JPH0746219B2 - Color image forming method - Google Patents

Description

The present invention relates to a color image forming method using a silver halide light-sensitive material.

(Prior Art and Its Problems) A general method of forming a color image using a silver halide photographic light-sensitive material is a method of forming or releasing a dye by a coupling reaction between an oxidant of a color developing agent and a coupler. .

Usually, a color developing agent (for example, an aromatic primary amine developing agent) is dissolved in an alkaline aqueous solution and used in a color developing solution. When the aromatic primary amine developing agent can be incorporated in the light-sensitive material, the development can basically be carried out only with an aqueous alkali solution. This facilitates the preparation of the developer and reduces the change in the composition of the developer,
Easy to manage. In addition, the BOD of the waste liquid is remarkably reduced, and the waste liquid can be easily treated. However, in general, incorporating an aromatic primary amine developing agent in a light-sensitive material causes sensitization of the light-sensitive material during storage, generation of fog or stain, and insufficient coloration due to processing. It has many drawbacks and has not yet been put to practical use.

Black-and-white developing agents such as hydroquinone and catechol can be incorporated in the light-sensitive material relatively stably. For example, U.S. Pat. No. 3,295,978 shows that a metal complex salt is incorporated. On the other hand, the aromatic primary amine developing agent is difficult to be stably incorporated in the light-sensitive material because of its instability.

Heretofore, several methods have been known as a method of incorporating an aromatic primary amine developing agent into a light-sensitive material. For example, U.S. Pat.No. 3,342,599 uses a Schiff base with salicylaldehyde as a developing agent precursor,
In US Pat. No. 3,719,492, it is used in combination with metal salts such as lead and cadmium. British Patent 1,069,061 uses a phthalimide type precursor by reacting an aromatic primary amine with phthalic acid. Other German Patent No. 1,159,758,
No. 1,200,679 and US Pat. No. 3,705,035 are known. However, none of the techniques can provide sufficient color density, desensitization when the light-sensitive material is stored, and generation of fog or stain.

In addition, the developing solution (activator solution) used in this case must have a high pH value or sufficient development will not occur. Normally, a high alkaline activator solution with a pH of more than 11 is used, but such a high pH solution can be stored or used during storage.
There are problems that carbon oxide is easily absorbed and deteriorated, and there is a danger in handling.

(Object of the Invention) Accordingly, an object of the present invention is to provide an image forming method capable of forming a high density and high S / N color image in a short processing time by using a photographic material excellent in storage stability and a processing solution. .

(Structure of the Invention) An object of the present invention is to provide a support having at least a photosensitive silver halide, a coupler, a compound represented by the following general formula (Z), and a halogenated compound having a water-insoluble basic metal compound. After the imagewise exposure, the silver light-sensitive material is subjected to development processing using a processing solution containing a complex-forming compound that releases a base by undergoing a complex-forming reaction with the metal ion forming the basic metal compound that is poorly soluble in water. And a color image forming method.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atom, halogen atom, hydroxyl group, amino group, substituted amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, substituted carbamoyl group. Represents a carbamoyl group, a substituted sulfamoyl group, a sulfamoyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, an acyloxy group or an alkoxycarbonyl group. A is a hydroxyl group, a group which gives a hydroxyl group by the action of a nucleophile, or (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a cycloalkyl group, a substituted cycloalkyl group, an aralkyl group or a substituted aralkyl group.). R ₅ represents a hydrogen atom or a fluorine atom. n represents an integer of 1 to 17. Also, R ₁ ~
When R ₄ is a hydrogen atom, a halogen atom, or a substituent other than a hydroxyl group, it may have an acceptable substituent. R _{1 to} R ₄ , R ₆ and R ₇ may be linked to each other to form an alicyclic ring, an aromatic ring, a hetero ring, or a ring composed of a combination thereof.

The present invention will be described in detail below.

R ₁ , R ₂ , R ₃ and R ₄ are independently a hydrogen atom, a halogen atom (preferably chlorine, bromine, fluorine, etc.), a hydroxy group, an amino group, a substituted amino group (for example, as a substituent, a carbon number 1 to 12 preferably 1 to 4 alkyl groups, 6 to 6 carbon atoms
18 aryl group, etc.), acylamino group (preferably having 1 to 12 carbon atoms), alkylsulfonylamino group (preferably having 1 to 8 carbon atoms), arylsulfonylamino group (preferably having 6 to 12 carbon atoms), substituted carbamoyl group (For example, as a substituent, an alkyl group having 1 to 12 carbon atoms, 6 to 18 carbon atoms
Aryl groups, etc.), carbamoyl groups, substituted sulfamoyl groups (eg, alkyl groups having 1 to 8 carbon atoms as substituents), alkyl groups (preferably having 1 to 18 carbon atoms), cycloalkyl groups (having 5 to 10 carbon atoms). ), An alkenyl group (having 2 to 10 carbon atoms), an aryl group (having 6 to 18 carbon atoms), an aralkyl group (having 7 to 18 carbon atoms), an alkoxy group (preferably having 1 to 18 carbon atoms), an acyl group (preferably carbon) The numbers 1 to 18), acyloxy groups (preferably having 1 to 18 carbon atoms) or alkoxycarbonyl groups (preferably having 2 to 19 carbon atoms) are shown.

When R _{1 to} R ₄ are a hydrogen atom, a halogen atom or a substituent other than a hydroxyl group, R _{1 to} R ₄ have an acceptable substituent (provided that they have a substituent atom, for example, a halogen atom, etc.). May be), an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, an aliphatic thio group, an aromatic thio group. Group, heterocyclic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, hydroxyl group, cyano group, carboxyl group, sulfo group, nitro group and the like.

Preferred examples of R _{1 to} R ₄ include a hydrogen atom, a halogen atom, an alkoxy group, an acylamino group, an aryl group, a carbamoyl group and a substituted carbamoyl group. In addition, these may be substituted with a substituent that is permissible for R _{1 to} R ₄ .

A is a hydroxyl group, a group which gives a hydroxyl group by the action of a nucleophile (for example, an acyloxy group (for example, acetoxy group, benzoyloxy group, etc.), an alkylsulfonyloxy group (for example, methanesulfonyloxy group, etc.), an arylsulfonyloxy group. Group (eg, benzenesulfonyloxy group), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group), dialkylphosphoryloxy group (eg, diethyl) A phosphoryloxy group), a diarylphosphoryloxy group (eg, a diphenylphosphoryloxy group), etc.}, or {R ₆ and R ₇ are hydrogen atoms, alkyl groups (preferably having 1 carbon atom
To 18), a substituted alkyl group (preferably having a carbon number of 1 to 18, for example, a methanesulfonylaminoethyl group, a hydroxyethyl group, etc.), an alkenyl group (preferably having a carbon number of 2 to 2).
12), a substituted alkenyl group (preferably having 2 to 12 carbon atoms),
Cycloalkyl group (preferably having 5 to 10 carbon atoms), substituted cycloalkyl group (for example, having 5 to 12 carbon atoms), aralkyl group (for example, benzyl group, β-phenethyl group, etc.), substituted aralkyl group (for example, p- Chlorobenzyl group, β-
(P-chlorophenyl) ethyl group and the like). } Is represented. Here, as the nucleophile, anionic reagents such as OH ⁻ , OR ⁻ (R: alkyl group, etc.), SO ₃ ²⁻ , 1 or 2
Examples thereof include compounds having a non-shared electron pair such as primary amines, hydrazines, hydroxylamines, alcohols and thiols.

R _{1 to} R ₄ , R ₆ and R ₇ are linked to each other, preferably 5
May form a 6-membered or 6-membered alicyclic ring, aromatic ring, or heterocyclic ring, or a ring composed of a combination thereof. For example, preferably, a benzene ring in which R ₁ and R ₂ or R ₃ and R ₄ are linked, a pair of R ₁ and R ₆ , a heterocyclic ring in which one or both of R ₃ and R ₇ are linked, and R ₆ and R ₇ are Examples thereof include linked heterocycles (eg, pyrrolidino group, piperidino group, morpholino group, etc.) and the like.

Preferred examples of A include a hydroxyl group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a dialkylphosphoryloxy group, a diarylphosphoryloxy group, and a dialkylamino group (wherein the alkyl group is substituted. May be used), pyrrolidino group, piperidino group, morpholino group and the like.

R ₅ represents a hydrogen atom or a fluorine atom. n represents an integer of 1 to 17.

Preferred specific examples of the developer represented by the general formula [Z] are shown below.

The developing agent used in the present invention can be easily obtained by a known method, that is, by fluoroacylating an aniline with an appropriate acylating agent.

The specific synthesis examples of the developing agent used in the present invention are shown below.

Synthesis Example (Synthesis of Exemplified Compound 1) 21.0 g of trifluoroacetic acid anhydride was added dropwise to a mixture of 35.6 g of 2,6-dichloro-4-aminophenol and 500 ml of acetonitrile under ice cooling. After the dropping, the mixture was stirred at room temperature for 1 hour, the precipitated crystals were separated, and the solvent was distilled off from the solution under reduced pressure. The obtained crude product was recrystallized from n-hexane to obtain 18.2 g of white crystals of Exemplified Compound 1. Melting point 158 ° C. The developing agent precursor of the present invention may be used alone or in combination of two or more kinds. Generally, it can be used in a range of 0.1-fold to 10-fold mol, preferably 0.2- to 3-fold mol, based on the total amount of coated silver constituting the photosensitive layer.

The developer precursor of the present invention can be incorporated into the light-sensitive material by many methods. According to a method generally known as an oil protect method, it may be dissolved in a hydrophobic oil to be emulsified and dispersed in water or a hydrophilic colloid solution as an oil-in-water dispersion, or by dissolving in a solvent miscible with water, Alternatively, it may be added as fine particles to the hydrophilic colloid solution, or the compound in the solid state may be introduced into water or the hydrophilic binder using a ball mill or the like.

The developer precursor represented by formula (Z) used in the present invention may be added to any layer constituting the color light-sensitive material. Examples thereof include a photosensitive silver halide emulsion layer, a hydrophilic colloid layer, an intermediate layer and the like.

Various types of couplers are known which bond with an oxidized product of a developing agent. For example, TH James “The theory of the
Any of the couplers described in "photographic process", 4th Ed., pp. 354-361, Shinichi Kikuchi, "Photochemistry", 4th edition (Kyoritsu Shuppan), pages 284-295, etc. can be used in the present invention.

In the present invention, both a 4-equivalent coupler having a hydrogen atom at a site where it binds to an oxidized product of a developing agent and a 2-equivalent coupler substituted with a leaving group can be used. Further, a so-called fisher dispersion type coupler having both a hydrophilic group and a hydrophobic diffusion resistant group in the coupler and an oil protect dispersion type coupler having only a hydrophobic diffusion resistant group can be used. Among couplers having a diffusion-resistant group, there is JP-A-58.
-149,046 and the like having a hydrophobic ballast group in the leaving group; coupler having a leaving group linked to the polymer main chain as described in JP-A-58-149,047; U.S. Pat.
952; 3,451,820; 4,080,211; 4,215,195; 4.409,32
Polymer couplers described in No. 0 and the like are included. Also, British Patent No. 1,330,524; Japanese Patent Publication No. 48-39,165; Japanese Patent Laid-Open No. 57-1.
Colored couplers containing a dye component in the leaving group described in 86,744; 57-207,250; 58-79,247 and the like are also useful in the present invention.

The couplers preferably used in the present invention are active methylene and active methine compounds, phenols, naphthols, pyrazoles and condensed pyrazole compounds, and particularly preferable ones are represented by the following general formulas (I) to (X).

In the above formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, Acylamino group, alkoxyalkyl group, aryloxyalkyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group,
A substituted sulfamoyl group, an alkylamino group, an arylamino group, an acyloxy group, an acyloxyalkyl group, a substituted ureido group, a cyano group, and a substituent selected from a heterocyclic residue, and these substituents are further Alkyl group, alkoxy group, halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, An aryl group,
It may be substituted with an aryloxy group, an aralkyl group or an acyl group. X ¹ represents a hydrogen atom or a coupling-off group, a halogen atom, an acyloxy group, a sulfonyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyloxy group, a dialkylcarbamoyloxy group, an imide group, N-
Heterocyclic residues and pyridinium groups are typical examples of coupling-off groups. Further, any ^one of R ₈ , R ₉ , R ₁₀ , R _{11 and} X ¹ is preferably a ballast group that imparts diffusion resistance, or these groups may be linked to the polymer main chain.

Diffusion resistant compounds (dye releasing couplers) which release a diffusible dye by undergoing a coupling reaction with an oxidized product of a developing agent can also be used in the present invention. Compounds of this type include US patents
The compounds listed in No. 3,227,550 are typical.
For example, one represented by the following formula (XI) can be given.

Coup-Link-Dye (XI) In the formula, Coup represents a coupler residue capable of coupling with an oxidized product of a developing agent, preferably a moiety obtained by removing X from the coupler represented by the general formula (I) to (X). Represents

Link is attached to the active site of the Coup part, and is represented by the above formula (XI).
Represents a group capable of cleaving the bond between the Coup moiety and the dye-releasing coupler during the coupling reaction with the oxidized product of the developing agent, such as an azo group, an azoxy group, or -O.
-, -Hg-, alkylidene group, -S-, -SS-,-
In addition to NHSO ₂ −, groups, etc., the coupling-off group X ¹ described above is also useful.

Dye stands for dye or dye precursor.

Among the dye-releasing couplers represented by the above formula (XI), Coup is preferably a phenol-type coupler residue, a naphthol-type coupler residue or an indanone-type coupler residue, and Link is bonded to Coup at an oxygen atom or a nitrogen atom. It is a thing.

The Dye of formula (XI) is preferably transferred to the image receiving element after being imagewise released.

In the present invention, the coupler can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg tributyl acetyl citrate) High-boiling organic compounds such as benzoic acid ester (octyl benzoate), alkylamide (eg diethyl laurylamide), fatty acid ester (eg dibutoxyethyl succinate, dioctyl azelate), trimesic acid ester (eg tributyl trimesate) Solvent or low boiling organic solvent having a boiling point of about 30 ° C to 160 ° C, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone β- ethoxyethyl acetate, methyl cellosolve acetate, then dissolved like cyclohexanone, they are dispersed in a hydrophilic colloid.
The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. Further, various surfactants can be used when dispersing the coupler in the hydrophilic colloid.
The surfactants listed on pages (37) to (38) of -157636 can be used.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less, relative to 1 g of the coupler used.

In the present invention, a reducing substance may be used in combination in the light-sensitive material. Examples of the reducing substance include auxiliary developing agents that can be used in combination with the developing agent precursor of the present invention. The auxiliary developing agent may be diffusible or non-diffusible.

Useful auxiliary developing agents include alkyl-substituted hydroquinone groups such as hydroquinone, t-butyl hydrodroquinone and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and methoxyhydroquinone. There are polyhydroxybenzene derivatives such as alkoxy-substituted hydroquinones and methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N, N-di (2-ethoxyethyl) hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-
Pyrazolidones such as 4-hydroxymethyl-1-phenyl-3-pyrazolidone, rectones, and hydroxytetronic acids are useful.

The auxiliary developing agent can be used within a certain concentration range. A useful concentration range is 0.00005 times mol to 10 times the total amount of coated silver.
Double molar, particularly useful concentration range is 0.001 molar
It is 0.5 times the mole.

In the image forming method of the present invention, the silver halide light-sensitive material contains a water-insoluble basic metal compound, and the processing liquid contains a metal ion forming the water-insoluble basic metal compound. A compound capable of undergoing a complex-forming reaction with the compound (hereinafter referred to as a complex-forming compound) is contained therein, and the two undergo a complex-forming reaction during processing to generate a base in the film of the photosensitive material.

In the present invention, the basic metal compound which is hardly soluble in water and is contained in the light-sensitive material is preferably one having a solubility in water (the number of grams of a substance soluble in 100 g of water) of 0.5 or less and represented by the formula TmXn.

Where T is a transition metal, such as Zn, Ni, Cu, Co, Fe, Mn
, Alkaline earth metals, such as Ca, Ba, Mg, etc.,
As X, a counter ion of M, which appears in the description of the complex-forming compound to be described later in water, and exhibits alkalinity, for example, carbonate ion, phosphate ion, silicate ion, borate ion, Represents an aluminate ion, a hydroxy ion, and an oxygen atom. m and n are T and X, respectively.
Represents an integer whose valences can be balanced.

Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (CO ₃ ) ₂ ), magnesium oxide, zinc oxide,
Tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide,
Manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate,
Basic zinc carbonate (2ZnCO ₃・ 3Zn (OH) ₂・ H ₂ O), basic magnesium carbonate (3MgCO ₃・ Mg (OH) ₂・ 3H ₂ O), basic nickel carbonate (NiCO ₃・ 2Ni (OH) ₂ ), basic bismuth carbonate (Bi
₂ (CO ₃ ) O ₂ · H ₂ O), basic cobalt carbonate (2CoCO ₃ · 3C
o (OH) ₂ ), aluminum magnesium oxide, copper hydroxide, basic copper carbonate, etc.

Among these compounds, those not colored are particularly preferable.

In the present invention, the complex-forming compound contained in the treatment liquid forms a complex salt having a stability constant of 1 or more in log K with the metal ion constituting the basic metal compound.

Examples of these complex-forming compounds include AEMartell and RMSmit.
h) Co-authored, “Critical Stability Constants, Volumes 1-5”,
See Plenum Press for details.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri,
Tetracarboxylic acids and compounds having substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, polyphosphoric acids, guanidines, amidines Alternatively, a salt such as a quaternary ammonium salt can be used.

Preferred specific examples include picolinic acid, 2,6-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-
2-carboxylic acid, 2-pyridylacetic acid, oxalic acid, citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, ED
TA, NTA, CDTA, hexametaphosphoric acid, tripolyphosphoric acid,
Tetraphosphoric acid, polyacrylic acid, HO ₂ CCH ₂ OCH ₂ CH ₂ OCH ₂ CO ₂ H, HO ₂ CCH ₂ OCH ₂ CO ₂ H, And the like, salts of guanidines, salts of amidines, quaternary ammonium salts and the like.

Of these, an aromatic heterocyclic compound having at least one —CO ₂ M and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -CO ₂ M
The position at which is bonded to the ring is particularly preferably the α position with respect to the N atom. M is one of an alkali metal, guanidine, amidine, and a quaternary ammonium ion.

More preferable compounds include those represented by the following formula.

formula In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, —CO ₂ M, a hydroxycarbonyl group, and an electron-donating group such as an amino group, a substituted amino group and an alkyl group. . Two Rs may be the same or different.

Z ₁ and Z ₂ are respectively the same as defined in R, and
Z ₁ and Z ₂ may combine with each other to form a ring condensed with a pyridine ring.

Next most preferable complex formation with water-insoluble basic metal compound
Examples of combinations with compounds are listed (where M is A
Lucari metal ion, substituted or unsubstituted guanidinium
Muion, amidininium ion or quaternary ammonium
Represents the um ion).

Calcium carbonateBasic zinc carbonate-Basic magnesium carbonate-Zinc oxide-Basic zinc carbonate-Basic magnesium carbonate-Calcium carbonateZinc oxide-Calcium carbonateBarium carbonate M O₂C-CO₂ M  Calcium carbonate-tripolyphosphate M Salt Calcium carbonate-M of citric acid Salt Calcium carbonate-Polyacrylic acid M Salt calcium carbonate-Magnesium oxide-Zinc hydroxide-Tin hydroxideMagnesium hydroxide-M of hexametaphosphoric acid Salt calcium carbonate-Basic magnesium carbonate-  M O₂C ・ CO₂ M  Calcium carbonateBasic zinc carbonate-These combinations may be used alone or in combination of two or more.
Can also be used.

Here, the mechanism of generating a base in the film of the light-sensitive material in the present invention will be described by taking a combination of potassium picolinate and zinc hydroxide as an example.

The reaction of both is shown by the following formula, for example.

That is, when water in the treatment liquid is involved, the picolinate ion causes a complex formation reaction with the zinc ion, and the reaction represented by the above formula proceeds, resulting in the generation of a base.

The progress of this reaction is due to the stability of the resulting complex.
However, picolinate ion (L ) And zinc ion (M )
Generate more ML, ML₂, ML₃Stability of complex represented by
The numbers are very large as shown below,
Describes the line well.

Basic metal compounds that are poorly soluble in water are disclosed in JP-A-59-174830 and JP-A-5-174830.
It is desirable to contain it as a fine particle dispersion prepared by the method described in 3-102733 or the like, and its average particle size is 50 μm.
The following is particularly preferable, 5 μ or less.

The addition position of the basic metal compound in the present invention in the light-sensitive material may be any layer such as an emulsion layer, an intermediate layer, a protective layer, an anti-halation layer, a white pigment layer and a back layer. Further, it may be contained in one layer or in two or more layers.

The addition amount varies depending on the type of treatment liquid, pH, complex formation compound species, compound species of basic metal compound, particle size, treatment temperature, etc., and cannot be specified unconditionally, but 0.01 to 20 g / m ² , preferably Is preferably about 0.1 to 5 g / m ² .

The addition amount of the complex-forming compound contained in the treatment liquid varies depending on the type of treatment liquid, pH, the type of complex-forming compound, etc., but it should be 1/5 or more of the number of moles of the basic metal compound that reacts. preferable. Generally, it is good to set it to about 0.01 to 5 mol / l.

The complex-forming compound is contained in the treatment liquid before treatment, but may be contained in the replenisher.

The silver halide photographic light-sensitive material of the present invention is not only an ordinary color photographic light-sensitive material using three types of (yellow, magenta, cyan) couplers, but also a photographic light-sensitive material using a coupler that forms a black image by color development. Good.

The development processing method of the silver halide photographic light-sensitive material of the present invention includes a bleaching step (desilvering) regardless of whether it comprises three steps of development, bleaching and fixing. A method of forming an image composed of a dye and metallic silver without performing the step) may be used. If the dye produced or released is diffusive, it may be diffused to an image receiving element to form an image. Bleaching in this case,
The fixing process becomes unnecessary.

The developing treatment used in the present invention is different from the conventional developing treatment in that the developing bath is an activator bath containing the complex forming compound, and the other steps can be used as they are.

The pH of the activator is in the range of about 7-11, especially about 7
The range of 10.5 is preferred. The temperature of the activator liquid is
It is selected in the range of 20 ° C to 70 ° C, preferably 30 ° C to 50 ° C.
℃.

The activator used in the present invention is basically a general developing solution (for example, a color developing solution) from which a developing agent and an extra alkaline agent are removed. As the activator buffer, etc., sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate, sodium or potassium triphosphate, potassium metaphorate, borax and the like are used alone or in combination. Further, for the purpose of giving a buffering capacity, convenience of preparation, or increasing ionic strength, further, sodium phosphate dibasic sodium phosphate, sodium phosphate dibasic sodium phosphate, potassium bicarbonate sodium phosphate, sodium phosphate Various salts such as acids, alkali nitrates and alkali sulfates can be used.

Also, an appropriate amount of antifoggant can be included.
These include inorganic halide compounds and known organic antifoggants. Typical examples of this inorganic halide compound are bromides such as sodium bromide, potassium bromide or ammonium bromide, and iodides such as potassium iodide or sodium iodide. On the other hand, examples of organic antifoggants include
6-nitrobenzindazole described in US Pat. No. 2,496,940, US Pat. No. 2,497,917, and US Pat. No. 2,656,271.
5-nitrobenzimidazole described in No. 11, diaminophenazine and o-phenylenediamine described in Vol. 11, page 48 (1948) of the Photographic Society of Japan, mercaptobenzimidazole, methylbenzthiazole, mercaptobenzoxazole. , Thiouracil, and 5-methylbenztriazole, and heterocyclic compounds represented by the compounds described in JP-B-46-41675. For other antifoggants, see "Scientific Photographic Handbook," Vol. 119, Maruzen, 1959.
Annual publication) can be used.

For surface layer development adjustment, Japanese Patent Publication Nos. 46-19,039 and 45-6,149
The development inhibitors known in US Pat. No. 3,295,976 and the like can also be used.

In addition, ammonium chloride, potassium chloride, sodium chloride and the like can be added if necessary. If necessary, any development accelerator can be added together. Among these, various pyridinium compounds represented by U.S. Pat.No. 2,648,604, JP-B-44-9,503, U.S. Pat.No. 3,671,247 and other cation compounds, cationic dyes such as phenosafuran, thallium nitrate and potassium nitrate. Salt, Japanese Patent Publication No.44-9,504, U.S. Patent 2,533,990
No. 2,531,832, No. 2,950,970, No. 2,577,127 polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, JP-B-44-9,509,
Organic solvents and organic amines described in Belgian Patent 682,862,
It includes ethanolamine, ethylenediamine, diethanolamine and the like. In addition, Photograph Processing Processing Chemistry by LFA Mason "Photog
raphic Processing Chemistry ”40-43 (Focal Press
-Includes accelerators detailed in London 1966).

In addition, benzyl alcohol, phenethyl alcohol described in US Pat. No. 2,304,925, Journal of the Photographic Society of Japan 14, 74
Pyridine, ammonia, hydrazine and amines described in (1952) are also effective development accelerators for some purposes.

Moreover, sodium sulfite, potassium sulfite, potassium bisulfite, and sodium bisulfite can be added.

Further, sodium hexametaphosphate, sodium tetrapolyphosphate, sodium polypolyphosphate or polyphosphoric acid compounds represented by potassium salts of the above polyphosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N- (hydroxymethyl) ) Aminopolycarboxylic acids represented by ethylenediaminetriacetic acid and diethylenetriaminepentacomplex acid can be used as the water softener. The amount added varies depending on the hardness of the water, but it is usually 0.5 to 10 g / l. Other calcium and magnesium impurities can also be used. These are from Belgisches Ch by J. Willems
emiches Industry "21, P325 (1956) and 23, P1105
(1958).

If necessary, organic solvents can be included.

Among these, ethylene glycol, hexylene glycol, diethylene glycol, methyl cellosolve, methanol, ethanol, acetone, triethylene glycol, dimethylformamide, dimethyl sulfoxide, other, JP-B-47-33,378, described in 44-9,509 Compounds are included.

The amount added varies widely depending on the component composition of the activator, but usually 50% or less of the used liquid, usually 10%.
It is the following. However, the solvent constituting the activator solution may sometimes be almost anhydrous.

N-methyl-p-aminophenol hemisulfate (commonly called methol), benzyl-p-aminophenol hydrochloride, N, N-diethyl-p-aminophenol hydrochloride, p-aminophenol sulfate, phenidone as an auxiliary developing agent , N, N, N ′, N-tetramethyl-p-phenylenediamine hydrochloride and the like can be used. The amount added is usually preferably 0.01 to 1.0 g / l.

In addition, if necessary, the following substances are added to the activator solution.

For example, as competing couplers (colorless couplers) such as citrazinic acid, J acid, and H acid, JP-B-44-9,505 and 44-44 are available.
-9,506, 49-9,507, 45-14,036, 44-9,508
U.S. Pat.Nos. 2,742,832, Degrees 3,520,690, and 3,560,21
Examples thereof include those described in No. 2, No. 3,645,737 and the like.

As a fogging agent such as alkali metal polo hydride, aminoborane and ethylenediamine, Japanese Patent Publication No. 47-38816.
There are some such as those listed in the issue.

The activator process of the present invention may be performed by any method. For example, a method of immersing a light-sensitive material in an activator bath, a method of adding a hydrophilic polymer known as a viscosity-imparting agent to an activator solution and applying it to a light-sensitive material, a method of putting the activator solution in a destructible pad, There are ways to deploy in between.

A conventionally known bath can be used for bleaching, fixing, bleach-fixing and washing or stabilizing treatment. This is described, for example, on pages 26 to 40 of Japanese Patent Application No. 61-70055.

As the silver halide used in the light-sensitive material in the present invention, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size 1 of the silver halide grains (the grain diameter in the case of spherical grains or grains close to a sphere, the grain length in the case of cubic grains, and the average based on the projected area) is preferably 2 μ or less, 0.4μ is especially preferred
It is the following. The particle size distribution may be narrow or wide.

The shape of these silver halide grains may be any of cubic crystal, octahedron, tabular and mixed crystal thereof.

Silver halide emulsions are usually water-soluble silver salts (eg silver nitrate)
It is prepared by mixing a solution and a water-soluble halogen salt (eg potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin.

Further, two or more kinds of silver halide photographic emulsions formed separately may be mixed. Further, even though the crystal structure of silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, and it is described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. The so-called conversion type may be used. Further, it may be of a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particles.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

Emulsions are usually free of soluble salts after precipitation or physical ripening.

As the silver halide emulsion, a so-called unripened (primitive) emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized.

For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. Can be used alone or in combination.

It may be preferable that the photosensitive material further contains various additives in order to obtain desired developing characteristics, image characteristics, film physical properties and the like. Examples of these additives include salt-form iodides and organic compounds having a mercapto free radical, such as phenylmercaptotetrazole and alkali metal iodide salts.
However, it is desirable to avoid using these in large amounts.

For the purpose of increasing the sensitivity, increasing the contrast, or accelerating the development of the light-sensitive material, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt compound, urethane derivative, urea derivative, It may contain an imidazole derivative, 3-pyrazolidones and the like.

For example, U.S. Patent Nos. 2,400,532, 2,423,549, and
Those described in 2,716,062, 3,617,280, 3,772,021, 3,808,003, British Patent 1,488,991 and the like can be used.

In general, an antifoggant added to the light-sensitive silver halide emulsion layer and the non-light-sensitive auxiliary layer of the light-sensitive material, and preferred specific examples thereof are heterocyclic organic compounds such as tetrazole, azaindene, triazoles aminopurine and the like.

As other additives, the light-sensitive material may contain a curing agent, a plasticizer, a lubricant, a surface agent, a brightening agent and other additives known in the photographic art.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bulletin Society (the Bull.So).
c.Sci.Phot.Japan) No. No. 16, page 30 (1966) Enzyme-treated gelatin may be used, or a hydrolyzate or enzymatic hydrolyzate of gelatin may also be used. .

If necessary, the photographic emulsion can be spectrally sensitized by using cyanine dyes such as cyanine, merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, the light-sensitive material used in the present invention is a silver halide having sensitivity in at least three different spectral regions. It is necessary to have an emulsion layer.

A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. Combination of sensitive emulsion layer and infrared-sensitive emulsion layer, blue sensitive emulsion layer, combination of green-sensitive emulsion layer and infrared-sensitive emulsion layer, blue-sensitive emulsion layer, red-sensitive emulsion layer and infrared-sensitive emulsion There are combinations of layers.
The infrared light-sensitive emulsion layer means an emulsion layer having sensitivity to light having a wavelength of 700 nm or more, particularly 740 nm or more.

The light-sensitive material used in the present invention may optionally have two or more emulsion layers having photosensitivity in the same spectral region depending on the sensitivity of the emulsion.

The light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

The light-sensitive material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These UV absorbers may be fixed in the hydrophilic colloid layer.

In the light-sensitive material, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based bleaching agent. These may be water-soluble, or a water-insoluble whitening agent may be used in the form of a dispersion.

In the light-sensitive material, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber, they may be mordanted with a cationic polymer or the like.

The light-sensitive material is used as an antifoggant or color mixture inhibitor.
It may contain a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol derivative and the like.

In the present invention, a known anti-fading agent can be used for the light-sensitive material or the image-receiving element. Organic anti-fading agents include hydroquinones, 6-hydroxychromans, 5
Of hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenols, hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and their respective compounds A typical example is an ether or ester derivative in which a phenolic hydroxyl group is silylated or alkylated. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol partial structures in the same molecule, as described in US Pat. No. 4,268,593, give good results. In order to prevent deterioration of the magenta dye image, especially deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results.

For the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). For example, various surfactants may be included for various purposes.

The light-sensitive material may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitalaldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halides (2,4-dichloro-6-hydroxy-s-). Triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid etc.), etc. can be used alone or in combination.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

The present invention is also applicable to multilayer natural color photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required.
It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

Further, the present invention is applied to a color image transfer method, an absorption transfer method, and the like.

Example 1 A silver halide color light-sensitive material was prepared by coating the following first layer (lower layer) to second layer (upper layer) on a paper support laminated on both sides with polyethylene to prepare samples 101 to 105.

Further, Samples 106 and 107 were also prepared in the same manner as Samples 101 and 102 except that the second layer of zinc hydroxide was not added.

In addition, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

After the light-sensitive material was imagewise exposed, it was developed according to the following developing process.

<Activator liquid> <Bleaching fixer> Water 400ml Ammonium thiosulfate (70% solution) 150ml Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (I) ammonium 55g Ethylenediaminetetraacetic acid 2Na 5g Water added 1000ml pH 6.70 Photographic results below Table 1 Shown in.

By treating a light-sensitive material containing zinc hydroxide and a developer precursor with an activator solution containing sodium picolinate complexed with zinc ions,
Color images of high density and low fog were obtained.

Further, the light-sensitive material was aged at 50 ° C. for 1 week and then subjected to the same treatment, and the minimum density was compared with that of a sample immediately after production. sample
The minimum concentration increased by 0.4 to 0.5 in 101 and 106, while it was less than 0.1 in samples 102 to 105 and 107.

From the above results, it was found that the method of the present invention can produce a photosensitive material which is stable over time and can obtain an excellent color image using a simple, stable and safe processing solution.

Also, when the pH of activator B was adjusted to 12 with potassium hydroxide, the maximum concentration of 1.85 and the minimum concentration of 0.25 were obtained for the light-sensitive material 102, but when this solution was left open for 4 weeks, it was processed. The maximum concentration dropped to 1.25. On the other hand, with the activator A of the present invention, the maximum concentration was obtained even after standing for 4 weeks, which was similar to that immediately after the preparation.

Example 2 A light-sensitive material 102 except that the coupler of the first layer was replaced by the following compound in an equimolar amount / m ^{2 in} the light-sensitive material 105 of Example 1.
Photosensitive materials 201 to 203 having the same structure as the above were prepared.

When the same treatment was carried out using the activator A solution of Example 1, the results shown in Table 2 were obtained.

When each photosensitive material was aged at 50 ° C. for 1 week and then subjected to the same processing, the minimum density increase with time was 0.1 or less in all cases.

Example 3 A method for preparing a silver halide emulsion for the first and fifth layers will be described.

0.295 each of sodium chloride and potassium bromide in a well-mixed gelatin aqueous solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C).
600 ml of an aqueous solution containing moles and an aqueous solution of silver nitrate (600 ml of water
0.59 mol of silver nitrate) was added simultaneously over 40 minutes at an equal flow rate. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol%) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 600g
It was.

Next, how to prepare a silver halide emulsion for the third layer will be described.

Add 0.29 each of sodium chloride and sodium bromide to a well-mixed gelatin aqueous solution (containing 1000 g of water containing 20 g of gelatin and 3 g of sodium chloride and kept at 75 ° C).
600 ml of an aqueous solution containing 5 mol and an aqueous solution of silver nitrate (water 600 m
0.59 mol of silver nitrate dissolved in 1) was added simultaneously over 40 minutes at an equal flow rate. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80%) having an average grain size of 0.35 μm was obtained.
Mol%) was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was performed at 60 ° C. Emulsion yield is 600g
It was.

Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.

5 g of the following yellow dye-donating substance (Y), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 2.5 g of triisononyl phosphonate as a high-boiling organic solvent were weighed, and acetic acid was added. Add 30 ml of ethyl,
It was heated and dissolved at about 60 ° C. to obtain a uniform solution. After stirring and mixing this solution with 100 g of a 10% solution of lime-processed gelatin,
The mixture was dispersed at 10,000 rpm for 10 minutes with a homogenizer. This dispersion is referred to as a yellow dye-donor substance dispersion.

Dispersions of magenta and cyan dye-donor substances were prepared in exactly the same manner as the dispersion of yellow dye-donor substances except that magenta dye-donor substance (M) and cyan dye-donor substance (C) were used. .

From these, a multi-layered color light-sensitive material as shown in the following table was produced. Note that the developing agents for the first, third, and fifth layers in the table are replaced with those shown in Table 3 (common to the first, third, and fifth layers), and photosensitive materials 301 to 306 are used.
It was created.

Next, how to make the dye fixing material will be described.

A dye fixing material was prepared by coating on a paper support laminated with polyethylene in the constitution shown in the following table.

A tungsten light bulb is used for the above-mentioned multi-layered color light-sensitive material, and G, R, and IR three-color separation filters whose densities are continuously changed (G is 500 to 600 nm, R is 600 to 700 nm bandpass filter, IR is Exposure was carried out for 1 second at 500 lux through a filter having a transmission of 700 nm or more).

20 ml / m ² of a 10% guanidine picolinate aqueous solution was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the dye-fixing material and the film surface were superposed. When the dye fixing material was peeled off from the light-sensitive material after being adhered for 180 seconds using a presser, a clear image of yellow, magenta and cyan was obtained on the fixing material corresponding to the three color separation filters of G, R and IR. It was The maximum density (Dmax) and the minimum density (Dmin) of each color were measured using a Macbeth reflection densitometer (RD-519).

The light-sensitive material was aged at 50 ° C. for 1 week and then processed in the same manner, and the minimum density at that time is shown in the following table.

According to the image forming method of the present invention, it is possible to obtain a color image of a light-sensitive material having good stability over time and having high density and low fog.

Claims (1)

[Claims] 1. A silver halide light-sensitive material having at least a light-sensitive silver halide, a coupler, a compound represented by the following general formula (Z) and a water-insoluble basic metal compound on a support is imaged. After exposure, a color image is developed by using a processing solution containing a complex-forming compound that undergoes a complex-forming reaction with the metal ion constituting the water-insoluble basic metal compound to release a base. Forming method. [In the formula, R ₁ , R ₂ , R ₃ and R ₄ are independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a substituted amino group,
Acylamino group, alkylsulfonylamino group, arylsulfonylamino group, substituted carbamoyl group, carbamoyl group, substituted sulfamoyl group, sulfamoyl group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, acyl group, alcoxy group Represents a group or an alkoxycarbonyl group. A is a hydroxyl group, a group which gives a hydroxyl group by the action of a nucleophile, or R ₆ and R ₇ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a cycloalkyl group, a substituted cycloalkyl group, an aralkyl group or a substituted aralkyl group. ) Is represented. R ₅ represents a hydrogen atom or a fluorine atom. n represents an integer of 1 to 17. Also, R _{1 to} R ₄
When is a substituent other than a hydrogen atom, a halogen atom, and a hydroxyl group, it may have an acceptable substituent. R _{1 to} R ₄ , R ₆ and R ₇ may be linked to each other to form an alicyclic ring, an aromatic ring, a hetero ring, or a ring composed of a combination thereof. ]