JP3358037B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to a method which is excellent in processing stability during continuous development processing and has excellent durability in a dye image formed by processing. The present invention relates to a method for processing a silver halide color photographic material (hereinafter, also referred to as a silver halide photographic material or a photographic material).

[0002]

2. Description of the Related Art In a method of continuously processing a photosensitive material (running processing), in order to prevent a change in characteristics of a finished print, the processing is generally performed while replenishing a processing solution. However, in this case, a large amount of overflow liquid is generated with the replenishment of the replenisher, and environmental destruction due to disposal of the overflow liquid is a major problem, and reduction of the replenisher (low replenishment) is strongly desired. . However,
It has been found that when the processing solution is replenished at a low level, the stability of the print during image processing, particularly the characteristic curve, greatly changes.

On the other hand, in recent years, photosensitive materials have been subjected to a running process by an automatic developing machine provided in a developing laboratory. In the processing of such photosensitive materials, as a part of improving the service to users, the day of development has been considered. It is required that the developer be processed within and returned to the user, and the development of rapid processing technology is required. In recent years, it has been required to return from the reception in tens of minutes, and the development of technology has been required more and more rapidly. Against this background, Eastman Kodak has proposed a rapid processing of color paper called process RA4. However, it has been found that when the processing time is significantly reduced, the stability during image processing, particularly the maximum color density, greatly changes. In recent years, processing that is even faster than the process RA4 has been put to practical use. However, it has been found that a dramatic reduction in the processing time significantly deteriorates the photographic performance in a processing solution fatigued by the running process.

Japanese Patent Application Laid-Open No. 4-265975 discloses a method in which a monohydric alcohol is added to a silver halide photographic material to improve the stability of a developing solution against a change in pH. However, it has been found that the effect is an effective means for changing the pH of the developing solution, but the effect is not sufficient for the overall deterioration due to the running of the processing solution.

Further, in a silver halide photographic light-sensitive material used for direct viewing, yellow, magenta and cyan dye-forming couplers are usually used as a color forming agent for forming a dye image. For these couplers, basic performance such as color reproducibility, color development and image storability in the obtained dye image is required, but in particular, in recent years, dye images do not discolor even if exposed to light for a long time. In addition, it is required that the uncolored portion does not yellow (hereinafter, also referred to as Y stain). However, it has been found that the compound disclosed in JP-A-4-265975 has no effect (improvement effect) on the improvement of the preservability of the dye image.

[0006]

Accordingly, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which photographic performance does not deteriorate even if the replenishment amount of a color developing solution is reduced during color developing processing. It is to provide. A second object of the present invention is to provide a method for processing a silver halide color photographic material in which photographic performance is not degraded even if the processing time during color development processing is reduced. A third object of the present invention is to provide a method of processing a silver halide color photographic light-sensitive material in which image deterioration such as fading or generation of Y stain is suppressed even when exposed to light after a running process. .

[0007]

The above object of the present invention is achieved by any of the following constitutions (1) to ( 3 ).

(1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support comprises the silver halide emulsion layer having the above general formula [II] or
Contains at least one polyhydric alcohol represented by [III] and at least one dye-forming coupler, and replenishes the silver halide color photographic light-sensitive material with a color developing solution per m ^{2 of the} light-sensitive material. A method for processing a silver halide color photographic light-sensitive material, wherein continuous processing is performed with a color developing solution of 120 ml or less and a color developing time of 45 seconds or less.

[0009]

[0010]

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

( 2 ) At least one layer of halogen on a support
Silver halide color photographic material having a silver halide emulsion layer
Is represented by the above general formula (VI) in the silver halide emulsion layer.
At least one polyhydric alcohol to be used and a pigment-forming cap
Silver halide containing at least one of
The replenishment amount of the color developing solution for the color photographic light-sensitive material is
In the color developer is not more than 1 m ² per 120 ml, and color current
Continuous processing with an image processing time of 45 seconds or less
For processing silver halide color photographic light-sensitive materials.

( 3 ) At least one layer of halogen on the support
Silver halide color photographic material having a silver halide emulsion layer
Has the above-mentioned general formula (VII)-in the silver halide emulsion layer
At least one polyhydric alcohol represented by [IX] and a color
Containing at least one element-forming coupler, and
The amount of replenishment of the color developing solution for silver
A color developing solution of 120 ml or less per 1 m ^{2 of the} photosensitive material ,
Continuous processing with a color development time of 45 seconds or less
A method for processing a silver halide color photographic light-sensitive material, comprising:

[0021]

[0022]

[0023]

[0024]

That is, the present inventors have achieved the above object of the present invention by providing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, The above general formulas (II), (III), (V
I) or at least one of the polyhydric alcohols represented by [VII] to [IX] and at least one of the dye-forming couplers, and the silver halide color photographic light-sensitive material is replenished with a color developing solution. Is a color developing solution of 120 ml or less per 1 m ² of the light-sensitive material, and the color developing time is 45 seconds or less. That is what I found. The replenishment amount of the color developing solution is preferably 20 ml or more and 120 ml or less per 1 m ² of the light-sensitive material.
The color development time is preferably 5 seconds or more and 45 seconds or less.

[0026]

[0027]

An object of the present invention is to provide a silver halide color photographic light-sensitive material with a replenishment rate of a color developer of 120 m / m ² of the light-sensitive material.
l is achieved by processing with a color developing solution that is less than
The effect is the amount of the replenisher of the color developing solution photosensitive material 1 m ² per 20
Appears when the volume is between 60 ml and 60 ml.

The effect of the present invention can be achieved by processing the silver halide color photographic light-sensitive material with a color development processing time of 45 seconds or less. The effect of the present invention is remarkably exhibited by the treatment, and the effect is further manifested by the treatment with the development processing time of 15 seconds or less.

Further, in the present invention, in the silver halide color photographic light-sensitive material, a dye-forming coupler represented by the above-mentioned formula [MI] [formula 1] is formed on the same layer as the layer containing a polyhydric alcohol. By incorporating at least one of the above, the effects of the present invention are clearly exhibited.

Further, in the silver halide color photographic light-sensitive material, the polyhydric alcohol is represented by the following general formula [I] (same as the general formula [I]). Alternatively, in the processing method for a silver halide photographic light-sensitive material described in 7, the effects of the present invention become apparent.

General formula [I] R _A1 -O-R _{A2 The} present invention will be specifically described below.

First, the coupler represented by the general formula [MI] will be described.

[0034]

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In the general formula [MI], the substituent represented by R is not particularly limited, but is typically an alkyl,
Aryl, anilino, acylamino, sulfonamide,
Examples of each group include alkylthio, arylthio, alkenyl, and cycloalkyl. Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro Compound residues and bridged hydrocarbon compound residues are also included.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

As the acylamino group represented by R, an alkylcarbonylamino group, an arylcarbonylamino group and the like can be mentioned.

As the sulfonamide group represented by R,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl and aryl components of the alkylthio and arylthio groups represented by R include the alkyl and aryl groups represented by R.

The alkenyl group represented by R has from 2 to 32 carbon atoms, and the cycloalkyl group has from 3 to 32 carbon atoms.
12, particularly preferably 5 to 7, wherein the alkenyl group may be linear or branched.

As the cycloalkenyl group represented by R, those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, are preferred.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group or an arylsulfinyl group; a phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group or an aryloxy group. Phosphonyl group, arylphosphonyl group, etc .; acyl group as alkylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group as alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group as alkylsulfamoyl group, aryl group, aryl Sulfamoyl group and the like; acyloxy group as alkylcarbonyloxy group and arylcarbonyloxy group and the like; carbamoyloxy group as alkylcarbamoyloxy group and arylcarbamoyloxy Group or the like; ureido group alkylureido group, an arylureido group or the like; sulfamethoxazole The sulfamoylamino group alkylsulfamoyl group, an aryl sulfamoylamino group or the like; 5 is a heterocyclic group
Preferred is a 7-membered one, specifically, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazole and the like;
As the heterocyclic group oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6-tetrahydropyranyl-2
-Oxy group, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, 4-diphenoxy-1,3,5-triazole-6-thio group and the like; siloxy group such as trimethylsiloxy group, triethylsiloxy group and dimethylbutylsiloxy group; and imide group as succinimide group and 3-heptadecylsuccinate Acid imide group, phthalimide group, glutarimide group, etc .; spiro compound residues include spiro [3.3] heptan-1-yl;
The bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.1.1 ^{3.1 7]} decan-1-yl,
7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0045]

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(R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z 'include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Those mentioned are mentioned.

The compound represented by the general formula [MI] is more specifically represented, for example, by the following general formulas [M-II] to [M-VII].

[0049]

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In the general formulas [M-II] to [M-VII], R _{1 to} R ₈ and X have the same meanings as R and X described above.

Among the couplers represented by the formulas [M-II] to [M-VII], couplers represented by the formulas [M-II] and [M-III] are preferable. More preferably, the following general formulas [M-VIII] and [M-IX]
It is represented by

[0052]

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In the above formula [M-VIII], R ₉ and R ₁₀ represent an alkyl group. X is the general formula [MI]
Has the same meaning as X in The alkyl group represented by R ₉ and R ₁₀ is preferably an alkyl group having 1 to 32 carbon atoms, may be linear or branched, and may further have a substituent. R ₉
And the substituent to be substituted on the alkyl group represented by R ₁₀ include:
The substituent represented by R in the general formula [MI] is exemplified. R ₉ is preferably a secondary or tertiary alkyl group.

[0054]

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In the general formula [M-IX], R ₁₁ and X have the same meanings as R and X in the general formula [MI], respectively. R ₁₂ represents a hydrogen atom or a substituent. R ₁₃ and R ₁₄ represent a substituent. n represents an integer of 0 to 3. Examples of the substituent represented by R ₁₂ , R ₁₃ and R ₁₄ include the substituent represented by R in the above formula [MI], preferably an alkyl group, an alkoxy group, an acylamino group, a sulfonamide group, a ureido group. , A sulfonyl group, an imide group or a halogen atom.

The following are specific examples of the coupler represented by the above general formula [MI].

[0057]

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[0058]

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[0059]

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[0060]

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In addition to the specific examples described above, examples of the coupler of the present invention include compounds represented by Exemplified Compounds 1 to 64 described on pages 5 to 9 of JP-A-63-253946 and JP-A-2-100048. Compounds represented by Exemplified Compounds M-1 to M-29 described on pages 5 to 6 of JP-A-62-215272, and pages 106 to 114 of JP-A-62-215272.
Exemplified compounds M-16 to M-34, M-37 to M-3 described on page
9, compounds represented by M-41 to M-47, compounds represented by M-1 to M-15 described on pages 12 to 14 of JP-A-2-96133, JP-A-61-292143. Compounds represented by 1 to 7 on page 6 and exemplified compounds 1 to 11, 15 to 16, 18 to 28, and 30 to 41 on pages 19 to 32 of JP-A-3-125143. Compounds, compounds represented by Exemplified Compounds 1 to 24 on pages 3 to 5 of JP-A-4-128744, JP-A-4-2422
Compounds represented by Exemplified Compounds 1 to 22 described on pages 5 to 7 of JP-A-49 can be mentioned.

These couplers are usually used in silver halide 1
1 × 10 ^-3 to 2 moles per mole, can be preferably employed in the range of 1 × 10 ^-2 mol to 7-× 10 ^-1 mol.

Next, the polyhydric alcohol used in the present invention will be described. In the present invention, the polyhydric alcohol refers to a compound having two or more alcoholic hydroxyl groups in a molecule, and includes a carbon atom in an aliphatic compound, an alicyclic compound, or a heterocyclic compound having no aromaticity. Is a compound having two or more substituted hydroxyl groups in the molecule.

The polyhydric alcohol of the present invention preferably has a total of 6 or more carbon atoms.

The polyhydric alcohol of the present invention preferably has a molecular weight of 5,000 or less, and is preferably liquid at ordinary temperature.

The polyhydric alcohol of the present invention preferably has a hydroxyl value of 50 or more.

The polyhydric alcohol of the present invention is preferably a log
P value is 3 or more.

The polyhydric alcohol of the present invention is preferably a compound represented by the following general formulas [I] to [VI].

Formula [I] R _A1 —O—R _A2 wherein R _A1 represents an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R _A2 represents an alkyl group, an alkenyl group or a cycloalkyl group. , Cycloalkenyl group,-(O =) CR _A3 , -SO ₂ -R _A4 ,-(O =) P <(-OR _A5 ) (-O
-R _A6 ),-(O =) P <(R _A7 ) (R _A8 ), -CON <(R _A9 ) (R _A10 ) or -SO ₂ N <(R _A11 ) (R _A12 ).

Here, R _{A3 to} R _A9 and R _A11 represent an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, respectively, and R _A10 and R _A12 represent a hydrogen atom or an alkyl group, an alkenyl group or a cycloalkyl group. Represents an alkyl group, a cycloalkenyl group, or an aryl group.

[0071] However, alkyl groups represented by R _A1, an alkenyl group, a cycloalkyl group, an alkyl group represented by cycloalkenyl group and / or R _A2, alkenyl group, cycloalkyl group, cycloalkenyl group and / or R _A3 to R _A12 And at least one position on the carbon atom of the alkyl group, alkenyl group, cycloalkyl group or cycloalkenyl group represented by is substituted with a hydroxyl group, and the total number of alcoholic hydroxyl groups in the molecule is 2 or more. Further, R _A1 and R _A2 are not fused to each other to form a ring. ]

[0072]

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[In the general formulas [II] and [III], R _A21 , R _A22 , R _A23 and R _A24 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, Represents an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group.

However, at least two of R _A21 , R _A22 , R _A23 and R _A24 are hydrogen atoms, and not all of them are hydrogen atoms. ]

[0075]

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Wherein R _A41 , R _A42 and R _A43 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a carbamoyl group, and L represents an alkylene group or an arylene group. Represents, Y
_A is a hydrogen atom or a carbamoyl group, a sulfamoyl group,
Represents an acyl group, and m represents 0 or 1. ]

[0077]

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[Wherein, R ₅₁ represents a substituted alkyl group or a substituted alkenyl group containing two or more hydroxyl groups, R ₅₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group; R _{51 to} R ₅₂ may be fused with each other to form a lactone ring. ]

[0079]

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[Wherein R ₆₁ represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group,
It represents an acyl group, a sulfonyl group, a carbamoyl group or a sulfamoyl group, and R ₆₂ and R ₆₃ each represent an alkyl group substituted with a hydroxyl group and / or an alkoxy group. However, R ₆₂ and R ₆₃ each have at least one alcoholic hydroxyl group. In the general formulas [I] to [VI], R _{A1 to} R _A12 , R _A21 to
The alkyl group represented by R _A24 , R _{A41 to} R _A43 , R ₅₂ and R ₆₁ may be linear or branched, and preferably has 1 to 32 carbon atoms, such as methyl, ethyl, isopropyl, t
-Butyl group, dodecyl group, heptadecyl group, 2-ethylhexyl group and the like are mentioned as typical examples.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43, alkenyl groups represented by R ₅₂ and R ₆₁ may be linear or branched, preferably one having 2 to 32 carbon atoms, such as vinyl group, propenyl group, 1,1-undecenyl, 1-methyl propenyl group And the like are typical examples.

The substituted alkyl group or substituted alkenyl group having two or more hydroxyl groups represented by R ₅₁ is the above-mentioned R _A1 to R _A1 .
Any two or more carbon atoms of the alkyl group and alkenyl group of R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₂ and R ₆₁ (including those each further substituted by a substituent) are hydroxyl groups. And typical examples thereof include a 1,2-dihydroxypropyl group and a 1,1-dihydroxymethylethyl group.

The alkyl groups represented by R ₆₂ and R ₆₃ are the same as those of R _{A1 to} R _A2 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₂ and R
_{61 represents} a group in which the carbon atom of an alkyl group is substituted by a hydroxyl group and / or an alkoxy group, and each may further have another substituent. R ₆₂ and R ₆₃ are preferably
− (CH ₂ CH ₂ O) _s H, − (CH ₂ CH ₂ CH ₂ O) _r H, − (CH ₂ CH (OH) CH ₂ O)
represents _t H. Here, s, r, and t each represent an integer of 1 to 5.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43, the cycloalkyl group represented by R ₅₂ and R _61, preferably has 3 to 12 carbon atoms, in particular 5-7, may have a branched structure, such as cyclohexyl group, cyclopentyl group, Propyl group, 2-methylcyclopropyl group and the like are mentioned as typical examples.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43, The cycloalkenyl group represented by R ₅₂ and R _61, preferably has 3 to 12 carbon atoms, in particular 5-7, may have a branched structure, for example, 1-cyclohexenyl group, 2 -Cyclopentenyl group and the like are mentioned as typical examples.

R _{A3 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
The aryl group represented by _A43 and R _52, carbon atoms 6
To 14 are preferable, and typical examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group and aryl group may be further substituted by a substituent. Examples of the substituent include the following.

Alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Each group such as alkenyl, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, Examples include aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and hydroxyl groups.

The acyl group represented by R _{A21 to} R _A24 , Y _A and R ₆₁ is preferably-(O =) CR _A3 (R _A3 is as described above).

The sulfonyl group represented by R _{A21 to} R _A24 and R ₆₁ is preferably —SO ₂ —R _A4 (R _A4 is as described above).

The phosphonyl group represented by R _{A21 to} R _A24 is preferably-(O =) P <(-OR _A5 ) (-OR _A6 ) (R _A5 and R _A6 are as described above).

[0092] _{R A21 ~R A24, R A41 ~R} A43, Y A and R
_{As the} carbamoyl group represented by ₆₁ , -CON <(R _A9 ) (R
_A10 ) (R _A9 and R _A10 are as defined above).

The sulfamoyl groups represented by R _{A21 to} R _A24 , Y _A and R ₆₁ include —SO ₂ N <(R _A11 ) (R _A12 ) (R _A11
And R _A12 are as described above). As the alkylene group represented by L, those having 1 to 32 carbon atoms are preferable,
It may be linear or branched. The arylene group represented by L is preferably a phenylene group. The alkylene group and the arylene group represented by L may further have a substituent, and the substituent includes the above-mentioned R _{A1 to} R _A12 , R _{A21 to} R _A24 , R
_{A41 to} R _A43 , R ₅₁ , R ₅₂ and R _{61 to} R ₆₃ include the substituents mentioned above. In the general formula [I], R _A1 and R _A2 are not fused to each other to form a ring, but R _A5 and R _A6 , R _A7 and R _A8 , R _A9 and R _A10, and R
_A11 and R _A12 may be fused to each other to form a ring.

Particularly preferred among the polyhydric alcohols of the present invention are the compounds represented by the above general formulas [II] and [III] and the following general formulas [VII] to [IX].

[0095]

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[Wherein R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group. , P represents an integer of 1 to 20. When p is 2 or more, a plurality of R ₇₃ may be the same or different. Where p is 1
When R represents any two of R ₇₁ , R ₇₂ and R ₇₃ are hydrogen atoms, and when p is 2 or more, at least two of R ₇₁ , R ₇₂ and a plurality of R ₇₃ are hydrogen atoms. And not all are hydrogen atoms. ]

[0097]

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[Wherein R _{81 to} R ₈₄ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group;
Represents an integer from to 20, and when q is 2 or more, a plurality of R ₈₃ , R
₈₄ may be the same or different. Where q
R ₈₁ but when representing a 1, R _82, at least two of R ₈₃ and R ₈₄ are hydrogen atoms, and not that all of them are hydrogen atoms, when q is 2 or more, R _81, R _At least two of ₈₂ , the plurality of R _83, and the plurality of R ₈₄ are hydrogen atoms, and not all are hydrogen atoms. ]

[0099]

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[Wherein R _{91 to} R ₉₆ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. However, at least two of R _{91 to} R ₉₆ are hydrogen atoms, and not all of them are hydrogen atoms. In the general formulas [VII] to [IX], R _{71 to} R ₇₃ and R ₈₁ to
Alkyl group represented by R ₈₄ and R ₉₁ to R _96, an alkenyl group, a cycloalkyl group, a cycloalkenyl group,
R _{A1 to} R in the general formulas [I] to [VI], respectively.
_A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₁ , R ₅₂ and R
The alkyl group represented by ₆₁ to R _63, alkenyl group, cycloalkyl group, include those described as a cycloalkenyl group.

The alkyl group, alkenyl group, cycloalkyl group and cycloalkenyl group may be further substituted by a substituent.
_{A1 ~R A12, R A21 ~R A24} , R A41 ~R A43, R 51, R 52
And the substituents for R _{61 to} R ₆₃ .

The acyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ is preferably-(O =) CR _A3 (where R _A3 is as described above).

The sulfonyl group represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ is preferably —SO ₂ —R _A4 (where R _A4 is as described above).

The phosphonyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include-(O =) P <(-OR _A5 ) (-O
-R _A6 ) (R _A5 and R _A6 are as defined above).

The carbamoyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include -CON <(R _A9 ) (R _A10 )
(R _A9 and R _A10 are as described above).

The sulfamoyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include —SO ₂ N <(R _A11 ) (R
_A12 ) (R _A11 and R _A12 are as defined above) are preferred.

Hereinafter, typical specific examples of the polyhydric alcohol of the present invention will be shown, but the present invention is not limited to these.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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In the present invention, the magenta coupler represented by formula (MI) (hereinafter also referred to as magenta coupler [MI]) and the polyhydric alcohol of the present invention are preferably green-sensitive halogenated compounds. It is contained in at least one of the silver emulsion layers.

In order to include the magenta coupler [MI] and the polyhydric alcohol in the silver halide emulsion layer,
A conventionally known method, for example, a mixed solution of a high-boiling solvent such as dibutyl phthalate or tricresyl phosphate and a low-boiling solvent such as butyl acetate or ethyl acetate, if necessary, using the magenta coupler and the polyhydric alcohol of the present invention. Alternatively, after dissolving in a solvent having only a low boiling point solvent, mixing with a gelatin aqueous solution containing a surfactant, and then emulsifying and dispersing using a high-speed rotary mixer or a colloid mill or an ultrasonic dispersing machine, and then into an emulsion. A direct addition method can be employed. Alternatively, the emulsified dispersion may be set, then cut into pieces, washed with water, and then added to the emulsion.

Further, in the silver halide color photographic light-sensitive material, the weight ratio of the polyhydric alcohol to the dye-forming coupler (polyhydric alcohol / dye-forming coupler) is 0.5 or more and 5 or less. The effect of the present invention can be clearly achieved in the method for processing a silver halide color photographic material described above.

The silver halide emulsion used in the silver halide color photographic light-sensitive material according to the present invention contains 95 to 9 silver chloride.
Silver content is preferably 9.95 mol%, and silver chlorobromide containing substantially no silver iodide is preferred. Silver chloride content 97 ~ 9
9.9 mol% is more preferred. To reduce the amount of replenishment of the color developing solution and development in a shorter time, 99.5 to 99.9
More preferably, it is mol%.

The silver halide grains used in the light-sensitive material of the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. U.S. Pat.Nos. 4,183,756 and 4,225,666
No., JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J.Ph
otogr.Sci.) 21, 39 (1973), etc., can be used to produce particles having a shape such as octahedron, tetradecahedron, dodecahedron, etc., and use them. Further, particles having a twin plane may be used.

As the silver halide grains used in the light-sensitive material of the present invention, grains having a single shape may be used.
Particles of various shapes may be mixed.

The grain size of the silver halide grains used in the light-sensitive material of the present invention is not particularly limited, but is preferably 0.1 in consideration of other photographic properties such as rapid processing property and sensitivity.
It is in the range of 1 to 1.2 μm, more preferably 0.2 to 1.0 μm. The particle size can be measured by various methods generally used in the technical field. A typical method is Loveland's “particle size analysis method” (A.
STM Symposium on Right Microscopy, pp. 94-122, 1955) or "Theory of Photographic Processing"
Third Edition "(co-authored by Mies and James, Chapter 2, published by Macmillan, 1966).

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains used in the light-sensitive material of the present invention may be polydisperse or monodisperse. Preferably the coefficient of variation is 0.22 or less,
More preferred are monodispersed silver halide grains of 0.15 or less. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one form of the simultaneous mixing method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor described in JP-A Nos. 57-92523 and 57-92524, published in Germany A device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt described in Patent 2,921,164, etc., and the reaction mother liquor was taken out of the reactor described in JP-B-56-501776, etc. An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

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

For reduction sensitization of the silver halide emulsion according to the present invention, a known method can be used. For example,
It is also possible to use a method of adding various reducing agents,
A method of ripening under high silver ion concentration conditions or a method of ripening under high pH conditions can be used.

The reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention includes stannous salts such as stannous chloride, borane such as tri-t-butylamine borane, sodium sulfite, potassium sulfite and the like. And reductones such as ascorbic acid, thiourea dioxide and the like. Of these, thiourea dioxide, ascorbic acid and its derivatives, and sulfites can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH at the time of ripening, the method using the above reducing agent is preferable because of its excellent reproducibility.

These reducing agents may be dissolved in a solvent such as water or alcohol and added to a silver halide emulsion for ripening, or may be added during the formation of silver halide grains and reduced at the same time as grain formation. You may feel.

The amount of these reducing agents to be added must be adjusted according to the pH, silver ion concentration and the like of the silver halide emulsion.
^-7 to 10 ^-2 mol is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Compounds used for such purposes include:
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide.

The silver halide emulsion according to the present invention is subjected to reduction sensitization, and can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, etc. can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be mentioned.

The gold sensitizer applied to the silver halide emulsion according to the present invention can be added as various gold complexes such as chloroauric acid, gold sulfide or gold thiosulfate. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of gold compound used is
Although it is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, and the like, it is usually preferably 1 × 10 ^-4 mol to 1 × 10 ^-8 mol per mol of silver halide. More preferably, it is 1 × 10 ^-5 mol to 1 × 10 ^-8 mol.

The silver halide emulsion according to the present invention is intended to prevent fog generated during the preparation process of the silver halide photographic light-sensitive material, to reduce fluctuations in performance during storage, and to prevent fog generated during development. And known antifoggants and stabilizers can be used. Examples of the compound that can be used for such purpose include a compound represented by the general formula (II) described in the lower column on page 7 of JP-A-2-46036, and specific compounds thereof include: (IIa-1)-(IIa-8), (IIb-1)-(II
b-7) and 1- (3-methoxyphenyl) -5-mercaptotetrazole. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻¹ mol per mol of silver halide, and more preferably about 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁵ mol. 1
× 10 ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × 10
An amount of about ^-9 mol to 1 × 10 ^-3 mol is preferred.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, spectral sensitization was performed in a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any of the known compounds can be used.
No. 124, pages 108 to 109, BS-1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 110 of the same specification are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described on pages 111 to 112 of the same specification are preferably used. When exposing the silver halide photographic light-sensitive material according to the present invention to a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, JP-A-4-28
The dyes of IRS-1 to 11 described in the specification of JP-A-5950, pages 12 to 14 are preferably used. It is preferable to use supersensitizers SS-1 to SS-9 described on pages 14 to 15 in combination with these dyes.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region,
AI-1 described in JP-A-3-251840, pages 117 to 118
To 11 are preferably used, and as the infrared absorbing dye, compounds represented by general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has characteristics and does not affect the photographic characteristics of the silver halide photographic emulsion and does not cause contamination due to residual color. Specific examples of preferred compounds include the lower left column on page 3 of the same specification,
Exemplary compounds (1) to (45) listed in the lower left column of page 5
Can be mentioned.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Although any compound that can be used can be used, particularly typical ones are a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical example is a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

As the yellow coupler that can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a coupler represented by the general formula (Y-I) described on page 8 of JP-A-4-114154 can be used. Can be mentioned.
Specific compounds are described in pages 9 to 11 of the same specification, YC-1 to YC-9.
Can be mentioned. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce yellow having a preferable color tone.

Cyan couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention include:
The general formula (C-) described in JP-A-4-114154, p.
Couplers represented by I) and (C-II) can be mentioned. Specific compounds are described in pages 18 to 21 of the same specification.
To CC-9.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is usually used. If necessary, the mixture is dissolved by using a low boiling point and / or water-soluble organic solvent in combination, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a betaine-based surfactant or another surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of the high boiling organic solvent that can be used to dissolve and disperse the coupler include phthalic acid esters such as dioctyl phthalate, and phosphoric acid esters such as tricresyl phosphate. The effect is exhibited more effectively.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described on page 33 of JP-A-4-114154 and the compound (A'-) described on page 35 of the same specification are described.
Compounds such as 1) can be used. In addition, a fluorescent dye-releasing compound described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 × 10 ^{−3 to} 5 mol, more preferably 1 × 10 ⁻³ mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

It is advantageous to use gelatin as a binder in the silver halide photographic light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

The total amount of gelatin used as a binder is preferably 10.0 g / m ² or less. Although the lower limit is not particularly limited, it is generally preferably 3 g / m ² or more from the viewpoint of physical properties or photographic performance.

As the reflective support according to the present invention, any material may be used, and examples thereof include polyethylene-coated paper containing white pigment, baryta paper, vinyl chloride sheet, polypropylene containing white pigment, and polyethylene terephthalate support. Can be used.

Among them, a support having on its surface a polyolefin resin layer containing a white pigment is preferred.

As the white pigment used in the reflective support according to the present invention, an inorganic and / or organic white pigment can be used, and preferably, an inorganic white pigment is used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as a content in the water-resistant resin layer. The content is preferably at least 13% by weight,
It is more preferable that the content be not less than weight%. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention is described in
It can be measured by the method described in JP-A-2-28640.
When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less, as the coefficient of variation described in the above publication.

The silver halide photographic light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion on the surface of the support, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material according to the present invention include aminophenol and p-phenylenediamine widely used in various color photographic processes. A system compound is used. In particular, aromatic primary amine color developing agents are preferably used.

The aromatic primary amine developing agents include (1) N, N-dimethyl-p-phenylenediamine hydrochloride (2) N-methyl-p-phenylenediamine hydrochloride (3) 2-amino-5- ( N-ethyl-N-dodecylamino) toluene (4) N-ethyl-N- (β-methanesulfonamidoethyl) -3-
Methyl-4-aminoaniline sulfate (5) N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-
Aminoaniline sulfate (6) 4-amino-3-methyl-N, N, -diethylaniline (7) 4-amino-N- (β-methoxyethyl) -N-ethyl-3-methylaniline-p-toluene Sulfonate (8) 4-amino-N-ethyl-N- (γ-hydroxypropyl) -3
-Methylaniline-p-toluenesulfonate These color developing agents are 1 × 10
^{-3 to} 2 × 10 ^-1 mol is preferably used.
More preferably, it is used in a range of from × 10 ^{-3 to} 2 × 10 ^-1 mol.

In the color developing solution, a known developing solution component compound can be added in addition to the aforementioned color developing agent. Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative,
A chelating agent or the like is used.

As the alkali agent used in the color developing solution for a silver halide photographic light-sensitive material according to the present invention, potassium carbonate, potassium borate, trisodium phosphate and the like are used, and water is mainly used for pH adjustment and the like. Sodium oxide,
Potassium hydroxide or the like is used. The pH of the color developer is
It is generally 9 to 13, and preferably 9.5 to 13.

For the purpose of suppressing development, halide salt ions are often used. However, in the image forming method according to the present invention, since it is necessary to complete the development in a very short time, chloride ions are mainly used. Potassium chloride, sodium chloride, and the like. The amount of chloride ions is approximately 3.0 × 10 ^-2 mol or more per liter of color developing solution,
Preferably, it is 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol. The bromide ion can be used in a range that does not impair the effects of the present invention, but has a large effect of suppressing development, and is approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ per liter of the color developing solution. It is desirable that:

Examples of preservatives include hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazide aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals , Alcohols, oximes, diamide compounds, and condensed amines are particularly effective organic preservatives. Particularly, dialkyl-substituted hydroxylamines such as diethylhydroxyamine and alkanolamines such as triethanolamine are preferably used.

As the chelating agent used in the color developing solution according to the present invention, compounds such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are used. In particular, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid is preferably used.

The color development temperature is usually 15 ° C. or higher, generally in the range of 20 to 50 ° C. Also, 30 for quick processing
It is preferable to carry out at a temperature of not less than ° C.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, and the photosensitive material may be transferred to a belt. An endless belt system in which the material is fixed and conveyed may be used. In particular, a system in which a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is conveyed may be used.

[0177]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

Example 1 (Preparation of silver halide emulsion) The following three types of silver halide emulsions were prepared by a neutral method and a simultaneous mixing method.

[0179]

[Table 1]

After completion of chemical sensitization, each silver halide emulsion was added with 2 × 10 ^-4 mol of STB-1 as an emulsion stabilizer per mol of silver halide.

(Preparation of color light-sensitive material) Each layer having the following structure was coated on a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side of the first layer. Thus, a multilayer color photosensitive material 101 was produced.

First layer coating solution 26.7 g of yellow coupler (Y-1), stain inhibitor (HQ
-1) 0.67 g, dye image stabilizer (ST-1) 10.0 g, (ST-
2) 60 ml of ethyl acetate was added and dissolved in 6.7 g and 6.7 g of a high boiling point solvent (DNP), and this solution was homogenized with 200 ml of a 10% aqueous gelatin solution containing 10 ml of 10% sodium alkylnaphthalenesulfonate (SU-1). The mixture was emulsified and dispersed to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (10 g of Em-1 in terms of silver) and a gelatin solution for coating to prepare a first layer coating solution.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

In addition, as a hardener, the second layer and the fourth layer
(H-1) was added to the seventh layer by adding (H-2). As coating aids, SU-1 and SU-2 and the surfactants shown in Table 3 were added to adjust the surface tension.

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[Table 2]

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[Table 3]

Tables 2 and 3 show the structural formulas of the compounds used.

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The DOP of 0.20 g / m ² shown in Table 3 was replaced as shown in Table 3, and 1 mmol / m ² of each magenta coupler was added to the third layer as shown in Table 3.
Samples 102 to 126 were prepared.

The obtained sample was subjected to wedge exposure using green light using a sensitometer KS-7 (manufactured by Konica Corporation), and the exposed sample was subjected to the following processing steps to prepare a color developing solution. After performing the running process until replenishing the color developing replenisher three times the tank capacity, the following evaluation was performed.

Processing step A Temperature Time Replenishment amount Color development 35.0 ± 0.3 ° C 45 seconds 120ml Bleaching and fixing 35.0 ± 0.3 ° C 45 seconds 51ml Stability 30-34 ° C 90 seconds 250ml (3 tank cascade) Drying 60-80 ° C 30 seconds Processing step B Temperature Time Replenishment amount Color development 37.0 ± 0.3 ° C 45 seconds 60ml Bleaching and fixing 35.0 ± 0.3 ° C 45 seconds 51ml Stability 30-34 ° C 90 seconds 250ml (3-tank cascade) Drying 60-80 ° C 60 seconds Processing solution The composition is shown below.

The replenishment amount is an amount per 1 m ² of the light-sensitive material.
The stabilization treatment was replenished by a countercurrent method to the stabilization tank 3 → 1.

Color developing solution (processing step A) Tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium chloride 2 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1 g N-ethyl-N-β -Methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate 5.4 g Potassium carbonate 27 g Make up to 1 l with water and adjust to pH with potassium hydroxide or sulfuric acid.
Adjust to 10.10.

Replenisher Pure water 800 ml Triethanolamine 18 g N, N-diethylhydroxylamine 9 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl- 4-Aminoaniline sulfate 8.2 g Potassium carbonate 27 g Add water to make 1 liter, and adjust the pH with potassium hydroxide or sulfuric acid.
Adjust to 10.60.

Color developing solution (processing step B) Tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 3.6 g Potassium chloride 4.5 g Diethylenetriamine pentaacetic acid 5.0 g Potassium sulfite 0.4 g N-ethyl-N-β- Methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 6.0 g Potassium carbonate 25 g Add water to make 1 l, and adjust the pH with potassium hydroxide or sulfuric acid.
Adjust to 10.10.

Replenisher Pure water 800 ml Triethanolamine 14 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.6 g N-ethyl-N-β-methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate 12 g Potassium carbonate 35 g Add water to make 1 liter, pH is adjusted with potassium hydroxide or sulfuric acid.
Adjust to 11.50.

Bleach-fix tank solution and replenisher Ferric ammonium ammonium salt of ethylenediaminetetraacetic acid 53 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70%) solution 123 g Ammonium sulfite (40%) solution 51 g Adjusted to pH 5.4 with ammonia water or glacial acetic acid Adjust and
Add water to bring the total volume to 1 l.

Stabilizing tank solution and replenisher orthophenylphenol 0.1 g Juvitex (Ciba-Geigy) 1.0 g zinc sulfate-7-hydrate 0.1 g ammonium sulfite (40%) solution 5.0 ml 1-hydroxyethylidene-1,1- Diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or glacial acetic acid.
Add water to bring the total volume to 1 l.

[Evaluation Method] First, the sensitometry of the emulsion layer, which was previously exposed and developed by wedge, is measured in accordance with a conventional method, and the γ value which is a numerical value indicating the gradation is calculated. Here, the γ value is a numerical value represented by the product of the reciprocal of the logarithm of each exposure necessary for obtaining the densities 0.3 and 0.8 and the above-mentioned density difference. The photographic performance was evaluated by comparing the difference between the γ value and the reflection density Dmax of the exposed sample before and after the running process.

Further, the evaluation of the light fastness was performed by storing each of the treated samples in the sunlight (exposure table) for 10 weeks,
Of the dye image remaining and the blue reflection density of the unexposed portion of the sample after the processing ( _Db : light Y stain) were evaluated. Table 4 shows the results.

[0204]

[Table 4]

As is clear from Table 4, DOP and Comparative HBS-1 showed the highest reflection density Dm in the processing step A.
Photographic performance such as ax and γ fluctuations are satisfactory, but image robustness is not satisfactory. Further, in the processing in which the replenishment amount of the developer is extremely small and the overflow liquid is practically eliminated as in the processing step B, the photographic performance of the DOP and the comparative HBS-1 is greatly deteriorated. Further, monoalcohols such as Comparative HBS-2 have a very large change in γ with respect to the highest reflection density, though the deterioration is small. Further, the fastness of the image is not at a satisfactory level in terms of both the residual ratio of the dye and the occurrence of yellow stain. On the other hand, it can be seen that the compounds of the present invention show excellent performance in both image fastness and photographic performance variability. In addition, even in a developing solution in which the replenishment amount is extremely small as in the processing step B, no deterioration in performance is observed, and it is understood that the effect of the present invention is remarkably exhibited.

Example 2 Samples 201 to 218 were produced in the same manner as in Example 1, and were exposed and developed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. However, as a development process, the following processing process C
The developing process was performed in process step D and process step A in Example 1. The fixing, bleaching and stabilization were performed in the same manner as in Example 1.

Processing Step C Temperature Time Replenishment amount Color development 39.0 ± 0.3 ° C. 25 seconds 120 ml Bleaching and fixing 35.0 ± 0.3 ° C. 45 seconds 51 ml Stable 30-34 ° C. 90 seconds 250 ml (3 tank cascade) Drying 60-80 ° C. 30 seconds Processing Step D Temperature Time Replenishment amount Color development 41.0 ± 0.3 ℃ 15 seconds 120ml Bleaching and fixing 35.0 ± 0.3 ℃ 45 seconds 51ml Stability 30-34 ℃ 90 seconds 250ml (3 tank cascade) Drying 60-80 ℃ 30 seconds Color developer (Treatment step C) Tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 3.6 g Potassium chloride 4.5 g Diethylenetriaminepentaacetic acid 5.0 g Potassium sulfite 0.4 g N-ethyl-N-β-methanesulfonamidoethyl-3 -Methyl-4-aminoaniline sulfate 7.0 g Potassium carbonate 25 g Add water to make 1 l, and adjust the pH with potassium hydroxide or sulfuric acid.
To 11.10.

Replenisher Pure water 800 ml Triethanolamine 12 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.6 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 9 g Potassium carbonate 35 g Add water to make 1 liter, pH is adjusted with potassium hydroxide or sulfuric acid.
Adjust to 12.50.

Color developing solution (processing step D) Tank solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 3.6 g Potassium chloride 4.5 g Diethylenetriamine-5-acetic acid 5.0 g Potassium sulfite 0.4 g N-ethyl-N-β- Methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 7.0 g Potassium carbonate 25 g Make up to 1 l with water and adjust the pH with potassium hydroxide or sulfuric acid.
To 11.10.

Replenisher Pure water 800 ml Triethanolamine 14 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.6 g N-ethyl-N-β-methanesulfonamide 9 g Ethyl-3-methyl-4-aminoaniline sulfate Potassium carbonate 35 g Add water to make 1 liter, pH is adjusted with potassium hydroxide or sulfuric acid.
Adjust to 12.80.

[0211]

[Table 5]

As is clear from Table 5, DOP and Comparative HBS-1 show the highest reflection density Dm in the processing step A.
Photographic performance such as ax and γ fluctuations are satisfactory, but image robustness is not satisfactory. Further, in processing in which the development processing time is extremely short, such as processing step C and processing step D, DOP and comparative HBS-1
Causes a great deterioration in photographic performance. Also compare
Monoalcohols, such as HBS-2, have a very large change in γ with respect to the highest reflection density, although the deterioration is small. Further, the fastness of the image is not at a satisfactory level in terms of both the residual ratio of the dye and the occurrence of yellow stain.
On the other hand, it can be seen that the compounds of the present invention show excellent performance in both image fastness and photographic performance variability. Also,
Even in a developing solution having a remarkably short development processing time such as the processing step C or the processing step D, no deterioration in performance is observed, and it is understood that the effect of the present invention is remarkably exhibited.

Example 3 Samples 301 to 328 were prepared in the same manner as in Example 1, exposed and developed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. However, the following processing step E is a development step.
And a developing process in the process step A of Example 1. In addition,
Fixing / bleaching and stabilization were carried out in the same manner as in Example 1. Processing step E Temperature Time Replenishment amount Color development 43.0 ± 0.3 ℃ 15 seconds 60ml Bleaching and fixing 35.0 ± 0.3 ℃ 45 seconds 51ml Stability 30-34 ℃ 90 seconds 250ml (3 tank cascade) Drying 60-80 ℃ 30 seconds Color developer (Treatment step E) Tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 3.6 g Potassium chloride 4.5 g Diethylenetriaminepentaacetic acid 5.0 g Potassium sulfite 0.4 g N-ethyl-N-β-methanesulfonamidoethyl-3 -Methyl-4-aminoaniline sulfate 7.0 g Potassium carbonate 25 g Add water to make 1 l, and adjust the pH with potassium hydroxide or sulfuric acid.
Adjust to 11.50.

Replenisher Pure water 800 ml Triethanolamine 14 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.6 g N-ethyl-N-β-methanesulfonamide 14 g Ethyl-3-methyl-4-aminoaniline sulfate Potassium carbonate 35 g Add water to make 1 liter, pH is adjusted with potassium hydroxide or sulfuric acid.
Adjust to 12.50.

[0215]

[Table 6]

As is clear from Table 6, DOP and Comparative HBS-1 showed the highest reflection density Dm in the processing step A.
Photographic performance such as ax and γ fluctuations are satisfactory, but image robustness is not satisfactory. Further, in the processing in which the replenishment amount of the developing solution is extremely small as in the processing step E, the overflow liquid is practically eliminated, and the processing and developing processing time is extremely short, the DOP and the comparative HBS-1 have extremely large deterioration in photographic performance. Occurs. Further, monoalcohols such as Comparative HBS-2 have a very large change in γ with respect to the highest reflection density, though the deterioration is small. Regarding the fastness of the image, both the residual ratio of the dye and generation of yellow stain are extremely large. On the other hand, it can be seen that the compounds of the present invention show excellent performance in both image fastness and photographic performance variability. Further, even in a developing solution in which the replenishing amount of the developing solution is extremely small as in the process step E, the overflow solution is practically eliminated and the processing time of the developing process is extremely short, the performance is not deteriorated and the effect of the present invention is remarkably improved. It can be seen that it appears remarkably.

Example 4 To the third layer were added the compounds shown in Table 7 (high-boiling solvent (HBS)) in the amounts shown in Table 7 and the magenta coupler at 1 mmol / m ² , respectively. Was prepared.

The obtained sample was subjected to wedge exposure using green light using a sensitometer KS-7 (manufactured by Konica Corporation), and the exposed sample was subjected to the following processing steps and Example 1 According to the processing steps A and B, a running process was performed until a color developing replenisher three times the tank volume of the color developing solution was replenished, and the same evaluation as in Example 1 was performed.

Processing step F Temperature Time Replenishment amount Color development 35.0 ± 0.3 ° C 45 seconds 150ml Bleaching and fixing 35.0 ± 0.3 ° C 45 seconds 51ml Stability 30-34 ° C 90 seconds 250ml (3 tank cascade) Drying 60-80 ° C 30 seconds Processing step G Temperature Time Replenishment amount Color development 30.0 ± 0.3 ° C 90 seconds 60ml Bleaching and fixing 35.0 ± 0.3 ° C 45 seconds 51ml Stability 30-34 ° C 90 seconds 250ml (3-tank cascade) Drying 60-80 ° C 60 seconds Processing solution The composition is shown below.

The replenishment amount is an amount per 1 m ² of the light-sensitive material. The stabilization treatment was replenished by a countercurrent method to the stabilization tank 3 → 1.

Color developing solution (processing step F) Tank solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium chloride 2 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1 g N-ethyl-N-β -Methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 5.4 g Sulfate Potassium carbonate 27 g Add water to make 1 l, and adjust the pH with potassium hydroxide or sulfuric acid.
Adjust to 10.10.

Replenisher Pure water 800 ml Triethanolamine 18 g N, N-diethylhydroxylamine 9 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl- 4-aminoaniline sulfate 7.82 g Potassium carbonate 27 g Add water to make 1 liter, and adjust the pH with potassium hydroxide or sulfuric acid.
Adjust to 10.60.

Color developing solution (processing step G) Tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 3.6 g Potassium chloride 4.5 g Diethylenetriaminepentaacetic acid 5.0 g Potassium sulfite 0.4 g N-ethyl-N-β- Methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 6.0 g Potassium carbonate 25 g Make up to 1 l with water, and add p with potassium hydroxide or sulfuric acid.
Adjust H to 10.10.

Replenisher Pure water 800 ml Triethanolamine 14 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.6 g N-ethyl-N-β-methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate 12 g Potassium carbonate 35 g Add water to make 1 liter, pH is adjusted with potassium hydroxide or sulfuric acid.
To 11.0.

[0225]

[Table 7]

As is clear from Table 7, the photographic performances such as the maximum reflection density Dmax and the γ variation can be sufficiently satisfied in the processing steps A and FG for the DOP and the comparative HBS-1. Image robustness is not a satisfactory performance. Further, in the processing in which the replenishment amount of the developer is extremely small and the overflow liquid is practically eliminated as in the processing step B, the photographic performance of the DOP and the comparative HBS-1 is greatly deteriorated. Also, like the comparison HBS-2,
As for the monoalcohols, as for the maximum reflection density, the fluctuation of γ is extremely large although the deterioration is small. Further, the fastness of the image is not at a satisfactory level in terms of both the residual ratio of the dye and the occurrence of yellow stain. On the other hand, it can be seen that the compounds of the present invention show excellent performance in both image fastness and photographic performance variability. In addition, even in a developing solution in which the replenishment amount is extremely small as in the processing step B, no deterioration in performance is observed, and it is understood that the effect of the present invention is remarkably exhibited.

In the processing step F, the replenishment amount was extremely large, and the concentration of unused developing agent which was environmentally unfavorable in the overflow solution was concentrated with time. On the other hand, in the processing step A, although the overflow liquid came out, the amount of the developing agent in the overflow liquid was kept to a minimum and the amount was in an equilibrium state.

When the processing time was lengthened as in the processing step G, no deterioration was observed in the performance of the processing liquid, but the processing amount decreased almost in inverse proportion to the processing time.

Further, the amount of the polyhydric alcohol of the present invention was reduced, and when the weight ratio of (polyhydric alcohol / dye-forming coupler) was 0.5 or less, it was found that the compound of the present invention could not obtain a sufficient effect. Was.

[0230]

According to the present invention, firstly, there is provided a method for processing a silver halide color photographic light-sensitive material in which photographic performance is not deteriorated even if the replenishment amount of a color developing solution is reduced during color developing processing. Can be. Secondly, it is possible to provide a method for processing a silver halide color photographic light-sensitive material in which photographic performance is not deteriorated even if the processing time during color development processing is reduced.
Third, discoloration or Y even when exposed to light after the running process is performed.
It is possible to provide a method for processing a silver halide color photographic light-sensitive material in which image deterioration such as generation of stains is suppressed.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7 / 388,7 / 32,7 / 407

Claims (3)

(57) [Claims] A silver halide color photographic material having at least one silver halide emulsion layer on a support,
In the silver halide emulsion layer, the following general formula (II) or
The silver halide color photographic light-sensitive material contains at least one polyhydric alcohol represented by the formula (III) and at least one dye-forming coupler, and the replenishment amount of the color developing solution is 120 ml / m ^{2 of the} light-sensitive material. A method for processing a silver halide color photographic light-sensitive material, wherein a continuous processing is carried out with a color developing solution of the following and a color developing time of 45 seconds or less. Embedded image Wherein R _A21 , R _A22 , R _A23 and R _A24 are each hydrogen
Atom, alkyl group, alkenyl group, cycloalkyl group,
Cycloalkenyl group, aryl group, acyl group, sulfoni
Group, phosphonyl group, carbamoyl group, sulfamoyl
Represents a group. _{However, R A21, R A22, R} A23 and R _A24
At least two are hydrogen atoms and all are hydrogen atoms
You cannot be a child. ] 2. Halogenation of at least one layer on a support
A silver halide color photographic light-sensitive material having a silver emulsion layer,
In the silver halide emulsion layer represented by the following general formula (VI)
At least one polyhydric alcohol and a dye-forming coupler
And at least one of the above silver halides
-Replenish the photographic light-sensitive material with the color developing solution by 1 m ^{2 of the} light-sensitive material.
Color developing solution less than 120 ml per
The processing time is 45 seconds or less.
A method for processing a silver rogenide color photographic light-sensitive material. Embedded image Wherein R ₆₁ is a hydrogen atom, an alkyl group, an alkenyl group,
Cycloalkyl group, cycloalkenyl group, acyl group,
Represents a sulfonyl group, a carbamoyl group or a sulfamoyl group.
R ₆₂ and R ₆₃ each represent a hydroxyl group and / or an alkoxy group;
Represents an alkyl group substituted with a group. However, R ₆₂ , R ₆₃
Each have at least one alcoholic hydroxyl group
You. ] 3. Halogenation of at least one layer on a support
A silver halide color photographic light-sensitive material having a silver emulsion layer,
The following general formulas (VII) to (I)
X] and at least one polyhydric alcohol represented by the formula
Containing at least one of the forming couplers, and
The replenishment amount of the color developing solution is changed to
In a less sensitive material 1 m ² per 120ml color developer, or
Color development processing time of 45 seconds or less
Characteristic processing of silver halide color photographic materials
Law. Embedded image [Wherein, R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom,
Kill group, alkenyl group , cycloalkyl group , cycloalkyl
Kenyl, acyl, sulfonyl, phosphonyl,
Represents a rubamoyl group or a sulfamoyl group, and p is 1 to 20
Represents an integer. When p is 2 or more , even if a plurality of R ₇₃ are the same,
It may be different. However, when p represents 1, R ₇₁ ,
Any two of R ₇₂ and R ₇₃ are a hydrogen atom, and p is
In the case of 2 or more, a small number of R ₇₁ and R ₇₂ and a plurality of R ₇₃
At least two are hydrogen atoms and all are hydrogen atoms
There is no. ] [Of 7] Wherein R _{81 to} R ₈₄ each represent a hydrogen atom, an alkyl group,
Alkenyl group, cycloalkyl group, cycloalkenyl
Group, acyl group, sulfonyl group, phosphonyl group, carbamo
Represents a yl group or a sulfamoyl group, and q is an integer of 1 to 20
And when q is 2 or more, a plurality of R ₈₃ and R ₈₄ each represent
They may be the same or different. However, when q represents 1
Means that at least two of R ₈₁ , R ₈₂ , R ₈₃ and R ₈₄ are water
Elementary atoms and not all hydrogen atoms,
When q is 2 or more, R ₈₁ , R ₈₂ , a plurality of R ₈₃ and a plurality
At least two of R ₈₄ are hydrogen atoms, and
Not all are hydrogen atoms. Embedded image [Wherein, R _{91 to} R ₉₆ each represent a hydrogen atom, an alkyl group,
Alkenyl group, cycloalkyl group, cycloalkenyl
Group, acyl group, sulfonyl group, phosphonyl group, carbamo
Represents an yl group or a sulfamoyl group. However, the R ₉₁ ~R ₉₆
At least two of them are hydrogen atoms and all are hydrogen
It cannot be an atom. ]