sensitive layer, the silver halide emulsion layer and the non-light-sensitive layer contain the same. The total amount of gelatin is 6.5 g or less per m ² , and is hardened by at least one hardener represented by the above general formula [HI], and the coating pH is 5.3 or more and 7 or less. A method for processing a silver halide photographic light-sensitive material, comprising applying a processing solution to the silver halide photographic light-sensitive material and processing the same. 7. The silver halide photographic material according to claim 1, wherein at least one fluorine-containing surfactant is used. 8. A non-photosensitive hydrophilic layer comprising at least one layer having a total gelatin content of 0.03 to 0.8 g / m ² between the light-sensitive silver halide emulsion layer closest to the support and the support. 3. The silver halide photographic light-sensitive material according to claim 2, further comprising a hydrophilic colloid layer. 9. The method according to claim 1, wherein the total silver halide contained in the silver halide emulsion layer is 0.6 g or less per m ^{2 in} terms of silver amount. 1
The silver halide photographic light-sensitive material according to the above item. 10. The silver halide photographic material according to claim 9, wherein said coating has a pH of 5.8 or more and 6.5 or less. 11. The silver halide photographic light-sensitive material according to claim 1, wherein the color developing bath has a thickness of 10 times the thickness of said silver halide photographic light-sensitive material when the silver halide photographic light-sensitive material is subjected to color development processing.
A method for processing a silver halide photographic material, wherein the processing is performed using an apparatus having a magnification of 0 or less. 12. A method for processing a silver halide photographic light-sensitive material, which comprises applying a processing solution to the silver halide photographic light-sensitive material according to claim 1 and processing.