JPH07191431A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material with which a color image with good reproducibility of colors and light fastness is obtd. without problems of static fogging by incorporating a specified compd. into a photosensitive silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer formed on a base material. CONSTITUTION:At least one of photosensitive silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer formed on a base material contains at least one kind of compd. expressed by formula. In formula, R0 is a hydrogen atom, alkyl group or aryl group, R1-R5 may be same or different and are hydrogen atoms, alkyl groups, aryl groups, hetero rings, alkenyl groups, OR6, halogen atoms, nitro groups, cyano groups, NR6R7, NR6R7, etc., and R6, R7 may be same or different and are hydrogen atoms, alkyl groups, aryl groups, heterocyclic groups, or alkenyl groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material which is excellent in color reproduction and static prevention and gives a light-fast dye image.

[0002]

2. Description of the Related Art Silver halide emulsions have a visible range (400 to 7
(00 nm) as well as sensitivity in the ultraviolet region (400 nm or less). With silver halide photographic light-sensitive materials for photography, ultraviolet rays (UV) are used for light rays in the ultraviolet range that the human eye cannot perceive.
Only light in the visible range reaches the silver halide emulsion layer by blocking with the filter layer. That is, in many light-sensitive materials for natural light photography, especially color light-sensitive materials, a so-called protective layer has a function of a UV filter layer. With this UV filter layer,
This prevents a color photograph that is more bluish than it actually is when you shoot a landscape with a lot of ultraviolet rays. In order to faithfully reproduce this color, a long wavelength (320 to 400 nm) UV absorber is important. U in color printing
A V filter layer is also used as a protective layer to prevent photobleaching of the dye image. Again, relatively long wave UV absorbers are important.

Since the silver halide color photographic light-sensitive material is photosensitive, it is felt to emit a slight amount of static electricity sparks during the manufacturing process, and after development, an undesired blackening or color-developing portion (star) is called fog. Tick mark). Static electricity is converted into light energy when a discharge occurs from the photosensitive material charged with static electricity or around the photosensitive material. This light is mainly ultraviolet light and blue light, especially short wavelength (less than 320 nm) and long wavelength (320 to 400 n).
m) Since it is rich in ultraviolet rays, it overlaps with the photosensitive area peculiar to silver halide. One of the methods for preventing static marks due to such discharge is an effective method for cutting light emission due to electrostatic discharge by incorporating a short-wavelength and long-wavelength ultraviolet absorber in the photosensitive material. . Conventionally, benzotriazole compounds have been used as short-wavelength UV absorbers, and aminostilbene compounds have been used as long-wavelength UV absorbers. However, since this aminostilbene compound is difficult to synthesize and expensive, development of an alternative material has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material which gives a dye image having good color reproduction and good color reproduction without static fog failure.

[0005]

The above objects of the present invention have been achieved by the structures described in (1) to (4) below. (1) At least one photosensitive silver halide emulsion layer or non-photosensitive hydrophilic colloid layer provided on a support contains at least one compound represented by the following general formula (I). A characteristic silver halide photographic light-sensitive material.

[0006]

[Chemical 2]

In the formula, R ₀ represents a hydrogen atom, an alkyl group or an aryl group, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and a hydrogen atom, an alkyl group, Aryl group, heterocyclic group, alkenyl group, OR ₆ ,
Halogen atom, nitro group, cyano group, NR ₆ R ₇ , CO
NR ₆ R ₇ , SO ₂ NR ₆ R ₇ , COR ₈ , SO
₂ R ₈ , NR ₇ COR ₈ , NR ₇ SO ₂ R ₈ , COOR
₆ , SO ₃ R ₆ , OCOR ₈ and OSO ₂ R ₈ ,
R ₆ and R ₇ may be the same or different and each is a hydrogen atom,
Represents an alkyl group, an aryl group, a heterocyclic group or an alkenyl group, and R ₈ represents an alkyl group, an aryl group, a heterocyclic group,
It represents an alkenyl group and may be linked with R ₆ and R ₇ to form a 5- or 6-membered ring. (2) The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the compounds represented by formula (I) is contained in at least one of the non-photosensitive hydrophilic colloid layers. (3) The silver halide photographic light-sensitive material according to claim 2, wherein the non-photosensitive hydrophilic colloid layer is a protective layer provided as an outermost layer or a layer adjacent thereto. (4) The silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein the light-sensitive silver halide emulsion layer contains a color-forming coupler.

The present invention will be described in detail below. In the present invention, a silver halide light-sensitive material which achieves the above objects can be obtained by containing the compound represented by the formula (I). It is surprising that the compounds of formula (I) are useful as UV absorbers, especially as long wavelength UV absorbers.

The ultraviolet absorber represented by the formula (I) of the present invention will be described. In formula (I), the alkyl group represented by R ₀ to R ₈ has a linear, branched or cyclic carbon number of 1 to
20 alkyl groups (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-octyl, isooctyl, dodecyl, hexadecyl, octadecyl, isooctadecyl, cyclopentyl, cyclohexyl) are preferred. , May have a substituent.

The aryl group represented by R ₀ to R ₈ is
An aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl) is preferable, and may have a substituent. The heterocyclic group represented by R ₁ to R ₈ is a 5- or 6-membered heterocyclic group (for example, 2-pyridyl, 4-pyridyl, 1-benzotriazolyl, 2-benzoxazolyl, 1-methyl- 2-morpholyl, morpholino, piperidino, pyrrolidino, furyl, and cenyl) may have a substituent.

The alkenyl group represented by R ₁ to R ₈ is an alkenyl group having 2 to 10 carbon atoms (for example, vinyl,
Allyl, 1-propenyl, 2-pentenyl, 1,3-butadienyl) are preferred. Examples of the above-mentioned substituent include a halogen atom (for example, fluorine, chlorine, bromine), a nitro group, a cyano group, a hydroxyl group, a carboxylic acid group, and a carbon number of 0.
40 amino groups (eg, dimethylamino, dioctylamino, didodecylamino), alkyl groups having 1 to 20 carbon atoms (eg, methyl, butyl, decyl, octadecyl), aryl groups having 6 to 10 carbon atoms (eg, phenyl) , Naphthyl), an alkoxy group having 1 to 20 carbon atoms (eg, methoxy, ethoxy, butoxy, hexyloxy,
Tetradecyloxy, hexadecyloxy), carbon number 6
-10 aryloxy group (for example, phenoxy, naphthoxy), C2-C20 alkoxycarbonyl or aryloxycarbonyl group (for example, methoxycarbonyl, propyloxycarbonyl, octyloxycarbonyl, phenoxycarbonyl), C2-C20 An acylamino group (eg, acetylamino, benzamide), an acyloxy group having 2 to 20 carbon atoms (eg, acetyloxy, benzoyloxy, lauroyloxy),
Examples thereof include an acyl group having 2 to 20 carbon atoms (eg, acetyl, benzoyl, lauroyl) and the like.

Examples of the halogen atom represented by R ₁ to R ₅ include fluorine, chlorine and bromine.
Examples of the 5- or 6-membered ring formed by connecting R ₆ and R ₇ include a pyrrolidine ring, a piperidine ring, a morpholine ring, an N-methylpiperazine ring and an imidazolidine ring. Preferred in the general formula (I) are those in which R ₀ , R ₁ and R ₃ represent a hydrogen atom, R ₂ and R ₅ each independently represent a hydroxyl group or an alkoxy group, and R ₄ represents an aryl group. .

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

The compound represented by the general formula (I) is represented by A, W
eissberger, EC Taylor, The Chemistry of Heterocy
clic Compounds, vol. 31 Chromenes, Chromanones and
Chromones, 495-555pp (1977), John Wiley & Sons,
Inc., RC Elderfield, Heterocyclic Compounds, vo
l. 2 p229-276, John Wiley & Sons, Inc, (1951),
A. Ahuja, Indian. J. Chem., 13, 26 (1974) and the like, or can be synthesized according to the method. For example, compounds I-1 and I-5 are commercially available from Tokyo Chemical Industry Co., Ltd., and compound I-10 is
It is described in German Patent (DT) 1772146. The exemplary compound I-1 of the present invention can also be obtained by removing a saccharide from a natural compound to which a saccharide is added.
In addition, when the exemplified compound I-1 of the present invention is alkylated according to a conventional method, other compounds of the present invention (for example, I-2,
I-3, I-4 and I-9) can be easily synthesized.

The ultraviolet absorber used in the present invention has an absorption maximum wavelength of 350 nm to 390 nm, preferably 365 to 3
Those at 80 nm are preferred. Furthermore, it is preferable that the long-wave end of the absorption spectrum extends to 390 to 410 nm. Further, the UV absorber of the present invention is effective for long-wave UV, but its absorption at 300 to 350 nm is not strong. Therefore, it is particularly preferable to use a short wave UV agent that absorbs UV of 320 nm or less. Specifically, it is preferable to contain one or more UV absorbers represented by the following general formula (II).

The ultraviolet absorber represented by the formula (I) of the present invention is contained in at least one of the photosensitive silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer. Further, in the present invention, the non-photosensitive hydrophilic colloid layer is preferably a protective layer provided as an outermost layer or a layer adjacent thereto. Further, this photosensitive silver halide emulsion layer is preferably a layer containing a color forming coupler. Another preferred embodiment is to co-emulsify the cyan coupler and the ultraviolet absorber represented by the formula (I) to be contained in the photosensitive silver halide emulsion layer. The coating amount of the ultraviolet absorber represented by the formula (I) of the present invention is 1 to 0.01 g / m ² , preferably 0.3 to 0.03 g / m ² . The compound represented by the formula (I) of the present invention is preferably used in combination with another ultraviolet absorber, in which case the ratio of the ultraviolet absorber of the present invention to the other ultraviolet absorber used is 10%. : 1
~ 1:10. Considering the band spectrum of N ₂ discharge, the short wavelength UV agent has an absorbance at 300 nm of 1 to 4, preferably 2 to 3, and the long wavelength UV agent has an absorbance of 350 to
It is preferred that the coating be performed so that the absorbance is 1 to 4, and preferably 2 to 3 at the maximum absorption wavelength between 400 nm.

The protective layer comprising the non-photosensitive hydrophilic colloid layer of the present invention may be a single layer or a plurality of layers of two or more layers, but a multilayer structure is more preferable from the viewpoint of adhesion resistance. In any case, it is preferable to contain the matting agent particles having the composition represented by the general formula (1) described in Japanese Patent Application No. 4-306240, which is coated farthest from the support in the entire coating layer. .

The film thickness of the outermost protective layer of the present invention is from 0.2 to
The thickness is 3.0 μm, preferably 0.5 to 2.0 μm. The film thickness referred to here is the thickness of the portion where the matting agent particles do not exist, and is a value calculated from a cross-sectional electron micrograph of the photosensitive material.

The ultraviolet absorber of the present invention can be used in combination with other ultraviolet absorbers. Specifically, Japanese Patent Publication 48-
No. 30492 and No. 56-211141, cinnamic acid type ultraviolet absorbers, Japanese Patent Publication Nos. 48-5496 and 50-
No. 25337, No. 55-36984, No. 49-261.
39, 51-6540, 47-1026, 61-190537, 1-306839.
No. 1-306840, No. 1-306841, No. 1-306842, No. 1-306843, and benzotriazole-based ultraviolet absorbers described in European Patent No. 57-160, Japanese Examined Patent Publication No. 50-33773, 56-
30538, U.S. Pat. Nos. 3,698,907 and 3,215.
No. 530, a benzophenone-based ultraviolet absorber,
JP-A-58-185677 and 58-111942
No. 58-178351, No. 61-169831.
No. 62-24247, No. 63-55542, No. 63-53544, No. 63-53543, and the like polymeric UV absorbers.

Particularly preferably used in combination are, for example, Japanese Patent Publication Nos. 55-36984 and 55-12587.
No. 58-214152 and 58-22184.
4, 59-46646, European Patent No. 57160A.
2- (2'-hydroxyphenyl) benzotriazoles described in JP-A No. 1 and 323408A1, for example, benzophenones described in JP-B-48-30492, JP-A-47-10537, and JP-A-58-111942, For example, JP-A-51-56620 and JP-A-53-128333.
Nos. 58-181040 and 53-97425, for example, European Patent No. 53125.
2-hydroxyphenyl triazines described in 8A1 and 530135A1 can be mentioned.

Next, preferable benzotriazole-based UV absorbers which can be used in combination with the UV absorber represented by the general formula (I) of the present invention will be exemplified.

[0027]

[Chemical 8]

In the formula, R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ may be the same or different and are a permissible substituent for a hydrogen atom or an aromatic group, and R ₃₁ and R ₃₂ May be closed to form a 5- or 6-membered aromatic ring composed of carbon atoms. Among these groups, those which may have a substituent may be further substituted with a permissible substituent.

The compounds represented by the general formula (II) can be used alone or in combination of two or more kinds. Below (I
Representative compounds are described in I) -1 to (II) -15.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

The ultraviolet absorbent of the present invention and used in combination therewith, when used in a protective layer, in the case where the protective layer is one layer, in the case where it is composed of two or more layers, any of the protective layers is used. However, it is more preferable to use it in the protective layer except the outermost layer.

The ultraviolet absorber used here can be incorporated in the light-sensitive material by a conventionally known method (oil-in-water dispersion method). For example, an ultraviolet absorber is dissolved in a mixture of a high boiling organic solvent such as tricresyl phosphate and a low boiling organic solvent such as ethyl acetate at a temperature of 55 to 65 ° C,
Then, it can be easily achieved by adding to a gelatin aqueous solution containing a surfactant typified by sodium dodecylbenzene sulfonate, followed by high-speed stirring to obtain an emulsion dispersion, and adding the obtained emulsion dispersion to a coating solution and coating. The ultraviolet absorbent which is in a liquid state at room temperature can be emulsified and dispersed without using a high-boiling organic solvent, and is preferably used in the present invention.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or Esters of phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate) Over DOO, di-2-ethylhexyl phenyl phosphonate), benzoic acid esters (e.g., 2
-Ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (For example, isostearyl alcohol, 2,4-di-t
ert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N, N) -Dibutyl-2
-Butoxy-5-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2 -Ethoxyethyl acetate, dimethylformamide.

In the light-sensitive material of the present invention, at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer containing a color-forming coupler on a support and a non-outermost layer. A protective layer comprising a photosensitive hydrophilic colloid layer is preferably provided, and the number of layers of the silver halide emulsion layer and the non-photosensitive layer and the layer order excluding the outermost protective layer are not particularly limited. As a typical example, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities and one protective layer are provided on a support. A silver halide photographic light-sensitive material, wherein the light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. Generally, the unit photosensitive layers are arranged in order from the support side in the order of the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer. However, in the case of a color print light-sensitive material, the above-mentioned installation order is generally reversed. Further, the installation order may be such that different color-sensitive layers are sandwiched in the same color-sensitive layer.

Various non-photosensitive layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer. It is preferable to provide an intermediate layer (color mixing prevention layer) between different color sensitive layers.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

When the photographic light-sensitive material of the present invention is a so-called color negative, the preferable silver halide contained in the silver halide emulsion layer contains about 30 mol% or less of silver iodide.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. In the case of so-called color paper, high silver chloride or silver chlorobromide is preferable.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure is uniform and may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferably silver iodide,
The content is 0.5 to 10 mol%.

The fine grain silver halide preferably has an average grain diameter (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The amount of silver coated on the light-sensitive material of the present invention is 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879

Various color-forming couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630, International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, No. 17643. 307105
VIII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. In addition, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases an image-forming nucleating agent or a development accelerator during development, there is described in British Patent No. 2,093.
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,47
No. 2, No. 4,338,393, No. 4,310,6
No. 18, etc., multi-equivalent couplers, JP-A-60-185.
950, DIR described in JP-A-62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
Nos. 73,302A and 313,308A, which release dyes that undergo color restoration after withdrawal, R.Y. D. No. 1
1449, 24241, and bleaching accelerator releasing couplers described in JP-A-63-75747, U.S. Pat.
5, 477, etc., ligand releasing couplers, leuco dye releasing couplers described in JP-A-63-75747, fluorescent dye releasing couplers described in US Pat. No. 4,774,181, and the like. To be

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and the above-mentioned oil-in-water dispersion method and latex dispersion method are typical.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color intermediate films, color reversal films for slides or televisions, and color positive films for movies.

[0069]

【Example】

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material.

The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. First layer; antihalation layer Black colloidal silver 0.18 UV absorber C-1 0.04 UV absorber C-2 0.18 HBS-2 0.09 Gelatin 1.50 Second layer; Intermediate layer Compound H- 1 0.30 Coupler C-7 0.07 HBS-1 0.11 HBS-2 0.01 Gelatin 1.50 Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion 0.50 (Silver iodide 5 Mol%, average particle size 0.4 μ) Sensitizing dye I 9.0 × 10 ⁻⁵ Sensitizing dye II 2.5 × 10 ⁻⁵ Sensitizing dye III 3.5 × 10 ⁻⁴ Sensitizing dye IV 2.5 × 10 ^-5 coupler C-3 0.26 coupler C-4 0.01 coupler C-5 0.01 gelatin 1.60

Fourth Layer: Second Red Sensitive Emulsion Layer Silver iodobromide emulsion 1.15 (silver iodide 6 mol%, average grain size 0.65 μ) Sensitizing dye I 6.6 × 10 ⁻⁵ Sensitizing dye II 2.0 × 10 ^-5 sensitizing dye III 2.7 × 10 ^-4 sensitizing dye IV 1.8 × 10 ^-5 coupler C-12 0.06 coupler C-3 0.04 coupler C-13 0. 01 coupler C-5 0.03 HBS-1 0.12 HBS-2 0.11 gelatin 1.05 fifth layer; third red-sensitive emulsion layer silver iodobromide emulsion 0.80 (silver iodide 10 mol%, Average particle size 0.75 μ) Sensitizing dye I 7.0 × 10 ⁻⁵ Sensitizing dye II 2.0 × 10 ⁻⁵ Sensitizing dye III 2.8 × 10 ⁻⁵ Sensitizing dye IV 2.1 × 10 ^{− 5} coupler C-12 0.04 coupler C-3 0.03 HBS-1 0.06 HBS-2 0.05 gelatin 0.65 sixth layer: intermediate layer compound H-1 .02 gelatin 1.10

Seventh layer: first green-sensitive emulsion layer Silver iodobromide emulsion 1.34 (silver iodide 5 mol%, average grain size 0.35 μ) Sensitizing dye V 4.5 × 10 ⁻⁴ Sensitizing dye VI 4.0 × 10 ^-5 coupler C-6 0.29 coupler C-7 0.05 coupler C-8 0.08 coupler C-4 0.06 HBS-1 0.31 gelatin 1.20 eighth layer; Second green-sensitive emulsion layer Silver iodobromide emulsion 0.55 (silver iodide 6 mol%, average grain size 0.65 μ) Sensitizing dye V 3.4 × 10 ⁻⁴ Sensitizing dye VI 2.5 × 10 ^{− 5} coupler C-6 0.03 coupler C-9 0.001 coupler C-8 0.001 HBS-1 0.034 gelatin 0.55 9th layer; 3rd green sensitive emulsion layer silver iodobromide emulsion 0.62 (silver iodide 10 mol%, average particle size 0.8 micron) sensitizing dye V 3.8 × 10 ^-4 sensitizing dye VI 3.0 × 10 ^-5 Cap Over C-6 0.03 Coupler C-8 0.001 HBS-1 0.04 Gelatin 0.50

10th layer: Yellow filter layer Yellow colloidal silver 0.040 Compound H-1 0.10 Coupler C-7 0.08 HBS-1 0.09 Gelatin 0.80 11th layer; 1st blue sensitive emulsion layer Silver iodobromide emulsion 0.30 (Silver iodide 6 mol%, average grain size 0.40 μ) Coupler C-10 0.41 Coupler C-14 0.03 HBS-1 0.16 Gelatin 0.50 12th layer Second blue-sensitive emulsion layer Silver iodobromide emulsion 0.45 (silver iodide 10 mol%, average grain size 0.70 μ) Coupler C-10 0.15 HBS-1 0.06 Gelatin 0.45 13th layer Third blue-sensitive emulsion layer Silver iodobromide emulsion 0.66 (silver iodide 14 mol%, average grain size 1.25 μ) Sensitizing dye VII 3.0 × 10 ⁻⁴ coupler C-10 0.05 HBS- 1 0.02 Gelatin 0.50

14th layer; 1st protective layer HBS-2 0.12 gelatin 1.10 15th layer; 2nd protective layer B-1 (X / Y / Z = 4/4/2) (average particle size 2 0.0μ) 0.14 B-2 0.01 B-3 0.05 Gelatin 0.80 In addition to the above composition, a gelatin hardening agent C-11 and a surfactant were added to each layer. The sample manufactured as described above was designated as Sample 101.

Samples 102 to 108 were prepared by using the compounds shown in Table 1 in the 14th layer of Sample 101 at 0.2 g / m ² . Then cut each sample into 35mm width and 10m length,
It is wound on a plastic spool for motion picture film with an outer diameter of 50 mm with a tension of 300 g and a temperature of 25 ° C. and a relative humidity of 65%
The sample was left for 7 days in an atmosphere of, and then for 48 hours at a temperature of 25 ° C. and a relative humidity of 10%. Then 50 in the same atmosphere
The sample was rewound at a speed of cm / sec and a static fog generation test was conducted. The unwound sample was developed under the conditions described below, 5 m of the intermediate portion of the developed sample 10 m obtained was selected, and the generation of static fog was examined with a magnifying glass. However, the relative humidity during the static fog generation test was 20%. The degree of static fog in Example 1 was determined as follows, and the results are shown in Table 1 by rank.

The results are listed in Table 1 by ranking them as follows.

Rank Static fog generation number / 5 m A 0 to 3 B 4 to 10 C 11 to 20 Development processing process temperature (° C.) time pre-bath 27 ± 1 10 ″ backing removal 27 to 38 − and rinse color development Current image 41.1 ± 0.1 3′00 ″ Stop 27-38 30 ″ Promotion 27 ± 1 30 ″ Persulfate bleaching 27 ± 1 3′00 ″ Water wash 27-38 1′00 ″ Fixed 38 ± 1 2'00 "water wash 27-38 2'00" final rinse 27-38 10 "dry 40-455'00"

(Pre-bath) Water at 27 to 38 ° C. 800 ml Borax (10-hydrate) 20.0 g Sodium sulfate 100 g Sodium hydroxide 1.0 g Water is added to 1 liter pH 27 ° C. 9.25 ± 0.1 Specific gravity 27 ° C. 1.094 ± 0.004 (color developer) 21 to 38 ° C. water 850 ml Kodak anti-calcium No. 4 2.0 ml sodium sulfite (anhydrous) 2.0 g Eastman Antifog No. 9 0.22 g Sodium bromide (anhydrous) 1.20 g Sodium carbonate (anhydrous) 25.6 g Sodium bicarbonate 2.7 g Color developing agent CD-3 4.0 g Water added 1 liter pH 27 ° C 10.2 ± 0 0.005 Specific gravity 27 ° C. 1.029 ± 0.003 (Stop bath) Water at 21 to 38 ° C. 900 ml 7.0 N sulfuric acid 50 ml Water is added to 1 liter

(Acceleration Bath) Water at 24-38 ° C. 900 ml Sodium metabisulfite (anhydrous) 10.0 g Glacial acetic acid 25.0 ml Sodium acetate 10 g Ethylenediaminetetraacetic acid tetrasodium 0.70 g (EDTA-4Na) Kodak persulfate bleach Accelerator PBA-1 5.5 g Water added 1 liter pH 27 ° C. 2.3 ± 0.2 Specific gravity 27 ° C. 1.016 ± 0.003 (Persulfate bleaching bath) 24-38 ° C. water 800 ml Gelatin 0 0.5 g Sodium persulfate 33 g Sodium chloride 15 g Sodium monobasic phosphate (anhydrous) 9.0 g Phosphoric acid (85%) 2.5 ml Water was added to 1 liter pH 27 ° C 2.3 ± 0.2 Specific gravity 27 ° C 1. 037 ± 0.03

(Fixing Bath) Water at 21 to 38 ° C. 700 ml Kodak Anticalcium No. 4 2.0 ml 58% ammonium thiosulfate solution 185 ml Sodium sulfite (anhydrous) 10.0 g Sodium bisulfite (anhydrous) 8.4 g Water was added to 1 liter pH 27 ° C. 6.5 ± 0.2 Specific gravity 27 ° C. 1.086 ± 0.003 (final rinse bath) Water at 21 to 38 ° C 900 ml Kodak Stabilizer Additive 0.14 ml Deerside 702 0.7 ml Add water to 1 liter

The chemical formulas of the compounds used in Example 1 are shown below.

[0082]

[Chemical 13]

[0083]

[Chemical 14]

[0084]

[Chemical 15]

[0085]

[Chemical 16]

[0086]

[Chemical 17]

[0087]

[Chemical 18]

[0088]

[Chemical 19]

[0089]

[Chemical 20]

[0090]

[Chemical 21]

[0091]

[Chemical formula 22]

[0092]

[Table 1]

As shown in Table 1, Sample 101, which does not use the ultraviolet absorbent of the present invention, shows a worsening of static fog and is practically defective. However, it can be seen that the deteriorated static fog was completely recovered in Samples 102 to 108 of the present invention in which the 14th layer contained an ultraviolet absorber. Also, sample 1
The color reproduction of 02 to 108 was excellent. Sample 102-
Each sample 108 was irradiated with a xenon fading tester (illuminance: 150,000 lux) for 2 weeks, and the residual ratio [D / D ₀ (%)] of the concentration of each dye at an initial concentration of 1.0 was determined ( D
₍₀ : initial density, D: density after irradiation) As a result, light fastness was also good.

[0094]

INDUSTRIAL APPLICABILITY As described above, the present invention makes it possible to obtain a silver halide light-sensitive material which is excellent in color reproduction and static prevention and gives a light-fast dye image.

Claims (4)

[Claims] 1. At least one of a photosensitive silver halide emulsion layer or a non-photosensitive hydrophilic colloid layer provided on a support.
At least one of the compounds represented by the following general formula (I)
A silver halide photographic light-sensitive material containing a seed. [Chemical 1] In the formula, R ₀ represents a hydrogen atom, an alkyl group or an aryl group, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and a hydrogen atom, an alkyl group, an aryl group, Heterocyclic group, alkenyl group, OR ₆ , halogen atom, nitro group, cyano group, NR ₆ R ₇ , CONR
₆ R ₇ , SO ₂ NR ₆ R ₇ , COR ₈ , SO ₂ R ₈ , N
R ₇ COR ₈ , NR ₇ SO ₂ R ₈ , COOR ₆ , SO ₃
It represents _{R 6, OCOR 8, OSO 2} R 8, R 6, R 7
May be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an alkenyl group,
R ₈ represents an alkyl group, an aryl group, a heterocyclic group, or an alkenyl group, and may be linked with R ₆ and R ₇ to form a 5- or 6-membered ring. 2. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the compounds represented by formula (I) is contained in at least one of the non-photosensitive hydrophilic colloid layers. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the non-photosensitive hydrophilic colloid layer is an outermost layer or a protective layer provided as a layer adjacent thereto. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the light-sensitive silver halide emulsion layer contains a color-forming coupler.