JP3322741B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a 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 are in the visible region (400 to 7).
00 nm) as well as in the ultraviolet region (400 nm or less). A silver halide photographic light-sensitive material for photographing emits ultraviolet rays (UV) that the human eye does not feel in the ultraviolet region.
By blocking the light with a filter layer, only light in the visible region reaches the silver halide emulsion layer. That is, in many photosensitive materials for natural light photography, particularly, in a color photosensitive material, a so-called protective layer has a function of a UV filter layer. With this UV filter layer,
This prevents color photographs that are more bluish than they actually are when shooting landscapes with a lot of ultraviolet rays. In order to make this color reproduction faithful, a long wavelength (320 to 400 nm) UV absorber is important. U for color printing
A V-filter layer is also used for the protective layer to prevent dye fading of the dye image. Again, long wave UV absorbers are important.

[0003] Since silver halide color photographic materials are photosensitive, they are perceived by the slight emission of sparks of static electricity generated during the manufacturing process. Tick mark). When a discharge occurs from a photosensitive material charged with static electricity or from the surroundings of the photosensitive material, the static electricity is converted into light energy. This light is mainly ultraviolet light and blue light, and in particular, has a short wavelength (less than 320 nm) and a long wavelength (320 to 400 nm).
m) Since it is rich in ultraviolet rays, it overlaps with the photosensitive region specific to silver halide. One of the methods for preventing the static mark due to such discharge is an effective method for cutting light emission due to electrostatic discharge by including a short wavelength and a long wavelength ultraviolet absorber in a photosensitive material. . Conventionally, benzotriazole-based compounds have been used as short-wavelength UV absorbers, and aminostilbene-based compounds have been used as long-wavelength UV absorbers. However, this aminostilbene-based compound is difficult to synthesize and is expensive, so that development of a substitute material has been desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material which has good color reproduction and provides a light-fast dye image without a static fog failure.

[0005]

The object of the present invention has been attained by the following constitutions (1) to (4). (1) at least one compound represented by the following general formula (I) in at least one of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer provided on a support , and
A silver halide photographic material comprising at least one compound represented by the following general formula (II) .

[0006]

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In the general formula (I) , 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 each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group, OR ₆ , a halogen atom, a nitro group, a cyano group, or NR.
₆ R ₇ , CONR ₆ R ₇ , SO ₂ NR ₆ R ₇ , CO
R ₈ , SO ₂ R ₈ , NR ₇ COR ₈ , NR ₇ SO
₂ R ₈ , COOR ₆ , SO ₃ R ₆ , OCOR ₈ , OSO
₂ R ₈ , wherein R ₆ and R ₇ may be the same or different and each represent 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; A alkenyl group, R ₆ and R ₇
To form a 5- or 6-membered ring. General formula
In (II), R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ are the same or
May be different and are permissible for hydrogen or aromatic groups
R ₃₁ and R ₃₂ are ring-closed carbon atoms
A 5- or 6-membered aromatic ring may be formed. (2) The silver halide photographic 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 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 material according to any one of claims 1 to 3, wherein the light-sensitive silver halide emulsion layer contains a color-forming coupler.

Hereinafter, the present invention will be described in detail. The present invention relates to a compound represented by formula (I) and a compound represented by formula (II):
A silver halide light-sensitive material having attained the above-mentioned objects can be obtained by containing the above compound . It is surprising that the compounds of formula (I) are useful as UV absorbers, especially as long wavelength UV absorbers.

The ultraviolet absorbent represented by the formula (I) of the present invention will be described. In the formula (I), the alkyl group represented by R ₀ to R ₈ is a linear or branched or cyclic C 1 -C 1 alkyl group.
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-benzooxazolyl, 1-methyl- 2-morpholyl, morpholino, piperidino, pyrrolidino, furyl, phenyl) may preferably 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, and bromine), a nitro group, a cyano group, a hydroxyl group, a carboxylic acid group, and a carbon number of 0 to 0.
40 amino groups (eg, dimethylamino, dioctylamino, didodecylamino), alkyl groups having 1 to 20 carbon atoms (eg, methyl, butyl, decyl, octadecyl), and aryl groups having 6 to 10 carbon atoms (eg, phenyl) , Naphthyl), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy, ethoxy, butoxy, hexyloxy,
Tetradecyloxy, hexadecyloxy), carbon number 6
Aryloxy group (e.g., phenoxy, naphthoxy), alkoxycarbonyl or aryloxycarbonyl group having 2-20 carbon atoms (e.g., methoxycarbonyl, propyloxycarbonyl, octyloxycarbonyl, phenoxycarbonyl), 2-20 carbon atoms An acylamino group (e.g., acetylamino, benzamide), an acyloxy group having 2 to 20 carbon atoms (e.g., acetyloxy, benzoyloxy, lauroyloxy),
An acyl group having 2 to 20 carbon atoms (eg, acetyl, benzoyl, lauroyl) and the like can be mentioned.

Examples of the halogen atom represented by R ₁ to R ₅ include fluorine, chlorine, bromine and the like.
Examples of the 5- or 6-membered ring formed by linking R ₆ and R ₇ include a pyrrolidine ring, a piperidine ring, a morpholine ring, an N-methylpiperazine ring, an imidazolidine ring and the like. Preferred in the general formula (I) are those wherein 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 present invention is not limited to these.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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The compounds represented by the general formula (I) include 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 described 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 exemplified compound I-1 of the present invention can also be obtained by removing a saccharide from a natural compound to which a saccharide has been added.
Further, when the exemplary 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 absorbent used in the present invention has an absorption maximum wavelength of from 350 nm to 390 nm, preferably from 365 nm to 390 nm.
Those at 80 nm are preferred. Further, 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 does not have strong absorption at 300 to 350 nm. Therefore, it is particularly preferable to use a short-wave UV agent that absorbs UV having a wavelength of 320 nm or less. In the present invention, the compound represented by the general formula (I)
In addition, one or more ultraviolet absorbers represented by the following general formula (II) are contained .

The ultraviolet absorbent represented by the formula (I) of the present invention is contained in at least one of a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer. 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. The photosensitive silver halide emulsion layer is preferably a layer containing a color-forming coupler. Another preferred embodiment is to coemulsify the cyan coupler and the ultraviolet absorber represented by the formula (I) and to incorporate them in the photosensitive silver halide emulsion layer. The coating amount of the ultraviolet absorbent 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 . Compound represented by the general <br/> formula (I) of the present invention is represented by the general formula (II)
Used in combination with a compound , in which case the general formula
A compound represented by formula (II) and a compound represented by formula (II)
The use ratio with the product is 10: 1 to 1:10. Considering the band spectrum of N ₂ discharge, short wavelength UV agent is 300
so that the absorbance at 1 nm is 1-4, preferably 2-3, and the long-wavelength UV agent has the same absorbance at 1-4 at the maximum absorption wavelength between 350-400 nm, preferably 2-3. It is preferably applied to

The protective layer comprising the non-photosensitive hydrophilic colloid layer of the present invention may be a single layer or 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 matting agent particles having a composition represented by the general formula (1) described in Japanese Patent Application No. 4-306240, which is provided farthest from the support in the entire coating layer. .

The outermost protective layer of the present invention has a thickness of 0.2 to 0.2.
It is 3.0 μm, preferably 0.5 to 2.0 μm. Here, the film thickness is a thickness of a portion where the matting agent particles are not present, 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 another ultraviolet absorber. More specifically,
Cinnamic acid-based ultraviolet absorbers described in JP-A Nos. 30492 and 56-21141;
No. 25337, No. 55-36984, No. 49-261
Nos. 39, 51-6540, 47-1026, JP-A-61-90537, JP-A-1-306839.
No. 1-306840, No. 1-306841, No. 1-306842, No. 1-306843, a benzotriazole ultraviolet absorber described in European Patent No. 57-160, JP-B-50-33773, Id 56-
No. 30538, US Pat. Nos. 3,698,907 and 3,215
No. 530, a benzophenone-based ultraviolet absorber,
JP-A-58-185677 and JP-A-58-111942.
No. 58-178351, No. 61-169831
No. 62-24247, No. 63-55542, No. 63-53544, and No. 63-53543.

Particularly preferred examples thereof include, for example, JP-B-55-36984 and JP-B-55-12587.
And JP-A-58-214152 and JP-A-58-22184.
No. 4, No. 59-46646, European Patent No. 57160A
2- (2'-hydroxyphenyl) benzotriazoles described in JP-A Nos. 1 and 323408A1, for example, benzophenones described in JP-B-48-30492, JP-A-47-10537, and 58-111942; For example, JP-A-51-56620 and JP-A-53-128333.
Nos. 58-181040 and 53-97425, for example, EP 53125
8-hydroxyphenyltriazines described in Nos. 8A1 and 530135A1.

Next, the benzotriazole-based ultraviolet absorber represented by the general formula (II) used together with the ultraviolet absorber represented by the general formula (I) of the present invention will be exemplified.

[0027]

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In the formula, R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ and R ₃₂ may be the same or different and are substituents permitted 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 further permitted substituent.

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

[0030]

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[0031]

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[0032]

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[0033]

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In the general formulas (I) and (II) of the present invention ,
When the ultraviolet absorber represented is used for the protective layer, the protective layer may be contained in any one of the protective layers when the protective layer is a single layer, and when the protective layer is composed of two or more layers, It is more preferable to use it for the protective layer excluding the outermost layer.

The ultraviolet absorber used here can be incorporated into the photosensitive material by a conventionally known method (oil-in-water dispersion method). For example, an ultraviolet absorber is dissolved at a temperature of 55 to 65 ° C. in a mixture of a high boiling organic solvent such as tricresyl phosphate and a low boiling organic solvent such as ethyl acetate.
Next, it can be easily achieved by adding an aqueous gelatin solution containing a surfactant typified by sodium dodecylbenzenesulfonate to form an emulsified dispersion by high-speed stirring, adding the obtained emulsified dispersion to a coating solution, and then coating. When the ultraviolet absorber is liquid at ordinary temperature, it can be emulsified and dispersed without using a high boiling point organic solvent in combination, and is preferably used in the present invention.

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

Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, 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 (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (For example, isostearyl alcohol, 2,4-di-t
ert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example, N, N -Dibutyl-2
-Butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and the like. -Ethoxyethyl acetate, dimethylformamide.

The light-sensitive material of the present invention comprises, on a support, at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing a color-forming coupler and at least one of the silver halide emulsion layers and the outermost layer. It is preferable to provide a protective layer composed of a photosensitive hydrophilic colloid layer, and there is no particular limitation on the number of silver halide emulsion layers and non-photosensitive layers, and the order of layers excluding the outermost protective layer. As a typical example, a support has at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities and one of protective layers. 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; In general, the arrangement of the unit photosensitive layers is arranged in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer from the support side. However, the order of installation is generally reversed for color print materials. Also, the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

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

In the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent 1,121,470 or British Patent 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the silver halide emulsion layers.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

When the photographic light-sensitive material of the present invention is a so-called color negative, a 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 preferred.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, 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 by Gatov, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineerine
g), Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226 and 4,414,310.
Nos. 4,433,048 and 4,439,520 and British Patent No. 2,112,157.

The crystal structure is uniform, and the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

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

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

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

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

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) Chemical sensitizer page 23 page 648 right column page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24 page 648 right column 866-868 super sensitizer page 649 right column Brightener Page 24 Page 647 Right column Page 868 5. 5. Fogging prevention page 24-25 page 649 right column pages 868-870 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, 〜 page 650, left column, UV absorber 7. Stain page 25 right column 650 page left column 872 inhibitor ~ right column 8. Dye image page 25 page 650 left column page 872 stabilizer Hardener page 26 page 651 left column pages 874 to 875 10. Binder page 26 page 651 left column pages 873-874 11. Plasticizers and 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 27 pages 650 right column pages 876-877 Inhibitors 14. Matting agent 878-879

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

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 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
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

Examples of the cyan coupler include phenol type and naphthol type couplers.
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 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622 and 4,333,999.
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,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is a Research Disclosure N
o. No. 17643, paragraphs VII-G; 307105
VIII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258 and British Patent No. 1,14.
No. 6,368 is preferred. Also, a coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, section VII-F and the same No. 307105, VII
Patents described in section -F, JP-A-57-151944
No., No. 57-154234, No. 60-184248
And JP-A-63-37346 and JP-A-63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator in the form of an image during development, British Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,47.
No. 2, No. 4,338,393, No. 4,310,6
No. 18, etc .;
No. 950, DIR described in JP-A-62-24252 and the like.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
No. 73,302A and Nos. 313,308A, couplers which release a dye which recolors after release. D. No. 1
Bleaching accelerator releasing couplers described in, for example, JP-A-63-75747, U.S. Pat.
No. 5,477, the ligand releasing coupler described in JP-A-63-75747, and the coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. Can be

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

Specific examples of the steps and effects of the latex dispersion method and examples of the latex for impregnation are described in US Pat.
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-63-257747, may be used.
272248, and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, It is preferable to add various preservatives or fungicides 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 a sample 101 as a multilayer color photosensitive material.

The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer. 1st layer; anti-halation 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 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 (10 mol% of silver iodide, 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 (5 mol% of silver iodide, average grain size 0.35μ) 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 8th layer; Second green-sensitive emulsion layer Silver iodobromide emulsion 0.55 (silver iodide 6 mol%, average grain size 0.65μ) 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 ninth layer; third 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

Tenth 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 Eleventh layer; First blue-sensitive emulsion layer Silver iodobromide emulsion 0.30 (silver iodide 6 mol%, average grain size 0.40μ) Coupler C-10 0.41 Coupler C-14 0.03 HBS-1 0.16 Gelatin 0.50 12th layer The second blue-sensitive emulsion layer silver iodobromide emulsion 0.45 (silver iodide 10 mol%, average grain size 0.70μ) coupler C-10 0.15 HBS-1 0.06 gelatin 0.45 thirteenth 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; first protective layer HBS-2 0.12 gelatin 1.10 15th layer; second protective layer B-1 (X / Y / Z = 4/4/2) (average particle size 2) 0.1μ) 0.14 B-2 0.01 B-3 0.05 Gelatin 0.80 In addition to the above composition, gelatin hardener C-11 and surfactant were added to each layer. The sample manufactured as described above was used 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 . Next, each sample was cut into 35 mm width and 10 m length,
The film is wound on a plastic spool for movie film with an outer diameter of 50 mm at a tension of 300 g, at a temperature of 25 ° C. and a relative humidity of 65%.
, 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 performed. The unwound sample was subjected to a developing treatment under the conditions described later, and an intermediate portion 5m of the obtained developed sample 10m was selected, and the occurrence of static fog was examined with a loupe. However, the relative humidity at the time of the static fogging 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 shown in Table 1 by ranking as follows.

Rank Number of occurrences of static fog / 5 m A 0 to 3 B 4 to 10 C 11 to 20 Development processing Processing step Temperature (° C.) Time Pre-bath 27 ± 110 ″ Backing removal 27-38 − and rinsing and coloring Present image 41.1 ± 0.1 3′00 ″ Stop 27-38 30 ″ Promotion 27 ± 1 30 ″ Persulfate bleaching 27 ± 1 3′00 ″ Rinse 27-38 1′00 ″ Fix 38 ± 1 2'00 "Rinse 27-38 2'00" Final rinse 27-38 10 "Dry 40-45 5'00"

(Pre-bath) Water at 27-38 ° C. 800 ml Borax (decahydrate) 20.0 g Sodium sulfate 100 g Sodium hydroxide 1.0 g Water was added to 1 liter pH 27 ° C. 9.25 ± 0.1 Specific gravity 27 ° C. 1.094 ± 0.004 (color developing solution) 850 ml of water at 21 to 38 ° C. 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 1 liter by adding water pH 27 ° C. 10.2 ± 0 0.005 Specific gravity 27 ° C 1.029 ± 0.003 (Stop bath) Water at 21-38 ° C 900ml 7.0N sulfuric acid 50ml Add water 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 bleaching Accelerator PBA-1 5.5 g Add water 1 liter pH 27 ° C 2.3 ± 0.2 Specific gravity 27 ° C 1.016 ± 0.003 (Persulfate bleaching bath) Water at 24-38 ° C 800 ml Gelatin 0 0.5 g sodium persulfate 33 g sodium chloride 15 g monobasic sodium phosphate (anhydrous) 9.0 g phosphoric acid (85%) 2.5 ml 1 liter by adding water pH 27 ° C 2.3 ± 0.2 Specific gravity 27 ° C 1. 037 ± 0.03

(Fixing bath) 700 ml of water at 21 to 38 ° C. 4 2.0 ml 58% ammonium thiosulfate solution 185 ml sodium sulphite (anhydrous) 10.0 g sodium bisulfite (anhydrous) 8.4 g 1 liter with water pH 27 ° C. 6.5 ± 0.2 specific gravity 27 ° C. 1.086 ± 0.003 (final rinsing bath) Water at 21 to 38 ° C 900 ml Kodak stabilizer additive 0.14 ml Deerside 702 0.7 ml Add water and 1 liter

The chemical formula of the compound used in Example 1 is shown below.

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[Table 1]

From Table 1, it can be seen that Sample 101 which does not use the ultraviolet absorbent of the present invention suffers from deterioration of static fog and has a practical disadvantage. However, the general formula (I) and the
It can be seen that in the samples 107 and 108 of the present invention containing the ultraviolet absorber represented by the general formula (II), the deteriorated static fog was completely recovered. The color reproduction of Samples 107 and 108 was excellent. Furthermore, after irradiating each of the samples 107 and 108 with a xenon discoloration tester (illuminance: 150,000 lux) for 2 weeks, the residual ratio of the concentration of each dye at the initial density of 1.0 [D / D ₀ (%)] (D ₀ ; initial concentration,
D; concentration) results after irradiation, light fastness was also good.

[0094]

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

Continuation of front page (56) References JP-A-2-227483 (JP, A) JP-A-4-290882 (JP, A) JP-A-5-301813 (JP, A) JP-A-5-333484 (JP) (A) Special table Hei 5-505641 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/815 G03C 1/76 501 G03C 7/00 510 G03C 7/00 530 G03C 7/30

Claims (4)

(57) [Claims] At least one of a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer provided on a support
At least one compound represented by the following general formula (I)
Species , and at least a compound represented by the following general formula (II)
A silver halide photographic light-sensitive material, characterized in that it contains at least one of the following . Embedded image In the general formula (I), 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; ,
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
R ₆ , OCOR ₈ , OSO ₂ R ₈ , R ₆ , R ₇
May be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, 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. In the general formula (II), R ₂₈ , R ₂₉ , R ₃₀ ,
R ₃₁ and R ₃₂ may be the same or different, and represent a hydrogen atom or
Is an allowable substituent for an aromatic group, and R ₃₁ and R
₃₂ is a ring-closing 5- or 6-membered aromatic consisting of carbon atoms
A ring may be formed. 2. The silver halide photographic 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 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 material according to claim 1, wherein the light-sensitive silver halide emulsion layer contains a color-forming coupler.