JPH05204083A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material excellent in sharpness and color reproducibility, and further excellent in color developing property and whiteness in base. CONSTITUTION:This photographic sensitive material contains a sensitizing dye and a cyan coupler and has a water-resistant resin layer formed on the side where a silver halide emulsion is applied. This resin layer contains >=14wt.% titanium dioxide. Further, the total amt. of gelatin in the silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer is <=8g/m<2>. The photographic sensitive material shows an excellent effect when a magenta coupler expressed by formula is used. In formula, J is -O-, -S- or -N(R26)-, R26 is a hydrogen atom or substituent,(n) is 0 or 1, R24 is an alkyl group or aryl group, R25 is a hydrogen atom or substituent, X is a hydrogen atom or a group which can be released by the reaction with the oxidized body of a color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in sharpness and color reproducibility, having high sensitivity and less fog.

[0002]

BACKGROUND OF THE INVENTION Recently, in the photographic industry, there has been a demand for a high-quality silver halide color photographic light-sensitive material capable of rapid processing and excellent in sharpness, color reproducibility and the like.

In a silver halide color photographic light-sensitive material, silver halide is spectrally sensitized with a sensitizing dye by a commonly used subtractive method, and a yellow color-forming coupler and a green-sensitive halogen are contained in a blue-sensitive silver halide emulsion layer. The silver halide emulsion layer contains a magenta color coupler and the red-sensitive silver halide emulsion layer contains a cyan color coupler, and after imagewise exposure, an aromatic primary amine color developing agent (hereinafter, simply referred to as color developing agent).
To develop a dye image, and then to perform a bleach-fixing process to obtain a dye image.

It is desired that the dye image thus obtained does not discolor even when it is exposed to light for a long period of time or stored under high temperature and high humidity. The former fastness to light is called fading, and the latter fastness to high temperature and high humidity is called dark fading. Among them, phenolic compounds having an alkyl group at the 5-position, which have been widely used as cyan couplers in the past. The cyan coupler has a problem that although the light fading property reaches a certain level, it is not sufficient, and the dark fading property is remarkably inferior.

A 2,5-diacylaminophenol-based cyan coupler is known as a cyan coupler having improved dark fading property, for example, US Pat. No. 2,895,82.
No. 6, JP-A Nos. 50-112038 and 53-1096.
30 and 55-163537. However, although these 2,5-diacylaminophenol cyan couplers are remarkably improved in the dark fading property of the dye image obtained, on the other hand, in many cases, the fading property is remarkably deteriorated.

A dye formed from a 2,5-diacylaminophenol cyan coupler is compared with a dye formed from a phenol cyan coupler having no acylamino group at the 5-position, which is generally used conventionally. Since the maximum absorption wavelength is on the short wave side and the secondary absorption near 550 nm is large, there is a drawback that a vivid green color cannot be sufficiently reproduced.

Most of the magenta couplers that have been widely used in the past were 5-pyrazolone rings.
The dye formed from this 5-pyrazolone coupler is
It has a yellow component due to the presence of unnecessary absorption around 430 nm, and has a drawback that vivid blue reproduction cannot be sufficiently performed.

On the other hand, the pyrazoloazole-based coupler developed in recent years has a coloring dye of 430 nm, unlike the conventionally used 5-pyrazolone-based magenta coupler.
Since it has no secondary absorption in the vicinity, it is basically advantageous for color reproducibility.

However, it is known that the magenta dye obtained from the pyrazoloazole-based magenta coupler is inferior in image storability, particularly the fading property, to the magenta dye obtained from the 5-pyrazolone-based magenta coupler,
Improvement of this is strongly desired.

On the other hand, improving the sharpness is one of the most important performances for improving the image quality, and as a means for improving the sharpness, the optical characteristics of the support are improved or halation is prevented or erased. There is known a method of coloring the silver halide photographic emulsion layer or other hydrophilic colloid layer with a dye that absorbs light of a specific wavelength in order to prevent radiation.

The dye used for such a purpose has good spectral absorption characteristics according to the purpose of use, is completely decolorized in a photographic processing solution, and is easily eluted from a light-sensitive material so that it can be dyed after processing. No residual color contamination due to photographic noise, no adverse effects such as increase or decrease or fog on the spectrally sensitized photographic emulsion, and excellent stability over time in a solution or a light-sensitive material and no fading. Must satisfy the conditions of.

To date, many efforts have been made and many dyes have been proposed in order to find dyes satisfying the above conditions. For example, US Pat. No. 506,385,
Oxonol dyes described in U.S. Pat. No. 3,247,127, Japanese Examined Patent Publication No. 43-13168, U.S. Pat. No. 1,845,4.
Styryl dye represented by No. 04, US Pat. No. 2,49
No. 3,747, No. 3,148,187, No. 3,28
Merocyanine dyes represented by 2,699, cyanine dyes represented by US Pat. No. 2,843,486, and the like,
Further, there are anthraquinone dyes represented by US Pat. No. 2,865,752.

Among these dyes, the oxonol dye having two pyrazolone skeletons has the property of being decolorized during photographic processing and easily flowing out from the light-sensitive material, and useful with little adverse effect on photographic emulsions. It has been used as a dye.

However, most of the oxonol dyes, when dissolved or decolorized dyes or decomposition products thereof are accumulated in the photographic processing solution, the following sensitized materials containing high chloride silver halide are used. It was found that such a problem would occur.

(1) The amount of the light-sensitive material to be processed, that is, the dye or its decomposition product accumulates in the color developing solution with running, which causes an increase in fog. This phenomenon occurs particularly in the cyan image area. Large, pH of color developer
Is more noticeable when fluctuates.

(2) By accumulating in a bleach-fixing solution,
The cyan dye-forming coupler has a drawback that the color recovery failure becomes large and a dye image having a high color density cannot be obtained.

Among these problems, the increase in fog is considered to be due to the fact that the dissolved or decolorized dye or its decomposition product becomes active in the color developing solution with respect to the light-sensitive material, which causes deterioration of the white background. And the p of the color developing solution
When H changes, the photographic performance changes and defective color restoration occurs, which is a serious problem in that a certain quality cannot be obtained due to the difference in processing control in the laboratory. This is a problem that is particularly noticeable when using a silver halide emulsion having a high silver chloride content or when a large amount of dye is used, but the use of high chloride silver halide is required to enable rapid processing. It is essential, and it is also an important technique to use a dye in order to improve the image quality of the photographic light-sensitive material.

From the above, it was difficult to obtain a silver halide photographic light-sensitive material capable of always maintaining stable high image quality even in rapid processing. Among the photographic performances, sharpness is one of the most important performances for improving the image quality of photographic light-sensitive materials, and in order to improve sharpness, increase the reflection density in each color sensitive wavelength range before development processing. It is necessary to add a large amount of dye to the photographic light-sensitive material for that reason, and in the current situation where environmental problems have become more serious and low replenishment of processing solution has become essential, Accumulation of dyes or decomposition products thereof becomes an increasingly serious problem.

[0019]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which is excellent in sharpness and color reproducibility and which can provide high image quality. Another object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color developability, does not cause fog rise and is excellent in whiteness.

[0020]

The above object of the present invention is achieved by the following configurations. (1) A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer provided on a support, the silver halide emulsion layer or other hydrophilic colloid At least one of the layers,
At least one of the compounds represented by the general formula [I], the general formula [II] or the general formula [III] is contained, and at least one of the silver halide emulsion layers has the general formula [C-1 ] A cyan coupler is contained, and titanium oxide particles are contained at a density of 14% by weight or more in the water-resistant resin layer on the side coated with the silver halide emulsion. The total amount of gelatin contained in the light-sensitive silver halide emulsion layer and the non-light-sensitive hydrophilic colloid layer on the side coated with the silver halide emulsion layer is 8 g /
A silver halide color photographic light-sensitive material characterized by having a size of m ² or less.

[0021]

[Chemical 6]

[In the formula, V ₁ and V ₂ are each a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, or -COOR.
₁ , -COR ₁ , -CONR ₁ R ₂ , -OR ₁ , -NR
₁ R ₂ , -NR ₁ R ₂ , -NR ₁ COR ₂ , -NR ₁ S
O ₂ R ₂ , an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group, W ₁ ,
W ₂ are each a hydrogen _{atom, -NR 3 R 4, -NR 3} COR
₄ , —NR ₃ SO ₂ R ₄ , an alkyl group, an aralkyl group,
It represents a cycloalkyl group, an aryl group, a heterocyclic group or an amino group, and X ₁ and X ₂ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, -COOR ₅ , -COR ₅ ,-.
_{CONR 5 R 6, -NR 5 R} 6, -NR 5 COR 6, -
_{NR 5 SO 2 R 6, -SO} 2 R 5, alkyl group, aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic _{group, L 1, L 2, L} 3 each represents a methine group, m is 0 1 or 2, n represents 1, 2 or 3, and M ^{n +} represents an n-valent cation. R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ are linked to form a 5- or 6-membered ring. May be. However, at least one of V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , and X ₂ represents a group containing a carboxyl group or a sulfo group. ]

[0023]

[Chemical 7]

[Wherein R ₇ represents an alkyl group, an aryl group or a heterocyclic group, and R ₈ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, —COR ₁₀ or —SO, respectively.
₂ represents R ₁₀ , and R ₉ is a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, COOR ₁₀ , or —CONR, respectively.
₁₁ R ₁₂ , -OR ₁₀ , -NR ₁₁ R ₁₂ , -NR ₁₁ COR ₁₂ ,
_{-NR 11 SO 2 R 12, -NR} 11 CONR 11 R 12, an alkyl group, an aryl _{group, L 4, L 5, L} 6 each represent a methine group, k ₁ represents 0, 1 or 2. Y ₁ and Y ₂ represent an oxygen atom or NR ₁₃ . R ₁₀ represents an alkyl group or an aryl group, and R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group or an aryl group. R ₁₃ represents a non-metal atomic group necessary for forming a 5-membered ring by linking with R ₇ . However,
At least one of R ₇ , R ₈ and R ₉ represents a group containing at least one carboxyl group or sulfo group. ]

[0025]

[Chemical 8]

[In the formula, R ₁₄ and R ₁₅ are respectively -CN and -CO.
It represents R _18, -COOR ₁₈ or -CONR ₁₉ R _20,
R ₁₆ and R ₁₇ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and L ₇ , L ₈ and
L ₉ represents a methine group, and k represents 0, 1 or 2.

R ₁₈ represents an alkyl group or an aryl group.
R ₁₉ and R ₂₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and one of R ₁₉ and R ₂₀ is a hydrogen atom. However, R ₁₄ , R ₁₅ ,
At least one of R ₁₆ and R ₁₇ represents a water-soluble group or a substituent containing a water-soluble group. ]

[0028]

[Chemical 9]

[In the formula, R ₂₁ represents an alkyl group having 2 to 6 carbon atoms. R ₂₂ represents a ballast group. Z ₁ represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

(2) A silver halide color photographic light-sensitive material characterized in that at least one of the silver halide emulsion layers described in the above-mentioned item 1 contains a magenta coupler represented by the general formula [MI]. material.

[0031]

[Chemical 10]

[Wherein J is -O-, -S-, -N
(R ₂₆₎ - represents, R ₂₆ represents a hydrogen atom or a substituent,
n represents 0 or 1. R ₂₄ represents an alkyl group or an aryl group. R ₂₅ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

The present invention will be described in more detail below. First, the compound represented by formula [I] will be described. In the general formula [I], V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X
₂ , examples of the alkyl group represented by R _{1 to} R ₆ include methyl, ethyl, propyl, isopropyl, butyl, t
-Butyl and the like, and these alkyl groups further include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom (for example, fluorine, chlorine, bromine and the like), an alkoxy group (for example, methoxy and ethoxy), an aryloxy group (for example, Phenoxy, 4-sulfophenoxy, 2,4-disulfophenoxy, etc.), an aryl group (eg, phenyl,
4-sulfophenyl, 2,5-disulfophenyl, etc.),
It may be substituted with a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl), etc.

V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R
Examples of the aryl group represented by _{1 to} R ₆ include phenyl, 2-methoxyphenyl, 4-nitrophenyl, 3-
Chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl, 3-sulfophenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro- 3-sulfophenyl, 2-chloro-5-sulfophenyl, 2-methoxy-5-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2,5-dichloro-4-
Sulfophenyl, 2,6-diethyl-4-sulfophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3
-Sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl ,
2,4-dicarboxyphenyl, 3,6-disulfo-α
-Naphthyl, 8-hydroxy-3,6-disulfo-α-
Examples include naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl and the like.

V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ , R
Examples of the heterocyclic group represented by _{1 to} R ₆ include a pyridyl group (2-pyridyl, 3-pyridyl, 4-pyridyl, 5-
Sulfo-2-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl,
2,3,5,6-tetrafluoro-4-pyridyl, 3-
Nitro-2-pyridyl), an oxazolyl group (5-sulfo-2-benzoxazolyl, 2-benzoxazole,
2-oxazolyl etc.), thiazolyl group (5-sulfo-2
-Benzothiazolyl, 2-benzothiazolyl, 2-thiazolyl, etc.), imidazolyl group (1-methyl-2-imidazolyl, 1-methyl-5-sulfo-2-benzimidazolyl, etc.), furyl group (3-furyl, etc.), pyrrolyl group ( Three
-Pyrrolyl etc.), thienyl group (2-thienyl etc.), pyrazinyl group (2-pyrazinyl etc.), pyrimidinyl group (2-
Pyrimidinyl, 4-chloro-2-pyrimidinyl, etc.), pyridazinyl group (2-pyridazinyl, etc.), purinyl group (8
-Prinyl, etc.), isoxazolinyl group (3-isoxazolinyl, etc.), selenazolyl group (5-sulfo-2-selenazolyl, etc.), sulforanyl (3-sulfolanyl, etc.), piperidinyl group (1-methyl-3-, etc. Piperidinyl etc.), pyrazolyl (3-pyrazolyl etc.), tetrazolyl group (1-tetrazolyl etc.) and the like.

X ₁ and X ₂ are especially --COOR ₅ and --COR.
_5, -CONR ₅ R ₆ it is preferred. The methine groups represented by L ₁ , L ₂ and L ₃ include those having a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom, etc.). Examples of the n-valent cation represented by M ^{n +} include N
a ⁺ , K ⁺ , Ca ²⁺ , NH ₄ ⁺ , HN (C
₂ H ₅ ) ₃ ⁺ , C ₅ H ₆ N ^{+ and the} like.

Typical specific examples of the dye of the present invention represented by the general formula [I] are shown below, but the dye of the present invention is not limited thereto.

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

These dyes are described in British Patent 1,278,6
No. 21, No. 1,512, 863, No. 1,579, 89
It can be synthesized using the method described in No. 9 or the like.

Next, the compound represented by the general formula [II] will be described. Examples of the alkyl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ include V ₁ , V ₂ , W ₁ , W ₂ , X ₁ and X _{2 in the} above general formula [I]. , And the same groups as the alkyl groups described for R _{1 to} R ₆ .

The aryl groups represented by R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ include V ₁ , V ₂ , W ₁ , W ₂ and X _{1 in the} above formula [I]. , X ₂ , and the same groups as the aryl groups described for R _{1 to} R ₆ . R ₇ , R ₈
The heterocyclic group represented by is a group similar to the heterocyclic group described in the above general formula [I] as V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , X ₂ and R _{1 to} R _6. Is mentioned.

The methine groups represented by L ₄ , L ₅ and L ₆ are
It also includes those having a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom).

Typical specific examples of the dye of the present invention represented by the general formula [II] are shown below, but the dye of the present invention is not limited thereto.

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

[0056]

[Chemical formula 24]

These dyes can be synthesized by reacting a dioxopyrazolopyridine compound with an appropriate monotin source, trimethine source or pentamethine source compound, and specifically, Japanese Patent Publication No. 39-22069. 43-
No. 3504, No. 52-38056, No. 54-3812
No. 9, 55-10059, JP-A-49-99620.
No. 59-16834 or U.S. Pat. No. 4,18
It can be synthesized using the method described in No. 1,225 and the like.

Further, the compound represented by the general formula [III] will be described. In the general formula [III], R ₁₆ , R
Examples of the alkyl group represented by ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ include
V ₁ , V ₂ , W ₁ , W ₂ , X in the general formula [I]
_{The same} groups as the alkyl groups described for ₁ , X ₂ , and R _{1 to} R ₆ can be mentioned.

Examples of the aryl group represented by R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ include V ₁ in the above general formula [I],
_{V 2, W 1, W 2} , X 1, X 2, include the same groups as the aryl group described for R ₁ to R _6. Examples of the alkenyl group represented by R ₁₉ and R ₂₀ include vinyl and allyl.

The heterocyclic groups represented by R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ include V ₁ and V in the above general formula [I].
_{The same} groups as the heterocyclic groups described in ₂ , W ₁ , W ₂ , X ₁ , X ₂ , and R _{1 to} R ₆ can be mentioned. Examples of the cycloalkyl group represented by R ₁₆ and R ₁₇ include cyclopentyl and cyclohexyl. R ₁₄ and R ₁₅ are especially —COO.
R _18, preferably -CONR ₁₉ R _20, also R _16, R ₁₇ particularly alkyl group, an aryl group is preferable.

Typical specific examples of the dye represented by the above general formula [III] used in the present invention are shown below, but the dye used in the present invention is not limited thereto.

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

[0066]

[Chemical 29]

These dyes are disclosed in JP-A-58-14334.
No. 2, No. 62-165656, etc. can be used for the synthesis. The dye used in the present invention may be contained in any one of the silver halide emulsion layer on the support and other hydrophilic colloid layers, but it is contained in the layer adjacent to the red-sensitive emulsion layer. Is preferred. However, when the dye diffuses to another layer, the same effect as that added to the adjacent layer can be obtained even if it is added to the intermediate layer or the protective layer other than the adjacent layer.

The addition amount of the dye used in the present invention is not particularly limited, but if too much dye is used, an unfavorable increase / decrease in photographic performance occurs. Are each 1 to 100 mg / m ² , and more preferably 3 to 60.
It is used by coating so as to have a mg / m ² .

In order to incorporate the dye used in the present invention into the photographic emulsion layer or other hydrophilic colloid layer, the dye or an organic / inorganic alkali salt of the dye is generally used in an aqueous solution or an organic solvent (for example, alcohols). , Glycols, cellosolves, dimethylformamide, dibutyl phthalate, tricresyl phosphate, etc.), if necessary emulsified and dispersed, and added to the coating solution for coating so that the photosensitive material can be contained.

The cyan coupler represented by the above general formula [CI] will be described. In the cyan coupler represented by the above general formula [C-I], the alkyl group having 2 to 6 carbon atoms represented by R ₂₁ may be linear or branched and includes those having a substituent. R ₂₁ is preferably an ethyl group.

The ballast group represented by R ₂₂ is of a size and shape that provides the coupler molecule with sufficient bulk to prevent the coupler from substantially diffusing from the layer to which it is applied to other layers. It is an organic group having. Preferred as the ballast group is —CH (R ₂₃ ) —O—Ar.
It is represented by.

R ₂₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent.

In the general formula [CI], the atom or group which can be split off by the reaction with the oxidized product of the color developing agent represented by Z ₁ is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, Examples thereof include a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, an alkoxy group. It is a base.

Specific examples of the coupler represented by the general formula [C-I] are shown below, but the couplers are not limited to these.

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

[0078]

[Chemical 33]

Specific examples of cyan couplers that can be used in the present invention, including these, are described in JP-B-49-11.
No. 572, JP-A Nos. 61-3142 and 61-9652.
No. 61, No. 61-9653, No. 61-39045, No. 6
1-50136, 61-99141, 61-1
No. 05545 and the like.

The above general formula [C-I] used in the present invention
The cyan coupler represented by can be used usually in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻² mol per mol of silver halide. The cyan coupler used in the present invention may be used in combination with a cyan coupler other than the present invention. Examples of couplers used in combination in this manner include a phenolic cyan coupler having a methyl group at the 5-position and 2,5-diacyl. Examples include aminophenol cyan couplers.

Next, the compound represented by the formula [M-1] will be described. In the general formula [M-1], the alkyl group represented by R ₂₄ preferably has 1 to 32 carbon atoms, and may be linear or branched. The aryl group represented by R ₂₄ is preferably a phenyl group. The alkyl group and aryl group represented by R ₂₄ may further have a substituent.

The substituent represented by R ₂₅ and R ₂₆ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition to these, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, aryloxy, heterocyclic oxy,
Siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxyarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio groups, and spiro compound residues , And bridged hydrocarbon compound residues.

The alkyl group represented by R ₂₅ and R ₂₆ preferably has 1 to 32 carbon atoms and may be linear or branched. The aryl group represented by R ₂₅ and R ₂₆ is preferably a phenyl group. Examples of the acylamino group represented by R ₂₅ and R ₂₆ include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₂₅ and R ₂₆ include an alkylsulfonylamino group and an arylsulfonylamino group. An alkylthio group represented by R ₂₅ and R ₂₆ , an alkyl component in the arylthio group,
The aryl component is an alkyl group represented by R ₂₅ and R ₂₆ above,
An aryl group is mentioned.

The alkenyl group represented by R ₂₅ and R ₂₆ is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. But you can also branch. The cycloalkenyl group represented by R ₂₅ and R ₂₆ has 3 to 12 carbon atoms, especially 5 carbon atoms.
The thing of -7 is preferable.

The sulfonyl group represented by R ₂₅ and R ₂₆ is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like; the phosphonyl group is an alkylphosphonyl group or an alkoxyphosphonyl group. Groups, aryloxyphosphonyl groups, arylphosphonyl groups, etc .; acylcarbonyl groups such as alkylcarbonyl groups, arylcarbonyl groups, etc .;
As the carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group and the like;

Examples of the sulfamoyl group include an alkylsulfamoyl group and an arylsulfamoyl group; examples of the acyloxy group include an alkylcarbonyloxy group and an arylcarbonyloxy group; and examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group. ;

The ureido group is an alkylureido group,
Aryl ureido group, etc .; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group is preferably 5 to 7-membered, specifically, 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- Phenyltetrazole-5-oxo group and the like;

The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,
3,5-triazole-6-thio group and the like; as siloxy groups, trimethylsiloxy group, triethylsiloxy group,
Dimethylbutylsiloxy group and the like;

As the imide group, a succinimide group, 3-
Heptadecyl succinimide group, phthalimide group, glutarimide group and the like; spiro compound residues include spiro [3.3] heptan-1-yl and the like; bridged hydrocarbon compound residues include bicyclo [2.2.1]. ] heptane-1-yl, tricyclo [3.3.1.1 ^{3, 7]} decane-1
And 7,7 dimethyl-bicyclo [2.2.1] heptan-1-yl.

Examples of the group which can be split off by the reaction with the oxidation product of the color developing agent represented by X are, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Each group of oxy, alkoxycarbonyloxy, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, nitrogen-containing heterocyclic ring of 6π or 10π electron system bonded by N atom Can be mentioned.

Among the magenta couplers represented by the above general formula [MI], particularly preferable compounds are those represented by the following general formula [M-II] or general formula [M-III].

[0093]

[Chemical 34]

In the formula, R ₂₇ represents an isopropyl group or a t-butyl group. R ₂₉ represents an alkyl group or an aryl group.
R ₂₈ represents a substituent, and X ₃ represents a group capable of splitting off upon reaction with an oxidized product of a color developing agent. The alkyl group represented by R ₂₉ is preferably one having 1 to 32 carbon atoms,
It may be linear or branched. The aryl group represented by R ₂₉ is preferably a phenyl group. The alkyl group and aryl group represented by R ₂₉ may further have a substituent.

Examples of the substituent represented by R ₂₈ include the substituent represented by R ₂₅ in the above formula [MI], preferably an alkyl group or an aryl group,
Particularly preferred is a group represented by the following general formula [M-IV] or general formula [MV].

[0096]

[Chemical 35]

In the formula, Z represents a carbon atom or a sulfur atom, m represents 1 when Z is a carbon atom, and 2 when Z is a sulfur atom. R ₃₀ represents an alkyl group or an aryl group. The alkyl group represented by R ₃₀ preferably has 1 to 32 carbon atoms, and may be linear or branched. R
_The aryl group represented by ₃₀ is preferably a phenyl group. The alkyl group and aryl group represented by R ₃₀ may further have a substituent.

[0098]

[Chemical 36]

In the formula, R ₃₁ represents a substituent, and k ₂ is 0 to 5
Represents the integer. Examples of the substituent represented by R ₃₁ include the substituent represented by R ₂₅ in the above general formula [MI].

The group represented by X ₃ which can be eliminated by the reaction with the oxidation product of the color developing agent is represented by the above general formula [M-
The group represented by X in I] can be mentioned, but preferably a fluorine atom, a chlorine atom, or the following general formula [MV
I] to groups represented by general formula [M-VIII].

[0101]

[Chemical 37]

In the formula, R ₃₂ represents a substituent, and p represents an integer of 0-5.

[0103]

[Chemical 38]

In the formula, R ₃₃ and R ₃₄ represent a substituent, and q is 0.
Represents an integer of 4;

[0105]

[Chemical Formula 39]

In the formula, Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring with a nitrogen atom. Examples of the substituent represented by R _{32 to} R ₃₄ include the substituent represented by R ₂₅ in the general formula [MI]. The substituent represented by R ₃₃ is preferably a group substituting through an oxygen atom or a nitrogen atom, and is sometimes preferably an alkoxy group or an acylamino group.

The general formula [M
Typical examples of the magenta coupler represented by the formula -I] are shown below, but the magenta coupler is not limited thereto.

[0108]

[Chemical 40]

[0109]

[Chemical 41]

[0110]

[Chemical 42]

[0111]

[Chemical 43]

[0112]

[Chemical 44]

[0113]

[Chemical 45]

In addition to the above specific examples, the magenta coupler used in the present invention is disclosed in JP-A-63-307453.
Presentation compounds (1) to (1) described on pages 6 to 7 of the publication.
5), the presentation compounds (1) to (31), (46) to (50) described on pages 8 to 14 of JP-A-64-7041.
(52) to (60), and the presentation compounds (I-1) to (I-2) described on pages 3 to 5 of JP-A No. 64-66646.
4), exemplary compounds (6) to (8), (10) and (12) to those described on pages 5 and 6 of JP-A-1-277236.
(15), (18), (20), JP-A-2-16023.
Exemplified compound (M-4) described on pages 11 to 18 of Japanese Patent Publication No. 3
~ (M-35), (M-37), (M-50) to (M-
53), exemplary compounds (M-1) to (M-89) described on pages 5 to 9 of JP-A-2-161430, JP-A-2-
Exemplified compounds described in pages 5 to 8 of 296241 (M
-1) to (M-6), (M-8) to (M-12), (M
-14) to (M-27), and Exemplified compounds (M-2) described on pages 5 to 7 and 35 of JP-A-3-138645.
To (M-29), (m-2) to (m-28), JP-A-HEI-3
Compounds (M-3) to (M-5), (M-7) to (M-12), described on pages 5 to 9 of JP-A-200413
(M-14), (M-16) to (M-30), Japanese Unexamined Patent Publication No. HEI 3
Exemplary compounds (M-1) to (M-38) described on pages 6 to 10 of JP-A-138644 can be mentioned.

The magenta coupler used in the present invention is
It can be synthesized according to the method described in the above publications and the like. The magenta coupler used in the present invention is 1 × 10 ⁻³ mol to 1 mol, preferably 1 mol, per mol of silver halide.
It is used in the range of x10 ^-2 mol to 7 x 10 ^-1 . In the present invention, an acylacetanilide type coupler can be preferably used as the yellow dye forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers preferably used in the present invention will be given below.

[0117]

[Chemical 46]

[0118]

[Chemical 47]

[0119]

[Chemical 48]

[0120]

[Chemical 49]

Further, in addition to the above compounds, JP-A-63-
No. 85631, Exemplified compounds Y-1 to Y described on pages 7 to 16
-146, ibid. 63-97951, pages 6-10, exemplary compounds Y-1 to Y-98, and JP-A-1-156748, pages 18-20, exemplary compounds Y-1 to Y-24, ibid. -298943, Exemplified Compound I-1 described on pages 4 to 7
~ I-50 and 114-1 of JP-A-62-215272
Exemplified compounds Y-1 to Y-48 described on page 20 may be mentioned.

Hydrophobic compounds such as dye-forming couplers are usually dissolved in a high-boiling organic solvent having a boiling point of about 150 ° C. or higher or a water-insoluble polymer compound in combination with a low-boiling and / or water-soluble organic solvent, if necessary. Then, emulsify and disperse the target hydrophilic colloid using a surfactant in a hydrophilic binder such as gelatin aqueous solution, using a dispersing means such as a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. It may be added in the layer.

Examples of the high boiling point organic solvent used in the present invention include esters such as phthalic acid ester and phosphoric acid ester,
Examples thereof include organic acid amides, ketones, hydrocarbon compounds and the like. Specific examples of these are, for example, JP-A 1-19.
No. 6048, exemplifying compounds A-1 to A-1 described on pages 4 to 7
20, Exemplified compounds II-1 to II- described on pages 8 to 9 of the same.
29, and the exemplified compounds H-1 to H- described on pages 14 to 15 thereof.
22, Exemplified compounds S-1 to S-69 described on pages 3 to 7 of JP-A-1-209446, Exemplified compounds I-1 to I-95 described on pages 10 to 12 of JP-A-63-253943, and the like. Can be mentioned.

Water-insoluble and organic solvent-soluble polymers used for dispersing couplers and the like include (1) vinyl polymers and copolymers, (2) polycondensates of polyhydric alcohols and polysalt acid, 3) Polyester obtained by ring-opening polymerization method, (4) In addition, polycarbonate resin, polyurethane resin, polyamide resin and the like. The number average molecular weight of these polymers is not particularly limited, but is preferably 200,000 or less, more preferably 5,000 to 100,000.

Specific examples of polymers preferably used are shown below. However, the copolymer represents the weight ratio of the monomers.

(PO-1) Poly (Nt-butylacrylamide) (PO-2) Nt-butylacrylamide-methylmethacrylate copolymer (60:40) (PO-3) Polybutylmethacrylate (PO- 4) Methyl methacrylate-styrene copolymer (90:10) (PO-5) Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) (PO-6) ω-methoxy polyethylene glycol acrylate (Additional mol number n = 9) -Nt-butylacrylamide copolymer (25:75)

Further, in addition to the above compounds, JP-A-64-5
Exemplified compounds P-1 to P-2 described in No. 37, pages 10 to 15
00 etc. can be mentioned. The support used in the present invention is basically a base paper, and a polyolefin resin is laminated on both sides of the base paper.

The raw paper used in the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for paper making. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely used.

Further, the support may contain additives such as a sizing agent, a fixing agent, a tension enhancer, a densifier, an antistatic agent and a dye, which are generally used in papermaking, and a surface sizing agent. Alternatively, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

As the support, one having a smooth surface having a weight of 50 to 300 g / m ² is usually used, and the plastic film laminated on both sides is ethylene,
The α-olefin, for example, a homopolymer such as polypropyne, and the copolymer of at least two kinds of the above-mentioned olefins can be selected from a mixture of at least two kinds of these various polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin is not particularly limited, but is usually 20,000 to 200,
Those in the range of 000 are used. The synthetic resin is generally laminated in a weight of 10 to 50 g / m ² . The polyolefin used to laminate the back side of the support (opposite the side on which the emulsion layer is provided) is usually a melt-laminated mixture of low density polyethylene and high density polyethylene. In general, this layer is often matted.

The characteristic feature of the support of the present invention is that fine particles of titanium oxide are dispersed in the water-resistant resin layer so that the density thereof is more than 14% by weight, preferably 15% by weight or more and 60% by weight or less. Especially.

The surface of fine particles of the titanium oxide pigment is combined with or separately from an inorganic oxide such as silica or aluminum oxide, or a divalent or tetravalent alcohol, for example, JP-A-58-1.
Surface treatment with 2,4-dihydroxy-2-methylpentane, trimethylolethane, etc. described in No. 7151 is preferably used. The water resistant resin layer containing fine particles of titanium oxide is used in a thickness of 2 to 200 μm, preferably 5 to 80 μm. In this case, the water-resistant resin containing fine particles of titanium oxide of the present invention is composed of a plurality of water-resistant resin layers having different contents, containing other white pigments, or containing no white pigment. May be used together with.

In such a case, it is preferable to dispose the water resistant resin layer containing titanium oxide fine particles according to the present invention in a layer farther from the support. In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment in the waterproof resin is
It is preferably 0.20 or less, more preferably 0.15 or less, and particularly preferably 0.10 or less.

The dispersibility of the titanium oxide fine particles in the resin layer is from the surface of the resin to about 0.1 μm, preferably 500.
Å About the thickness of the surface is scattered by the ion-sputtering method with glow discharge, the exposed pigment fine particles are observed with an electron microscope, and the area occupied by the image is determined and determined by the coefficient of variation of the occupied area ratio (%). Can be evaluated.

The ion sputtering method is described by Yoichi Murayama,
Kunihiro Kashiwagi “Surface treatment technology using plasma”, Machinery Research Vol.33 No.6 (1981), etc. In order to control the coefficient of variation of the white pigment particles to 0.20 or less, it is preferable to sufficiently knead the white pigment in the presence of the surfactant, and to make the surface of the pigment particles 2 as described above.
It is preferable to use the one treated with a tetrahydric alcohol.

The occupying area ratio (%) of the white pigment fine particles per defined unit area is most typically observed by dividing the observed area into adjacent 6 μm × 6 μm unit areas. Occupied area ratio (%) of projected fine particles
It can be determined by measuring (Ri). The coefficient of variation of the occupied area ratio (%) is Ri with respect to the average value (R) of Ri.
Can be obtained by the ratio s / R of the standard deviation s of.
The number (n) of the target unit areas is preferably 6 or more.
Therefore, the coefficient of variation s / R is

[0138]

[Equation 1]

It can be obtained by White pigments other than titanium oxide may be contained in the water resistant resin. For example, barium sulfate, calcium sulfate, silicon oxide, zinc oxide, titanium phosphate and aluminum oxide are preferably used as white pigments. In addition, various additives such as colored pigments, optical brighteners and antioxidants may be added.

In forming a laminate on the front and back sides of the support, generally, in order to enhance the flatness of the developed photographic paper in a normal environment, the density of the resin layer on the front side may be made slightly larger than that on the back side or the amount of the laminate on the back side than the front side. And the like are used.

In general, the front and back surfaces of the support can be laminated by melt extrusion coating of the polyolefin resin composition on the support. To carry out this melt extrusion coating method, a polyolefin resin composition is usually melt extruded and coated on a running support from a slit die of an extruder in a single-layer or multi-layer form. Usually, the melt extrusion temperature is preferably 200 to 350 ° C. Further, it is preferable that the support is subjected to activation treatment such as corona discharge treatment and flame treatment.

In addition, the surface of the support or, if necessary, both front and back surfaces may be subjected to activation treatment such as corona discharge treatment and flame treatment. If necessary, a sub-coat layer for improving the adhesiveness with the photographic emulsion on the surface of the surface laminate layer or a back-coat layer for improving the printability and antistatic property on the back laminate layer may be provided. Good.

The light-sensitive emulsion to be coated on the surface laminating layer of the support may be a normal black-and-white emulsion or a color emulsion, generally containing several tens of mg of silver per 100 ml of emulsion, Further, the concentration of gelatin contained therein is about 4 to 8% (by weight), and the dry weight of the photographic emulsion layer on the photographic paper is about 10 g / m ² , and conventional ones can be applied.

As the binder in the light-sensitive silver halide emulsion layer and the non-light-sensitive hydrophilic colloid layer used in the present invention, gelatin is advantageous and generally used, but a gelatin derivative may be used instead of gelatin. The gelatin used in the present invention includes these substitutes.

As defined above, which is contained in the light-sensitive silver halide emulsion layer and the non-light-sensitive hydrophilic colloid layer on the side coated with the silver halide emulsion layer from the support of the photographic constituent layer used in the present invention. The total amount of gelatin is 8 g or less per 1 m ² of the light-sensitive material, more preferably 5 g or more and less than 7 g.

The silver halide used in the silver halide emulsion layer according to the present invention includes silver chloride, silver bromide, silver iodide,
Any silver halide such as silver chlorobromide, silver iodobromide and silver chloroiodide can be used.

The silver halide grains preferably used in the present invention have a silver chloride content of 95 mol% or more,
The silver bromide content is preferably 5 mol% or less, and the silver iodide content is preferably 0.5 mol% or less. More preferably, it is a silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. It may also be used as a mixture with silver halide grains having a silver chloride content of 95 mol% or less.

In a silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more, the silver chloride content in the total silver halide grains contained in the emulsion layer is 95. The proportion of silver halide grains of mol% or more is 60% by weight or more, preferably 80% by weight or more. The composition of the silver halide grain may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grain is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 2.5 μm. It is in the range of 1.2 μm. The grain size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation. Coefficient of variation = standard deviation of particle size distribution / average particle size

The silver halide grains used in the present invention are:
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time, or may be grown after forming seed particles. The method of making seed particles and the method of growing seed particles may be the same or different.
The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 may be used.

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

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, US Pat. Nos. 4,183,756 and 4,22
5,666, JP-A-55-26589, JP-B-55
-42737, etc. and The Journal of Photographic Science (J. Photogr. Sc
i. ), 21, 39 (1973) and the like, particles having a shape such as an octahedron, a tetrahedron and a dodecahedron can be prepared and used. Further, grains having twin planes may be used. The silver halide grain used in the present invention may be a grain having a single shape or a mixture of grains having various shapes.

In the present invention, in the process of forming and / or growing silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt). ), An iron salt (including a complex salt) may be added to the metal ions to make them contained inside the particles and / or on the surface of the particles, and by placing them in an appropriate reducing atmosphere, Alternatively, reduction sensitizing nuclei can be provided on the grain surface.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of silver halide grains has been completed, or they may be contained therein. In the present invention, the silver halide grain used in the emulsion may be a grain in which a latent image is mainly formed on the surface,
Also, particles formed mainly inside the particles may be used. Grains whose latent image is mainly formed on the surface are preferable.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound. Sensing methods and the like can be used alone or in combination.

Further, the emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye can be used. Specific examples thereof include the exemplified compounds BS-1 to BS-9, GS-1 to GS-5, RS- described in Japanese Patent Application No. 2-76278, pages 76 to 82.
1 to RS-8, IRS-1 to IRS-10 and the like. Further, as a supersensitizer that can be used in combination with these, for example, Japanese Patent Application No. 2-7627.
No. 8, pages 84 to 85, exemplified compounds SS-1 to S
S-9 etc. can be mentioned.

The light-sensitive material of the present invention contains a color antifoggant,
Image stabilizer, hardener, plasticizer, polymer latex,
An ultraviolet absorber, a formalin scavenger, a development accelerator, a development retarder, a fluorescent chromophore, a matting agent, a lubricant, an antistatic agent, a surfactant and the like can be optionally used. Regarding these compounds, for example, JP-A-62-21527.
No. 2, 63-46436 and the like. or,
An image can be formed by subjecting the light-sensitive material of the present invention to color development processing known in the art.

[0158]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 A Canadian Standard Freeness (J
ISP-8121-76) 20% softwood sulphate pulp (NBSP) beaten to 250 ml, and hardwood bleached sulphate pulp (LSP) beaten to 280 ml freeness.
BSP) 80% was mixed to prepare a papermaking raw material. The papermaking additive was used in the amount shown below based on the absolute dry weight of the pulp.

Cationized starch 2.0% Alkyl ketene dimer resin 0.4% Anionic polyacrylamide resin 0.1% Polyamide polyamine epichlorhydrin resin 0.7% Adjusted to pH 7.5 with sodium hydroxide

A papermaking raw material containing the above additives was paper-made by a Fourdrinier machine and subjected to a size press and a machine calender to produce a base paper having a rice basis weight of 170 g / m ² , a tenacity of 1.0 and a water content of 8%. ..

A 5% size liquid prepared by dissolving carboxyl-modified PVA and sodium chloride in water at a ratio of 2: 1 was used as a size press treatment agent, and this was applied to both sides of the base paper at 2.2 g / m ² . The coating amount was applied.

Corona discharge was applied to both the front and back sides of the obtained base paper, and the surface thereof was subjected to extrusion coating to form a high density polyethylene containing the anatase type titanium dioxide having the concentration shown in Table 1 (specific gravity 0.94, MI = 6. Consisting of 8) 35
forming a polyolefin resin coating layer having a thickness of μm, and
A polyethylene resin coating layer was formed on the back surface of the polyethylene by a coextrusion coating method without using titanium dioxide, and the obtained laminate was pressed against a cleaning roll having a smooth surface at 20 ° C. for photographic printing paper. The support was manufactured.

On the support, each layer having the following constitution was coated on the polyethylene resin coating layer side containing titanium dioxide to prepare a multilayer silver halide color photographic light-sensitive material. The coating liquid was prepared as follows.

First layer coating liquid: 26.7 g of yellow coupler (YC-11), 10.0 g of dye image stabilizer (ST-1), (ST-2) 6.6.
Ethyl acetate (60 ml) was added to and dissolved in 7 g, stain inhibitor (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g, and this solution was added with 20% surfactant (SU-2) 7 ml. A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (HH-1) was added to the second and fourth layers, and (HH-2) was added to the seventh layer.
As coating aids, surfactants (SU-1), (SU-
3) was added to adjust the surface tension. The pH of the coating solution is
Prepared to 5.9 using dilute sulfuric acid or dilute potassium hydroxide. The layer structure of the silver halide photographic light-sensitive material used in the present invention is shown in Table 1.

[0167]

[Table 1]

The additives used in each layer are as follows.
It HH-1: tetrakis (vinylsulfonylmethyl) meta
HH-2: 2,4-dichloro-6-hydroxy-s-to
Riazine / Sodium SU-1: Tri-i-propylnaphthalene sulfonate
Thorium SU-2: Di (2-ethylhexyl) sulphosuccinate
Ter-sodium SU-3: sulfosuccinate di (2,2,3,3,4,4,4)
5,5-Octafluoropentyl) ester / Natriu
Mu ST-3: 1,4-dibucitoxy-2,5-t-butyl
Benzene DOP: Dioctyl phthalate DNP: Dinonyl phthalate DIDP: Di-i-decyl phthalate PVP: Polyvinylpyrrolidone HBS-1: 1-dodecyl-4- (p-toluenesulfo)
Amido) benzene HQ-1: 2,5-di-t-octyl haloid quinone HQ-3: 2,5-di-sec-dodecyl haloid quinone
HQ-4: 2,5-di-sec-tetradecylhydro
Quinone HQ-5: 2-sec-dodecyl-5-sec-tetra
Decyl hydroquinone HQ-6: 2,5-di (1,1-dimethyl-4-hexyl)
Luoxycarbonylbutyl) hydroquinone F-1: 2-methyl-5-chloro-isothiazoline-3
-On

[0169]

[Chemical 50]

(Em-B) tone of blue-sensitive silver halide emulsion
The following (solution A) and (solution B) were added to 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C. to obtain pAg = 6.5,
Simultaneously added over 30 minutes while controlling pH = 3.0, and further the following (solution C) and (solution D) were pAg = 7.3, pH =
Simultaneous addition was carried out over 180 minutes while controlling at 5.5. At this time, pAg was controlled according to the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water and 200 ml (Liquid B) Silver nitrate 10 g Water and 200 ml (Liquid C) Sodium chloride 102.7 g Potassium bromide 1. 0 g Water is added to 600 ml (D liquid) Silver nitrate 300 g Water is added to 600 ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were desalted, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, coefficient of variation = 0.07, and silver chloride content of 9
A 9.5 mol% monodisperse cubic emulsion EMP-1 was obtained. The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em
-B) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-4 1 × 10 ^-4 mol / mol AgX

Tone of green-sensitive silver halide emulsion (Em-G)
Manufacturing time of (A liquid) and (B liquid) and (C liquid) and (D liquid)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-2 having an average grain size of 0.43 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained. For EMP-2, the following compounds were used at 1
After 20 minutes of chemical ripening, a green-sensitive halogenated emulsion (Em-
G) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-2 4 × 10 ⁻⁴ mol / mol AgX

Tone of red-sensitive silver halide emulsion (Em-R)
Manufacturing time of (A liquid) and (B liquid) and (C liquid) and (D liquid)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 μm, a variation coefficient of 0.08, and a silver chloride content of 99.5 mol% was obtained. For EMP-3, the following compound was used at 60 ° C.
After chemical ripening for 0 minutes, a red-sensitive silver halide emulsion (Em-
R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-3 1 × 10 ⁻⁴ mol / mol AgX

[0178]

[Chemical 51]

[0179]

[Chemical 52]

The first layer to the seventh layer of the sample manufactured as described above.
Sample No. 3 having the same constitution except that the amount of titanium dioxide contained in the polyethylene on the side coated with the layer and the dye of the fourth layer and the cyan coupler of the fifth layer were changed as shown in Table 1. 1 to
21 was produced.

[0181]

[Chemical 53]

Using the sample thus produced, continuous treatment was performed according to the treatment steps shown below.

Processing step Processing temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds The composition of the treatment liquid is shown below. The replenishment amount of each processing solution is 80 ml per 1 m ² of the light-sensitive material.

Color developing solution tank solution Replenishing solution Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g 1. 8g Potassium carbonate 27g 27g Add water to make the total volume 1 liter.
The pH of the replenisher solution is adjusted to 0.10 and 10.60.

Bleach stabilizing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 millitorr Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher are the same) F-1 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide ( 20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide. To do. After continuous treatment, the following evaluation was performed on each of the obtained samples.

<Sensitometry> PD for each treated sample
The sensitivity, gradation and maximum red light reflection density (Dmax ^R ) were determined using an A-65 densitometer (manufactured by Konica Corporation).

<Sharpness> After a resolution test chart was printed on each sample with red light and the above treatment was performed, the density of the obtained cyan image was measured with a microdensitometer PDM-5D (manufactured by Konica Corporation). Then, the value represented by the following formula was defined as the sharpness. Sharpness (%) = (5m / mm Dm of dense line print image
ax-Dmin) / (Dmax-Dmi in large area part
n) Here, Dmax: maximum density, Dmin: minimum density, the larger this value, the better the sharpness.

<Whiteness> Konica Color Printer / Processor CL-PP1701QA (manufactured by Konica Corporation) was used for each sample, CPK-2-20 was used as the processing liquid, and the cumulative value of the replenishment amount was the liquid at the start. Continuous replenishment processing is performed until the amount exceeds the limit, and the red light reflection density (Dma
n ^R ) was measured and determined in the same manner as above.

The smaller the D _R , the better the whiteness. D
_If the value of _R is 0.02 or less, it is an acceptable level, but if it exceeds 0.020, the whiteness is visually noticeable, and if it exceeds 0.025, the photographic quality is seriously degraded. cause. The obtained results are shown in Table 2 together with the contents of each sample.

[0191]

[Table 2] From the results in Table 2, it can be seen that sufficient sharpness and sufficient color developability are obtained and the level of white background that does not cause deterioration of color photographic quality is maintained only in the constitution of the present invention.

Example 2 In the same manner as in Example 1, the sample No. 1 of Example 1 was used. Sample No. 8 having exactly the same constitution except that the cyan coupler of the fifth layer and the magenta coupler of the third layer are changed as shown in Table 2 in the constitution of No. 8. 22-33 were produced. Each of these samples
The same processing as in Example 1 was performed and the following evaluations were performed.

<Color Reproducibility> A color chart (manufactured by Macbeth) was photographed and developed with Konica Color DD100 (manufactured by Konica), and the tone of the gray scale portion was adjusted using a negative film. The color reproducibility (yellow, magenta, cyan, red, blue, green) of each hue of the print obtained by the processing was visually evaluated comprehensively. ○ ・ ・ ・ ・ Good color reproduction close to the original ○ △ ・ ・ ・ Slightly cloudy, slightly insufficient color reproduction △ ・ ・ ・ ・ Slightly cloudy, insufficient color reproduction

<Light fading> The obtained sample was stored outdoors in the sun (exposure table) for one month, and evaluated by determining the residual ratio (%) of the dye image at an initial density of 1.0.

<Dark fading property> The obtained sample was treated at 85 ° C and 60 ° C.
It was evaluated by determining the residual rate (%) of the dye image at an initial density of 1.0 after storing it for 20 days under% RH conditions.

[0196]

[Chemical 54]

[0197]

[Table 3]

From the results shown in Table 2, the cyan coupler [C-
I] and magenta coupler [MI] are used, a good photographic image having excellent color reproducibility, light fading and dark fading can be obtained.

Example 3 Sample No. 2 of Example 2 29, except that the total amount of gelatin in the photographic constituent layers was changed as follows. 29
Samples A, B and C were prepared in exactly the same manner as in Example 1
When the same evaluation as described above was performed, Sample A → Sample B → Sample C
Therefore, it was found that the effect of the present invention synergistically manifested more remarkably in the whiteness and color forming property in the constitution in which the dye of the present invention, the cyan coupler of the present invention and the titanium dioxide content of the present invention were combined. It was Sample A: Total gelatin amount 8.5 g / m ² Sample B: Total gelatin amount 7.4 g / m ² Sample C: Total gelatin amount 6.8 g / m ²

[0200]

EFFECTS OF THE INVENTION According to the constitutional requirements of the present invention, a silver halide color photographic light-sensitive material excellent in sharpness and color reproducibility, high image quality, and excellent in color developability and white background without fog rise is provided. can get.

Claims (2)

[Claims] 1. A photosensitive halo of at least one layer on a support.
Providing a silver genide emulsion layer and a non-photosensitive hydrophilic colloid layer
In a silver halide photographic light-sensitive material consisting of
At least silver halide emulsion layer or other hydrophilic colloid layer
General formula [I], general formula [II] or general formula [I
II] containing at least one of the compounds
And in at least one of the silver halide emulsion layers,
Containing a cyan coupler represented by the general formula [C-1],
And the water-resistant resin on the side coated with the silver halide emulsion
When the density of titanium oxide particles in the layer is 14% by weight or more
Silver halide milk contained from the support of the photographic constituent layers.
Of the photosensitive silver halide emulsion layer on the side coated with the agent layer
The total amount of gelatin contained in the photohydrophilic colloid layer is
8 g / m²The following are silver halide masks characterized by
Photographic material. [Chemical 1][In the formula, V₁, V₂Are hydrogen atom, cyano group, and hydr
Roxyl group, carboxyl group, -COOR₁, -COR
₁, -CONR₁R₂, -OR₁, -NR₁R₂, -N
R₁R₂, -NR₁COR₂, -NR₁SO₂R₂, A
Rualkyl group, aralkyl group, cycloalkyl group, aryl
Represents a group, a heterocyclic group or an amino group, and W₁, W₂Are each
Hydrogen atom, -NR₃R_Four, -NR₃COR_Four, -NR₃
SO₂R _Four, Alkyl group, aralkyl group, cycloalkyl
Represents an alkyl group, an aryl group, a heterocyclic group or an amino group,
X₁, X₂Are respectively hydrogen atom, cyano group, carboxyl
Group, sulfo group, -COOR_Five, -COR_Five, -CONR
_FiveR₆, -NR_FiveR₆, -NR_FiveCOR₆, -NR_FiveS
O₂R₆, -SO₂R_Five, An alkyl group, an aralkyl group,
Represents a cycloalkyl group, an aryl group or a heterocyclic group, L
₁, L₂, L₃Each represents a methine group, m is 0, 1 or
2, n is 1, 2 or 3, and M^{n +}Is an n-valent tick
Indicates ON. R₁, R₂, R₃, R_Four, R_FiveAnd R₆Is
Hydrogen atom, alkyl group, aryl group or heterocyclic group, respectively
Represents R₁And R₂, R₃And R_FourOr R_FiveAnd R₆Is connected
May form a 5- or 6-membered ring. However, V₁,
V₂, W₁, W₂, X₁, X₂At least one of
Represents a group containing a carboxyl group or a sulfo group.
You ] [Chemical 2][In the formula, R₇Are each an alkyl group, an aryl group or a hetero group
Represents a ring group, R₈Are a hydrogen atom, an alkyl group, and an ant, respectively.
Group, heterocyclic group, -COR_TenOr-SO₂R_TenThe table
And R₉Are hydrogen atom, cyano group, hydroxyl
Group, carboxyl group, COOR_Ten, -CONR₁₁R₁₂,
-OR_Ten, -NR₁₁R₁₂, -NR₁₁COR₁₂, -NR₁₁
SO₂R₁₂, -NR₁₁CONR₁₁R₁₂, Alkyl group,
Represents the reel base, L_Four, L_Five, L₆Are methine groups
Then k₁Represents 0, 1 or 2. Y₁, Y₂Is an oxygen atom
Or NR₁₃Represents R_TenIs an alkyl group or an aryl group
Represent, R₁₁, R₁₂Are each a hydrogen atom, an alkyl group or
Represents a reel group. R₁₃Is R₇To form a 5-membered ring
Represents a group of non-metal atoms required for However, R₇, R₈,
R₉At least one of at least one carboxy
Represents a group containing a sulfonyl group or a sulfo group. ] [Chemical 3][R in the formula₁₄, R₁₅Are -CN and -COR, respectively.₁₈, -CO
OR₁₈Or -CONR₁₉R₂₀Represents R₁₆, R₁₇Is each
, Hydrogen atom, alkyl group, cycloalkyl group, aryl
L group or heterocyclic group, L₇, L₈, L₉Are each
Group, and k represents 0, 1 or 2. R₁₈Is alkyl
Represents a group or an aryl group. R₁₉, R₂₀Is hydrogen source
Child, alkyl group, alkenyl group, aryl group or heterocycle
Represents a group, R₁₉And R₂₀One of is a hydrogen atom
It However, R₁₄, R₁₅, R₁₆, R₁₇At least of
One represents a water-soluble group or a substituent containing a water-soluble group. ] [Chemical 4][In the formula, R_{twenty one}Represents an alkyl group having 2 to 6 carbon atoms.
R_{twenty two}Represents a ballast group. Z₁Is hydrogen atom or color development
Atoms or groups that can be removed by reaction with the oxidant of the main drug
Represents ] 2. A silver halide color photographic light-sensitive material characterized in that at least one of the silver halide emulsion layers according to claim 1 contains a magenta coupler represented by the general formula [MI]. [Chemical 5] Wherein, J is -O -, - S -, - N (R 26) - represents,
R ₂₆ represents a hydrogen atom or a substituent, and n represents 0 or 1. R ₂₄ represents an alkyl group or an aryl group. R ₂₅ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]