JP3058838B2 - Method for producing hydrogen storage alloy powder, and electrode using hydrogen storage alloy powder obtained by the method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen storage alloy powder having excellent storage stability, and more particularly, to the production of a hydrogen storage alloy powder having a good initial activity when used as a negative electrode of a nickel-metal hydride secondary battery. And an electrode using the obtained powder.

[0002]

2. Description of the Related Art Since the discovery of a hydrogen storage alloy that absorbs and releases hydrogen, it has been applied not only to hydrogen storage means but also to batteries and the like. In particular, alkaline secondary batteries have already been put into practical use. The capacity of the hydrogen storage alloy used and the service life of the hydrogen storage alloy have been increased one after another. That is, a LaNi ₅ alloy having a CaCu ₅ type crystal structure, which was initially studied,
By replacing a part of La with a rare earth element of Ce, Pr, and Nd at that step, and replacing a part of Ni with a transition metal element such as Al, Co, and Mn, high capacity and long life can be achieved. I was

However, when such a hydrogen storage alloy is used as a negative electrode for a battery, the capacity and the life of the battery can be increased, but the initial activity decreases. The initial activity is generally represented by the number of charge / discharge cycles required to reach the maximum capacity, and the smaller the number of cycles, the higher the initial activity. Usually, the initial activity is evaluated by the capacity in the first cycle and the number of charge / discharge cycles until the capacity reaches the maximum capacity.

[0004] When a battery having a low initial activity is sealed, the balance between the positive electrode and the negative electrode is lost, and there is a disadvantage that the capacity and the life are reduced. Therefore, in order to solve the above-mentioned drawbacks, conventionally, a hydrogen storage alloy has been subjected to an acid or alkali treatment. However, in these treatments, surface oxidation during the treatment is likely to occur, and oxidation during drying and storage is also likely to occur. Therefore, there is a disadvantage that handling and safety are not sufficient.

[0005]

In order to solve the above-mentioned drawbacks, the present inventors have conducted intensive studies on a hydrogen storage alloy powder for a negative electrode and a method for producing the same. After the alkali treatment, when treated with a solution containing a conjugated unsaturated compound having 5 or more conjugated π bonds in one molecule and a molecular weight of 100 or more (hereinafter referred to as a highly conjugated unsaturated compound), Hydrogen-absorbing alloy powder with excellent operability and handleability can be easily produced, and when it is used for the negative electrode of a nickel-metal hydride storage alloy secondary battery, without reducing the capacity and life of the battery. The inventors have found that the initial activity can be improved, and have reached the present invention.

Accordingly, a first object of the present invention is to provide a method for producing a hydrogen-absorbing alloy powder having excellent storage stability and handleability. A second object of the present invention is to provide a negative electrode for a nickel-metal hydride storage alloy secondary battery having excellent initial activity.

[0007]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
After the pulverized hydrogen storage alloy is treated with an alkali, the treatment is performed using a solution containing a conjugated unsaturated compound having 5 or more conjugated π bonds in one molecule and a molecular weight of 100 or more. This was achieved by a method for producing a hydrogen storage alloy powder.

[0008] The hydrogen storage alloy used in the present invention is not particularly limited, and can be appropriately selected from known hydrogen storage alloys used for the negative electrode. From the viewpoint of improving the life, it is preferable to use an MmNi ₅ -based hydrogen storage alloy. Mm in the metal is a so-called misch metal composed of a mixture of rare earth elements such as La, Ce, Pr, and Nd. From the viewpoint of improving the cycle life, the MmNi ₅ -based hydrogen storage alloy is preferably an alloy in which a part of Ni is replaced by Mn and replaced by Al, and further, an alloy replaced by Co It is preferred that

In the present invention, from the viewpoint of improving the initial activity in the case of a battery, and producing a hydrogen storage alloy powder excellent in storability and handleability, a highly conjugated unsaturated compound is obtained after alkali treatment. Treat with solution containing.
Neutralization with a mineral acid at the time of washing with water after the alkali treatment is an effective means and may sometimes improve characteristics. The alkali used in the present invention is not particularly limited, and may be appropriately selected from known alkalis. At least one alkali selected from lithium hydroxide, sodium hydroxide and potassium hydroxide may be used. It is preferable to use seeds, and it is particularly preferable to use lithium hydroxide.

The treatment temperature is from room temperature to 130 ° C. when the solution is treated with a solution containing a highly conjugated unsaturated compound, and from room temperature to 150 ° C. when the treatment using an alkali is performed.
The temperature is preferably from 10 ° C to 130 ° C. if needed,
The treatment may be performed in a closed container under a pressure of 10 kgf / cm ² or less. Performing the treatment at a high temperature or with cooling is not economical because the equipment costs for industrial production are too high. In particular, when the alkali treatment is performed at 150 ° C. or higher, the treatment proceeds not only to the surface but also to the inside, resulting in a decrease in capacity. On the other hand, if the processing is performed with cooling, the processing time is too long, which is not practical.

The treatment time with an alkali is 0.5 to 20 hours, and the treatment with a highly conjugated unsaturated compound is 10 to 20 hours.
It is preferable to set the time from minutes to 10 hours. The temperature may be appropriately adjusted so as to be short when the temperature is high and long when the temperature is low. In addition, the concentration of the processing bath
For 1.0 to 10.0 normal conjugated unsaturated compounds, the content is preferably 0.1 to 10% by weight based on the hydrogen storage alloy to be treated.

The highly conjugated unsaturated compound used in the present invention is an aromatic compound or a heterocyclic compound containing five or more conjugated π bonds in one molecule. Here, “conjugated π bond”
Means two or more double bonds and / or triple bonds in a conjugate relationship. In the present invention, the molecular weight of these highly conjugated unsaturated compounds is 100 or more, but especially 200
It is preferable that it is above.

Examples of the aromatic compound having 5 or more conjugated π bonds used in the present invention include benzene derivatives, naphthalene derivatives, polynuclear aromatic compounds, quinones,
Non-benzene-based aromatic compounds and the like, and conjugated π
Examples of the heterocyclic compound having 5 or more bonds include, for example, an oxygen-containing heterocyclic compound, a nitrogen-containing heterocyclic compound, a sulfur-containing heterocyclic compound, other direducible compounds sharing a nitrogen atom, and alkaloids. No.

First, as the benzene derivative, phenols and their derivatives, for example, 2,6-di-tert
-Butylphenylphenol, catecholphthalein,
2,2-diphenylolpropane, 3,7-dioxy-
10-methylxanthene, phenolphthalein, 7-
Oxy-2,4-dimethylbenzopyroxonium chloride, oxyanthraquinone, purprogalin, gallein, diphenyl ether, α-methoxyphenazine,
Chlorogluside, 2,3-dioxyanthraquinone,
5,7-dioxy-4-methylcoumarin, dioxyacridone, salicylic acid, α-hydrindone, β-phenylbutyrophenyl, N-2,4-dinitrophenyl-N-
Phenylhydroxylamine, acetophenone, 1- (4
-Nitrophenyl) -3,5-dimethylvirazole,
9,10-diphenylphenanthrene;

Aromatic amines and their derivatives, for example, N-phenyl-p-benzoquinonediimine, quinoline, safranin B, rosaniline, indulinine spirit soluble, aniline black, pararosaniline, methyl violet, methyl orange, methyl Red, indigo, carbazole, methylene blue, o-phenanthroline, p-phenanthroline, 3,6-diaminoacridine, indanthrene scarlet 2G, 4
-Aminodiphenylamine, acridine yellow, 3-
Aminophenothiazine, N′-diphenyl-p-phenylenediamine, rhodamine, 7-amino-4-methylcoumarin, 2-aminophenazine, phenothiazine, diphenylamine, N-methyldiphenylamine, N-phenyltolylamine, ditolylamine, 2- Oxy-4
-Methylquinoline, Heiza Yellow G, N, N'-diphenylformamidine, phenanthrophenazine, bismarck brown G, 2,3-diaminophenazine, 2-
Aminodiphenylamine, chrysodine R, 2,3,7,
8-tetraaminophenazine, aminophenoxazone,
Oxyphenoxazone, trifendioxazine, 2,
4-dinitrophenoxazine, 2 ', 4'-dinitro-
4-oxy-3-aminophenylamine;

Nitro and nitroso derivatives such as p
-Nitrosodiphenylhydroxylamine, phenazine, phenazine oxide, 1-phenylazo-2-naphthol, triphendioxazine, 4-nitroxanthone, 4'-nitroso-2-nitrodiphenylamine;

Phenylhydroxylamine derivatives such as 4,4'-dinitrodiphenylamine, bis (β-phenylhydrazine) oxalate, bis (β-phenylhydrazine) malonate, bis (β-phenylhydrazine) succinate, phthalic acid Bis (β-phenylhydrazine);
Aromatic halides, such as biphenyl chloride;

Aromatic aldehydes such as 2-phenyl-1-benzylbenzimidazole, leucomalachite green, malachite green, tetrachlorohydroquinone monobezoate, benzoflavin, 2-phenylbenzthiazole, 4-benzhydrylbenzaldehyde, bis Phenylhydrazone, bis (4-nitrophenylhydrazone);

Aromatic ketones such as triphenylisoxazole, potassium benzophenone, 4-methylbenzophenone, p-toluic acid anilide, benzoic acid toluidide, julyl phenyl ketone, 2,4,2 ',
4'-tetramethylbenzophenone, chalcone phenylhydrazone, 1,3,5-triphenylpyrazoline, dinitrobenzyl; benzoic acids, phthalic acids and derivatives thereof, for example, quinizarin, nitrodiphenyl ether;

Benzene derivatives having one more substituent in addition to the aldehyde group, for example, disaltyraldehyde, coumarin, 2-benzoylcoumarone, 1-oxy-
2,4-dimethylfluorone, 3-phenylcoumarone,
Coumarin-3-carboxylic acid ethyl ester, 3-acetylcoumarin, hydrovanilloin, 4-oxy-3-methoxy-ω-nitrostyrene, α- (nitrophenyl)-
β-benzoylethylene oxide, dinitrophenylindazole, 5-chloro-3- (4-oxyphenyl)
Anthranil, 3-nitroacridone, 6-nitro-3
-Phenylanthranyl, 2,8-dimethyl-1,9-
Anthrazolin, carbostyril, 1,3-dioxyacridine, oxyquinacudine, florquinyl, 2-methylquinazoline, 3-acetyl-2-methylquinoline,
2-oxy-3-phenylquinoline, 3-nitroquinoline, quinoline-2,3-dicarboxylic acid ester;

A benzene derivative further having one substituent other than the acyl group, for example, 7-oxyflavanone,
-Oxyflavone, 7,8-dioxyflavone, 7-acetoxy-4-methyl-3-phenylcoumarin, 7,8
-Diacetoxy-4-methyl-3-phenylcoumarin,
o-oxybenzophenone, xanthone, 2-phenylbenzoxazole, m-oxybenzophenone, p-
Oxybenzophenone, 2-benzoylxanthone,
2,4-dioxybenzophenone, 2,5-dioxybenzophenone, 2,2′-dioxybenzophenone, xanthene, aurin, trioxybenzophenone, 6,
7-dimethoxy-3-phenylcoumarone, o-nitrobenzophenone, m-nitrobenzophenone, 4,4'-
Dibenzoylazoxybenzene, 2- (2aminophenyl) -4-methylquinone, 2-oxy-4-methylquinone, acridone, 2,4, -dimethylquinazoline, 3-
Cyan-2-oxy-4-methylquinoline, fluorene, anhydro (2-aminobenzophenone) dimer, 2-oxy-3-phenylindazole, 3-phenylindazole, 2-phenylbenzimidazole,
2-methyl-8-benzoylquinoline, 2-methyl-4
-Phenylquinoline, 4-phenyl-2-quinazolone,
Aminobenzophenone, chlorobenzophenone, 4-phenylbenzo-1,2,3-triazine-3-oxide, diaminobenzophenone, 7-methyl-3-phenyl-4,5-benzo-1,2,6-oxydiazine,
4,4′-bisdimethylaminobenzophenone, 4,
4′-bisdimethylaminobenzophenone imide, 2,
4-dinitro-9-phenylacridine, 4,4'-dibenzoyldiphenyl;

Benzene and toluene derivatives having three or more different substituents, for example, tetramethoxyindigo, 5,6,5 ', 6'-bismethylenedioxyindigo, 7-acetoxy-8-methoxy-3- (2-nitrophenyl) carbostyryl, 2,2'-dinitrodiphenyldisulphide-4-4'-dialdehyde, 6-chloro-3-benzoylflavone, 1,3,8-trinitrophenoxazine; aralkyl compound For example, 9-benzylacridine;

Diazo compounds and azo compounds, for example,
Azobenzene, azotoluene, 2,2-dimethoxyazobenzene, 4,4'-dichloroazobenzene, 1,1 '
-Azonaphthalene, 2,2'-dioxyazobenzene,
2,2'-dioxy-5,5'-dimethylazozenbene, p-bromoazobenzene, p-nitroazobenzene, phenazoxide;

Aromatic unsaturated compounds such as 2,3
4,5-tetraphenylcyclopentan-2-ene-1
-One, 1,2,3-triphenylazulene, 2,2 ′
-Dimethyldiphenylacetylene, 4,4'-diethyldiphenylacetylene, 3,4,3 ', 4'-tetramethyldiphenylacetylene, 2,2'-dichlorodiphenylacetylene, 2,2'-dibromodiphenylacetylene, 2 -Nitrodiphenylacetylene, 2,2'-dinitrodiphenylacetylene, 2,2'-diaminodiphenylacetylene, 2,2'-dimethoxydiphenylacetylene, stilbene, α-methylstilbene, α-ethylstilbene, α, β-dimethylstilbene , Α, β
-Diethylstilbene, α, β-dichlorostilbene,
α, β-dibromostilbene, 2-chlorostilbene,
4,4′-diiodostilbene, α-nitrostilbene, α, β-dinitrostilbene, 2,4,6-trinitrostilbene, 2-aminostilbene, 2,2′-diaminostilbene, 4,4′-di (Dimethylamino) stilbene, 2,2′-dicyanstilbene, 2-oxystilbene, 2-methoxystilbene, 2,2′-dioxystilbene, 2,2′-dimethoxystilbene,
4,4′-dialkoxystilbene, 3,5,2 ′,
4'-tetraoxystilbene; and polyphenyls and derivatives thereof, for example, biphenyl, terphenyl, quaterphenyl, kinkphenyl, sexiphenyl, sebutiphenyl, octiphenyl, nobiphenyl,
Desiphenyl and the like.

Next, as the naphthalene derivative, alkyl, alkenyl and phenylnaphthalenes such as 1
-Methylnaphthalene, 2-methylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1,2-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 1,7
-Dimethylnaphthalene, 2,3-dimethylnaphthalene,
2,6-dimethyl naphthalene, 2,7-dimethyl naphthalene, 1-propyl naphthalene, 1-isopropyl naphthalene, 2-isopropyl naphthalene, trimethyl naphthalene, diisopropyl naphthalene, 1-vinyl naphthalene, 2-vinyl naphthalene, 1-propenyl naphthalene, 1-allylnaphthalene, 1-isopropenylnaphthalene, 2-isopropenylnaphthalene, 1-phenylnaphthalene, 2-phenylnaphthalene, 1,4-diphenylnaphthalene, 1,2,4-triphenylnaphthalene;

Dinaphthyls, for example, 1,1'-dinaphthyl, 1,2'-dinaphthyl, 2,2'-dinaphthyl;
Naphthylarylmethanes, for example, 1-benzylnaphthalene, 2-benzylnaphthalene, 1- (α-chlorobenzyl) naphthalene, 1- (α, α-dichlorobenzyl) naphthalene, diphenyl-α-naphthylmethane, diphenyl-β -Naphthylmethane, 1,8-dibenzylnaphthalene, di-α-naphthylmethane, α-naphthyl-β
-Naphthylmethane, di-β-naphthylmethane;

Naphthylarylethanes such as 1-
Phenethylnaphthalene, 1,2-di-α-naphthylethane, 1,2-di-β-naphthylethane, 1,1-α-dinaphthylethane; hydronaphthalenes, for example, 1,
2, -dihydronaphthalene, 1,4-dihydronaphthalene, 1,2,3,4-tetrahydronaphthalene;

Nitronaphthalene and its derivatives, for example,
Dinaphthopyridazine, 7,8-benzoquinone, 5,6-
Benzoquinone, naphthazaline, diperimidine, nitromethylnaphthalene, nitroalkylnaphthalene, nitrophenylnaphthalene, halonitronaphthalene, halodinitronaphthalene, nitrosonaphthalene, dinitrotetralin, dibenzophenazine, methylbenzoindole, 9
-Chloro-1-azaanthracene, quinolinoquinoline,
1,2,3-triazaphenalene, perimidone, perimidine, dibenzoacridine, benzophenazine-12-
Oxide, diaminonaphthalene, triaminonaphthalene, tetraaminonaphthalene, N-ethyl-α-naphthylamine, N-methylnaphthylamine, N, N-dimethylnaphthylamine, N-methyl-N-ethylnaphthylamine, trimethylnaphthylammonium salt, N-phenyl Naphthylamine, N-benzylnaphthylamine, N-
Naphthylethylenediamine, N-naphthylglycine, N
-Β-cyanomethylnaphthylamine, N-cecetylnaphthylamine, N-formylnaphthylamine, N-benzoylnaphthylamine, N-phthaloylnaphthylamine,
Aminomethylnaphthalene, nitronaphthylamine, dinitronaphthylamine, halonitronaphthylamine, aminotetralin, diaminotetralin;

Halogenated naphthalenes, for example, 1-fluoronaphthalene, 1-chloronaphthalene, 1-chloro-3,4-dihydronaphthalene, 1-iodonaphthalene, 1-bromonaphthalene, 1-chloro-4-chloromethyl Naphthalene, 1-bromo-2-bromomethylnaphthalene, 1,4-difluoronaphthalene, 1,2-dichloronaphthalene, 1,6-dichloronaphthalene, 1,7-
Dichloronaphthalene, 1,5-dichloronaphthalene,
1,8-dichloronaphthalene, 2,3-dichloronaphthalene, 1,4-dibromonaphthalene, 1,4-diiodnaphthalene, perylene, 1,2,3-trichloronaphthalene, 1,2,4-tri Bromnaphthalene, 1,2,
3,4-tetrachloronaphthalene, 1,4,5-tribromo-3,8-dimethylnaphthalene, 1,3,6,7-
Tetrachloronaphthalene, 1,3,5,8-tetrabromonatephthaline, 1,2,3,4,5-pentachloronaphthalene;

Naphthylhydroxylamine, naphthylpyrazine and naphthylureas, for example α-naphthylhydroxylamine, N′-phenyl-N-α-naphthyl-N-oxyurea, β-naphthylthiohydroxylamine, N-nitroso-α -Naphthylhydroxylamine,
Neocuferon, 2-oxy-1,1′-azonaphthalene, α-naphthylhydrazine, 1,2-dibenzocarbazole, 4,4-diamino-1,1′-binaphthyl,
3,4-benzcarbazole, 2,2′-diamino-
1,1′-binaphthyl, N′-acetyl-N-β-naphthylhydrazine, N′-lauroyl-N-β-naphthylhydrazine, N′-phenyl-N-α-naphthylhydrazine, N ′-(2,4 -Dinitrophenyl) -N-α-
Naphthylhydrazine, 2-α-naphthyl-5-nitrobenztriazole, N, N′-di-α-naphthylhydrazine, 1,1′-diamino-2,2′-binaphthyl,
N, N'-di-5-tetralylhydrazine, N'-
(2,4-dinitrophenyl) -N-β-naphthylhydrazine, 2-β-naphthyl-5-nitrobenztriazole, N′-triphenylmethyl-N-β-naphthylhydrazine, N, N′-di-β -Naphthylhydrazine, N
-Methyl-N- (2,4-dinitro-1-naphthyl) hydrazine, 2-amino- (naphth-1 ', 2': 4,5
-Thiazole), 1,2: 5,6-dibenzophenazine, 2-amino- (naphth-2 ', 1': 4,5-thiazole), 2,3-dihydrazinonaphthalene, 2-phenyl-1, 3-bisbenzylideneamino (naphth-2 '
, 3 ': 4,5-imidazoline), N-acetyl-α
-Naphthylnitrosamine, N-ethyl-α-naphthylnitrosamine, N-phenyl-α-naphthylnitrosamine, α, α′-dinaphthylnitrosamine, bis (β-naphthylnitrosamide), N-ethyl-
β-naphthyl nitrosamine, N-phenyl-β-naphthyl nitrosamine, N-acetyl-2-methyl-1-
Naphthylnitrosamine, 4,5-benzindazole, naphthylnitrosamine, 4,5-benzindazole, naphthylnitrosamine, 1-nitro-2-naphthylamine, α-naphthylurea, N, N′-di-α-naphthylurea, 4- Chlor-1-naphthylcarbamoyl chloride, 2,4′-dichloro [naphth-1 ′, 2 ′:
4,5-thiaazole], 2-mercapto [naphtho-
1 ′, 2 ′: 4,5-thiazole], 2-chloro [naphth-1 ′, 2 ′: 4,5-thiazole], 2-mercapto [naphth-2 ′, 1 ′: 4,5-thiazole] , 2-
Chloro [naphth-2 ', 1': 4,5-thiazole];

Naphthalene aralkyl compounds, for example,
Dibenzoanthracene, acenaphthene, α-chloroethylnaphthalene, phenylnaphthylchloromethane, diphenylnaphthylchloromethane, nitromethylnaphthalene,
Aminomethylnaphthalene, (naphthylmethyl) amine,
α-phenyl (naphthylmethyl) amine, N-benzyl (naphthylmethyl) amine, trimethyl (naphthylmethyl) ammonium salt, tri (naphthylmethyl) amine,
Di (naphthylmethyl) amine, (β-naphthylethyl)
Alcohol, dimethyl naphthyl carbinol, phenyl naphthyl carbinol, diphenyl naphthyl carbinol, 9-phenylbenzofluorene, naphthyl propylene oxide, ethyl (naphthyl methyl) ether, phenyl (naphthyl methyl) ether, naphthyl acetaldehyde, naphthyl acetone, ω-naphthyl Acetophenone, acenaphthenone, dihydrophenalone, phenalone, benzoindanone, naphthyl acetonitrile, 9,
9'-dichlorodibenzofluorene, α-nitro-β-
Naphthyl ethylene, γ-naphthyl allyl alcohol, β
-Naphthyl acrolein, methyl (β-naphthyl vinyl) ketone, naphthyl phenanthylene dicarboxylic anhydride;

Naphthol, naphthalenesulfonic acids such as 9-oxynaphthacenequinone, 2'-naphthalene-2-indoleindigo, 1-methoxynaphthalene,
1-ethoxynaphthalene, 1-phenoxynaphthalene,
α-naphthol-salicylate, β-naphthol,
α-naphthol, α-naphthol benzoate, α
Naphthol acetate, phenyl-β-oxynaphthylbenzaliminomethane, β-naphtholphenylmethylamine, methylene-di-β-naphthol, dinaphthopyran, 1′-naphthol-2-indoleindigo,
2-methoxynaphthalene, 2-ethoxynaphthalene, N
-P-oxyphenyl-naphthylamine base, β-naphthol salicylate, 2-methyl-1-naphthol, 1,2-naphthalmethylenequinone, 1,2-dioxynaphthalene, naphthaleneindoleindigo, α, β
-Naphthophenoxazine, β, γ-naphthophenoxazine, 4-oxy-10-methyl-1 ′, 2′-benzocarbazole, dioxynaphthofluoran, dinaphthoquinone, 2,6-naphthoquinone, oxybenzoacridine,
9-oxy-3-dimethylaminonaphthophenoxazine, 1,2,4-trioxynaphthalene, 1,4,5
6-tetraoxynaphthalene, thio-α-naphthol,
4-mercapto-1-naphthol, 1,5-naphthalenedithiol, methyl-α-naphthylsulfide, 1,
1′-naphthyl sulfide, 1,1′-thiodi-2-naphthol, 1,1′-naphthyl disulfide, 1,1 ′
-Dithiodi-1-naphthol, thio-β-naphthol,
Naphthothioindigo, 1-amino-2-naphthalenethiol, naphthothianthrene, 2-mercapto-1,2-
Naphthothiazole;

Naphthaldehydes and derivatives thereof, for example, α-naphthaldehyde, 2- (2,4-dinitrophenyl) -1- (α-naphthyl) ethylene, 2-methyl-1-naphthaldehyde, 2,3- Dimethyl-1-naphthaldehyde, 4-bromo-1-naphthaldehyde,
4-nitro-1-naphthaldehyde, 2,4-dinitro-1-naphthaldehyde, 4-amino-1-naphthaldehyde, 2-oxy-1-naphthaldehyde, 1-naphthalin-2′-indoleindigo, 2-bis (2
-Oxy-1-naphthyl) ethylene, 1,2: 7,8-
Dibenzoxanthylium chloride, 2-oxy-1-naphthylethynylpyrylium salt, 5,6-benzocoumarin, bis (2-methyl-3-indolyl) (2-oxy-1-naphthyl) methane, 4,5- Benzindoxazene, 2-acetoxy-1-naphthonitrile, 4-tomex-1-naphthaldehyde, 1,4-bis (4-methoxy-1-naphthyl) -1,3-butadiene, 2-naphthalin-2 ' -Indole indigo, 3-acetyl-6,
7-benzocoumarin, 4-chloro-1-oxy-2-naphthaldehyde, naphthalene dialdehyde, 5-oxy-2-naphthalin-indole-indigo, 5,6
7,8-tetrahydro-2-naphthaldehyde, imidochloride, naphthamide, naphthanilide, naphthonitrile, β-naphthoimidic acid ethyl ester, β-naphtamidine, α-naphthamidoxime, α-naphthohydrazide, naphthostyryl, oxynaphthonitrile, 1, 2:
7,8-dibenzoxanthone, 1,2-benzoxanthone, 1,1′-binaphthylene-2,8 ′: 8,2′-dioxide, 2,3: 6,7-dibenzoxanthone, 3-
Oxy-2-naphthoanilide, 1,3-bis (3-oxy-2-naphthoyloxy) benzene, 2,4-dioxyphenyl-3-oxy-2-naphthyl ketone, 4-arylazo-3-oxy-2 -Naphthoanilide, 3,4
-Dihydronaphthalene-1,2-dicarboxylic anhydride,
2-aminonaphthalimide, naphthalohydrazide, α-
Pyridonaphthalone, N-methylnaphthalimide; and

Acetonaphthene, benzoylnaphthalenes such as 1,2,5,6-dibenzanthracene,
2′-methyl-2,1′-dinaphthyl ketone, 2-methyl-1,1′-dinaphthyl ketone, styryl-2-naphthyl ketone, β-naphthoylacetone, β-naphthoylacetophenone, 1- (β -Naphthyl) -1-chloroethylene, 2- [tris (β-cyanethyl) acetyl]
Naphthalene, 1,3,5-tri (β-naphthyl) benzene, dimethyl-2-naphthylcarbinol, 4,5:
4 ′, 5′-Dibenzothioindigo, styryl-1-naphthyl ketone, β-acetonaphthone, 1-propionylnaphthalene, 1-butylnaphthalene, 1-isobutylnaphthalene, 1-stearoylnaphthalene, 1-benzoylnaphthalene, 1-o- Toluyl naphthalene, p-biphenyl-1-naphthyl ketone, 1,2,5,6-dibenzanthracene, 1-acetyl-3,4-dihydronaphthalene, 1-acetyl-7-bromonaphthalene, 1-aminenoacetylnaphthalene 2-aminobenzoylnaphthalene, 1-acetyl-2-oxynaphthalene, 1-acetyl-2-methoxynaphthalene, 1-acetyl-4-ethoxynaphthalene, 2-cinnamoyl-1-naphthol, 7,8-benzochromone, 3-acetyl-2-methyl-7,8-benzo Solomon, 3,4-dimethyl-7,
8 Benzocoumarin, 4-methyl-3-phenyl-7,
8-Benzocoumarin, 1-Benzoyl-2-oxynaphthalene, 4-Oxybenzanthrone, 4-Benzoyl-1-naphthol, 3-Oxy-1,2-Benzofluorenone, 2-Acetyl-4-chloro- Examples thereof include 1-oxynaphthalene, α-naphthylglyoxal, β-naphthylglyoxal, 1,4-dibenzoylnaphthalene, and phenyl-4-methyl-1-naphthyldiketone.

The polynuclear aromatic compounds include anthracenes and derivatives thereof, for example, anthracene,
1,2-dihydroanthracene, 1-chloroanthracene, 1,4-dichloroanthracene, 1,2,7-trichloroanthracene, 1,2,3,4-tetrachloroanthracene, 1-nitroanthracene, 9,10- Dinitroanthracene, 1-aminoanthracene, 2-dimethylaminoanthracene, 2-anilinoanthracene,
9-methylaminoanthracene, 1,4-diaminoanthracene, 1-oxyanthracene, 9,10-dihydroanthrol, 10-methylanthranol, 10-
Phenylanthranol, 10-nitroanthranol, 2-amino-1-anthranol, 1,2-dioxyanthracene, 9,10-dioxyanthracene diacetate, 1-methylanthracene, 4-chloro-1-
Methylanthracene, 1,5-dichloro-2-methylanthracene, 9-ethylanthracene, 9-vinylanthracene, 9-propylanthracene, 9-isopropylanthracene, 9-butylanthracene, 9-isobutylanthracene, 9-isoamylanthracene, ,
3-dimethylanthracene, 9,10-diethylanthracene, 1-phenylanthracene, 9-phenylanthracene, 1,5-dichloro-9-phenylanthracene, 10-nitro-9-phenylanthracene, 9-benzene Zilanthracene, 1-benzhydrylanthracene, 9,10-diphenylanthracene, 9,10-dibenzylanthracene, 9,10-diphenylanthracene
0-dihydroanthracene, 1- (β-naphthyl) anthracene, 9- (α-naphthyl) -10-phenylanthracene, 9,10-di (α-naphthyl) anthracene, 1,1′-bianthryl, 2,2 '-Bianthryl, 9,9'-bianthryl, anthracene-9-aldehyde, 1-acetylanthracene, 9-benzoylanthracene, 10-nitroanthraphenone, 9,10
-Dibenzoyl anthracene, anthrone, 9-mercaptoanthracene, 9,10-disodium-9,10
-Dihydroanthracene, 10-bromo-9-anthrylmagnesium bromide, anthryl mercury chloride;

Phenanthrenes and derivatives thereof, for example, phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydrophenanthrene, 1
-Chlorphenanthrene, phenanthrene-9,10-
Dichloride, 1-bromophenanthrene, 1-iodophenanthrene, 9- (chloromethyl) phenanthrene,
1- (bromomethyl) phenanthrene, 4,5-bis (bromomethyl) phenanthrene, 1-nitrophenanthrene, 10-bromo-9-nitrophenanthrene, 1
-Aminophenanthrene, 9,10-diaminophenanthrene, 9,9'-azoxyphenanthrene, 9,9 '
-Azophenanthrene, 1-oxyphenanthrene, cholesterol, estrone, androsterone, 10-
Brom-9-phenanthrol, 9-nitro-3-phenanthrol, 4-amino-1-phenanthrol, 1
0-benzoazo-9-phenanthrol, 1,2-dioxyphenanthrene, letter-3,8-diol, 2,
3,5,6-tetraoxyphenanthrene, 1-methylphenanthrene, 1-ethylphenanthrene, 1-vinylphenanthrene, 1,2-dimethylphenanthrene,
9,10-diethylphenanthrene, 9,10-dipropylphenanthrene, 2-ethyl-1-methylphenanthrene, 7-isopropyl-1-methylphenanthrene, 9,10-dihydroretene, aminoretene, 3 -Acetaminoretene, 6-acylaminoretene, 9-phenylphenanthrene, 9-benzylphenanthrene, 1
-(Α-naphthyl) phenanthrene, 1,1′-biphenanthryl, 9,9′-biphenanthryl, 1-phenanthraldehyde, 2-phenanthraldehyde, 9-phenanthraldehyde, 1-acetylphenanthrene, 2-
Propionylphenanthrene, 3-acetylretene, 1
Benzoyl phenanthrene;

Phenanthrenequinones, for example, phenanthrene-1,2-quinone, phenanthrene-1,4-
Quinone, phenanthrene-3,4-quinone, phenanthrene-9,10-quinone, 2-phenyl-3-acetoxy-4,5-biphenylenefuran, 7-isopropyl-
1-methylphenanthrenequinone, 1-chlorophenanthrenequinone, 2-bromophenanthrenequinone, 2-
Iodophenanthrenequinone, 2,7-dibromophenanthrenequinone, 2-nitrophenanthrenequinone,
2,5-dinitrophenanthrenequinone, 2-aminophenanthrenequinone, 2,7-diaminophenanthrenequinone, 3,6-diaminophenanthrenequinone, 2,
5-diaminophenanthrenequinone, 2-oxyphenanthrene-1,4-quinone, 3-oxyphenanthrenequinone, 2-oxyretenquinone, 3-oxyretenquinone, 6-oxyretenquinone, 2-oxy -3,4-
Dinitrophenanthrenequinone, 2-amino-3-oxyphenanthrenequinone; and

Polynuclear aromatic compounds and derivatives thereof, for example, pentacene, hexacene, benzophenanthrene,
Benzo [a] anthracene, naphtho [2,1, a] pyrene, dibenzo [a, j] anthracene, pyrene, coronene, 1,12-benzoperylene, ovalene, dibenzoanthracene, naphthacene, Terramycin, aureomycin, rubrene, o-toluoyl-1-naphthalene, benzoanthraquinone, 5,6-dioxy-5,6-dihydrobenzoanthracene, chrysene, triphenylene,
Dibenzonaphthacene, hexahydropyrene, perylene,
3,9-dichloroperylene, tetrachloroperylene,
3,9-dibromoperylene, 3,10-dinitroperylene, 4,6-dibenzoyl-1,3-dimethylbenzene, 6,13-dihydropentacene, naphtho [2,3-
a) anthracene, dispiran, dibenzo [a, h] anthracene, picene, picylene ketone, picene-5,6
Quinone, dibenzo [c, g] phenanthrene, benzo [a] pyrene, benzo [a] pyrene-1,6-quinone,
Mesobenzoanthrone pericarboxylic anhydride, anthraceno [2,1-a] anthracene, dibenzo [a, 1]
Naphthacene, phenanthrene [2,3-a] anthracene, naphtho [2,3-a] pyrene, dibenzo [a, h]
Pyrene, dibenzo [a, 1] pyrene, zetrene, anthantrene, benzo [1,12] perylene, heptacene, tetrabenzo [a, c, h, j] anthracene, triben Zo [a, i, 1] pyrene, tetrahydrodimethyldinaphthyl, mesonaphtodianthrene, mesoantolothylenethrene, 2,3; 8,9-dibenzozocoronene, pyranthrene and the like.

The quinones and derivatives thereof include benzoquinones and derivatives thereof, for example, dibenzoquinoyl disulphide, 2,5-bis (phenylthio) -p-benzozoquinone, bibenzoquinone, Bitolquinone, Phenicin, Ausporin, Indophenol,
Indoaniline, hydron blue, indamine, meldra blue, wurster blue, wurster red, 4,
4′-diphenoquinone, 4,4′-stilbenequinone,
3,5,3,5-tetramethyl-4,4'-diphenoquinone, 3,5,3 ', 5'-tetra-tert-butyl-4,4'-diphenoquinone, 3,5,3', 5 '-Tetramethyl-4,4'-stilbenequinone, 3,5
3 ′, 5′-tetra-tert-butyl-4,4′-stilbenequinone;

Naphthoquinones and derivatives thereof, for example, 1,2-naphthoquinone, 3-oxy-2,2'-binaphthyl-1,4; 3 ', 4'-diquinone, 5,6-benzoquinoxaline, 2-benzophenazine, 2-benzene-1-naphthol, 4- (2,4-dioxyphenyl) -1,2-dioxynaphthalene, 4- (3
4,5-trioxyphenyl) -1,2-dioxynaphthalene, 1,2-naphthoquinone-1-phenylimide,
1,2-benzophenoxazine, 1,2-naphthoquinone-2-chloroimide, 1,2-naphthoquinone-bis-chloroimide, 2-anilino-1,4-naphthoquinone-4
-Anil, 2-oxy-1,4-naphthoquinone-4-anil, 1,2-naphthoquinone-1-oximebenzoate, 1,2-naphthoquinone-1-oxime methyl ether, 1-nitroso-2-naphthol, 2 -Nitroso-1
-Naphthol, naphtho [1 ', 2'; 3,4] furazan, 1,2-naphthoquinone-2-oximebenzoate, 1,2-naphthoquinone-2-oxime methyl ether, 3-anilino-1,2; 8 , 9-dibenzophenazine, naphthyl blue, naphthyl violett, 1,2;
5,6-dibenzophenazine, naphtho [1'2 ': 3
4] Furazan-2-oxide, triphthaloylbenzene, hexoxynaphthalene anhydride, 2,2′-binaphthyl-1,4; 1 ′, 4′-diquinone, 1 ′, 4′-dioxynaphtho (2 ′, 3 ': 3,4) pyrazole, 4,
7-dioxy-3,3-diphenyl-5,6-benzindiazene, 2-diphenylmethyl-1,4-naphthoquinone, methylnaphtho [2 ', 3': 4,5] triazole-1 ', 4'-quinone, , 2,4-triacetoxynaphthalene, 1,4-naphthoquinonephenylimide,
1,4-naphthoquinone-mono- (p-dimethylaminoanil), 1,4-naphthoquinonealkylimide, 4-nitroso-1-naphthol, phenylcarbamate, 4-nitroso-1-naphthylamine, 4-benzhydryl-
1,2-naphthoquinone, 2-venzhydryl-1,4-
Naphthoquinone, 3-benzhydryl, 2-methyl-1,
4-naphthoquinone, 3-geranyl-2-methyl-1,4
-Naphthoquinone, 3-fanesyl-2-methyl-1,
4-naphthoquinone, 2-methyl-3-phytyl-1,4
- naphthoquinone, vitamin K _1, vitamin K _2, 3- allyl-2,6-dimethyl-1,4-naphthoquinone, 2,
6-dimethyl-3-phytyl-1,4-naphthoquinone,
2,3-diallyl-6; 7-dimethyl-1,4-naphthoquinone, 2-phenyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2,6-dimethyl-3-
Phenyl-1,4-naphthoquinone, 3-benzyl-2-
Methyl-1,4-naphthoquinone, 2-methyl-3- (β
-Phenylethyl) -1,4-naphthoquinone, 3-cinnamyl-2-methyl-1,4-naphthoquinone, 2-benzhydryl-1,4-naphthoquinone, 4,7-diketo-
8-diphenylmethyl-4,7,8,9-tetrahydro-5,6-benzindiazene, 2-methyl-3-diphenylmethyl-1,4-naphthoquinone, 2,3-diphenyl-1-naphthol, naphtho [2 ' 3 ': 3, 4]
-Pyrazole-1 ', 4'-quinone, 3,4-dichloro-1,2-benzophenazine, 2-iodo-1,4-naphthoquinone, 1,4,5,8-tetraoxy-2,3;
6,7-dibenzothiantrene, 5,8-dioxy-
2,3; 6,7-dibenzothianthrene-1,4-quinone, 2,3-diphenoxy-1,4-naphthoquinone, dinaphtho [2 ', 3': 2,3] [1 ", 2": 5 , 4]
Furan-1 ', 4'-quinone, 2,3,5,8-tetrachloro-1,4-naphthoquinone, N, N'-bis-
(1,4-naphthoquinone-2-yl) -benzidine, 2
-Anilino-1,4-naphthoquinone-4-anyl, 4-
Anilino-1,2-naphthoquinone-2-anyl, phenylrosindarin, 2-anilino-1,4-naphthoquinone-4- (p-dimethylaminoanyl), 2-anilino-
1,4-naphthoquinone dianyl, 2-anilino-3-phenyl-1,4-naphthoquinone, 2-anilino-3-bromo-1,4-naphthoquinone, 2-anilino-4-chloro-1,4-naphthoquinone, 2,3-dianilino-1,
4-naphthoquinone, 2,3-dianilino-1,4-naphthoquinone dianyl, nitrosoaminonaphthoquinone, 3-
Chlor-2-phenylnitrosamino-1,4-naphthoquinone, phenyl-bis- (3-anilino-1,4-naphthoquinone-2-yl) -amine, 3-chloro-2-
(P-tolylnitrosamino) -1,4-naphthoquinone, 2,7-dioxy-1-nitrosonaphthalene, 4-
Benzenazo-1,3-dioxynaphthalene, di- (3
-Oxy-1,4-naphthoquinonyl-2-) methane, anhydroalkanenin, diquinoxalino [2 ′, 3 ′:
1,2; 2 ", 3",: 3,4] naphthalene, 3,4-
Phthaloylfurazan; and

Anthraquinones and derivatives thereof, for example, 1,2-anthraquinone, 2,3-anthraquinone, 1,4-anthraquinone, 9,10-anthraquinone, 1,5-anthraquinone, 2,6-anlaquinone,
1,10-anthraquinone, 9,9-bis (p-oxyphenyl) anthrone, anthraquinone bisdiphenylmethide, bisphenylhydrazone, benzanthrone,
Anthrahydroquinone, β-ethylanthraquinone,
1,3,5,7-tetramethylanthraquinone, 2,
2′-dianthraquinonylethane, 2,2′-dianthraquinonylethylene, 1,2,3-trioxyanthraquinone, anthracurisone, entrooxyanthraquinone, alizarin, quinizarin, anthralphine, chrysazine, histazaline, anthraflavin, Isoanthlavlavin, anthragalol, perpurin, oxyantralphine, anthrapargine, oxychrysadine, oxyflavopurine, rufiopin, quinalizarin, alizarin pentocyanine, rufuigalol,
Anthracene blue WR, alizarin hexacyanine,
2-chloroquinizarin, 1-nitroanthraquinone, purpurin, 2,4,6,8-tetrabromoanthracurisone, 31-aminoanthrapurine, 1,8-dinitroanthraquinone, α-aminoanthraquinone, 1,
1′-dianthraquinonyl, dianthraquinone imide,
1,4-dimethylaminoanthraquinone, 5-amino-
1-nitro-6,8-dibromoanthraquinone, 1,5
-Tetramethyldiamino-4,8-dinitroanthraquinone, anthraquinone acridone, bis-N- (2-oxyanthraquinolyl) -p-phenylenediamine, leucoquinizarin, quinizarin green, 1-amino-
2,4-dibromoanthraquinone, 1,4-diacylaminoanthraquinone, anthraquinone-β-aldehyde, o-diazine, 6,7-phthaloyl-1,9-benzanthrone, oxynitrosoanthraquinone,
1′-dianthraquinonyl, azoxyanthraquinone,
8-chloropyrazoleanthrone, 2,6-dihydrazinoanthraquinone, anthraquinonediazonium salt, β
-Anthraquinone hydrazine, azoxy anthraquinone, pyrazole anthrone, 1- (anthraquinonyl-
2-)-3-methylpyrazolone, 1-hydroxylaminoanthraquinone, 1,5-dihydroxylaminoanthraquinone, 1-nitrosoanthraquinone, 1-hydrazinoanthraquinone, 1,5-dihydrazinoanthraquinone, 1-azidoanthraquinone, 2 -Azidoanthraquinone, anthraquinone methylsulfoxide, 1,4-
Dirodane anthraquinone, β, β′-dianthraquinonyl sulfide, anthraquinone sulfenyl chloride,
2,2′-dianthraquinonyl, 1,1′-dianthraquinonyl, helianthrone, mesobenzodianthrone,
2,2′-diamino-1,1′-dianthraquinonyl,
Flavanthrone, 2,2′-dianthryl, mesonafhtdianthrone, 1,1′-dianthraquinonylamine,
Quinizarin quinone, histazaline quinone, alizarin quinone, 6-oxyquinizarin quinone and the like.

Further, examples of the non-benzene aromatic compound include azulene, cyclodecapentane, cyclotetradecaheptane, cyclooctadecanonaene, cyclotetracosadodecaene, heptalene, fulvalene, sesquifulvalene and heptafulvalene , Perinaphthene, indeno [2,1-a] perinaphthene, dibenzo [bf] oxepin, dibenzo [bf] thiepin, indolizine,
Cyclo [3,2,2] azine, 4,5-benzotropolone, 3,4-benzotropolone, 5H-benzocycloheptene, 7H-benzocycloheptene, colchicine, colhistine, colhinol methyl Ether, ditropyl ether, ditropyl sulfide, cyclopentadienyl tropylidene, benzoazulene, carbinol, psoipon, 4,5-benzotropone, 2-phenyltropone,
Naphthocycloheptadienone, naphthotropone, tribenzotropone, 1-amino-1,3-dicyanazulene, benzoylhydrazone, 3-phenyl-1-oxaazulanone-2, 2-benzyltropone, 3-methyl-
2-phenyltropone, 2,7-diphenyltropone,
2- (α-naphthyl) -tropone, 2,7-tetramethylene-4,5-benzotropone, 2,7-diphenyl-
4,5-Venzotropone, naphtho [2 ', 3'-4,
5] Tropon, naphtho [2 ', 1'-2, 3] Tropon, dibenzosberan, naphtho [1', 2'-2, 3]
Tropone, dibenzosuberol, 4-oxy-2-phenyltropone, 4,5,7-tribromo-2-phenyltropone, 3,5'-ditropolone, 3- (p-methoxyphenyl) tropolone, 4-oxy-2-phenyltropone , 3- (α-naphthyl) tropolone, 3,4-diphenyltropolone, 3,7-dibenzyltropolone,
4- (γ-phenylpropyl) tropolone, 3,5′-
Vitropolonyl, 4- (p-nitrostyryl) tropolone methyl ether, 2-amino-1,3-dicyanazulene, benzo [b] tropothiazine, 5-bromo-2-
Examples thereof include phenyltropone, 4-bromo-2,7-diphenyltropone, diphenylbiphenylcarbinol, and thiazinotropone.

Next, specific examples of the heterocyclic compound having five or more conjugated π electrons include the following compounds.
First, as the oxygen-containing heterocyclic compound, furan and its derivatives, for example, 2,5-diphenylfuran, 2-phenylfuran, 3-methyl-diphenylfuran, lepidene, pyridoxine, 2,4-diphenylfuran;

Benzofuran, isobenzofuran, dibenzofuran and derivatives thereof such as dibenzofuran,
Furano [2 ', 3'-7, 8] flavone, egonol,
Euparin, 1,3-diphenylisobenzofuran, tetraphenylglycol, tetraphenylphthalane, 9
-Phenylanthracene, o-oxymethyltriphenylcarbinol, 3,3'-diphenylphthalide, 1-
Phenylfuratan, 1,1-phenylfuratan, 3,3
-Diphenylphthalide, rubrene, α-solinine, dibenzofuran, 2,2′-dioxybiphenyl, 2,2 ′
-Diaminobiphenyl, phenazone, dibenzoquinone,
2-hydroxybenzofuran, 2-methylbenzofuran, benzo [a] benzofuran, benzo [b] benzofuran, dibenzo [a, f] dibenzofuran, dibenzo [c, d] dibenzofuran, dibenzo [c, e] dibenzofuran, bi (2-dibenzofuryl), bi (3-dibenzofuryl);

Pyran and pyrone derivatives, for example 2-
p-oxyphenyl-4,6-diphenylpyrylium phenyl chloride, anhydrobase, benzopyran, 4-
p-oxyphenyl-2,6-diphenylpyrylium phenyl chloride, 6-phenylcoumarin;

Chromenol and chromene derivatives such as 6-methyl-2,3-diphenylchromone, 6-methyl-2,3-diphenyl-4- (p-tolyl) -1,
4-benzopyran-4-ol, chromanol, γ-chromene, oxycoumarone, chromene, cyanidin chloride, chloride, fusetine, 6-oxy-3-methoxy-5,7-dimethylflavylium chloride, 4,4′-
Diflavirene-3,3′-oxide, chrysinidine, apigenidine, rotoflavinidine, luterinidine, galanginidine, fusenidine, molinidine, flavonimine, pelargonidin, cyanidin, delphinidin, petunidin, syringidine, hirustidine, apigendolinine, collazidrine, collaziulindine

Flavones, flavonols and isoflavone derivatives such as flavonols, flavones and fukugetin; coumarin and isocoumarin derivatives such as 7-
Oxy-3,4-benzocoumarin, dicoumarol, angelicin, psoralen, bergabutene, belcaptol, xanthotoxin, xanthotoxal, isopinpinerine, pinpinelin, oroserol, oroserone,
ぺ sedanine, oxy ぺ sedanine, ostritol,
Medakenin, nodaquenetin, seserin, xanthyretin, xanthoxyletin; and xanthone and related compounds such as dixanthylene, 9-phenylxanthene, isoxanthon, 1,2,7,8-dibenzoxanthene, 3,9-diphenyl Xanthene, 9,9-
And diphenylxanthene.

Next, examples of the nitrogen-containing heterocyclic compound include pyrroles, for example, 1-phenylpyrrole, 5-phenylpyrrole-2-aldehyde, phenyl-2-pyrylketoneoxymium, 2-phenyl. Pyrrole, 2-methyl-
1-phenylpyrrole, 2-methyl-4-phenylpyrrole, 2-methyl-5-phenylpyrrole, 3-methyl-5-phenylpyrrole, 2,4-diphenylpyrrole, 2,5-diphenyl Pyrrole, 2,3-diphenylpyrrole, 2,3,5-triphenylpyrrole, 1,
2,3,5-tetraphenylpyrrole, 2,3,4,5
-Tetraphenylpyrrole, diphenyl-2-pyrylcarbinol, pyrrolecyclotrimethine dye, pyrrolepolymethylene dye, biliverdin, bilirubin, prodigiosin, stercovirin;

Indoles such as 5,7-dichloro-2-phenylindole, 7-chloro-2-phenylindole, 5,7-dibromo-2-phenylindole, 7-bromo-5-chloro- 2-phenylindole, 2- (3′-indolyl) -3-isonitrosoindolenine, rose indole, tributuan blue,
Indolo [3,2-c] quinoline, Indolo [1,2-
c] quinazoline, 2-phenylindole, 3-nitro-2-phenylindole, 3-phenylindole,
N-methyl-3-phenylindole, 3- (o-nitrophenyl) indole, 2,3-diphenylindole, 3-triphenylmethylindole, 2-methyl-
3-triphenylmethylindole, 2-phenyl-3
-Triphenylmethylindole, 2- (1-naphthyl) -3-triphenylmethylindole, 2- (2-
Naphthyl) -3-triphenylmethylindole, 3,
3′-diindolyl, 3,2′-diindolyl, 3,
3'-dehydrodiindole, rose indole, 3-
Nitroso-2-phenylindole, 3-nitro-2-
Phenylindole, 2-methyl-3-phenylazoindole, 2-phenyl-3-phenylazoindole, 6-oxy-3-phenylindole, tryptophan, 4,5-benzotryptophan, 6, 7-benzotryptophan, zeorasein;

Oxo derivatives of indole, for example 3-
(4-ethoxy-1-naphthyl) oxindole, indophenine, indigoazine, indigoero-3G;
Isoindoles such as 1-chloro-4-methylphthalazine, 1-benzylidenephthalimidine, 2-methyl-3-phenylphthalimidine, 2-methyl-1,3
-Diphenylisoindole, 2,5-diphenylisoindole, β-isoindigo, dimethylimino-β-
Isoindigo;

Carbazoles such as 1-phenyl-
1,2,3-benzotriazole, 2,2′-diaminodiphenyl, 1,1′-dicarbazole; polyphylines such as polyphyrazine, magnesium octamethyltetraazaporphyrin, azadipyrromethine, phthalocyanine, diazacoproporphyrin , Porphyn, mesotetraphenylporphyrin, chlorofile-b, chlorofile-a;

Oxazoles, for example, 2-phenyloxazole, 4-phenyloxazole, 5-phenyloxazole, 2-methyl-4-phenyloxazole, 2-methyl-5-phenyloxazole, 4-methyl-2 -Phenyloxazole, 5-methyl-2-phenyloxazole, 4,5-dimethyl-2-phenyloxazole, 2,4-diphenyloxazole, 2,5
-Diphenyloxazole, 4,5-diphenyloxazole, 2-methyl-4,5-diphenyloxazole, 2,4,5-triphenyloxazole, 2- (o
-Nitrophenyl) oxazole, 2- (p-nitrophenyl) oxazole, 2-amino-5-phenyloxazole, 2- (p-aminophenyl) oxazole,
2- (o-aminophenyl) oxazole, 4,5-dimethyl-2-phenyl oxide oxazole, 4-methyl-2,5-diphenyl oxide oxazole, 2,
4,5-triphenyl oxide oxazole, 4- (o
-Methoxycarbonylbenzene) -2-phenyl-5-
Oxazolone, oxacarbocyanine dye, phenanthrooxazole;

Isoxazoles such as 4-nitro-3-phenylisoxazole, 5-amino-3-methyl-4-phenylisoxazole, 5-benzoyl-3,4-diphenylisoxazole; thianol , Such as 4-phenylthiazole, 5-phenylthiazole, 5- (p-florphenyl) thiazole,
-Methyl-4-phenylthiazole, 4-methyl-5
Phenylthiazole, 5-methyl-4-phenylthiazole, 4,5-diphenylthiazole, 2-methyl-
4,5-diphenylthiazole, 1,4-bis (4-methyl-2-thiazolyl) benzene, p, p′-bis (4
-Methyl-2-thiazolyl) biphenyl, 2-amino-
4-phenylthiazole, 2-amino-5-phenylthiazole, 2-amino-4,5-diphenylthiazole, 2-phenylazothiazole, 2-amino-4-methyl-5-phenylazothiazole, 4-methyl-2-
Phenylazothiazole, α-naphthothiazole, β-
Naphthothiazole, naphtho [2,3] thiazole, naphtho [1,2] thiazole, 2-methyl [1,2] thiazole, 2-phenylnaphtho [1,2] thiazole, 2-
Methylnaphtho [2,1] thiazole, 4-bromo-2-
Phenylnaphtho [2,3] thiazole, 2-oxynaphtho [2,1] thiazole, 2-aminonaphtho [1,2]
Thiazole, 2-aminonaphtho [2,1] thiazole,
2-mercaptonaphtho [1,2] thiazole, 2-mercapto [2,1] thiazole;

Imidazoles such as 2-phenylimidazole, 4-phenylimidazole, 4-methyl-
2-phenylimidazole, 2,4-diphenylimidazole, 4,5-diphenylimidazole, 2,4,5
-Triphenylimidazole, 2-bromo-4-phenylimidazole, 5-chloro-1-ethyl-2-phenylimidazole, 5-chloro-1,2-diphenylimidazole, 2-phenylazoimidazole, 2-methyl-4-phenylazo Imidazole, 2- (o-aminophenyl) benzoimidazole;

Pyrazoles such as 3-phenylpyrazole, 5-phenylpyrazole, 4-phenylpyrazole, 1-methyl-3-phenylpyrazole, 1-methyl-5-phenylpyrazole, 3-methyl-5-phenylpyrazole , L, 3-diphenylpyrazole, 1,5
-Diphenylpyrazole, 1,3,4-triphenylpyrazole, 1,3,5-triphenylpyrazole, 1,
4,5-triphenylpyrazole, 5-amino-3-phenylpyrazole, 3-amino-5-phenylpyrazole, 5-methyl-1,3-diphenylpyrazole-4-
Aldehyde, 3,5-diacetyl-4-phenylpyrazole, 4-benzoyl-1,5-diphenylpyrazole;

Oxadiazoles, for example, 3-phenylfurazan, 3,4-diphenylfurazan, naruto [1,2] furazan, phenylfuroxane, 3-methyl-5-phenyl-1,2,4- Oxadiazole, 2,
5'-diphenyl-1,3,4-oxadiazole; thiadiazoles such as 5-phenyl-1,2,3-
Thiadiazole, 2-phenyl-1,3,4-thiadiazole, 5,5′-diphenyl-2,2′-bis (1,
3,4-thiadiazole), 2-oxy-5-phenyl-1,3,4-thiadiazole, 2-methylsulfonyl-5-phenyl-1,3,4-thiadiazole;

Triazoles, for example, 2-phenyl-
1,2,3-triazole, 5- (p-aminophenyl) -3-mercapto-1,2,4-triazole; tetrazoles such as 5-phenyltetrazole
1,5-diphenyltetrazole, 1-oxy-5-phenyltetrazole, 1-amino-5-phenyltetrazole;

Pyridine-related compounds, for example, 2-phenylpyridine, 2,2'-dipyridyl, 2-chloro-6-
Phenylpyridine, 2,6-dichloro-3-phenylpyridine, 2,2′-azopyridine, 3,3′-azopyridine, benzene-4-azopyridine, 5-chloro-2,
2'-azopyridine, 5,5'-dichloro-2,2'-
Azopyridine, 4-pyridylazoresorcin, 4-pyridyl-m-phenylenediamine, 3-pyridyl-m-phenylenediamine;

Quinoline and related compounds such as quinoline, quinaldine, quinaldine-N-oxide, ethylquinaline, 2-phenylquinaline, 3-methylquinaline, 3-phenylquinaline, 4-methylquinaline,
Phenylquinoline, 6-methylquinoline, 6-ethylquinoline, 6-phenylquinoline, 2,4-dimethylquinoline, 2,4-diphenylquinoline, quinoline-4-methanol, quinoline [6,5-f] quinoline Quinophthalone, flavaaniline, quinoline blue, ethyl redo, binacyanol, naphthocyanol, cryptocyanine, xenocyanine, azacyanine, 6,6'-octahydroquinoline, besten red, 2,3'-biquinoline, 2,5'-biquinoline , 2,6′-biquinoline,
2,7′-biquinoline, 3,3′-biquinoline, 4,
5'-biquinoline, 4,6'-biquinoline, 5,5'-
Biquinoline, 6,6′-biquinoline, 6,7′-biquinoline, 6,8′-biquinoline, 7,7′-biquinoline,
8,8'-biquinoline, 2-fluoroquinoline, 3-fluoroquinoline, 4-fluoroquinoline, 5-fluoroquinoline, 6-fluoroquinoline, 7-fluoroquinoline, 8-fluoroquinoline, 3 -Bromoquinoline, 4-
Chlorquinoline, 2,4-dichloroquinoline, 3-nitroquinoline, 4-nitroquinoline, 2,3-quinolinediol, quinoline-2-thiol, 2-oxyquinoline-3-thiol, 2-aminoquinoline, 8-aminoquinoline Aminoquinoline, 2-hydraziquinoline, pyrroloquinoline, thiazoloquinoline, pyrimido [4,5-b] quinoline, benzo [f] quinoline;

Isoquinolines and related compounds such as
1-methylisoquinoline, 3-bromomethylisoquinoline, 1-phenylisoquinoline, 4-phenylisoquinoline, 1,1′-biisoquinoline, 5,5′-biisoquinoline, 1-chloroisoquinoline, 5-iodoisoquinoline, 5 -Bromoisoquinoline, 5-nitroisoquinoline, isoquinoline-1,3-diol, 6,7-methylenedioxyisoquinoline, 1-aminoisoquinoline,
-Cyanoisoquinoline, 1-phenylbenzo [g] 3,
4-dihydroisoquinoline, 3- (p-aminophenyl) -5,8-dihydro-8,9-dimethoxyimidazo [5,1-a] isoquinoline;

Acridine and related compounds such as acridine, 1-methylacridine, 9-phenylacridine, 9- (3-pyridinyl) acridine, 2-chloroacridine, 2-bromoacridine, 2-acridinol, acridine-3, 6-diol, 4-methoxyacridine, 9-phenoxyacridine, 1-nitroacridine, 4-aminoacridine, 1-aminoacridine,
9-phenylaminoacridine, 9-oxyacridine, chrysanilin, acriflavine, 3,6-diamino-4,5-dimethylacridine, acrinol;

Phenanthridines, for example, 3,4-benzoquinoline, 6-methylphenanthridine, 6-aminomethylphenanthridine, 6-phenylphenanthridine, 6-chlorophenanthridine, 6-bromo Phenanthridine, 6-nitrophenanthridine, 1-aminophenanthridine, 3-oxyphenanthridine; anthrazolines such as pyrido [2,3-g] quinoline, 2,7-diphenyl [2,3- g] quinoline, 2,
8-diphenylpyrido [3,2-g] quinoline;

Phenanthroline and related compounds such as 1,7-phenanthroline, 1,10-phenanthroline, 4,7-phenanthroline, 8-methyl-1,
7-phenanthroline, 4,10-dioxy-1,7-
Phenanthroline, 3,5-dichloro-1,10-phenanthroline, 2-amino-1,10-phenanthroline, 5-oxy-4,7-phenanthroline, 5-amino-4,7- Phenanthroline;

Pyridindoles, for example, 1,9-pyridindole, 2,9-pyridindole, 4,9-
Pyridoindole; naphthyridine and related compounds such as 1,5-naphthyridine, 1,7-naphthyridine,
1,8-naphthyridine, 1,6-naphthyridine, 2,6
-Naphthyridine, 2,7-naphthyridine, 1,5-naphthyridin-4-ol, 3-amino-1,5-naphthyridine, 2-amino-1,5-naphthyridine, 2-oxy-1,7-naphthyridine;

Oxazines and related compounds such as phenoxazinone, resazurin, carocyanine, Nile Bull-A, Meldora blue, brilliant cresyl blue; thiazines and related compounds such as o-benzoaminophenyl-β-phenoxycarbonyl Ethylsulfide, phenothiazine, nitrophenothiazine, 3-chloro-10-ethylphenothiazine, 4-amino-4 '
-Anilinodiphenyl disulphide, 2-chloro-10
-(3-Dimethylaminopropyl) phenothiazine, chlorpromazine, 10- (2-dimethylamino-1-propyl) phenothiazine hydrochloride, 10- [2- (1-pyrrolidyl) ethyl] phenothiazine hydrochloride, 10- (1
-Methyl-3-piberidylmethyl) phenothiazine, 2
-Acetyl-10- (3-dimethylaminopropyl) phenothiazine, methylene blue;

Pyridazine and related compounds such as cinnoline, 3-methylcinnoline, 4-chlorcinnoline, 3-bromocinnoline, 4-cinnolinol,
Aminocinnoline, phthalazine, 4-ethyl-2-phenylphthalazinone, phthalazinethiol, 1 (2H)-
Phthalazinone, 3-phenylpseudophthalazine, 4-
Methyl-3-phenylpseudophthalazone, 2,3-dihydro-1,4-phthalazinedione;

Pyrimidine and related compounds, such as 2
-Cinnamethylpyrimidine, 4,6-dimethyl-2-phenylpyrimidine, 2,4,6-triphenylpyrimidine, alloxanthin, 2,6-dioxy-4-phenylpyrimidine, 4,6-dioxy-2- phenylalanine pyrimidine, 5-chloro-4,6-dioxy-2-phenylpropyl pyrimidine, Surufuajiajin, Surufuisomijin, hydrochloric Torijiruamin, vitamin B _1, Chiokuromu, cocarboxylase, aroma leucine, 6- (2-furfuryl) aminopurine, Pteridine, 2,4-pterindiol, 2
-Amino-6-methyl-4-pteridinol, xantopterin, leucopterin, isoxanthopterin, quinazoline, 4-chloroquinazoline, 2,4-dichloroquinazoline, 4-quinazolinone, 2,3-diphenyl-4
-Quinazoline;

Pyrazine-related compounds, for example, 3,6-diphenylpyrazinol, quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, 2-chloroquinoxaline, 2,3-dichloroquinoxaline, 2-
(O-Aminoaniline) quinoxaline, N, N'-diphenyl-2,3-piperadion, 2-quinoxalinol, 2,3-quinoxalinediol, 2-aminoquinoxaline, 2,3-diaminoquinoxaline, methylquinoxaline-2 -Carboxylic acid esters, 2- (d-arabotetraoxybutyl) quinoxaline, flavazole, glucadidone, phenazine, phenazine-5-oxide, phenazine-5,10-dioxide, 5-methylphenazinium methylsulfate, 10 -Methyl-5,10-
Dihydro-2-phenazinecarbonitrile, 2-phenazinecarbonitrile, 1-phenazinol, 1-methoxyphenazine, 2-phenazinol, 1,6-dioxyphenazine-5,10-dioxide, 1-aminophenazine , 2-aminophenazine, 2,3-diaminophenazine, neutral red, 5,10-dihydrophenazine, 5-methyl-5,10-dihydrophenazine,
2,3,4-tetrahydrophenazine;

Tri- and tetra-hetero 6-membered cyclic compounds such as 2,4,6-triphenyl-S-triazine, 2,4-dichloro-6-o-chloroaniline-s-
Triazine, 5,6-diphenyl-as-triazine,
2,6-diphenyl-2,3,4,5-tetrahydro-
as-triazine, 5,6-diphenyl-as-triazin-3-ol, 1,2,4-benzotriazine,
1,2,4-benzotriazin-3-ol, 3-phenyl-1,2,3-benzotriazine-4- (3H)-
On, 1,2,3-benzotriazin-4-ol,
1,2,3-benzotriazine-4-thiol, 3-amino-1,2,3-benzotriazine, 2,3-diphenyloxotetrazine, 5,6-dimethyl-2,3-diphenylosotetra Gin, 5-cyan-2,3-diphenyloxotetrazine, 5,6-dibenzoyl-2,3-diphenyloxotetrazine, 2,3-dibenzoyl-5-
Methyl oxotetrazine, 2,3-dibenzoyl-5,6
-Dimethyl oxotetrazine, 2,3-dibenzoyl-
5,6-diphenyloxotetrazine, 2,3-bis (2,4-dichlorophenyl) -5,6-diphenyl-
1,2,3,4-tetrahydro-ν-tetrazine, 1,
2,3,4-tetraethoxycarbonyl-5,5-
Diphenyl-1,2,3,4,5,6-hexahydro-
v-tetrazine, 7-methyl-2- (4-methylphenyl) -1,2-dihydrobenzotetrazine, 3,6-diphenyl-1,2-dihydro-s-tetrazine, 1,3
-Diphenyl-1,4,5,6-tetrahydro-s-tetrazine, 3,3,6,6-tetraphenyl-1,2,2
3,6-tetrahydro-s-tetrazine, and the like.

Further, as the sulfur-containing heterocyclic compound, sulfur-containing ancyclic compounds such as 2-phenylthiophene, 2,4-diphenylthiophene, 2,3,3
4,5-tetraphenylthiophene, metaphenylene hydrochloride, methapyrilene hydrochloride, chlorothene citrate, thenyldiamine hydrochloride, α-kinkthienyl, α-sexityienyl;

Condensed thiophene compounds, for example, 3,
3'-diiminothioindigo, indigolone, dihydronaphtho [2,1-b] thianaphthene, 1,3-diphenylisothianaphthene, dibenzothiophene, 2-nitrodibenzothiophene, aminodibenzothiophene, 2,
8-diaminodibenzothiophene, dibenzothiothione-5-dioxide, 4-oxydibenzothiophene,
2,8-dioxydibenzothiothioene, 2-chlorodibenzothiophene, 1-bromodibenzothiophene, 2,
8-dibromodibenzothiophene, 2-iododibenzothiophene, 2-acetyldibenzothiophene, 2,8
-Diacetyldibenzothiophene, naphthothiophene,
3-oxythiophenthantrene, 2,3-thiophenthraquinone, naphtho [2,3-c] thiophene, naphtho [1,2-b] thiophene, naphtho [2,1-b] thiophene, naphtho [1,2 -C] thiophene, 1,2-naphtho [2,1-b] thiophenequinone, 1-oxy-2
-Naphtho [2,1-b] thiophenealdehyde, naphtho [1,21c] thiophene, 2H-naphtho [1,8] thiophene, benzo [b] thiophanthrene, 6,11-
Benzo [b] thiophanthraquinone, benzo [g] thiophanthrene, 4,5-benzothiophenanthrene, 8,
9-benzothiophene anthrene;

A five-membered monocyclic compound containing two heteroatoms,
For example, 5-phenyl-1,2-dithiol-3-thione, 3,4-dihydronaphth-2,1-trithione, thiaflavon, tiacmarin, thiaxanthen, thiaxanthydrol, thiaxantone, miracil D, bisthiaxane Tylene;

Six-membered cyclic compounds having two or more hetero atoms, for example, 2,5-diphenyl-1,4-dithiadiene, thiophenealdehyde, thianthrene, 2,7-
Dimethylthianthrene, 1-thianthrenyllithium,
1-chlorothiantren, phenoxathiin, 2-vinylphenoxatiin, 2-aminophenoxathiin, 2
-Nitrophenoxathiin, 3,7-dinitrophenoxathiin, 10,10-diphenylphenoxathiin,
2,5-diphenylthiophene; and the like.

Still further, as other compounds, bicyclic compounds sharing a nitrogen atom, for example, cinchonine,
-Phenylpyrocholine, 3-ethyl-2-phenylpyrocholine, 3-benzyl-2-phenylpyrocholine, 3-
Nitroso 2-phenylpyrocholine, 2: 3-benzopyrocholine, 1,5,8-trimethyl-2: 3-benzopyrocholine, 1-ethyl-5,8-dimethyl-2: 3-benzopyrocholine, 1,8- Dimethyl-2: 3-benzopyrocholine, 3-phenyl-7: 8-benzopyrocholine,
Cyclo [3.3.3] azine, cyclo [3.2.2] azine, 2-phenylcyclo [3.2.2] azine, 2,
3-diphenylcyclo [3.2.2] azine, tricyclazine, 7-methylbenzo [a] quinolidinium bromide, 7-phenylbenzo [a] quinolidinium bromide,
Benzo [b] quinolidinium salt, tetrahydro-Ψ-berberine, tetrahydroberberine, laudanosolin,
Tetrahydro-2,3,9,10-tetraoxy-7-
Methyl dibenzopyrocollinium chloride, homolaudanozolin, octadehydromatrine, canadine methiodide, tetrahydropalmatine methiodide;

Alkaloids such as nicotilin,
3 ', 2-dipyridyl, cusparin, galliporin, 1-
Methyl-2-quinolone, cashimiloin, 2-pentylquinoline, 4-oxy-2-pentylquinoline, 4-methoxy-2-pentylquinoline, 1-methyl-2-pentyl-4-quinolone, 4-methoxy-2-f Enilquinoline, 7-methoxy-1-methyl-2-phenyl-4-quinolone, cuspalein, dictamnin, skinmianine, evolitrin, macrin, coxsagine, coxsagine, macrosidine, flindersiamine, evoxoidin, evoxine, eboratin, acronicidine, medicosmin, acronidin , Γ-fagarin, cinchonine,
Quininone, quinotoxin, N-bromoquinotoxin, dihydrocinconisin, heterokinin, evoxanthin, xanthoxoline, 1,3-dimethoxy-10-methylacridone, evoxanthin, xanthovoquine,
Mericopine, melicopidine, mericopicin, acronisin, frindersin, hapaverine, papaveraldine, laudanosine, laudanin, kodamine, protopapaverine, almepavin, 4,4'-5-trimethoxy-2-
Vinylstilbene, coclaurine, d-isococlaurin, neprotin, corpaverine, ferrodendrin, magnoclaline, cochranolin, narcotin, narcotrin, aponalcein, cinchonine, synchotoxin, didehydrohydrastine, bicuculline, adormidine, corlumidine, cordramin mag Berbamine, o-methyl belbamine, and the like.

When a conjugated π-bonded compound is used in the method of the present invention, a dye and / or a pigment can be used in combination. Examples of such dyes and pigments include azo dyes and pigments such as monoazo and polyazo dyes and pigments, metal complex azo dyes and pigments, stilbene azo dyes and thiazole azo dyes; anthraquinone derivatives and anthrone derivatives Anthraquinone dyes and pigments such as;

Indigo dyes / facials such as indigo derivatives and thioindigo derivatives; phthalocyanine dyes / pigments;
Carbonyl dyes / pigments such as diphenylmethane dyes, triphenylmethane dyes / facials, xanthene dyes and macridine dyes; quinone imine dyes such as azine dyes, oxazine dyes and thiazine dyes; methine dyes such as polymethine or cyanine dyes; quinoline dyes; Dyes: Benzoquinone and naphthoquinone dyes; Naphthalimide dyes
Pigments; perinone dyes; sulfur dyes; fluorescent dyes; azoic dyes; and reactive dyes. These may be used alone or in combination of two or more.

In the present invention, among these dyes and pigments, azine dyes are particularly preferred. More specific examples of these dyes / pigments are as follows. The azo dyes and pigments include the following. Monoazo and polyazo dyes include, for example, Basic Yellow 32, 34 and 36; Basic Orange 2, 32, 33 and 34;
8, 22, 23, 24, 32, 34, 38, 39 and 40; basic violets 26 and 28; basic blue 58, 59, 64, 65, 66, 67 and 68;

Base Brown 1, 4, 11 and 1
2; base black 8; azoic diazo components 4, 21, 27 and 38; disperse yellow 3, 4, 5, 7, 8, 23, 50, 60, 64, 6
6, 71, 72, 76, 78 and 79; disperse orange 1, 3, 5, 13, 20, 21, 30, 32,
41, 43, 45, 46, 49, 50 and 51; disperse beads 1, 5, 7, 12, 13, 17, 43,
52, 54, 56, 58, 60, 72, 73, 74, 7
5, 76, 80, 82, 84, 88, 90, 97, 9
9, 101, 103, 113, 117, 122, 12
5, 126, 128 and 129;

Disbirds Violet 10, 24, 3
3, 38, 41, 43 and 96; disperse blue 85, 92, 94 and 106; disperse brown 3 and 5; disperse black 1, 2, 10, 2
6, 27, 28, 29, 30 and 31; Solvent Yellow 2, 6, 14, 15, 16, 19, 21 and 5
6; Solvent Orange 1, 2, 5, 6, 14 and 4
5; Solvent led 1, 3, 23, 24, 25, 27
And 30; Solvent Brown 3, 5 and 20;

Solvent Black 3: Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 1
3, 14, 15, 16, 17, 23, 65, 73 and 83; Pigment Orange 1, 2, 5, 13, 14, 1
5, 16, 17, 24 and 31; Pigment Reds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 1
2, 13, 14, 15, 16, 17, 18, 19, 2,
1, 22, 23, 30, 31, 32, 37, 38, 3
9, 40, 41, 48, 49, 50, 51, 52, 5
3, 54, 55, 57, 58, 60, 63, 64, 6
8, 112, 114 and 163;

Pigment Blue 25; Pigment Green 10; Pigment Brown 1 and 2; Pigment Black 1;
24, 26, 27, 28, 33, 44, 50, 58, 8
5, 86, 87, 88, 89, 98, 100 and 11
0; direct orange 1, 6, 8, 10, 26, 2
9, 39, 41, 49, 51, 57, 102 and 10
7; direct leds 1, 2, 4, 13, 17, 20,
23, 24, 28, 31, 33, 37, 39, 44, 4
6, 62, 63, 75, 79, 80, 81, 83, 8
4, 89, 95, 99, 113, 197, 201, 2,
18, 220, 224, 225, 226, 227, 22
8, 229, 230 and 231;

Direct biolets 1, 7, 9, 1
2, 22, 35, 51, 63, 90, 94 and 98;
Direct Blue 1, 2, 6, 8, 15, 22, 25,
71, 76, 77, 78, 80, 120, 123, 15
8, 160, 163, 165, 168, 192, 19
3, 194, 195, 196, 203, 207, 22
5, 236, 237, 246, 248 and 249;

Direct Green 1, 6, 8, 28, 3
0, 31, 33, 37, 59, 63, 64 and 74;
Direct Brown 1A, 2, 6, 25, 27, 44,
58, 59, 101, 106, 173, 194, 19
5, 209, 210 and 211; direct black 17, 19, 22, 32, 38, 51, 56, 71, 7
4, 75, 77, 94, 105, 106, 107, 10
8, 112, 113, 117, 118, 132, 133
And 146;

Acid Yellow 11, 17, 19, 2
3, 25, 29, 36, 38, 40, 42, 44, 4
9, 61, 70, 72, 75, 76, 78, 79, 11
0, 127, 131, 135, 141, 142, 164
And 165; Acid Orange 1, 7, 8, 10, 1
9, 20, 24, 28, 33, 41, 43, 45, 5,
1, 56, 63, 64, 65, 67 and 95;

Acid blades 1, 6, 8, 9, 13, 1
4, 18, 26, 27, 32, 35, 37, 42, 5,
7, 75, 77, 85, 88, 89, 97, 106, 1
11, 114, 115, 117, 118, 119, 12
9, 130, 131, 133, 134, 138, 14
3, 145, 154, 155, 158, 168, 24
9,252,254,257,262,265,26
6, 274, 276, 282, 283 and 303;

Acid Violet 7, 11, 97 and 106; Acid Blue 29, 60, 92, 113,
117 and 120; Acid Green 19, 20, and 48; Acid Brown 2, 4, 13, 14, 20,
53, 92, 100, 101, 236, 247, 26
6, 268, 276, 277, 282, 289, 301
And 302; Acid Black 1, 7, 24, 26,
29, 31, 44, 76, 77, 94, 109 and 1
10;

Modant Yellow 1, 3, 5, 23, 2
6, 30, 38 and 59; modant orange 1,
4, 5, 6, 8, 29 and 37; modern leds 7, 9, 17, 19, 21, 26, 30, 63 and 8
9; modant biolets 5 and 44; modant blue 7, 13, 44, 75 and 76; modant green 11, 15, 17 and 47; modant brown 1, 14, 15, 19, 21, 33, 38. , 40, 5
2 and 87; mod black 1, 3, 7, 9, 1
1, 17, 26, 32, 38, 43, 44, 51, 5,
4, 65, 75, 77, 84, 85, 86 and 87;
Food yellows 3 and 4; food leds 7 and 9;

As the metal complex salt azo dyes, for example, Solvent Yellow 61 and 80; Solvent Orange 3
7, 40 and 44; Solvent Red 8, 21, 8
3, 84, 100, 109 and 121; Solvent Brown 37; Solvent Black 23; Acid Black 51, 52, 58, 60, 62, 63, 64, 67,
72, 107, 108, 112, 115, 118, 11
9, 121, 122, 123, 131, 132, 13
9, 140, 155, 156, 157, 158, 159
And 191;

Acid Yellow 59, 98, 99, 11
1, 112, 114, 116, 118, 119, 12
8, 161, 162 and 163; Acid Orange 7
4, 80, 82, 85, 86, 87, 88, 122, 1
23 and 124; acid blades 180, 183, 1
84, 186, 194, 198, 199, 209, 21
1, 215, 216, 217, 219, 256, 31
7, 318, 320, 321 and 322;

Acid Violet 75 and 78; Acid Bull 151, 154, 158, 161, 16
6, 167, 168, 170, 171, 175, 18
4, 187, 192, 199, 229, 234 and 2
36; Acid Green 7, 12, 35, 43, 56,
57, 60, 61, 65, 73, 75, 76, 78 and 79; Acid Brown 19, 28, 30, 31, 3
9, 44, 45, 46, 48, 224, 225, 22
6, 231, 256, 257, 294, 295, 29
6, 297, 299 and 300;

Direct Yellow 39; Direct Biolets 47 and 48; Direct Blue 90, 9
8, 200, 201, 202 and 226; direct brown 95, 100, 112 and 170; as stilbene azo dyes, for example, direct black 62;
Examples of the thiazole azo dye include Direct Reds 9 and 11.

The following are examples of the anthraquinone dye / pigment. As anthraquinone derivatives, for example, basic violet 25; basic blue 2
1, 22, 44, 45, 47, 54 and 60; Azoic diazo component 36; Bat yellow 2,
3, 10, 20, 22 and 23; Butt orange 13
And 15; butts 10, 13, 16, 31, 3
Butt Biolets 13 and 21; Butt Blue 4, 6, 8, 12, 14, 64, 66, 67
And 72; Butt greens 8, 13, 43, 44 and 45; Butt browns 1, 3, 22, 25, 39, 4
1, 44, 46, 57, 68, 72 and 73; butt blacks 8, 14, 20, 25, 27, 36, 56, 5
9 and 60;

Disperse orange 11; disperse red 4, 9, 11, 15, 53, 55, 65, 91,
92, 100, 104, 116 and 127; Disperse Violets 1, 4, 8, 23, 26, 28, 30
And 37; Disperse Blue 1, 3, 5, 6, 7,
20, 26, 27, 54, 55, 56, 60, 61, 6
2, 64, 72, 73, 75, 79, 81, 87, 9
0, 91, 97, 98, 99, 103, 104 and 1
05; Day Spurs Yellow 51;

Solvent Violets 13 and 14;
Solvent Blue 11, 12, 35 and 36; Solvent Green 3; Pigment Reds 83 and 89; Pigment Blue 22; Acid Violet 31, 3
4, 35, 41, 43, 47, 48, 51, 54, 66
And 68; Acid Blue 23, 25, 27, 40,
41, 43, 45, 54, 62, 72, 78, 80, 8
2, 112, 126, 127, 129, 130, 13
1, 138, 140, 142, 143, 182, 18
3, 203, 204 and 205; Acid Green 2
5, 27, 28, 36, 40, 41 and 44; Acid Brown 27; Acid Black 48 and 50; Modern Dreads 3 and 11, Modern Blue 8 and 48; Modern Black 13, Pigment Violet 5;

As anthrone derivatives, for example, Bat Yellows 1 and 4; Bat Oranges 1, 2, 3, 4 and 9; Bat Violets 1, 9 and 10; Bat Blues 18, 19 and 20;
3 and 9; Butt blacks 9, 13, 29 and 5
7; butled 13; acid reds 80, 82 and 83;

The following are examples of the indigoid dye / pigment. As indigo derivatives, for example, Bat Blue 1, 3, 5, 35 and 41; Reduced Bat Blue 1; Pigment Biolets 19 and 12
2; Acid Blue 74 and 102; Solution-Built Blue 5 and 41;
Butt Black 1; Food Blue 1;

The thioindigo derivatives include, for example, Vat Orange 5; Pattlets 1, 2 and 61; Vat Violet 2 and 3; Pigment Red 87 and 88; Examples of phthalocyanine dyes / pigments include Solvent Blue 55; Pigment Blues 15, 16, and 17; Pigment Greens 36, 37, and 38; Direct Blues 86 and 199;

The following can be mentioned as the carbonium dyes / pigments. As diphenylmethane dyes, for example, base yellow 2, as triphenylmethane dyes, for example, base 9, bases 1, 3, and 14; bases 1, 3, and 14;
7, 19, 26, 28, 29, 40 and 41; Basic Greens 1 and 4; Solvent Violet 8;
Solvent Blue 2 and 73; Pigment Violet 3; Pigment Blue 1, 2 and 3; Pigment Green 1, 2 and 7; Direct Blue 41; Acid Violet 15 and 49;
7, 9, 15, 22, 83, 90, 93, 100, 10
3 and 104; Acid Green 3, 9 and 16;
Modant Biolett 1; Modulable Bull-1, 29
And 47; food biolett 2; food blue 2;
Food green 2;

Examples of the xanthene dyes include, for example, Base 1; Solvent Red 49; Pigment Reds 81 and 90; Pigment Violet 1, 2, and 23;
4; modern leds 15 and 27; food led 1
4; Examples of acridine dyes include Basic Oranges 14 and 15. The quinone imine dyes include the following. As azine dyes, for example, Basic Red 2; Basic Black 2; Solvent Blacks 5 and 7; Acid Blue 59; Acid Black 2;

The oxazine dyes include, for example, Basic Blue 3; Direct Blue 106 and 108; the thiazine dyes include, for example, Basic Yellow 1; Basic Blue 9, 24, and 25. The following are mentioned as a methine dye. Examples of polymethine (or cyanine) dyes include, for example, Basic Yellow 11, 13, 14, 19, 21, 25, 28, 3
3 and 35; base oranges 21 and 22; bases 12, 13, 14, 15, 27, 29,
35, 36 and 37; basic violets 7, 1
5, 21 and 27.

Examples of the quinoline dye include Base Green 6; Disperse Yellow 54 and 56;
Solvent Yellow 33; Acid Yellow 3; Nitro dyes include, for example, Disperse Yellow 1, 33, 39, 42, 49 and 54; Acid Yellow 1. Benzoquinone and naphthoquinone dyes include, for example, Disperse Blue 58 and 108; Acid Brown 103, 104, 10
6, 160, 161, 165, and 188. Naphthalimide dyes and pigments include, for example, Pigment Red 123; Butt Violet 23 and 2
9; Acid Yellow 7; Verinone dyes include, for example, Bat Orange 7 and 15.

Examples of the sulfur dyeing family include Sulfurized Sulfur Yellow 2, Sulfur Yellow 4, Sulfur Orange 3, Sulfur Reds 2, 3,
5 and 5; Solitized Sulfur Blue 1
5; Sulfur Blue 2, 3, 4, 6, 7, 9 and 1
3; Sulfur Green 2, 3, 6, 14, and 27;
Solution-billed Sulfur Brown 1 and 5
1; Sulfur Brown 7, 12, 15, and 31; Sulfur Black 1, 2, 5, 6, 10, 11, and 1
5; Butt Yellow 35, 42 and 43;

As the fluorescent paint, for example, Fluorescent Brightening Agents 14, 22, 24,
30, 32, 37, 45, 52, 54, 55, 56, 8
4, 85, 86, 87, 90, 91, 104, 112,
121, 134, 135, 153, 162, 163, 1
64, 166, 167, 168, 169, 170, 17
1, 172, 173, 174, 175, 176 and 1
77.

Examples of the azoic dye include, for example, azoic diazo components 17, 20, 22, 24, 2
6, 31, 35, 41, 47, 48, 109 and 12
1: Azoic coupling components 2, 3,
4, 5, 7, 8, 10, 11, 12, 14, 15, 1
6, 17, 18, 19, 20, 23, 26, 28, 2
9, 35, 36, 37, 41 and 108; Azoic Brown 2, 7, 11 and 15; Azoic Blacks 1 and 5; Azoic Yellows 1 and 2; Azoic Oranges 2, 3 and 7; ,
6, 9, 16 and 24; Azoic violet 1,
2, 6, 7, 9 and 10;

The reactive dyes include, for example, reactive yellow 1, 2, 3, 4, 6, 7, 11, 12, 13,
14, 15, 16, 17, 18, 22, 23, 24, 2
5, 26, 27, 37 and 42; Reactive Orange 1, 2, 4, 5, 7, 13, 14, 15, 16, 1
8, 20, 23 and 24; react bread 1,
2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 1
5, 16, 17, 19, 20, 21, 22, 23, 2,
4, 28, 29, 31, 32, 33, 34, 35, 3
6, 37, 38, 39, 40, 41, 42, 43, 4
5, 46, 49, 50, 58, 59, 63 and 64;

Reactive violet 1, 2, 4,
5, 8, 9 and 10; reactive blue 1, 2,
3, 4, 5, 7, 8, 9, 13, 14, 15, 17, 1
8, 19, 20, 21, 25, 26, 27, 28, 2
9, 31, 32, 33, 34, 37, 38, 39, 4
0, 41, 43, 44 and 46; Reactive Greens 5, 6, 7 and 8; Reactive Brown 1, 2,
5, 7, 8, 9, 10, 11, 14 and 16; reactive blacks 1, 3, 4, 5, 6, 8, 9, 10, 1
2, 13, 14 and 18.

In the present invention, when the conjugated π-bonded compound is used together with the above-mentioned dye / pigment in some cases, the solution may be prepared as it is or dissolved or dispersed in an appropriate solvent. The concentration of the processing solution is usually 0.1.
It is preferably at least 01% by weight. As a solvent for preparing the treatment liquid, water, various organic solvents, for example,
Gasoline, petroleum, benzine, mineral spirits, petroleum naphtha, M. & P. Aliphatic hydrocarbons such as naphtha, decalin, tetralin, and p-cymene; aromatic hydrocarbons such as benzene, toluene and xylene;

Halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chloroform, carbon tetrachloride, ethylene trichloride, benzene monobromide, benzene monochloride and benzene dichloride; amyl alcohol, ethyl alcohol, isopropyl Alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, methyl amyl alcohol,
Alcohols such as benzyl alcohol and butyl alcohol;

Acetone, acetonylacetone, diisobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone, methyl cyclohexanone, methyl dipropyl ketone, methyl ethyl ketone, methyl orthohexyl ketone, methyl isobutyl ketone, methyl propyl ketone, Ketones such as medisyl oxide;

Esters such as acetates, butyrates, propionates and formates;
Alcohol esters such as butyl lactate, isopropyl lactate, ethyl lactate, ethyl oxypropionate and diethyl maleate; ketone esters such as ethyl acetoacetate and ethyl pyruvate; isopropyl ether, ethyl ether, diethyl carbitol, diethyl cellosolve, butyl ether Ethers such as acetonitrile, ketone alcohols such as diacetone alcohol, dihydroxyacetone, and pyruvyl alcohol;

Isopropyl cellosolve, carbitol,
Ether alcohols such as glycidol, cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butyl cellosolve, methyl daritol, methyl cellosolve, triethylene glycol monoethyl ether; acetal ethyl ether, acetonylmethanol ethyl ether, methyl ethoxyethyl Ketone ethers such as ethers; ester ethers such as butyl carbitol acetate, butyl cellosolve acetate, carbitol acetate, cellosolve acetate, 3-methoxybutyl acetate, methyl carbitol acetate, methyl cellosolve acetate;
Etc. can be used.

Examples of the organic solvent include methyl alcohol, ethyl alcohol, allyl alcohol, and n which are highly compatible with water.
Alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone, acetonylacetone and diacetone alcohol; esters such as ethylene glycol monomethyl ether acetate, diethylene glycol methyl ether acetate and monoethyl ether acetate; dioxane and ethylene glycol monomethyl Ethers such as ether and ethylene glycol monoethyl ether; furans such as tetrahydrofuran and furfuryl alcohol; aprotic solvents such as acetonitrile, N, N-dimethylformamide and N, N-dimethylacetamide; Water can be added to the solution within a range that does not impair the solubility and dispersibility of the conjugated π-bonded compound, thereby improving the economy of the solution and the safety during transportation and storage.

It is also useful to use a phosphorus compound such as hypophosphorous acid, pyrophosphoric acid or polyphosphoric acid in combination. Specifically, after the treatment with the phosphorus compound-containing solution, treatment with a highly conjugated unsaturated compound may be performed, or treatment may be performed in the reverse order. Further, the treatment may be performed simultaneously using a phosphorus compound and a highly conjugated unsaturated compound.

The amount of highly conjugated unsaturated compound used is
The amount is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the hydrogen storage alloy. When the amount is less than 0.05 part by weight, the effect of the treatment cannot be obtained, and when the amount is more than 10 parts by weight, the capacity is reduced. The treatment may be performed at room temperature to 100 ° C., and it is not economical to perform the treatment by cooling at 100 ° C. or more, or cooling, because equipment costs for industrial production are too high.
The effect of the processing cannot be obtained. The processing time may be 10 minutes or more, preferably 30 minutes to 10 hours.
If the time is less than 10 minutes, the effect of the treatment cannot be obtained.

The treatment method in the present invention is not particularly limited, and may be carried out by using a known method such as a method of immersing the hydrogen storage alloy in the above-mentioned solution. It is preferable to immerse the powdered hydrogen storage alloy in the treatment solution. Particularly, when the powder is stirred, the initial activity of the electrode using the obtained powder can be further improved.

When the hydrogen storage alloy powder of the present invention is used for a negative electrode of a nickel-metal hydride secondary battery, the initial activity of the battery is clearly improved. This is presumed to be due to the fact that a high degree of conjugated unsaturated compound is adsorbed on the activated surface where the rare earth oxide on the surface of the hydrogen storage alloy has been removed by the alkali treatment, thereby improving the resistance to oxidation.

[0118]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, for example, a mixture of metal elements having the above-described composition is melted using a known high-frequency induction furnace or the like to obtain a hydrogen storage alloy, which is pulverized to obtain a powder. Then, the resultant is subjected to an alkali treatment, and then immersed in a solution containing a highly conjugated unsaturated compound, stirred, and dried to obtain the hydrogen storage alloy powder of the present invention.

[0119]

According to the present invention, it is possible to obtain a hydrogen storage alloy powder which is excellent in storability and handleability in spite of high activity. Further, by using the hydrogen storage alloy powder, a nickel hydrogen storage alloy secondary battery having excellent initial activity can be obtained. Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[0120]

【Example】

Examples and Comparative Examples As a misch metal, Mm of La 61% by weight, Ce 7% by weight, Pr 23% by weight, and Nd 9% by weight was used.
The respective elements were weighed so that the atomic ratio of Al, Co, Mn, and Ni was 0.3, 0.75, 0.2, and 3.75, respectively, with respect to 1.00. Melting was performed in a melting furnace to obtain a hydrogen storage alloy. The obtained hydrogen storage alloy was heat-treated at 1020 ° C. and then pulverized to obtain a hydrogen storage alloy powder having an average particle size of 32 μm. The obtained powder was immersed in an alkaline solution of 6.8N-KOH and 0.8N-LiOH and stirred. Then, after washing with water, it was immersed in a solution containing a highly conjugated unsaturated compound and stirred and mixed. After filtering, the powder obtained by drying with hot air at 80 ° C.
The evaluation was performed by evaluating the characteristics of the battery used for the electrode.

2 g of the prepared powder was collected, and 0.5 g of a 3% by weight aqueous solution of polyvinyl alcohol (degree of polymerization 2000) was added and mixed to obtain a paste. The obtained paste is mixed with fibrous Ni.
After coating on the support and drying, it was molded under pressure to obtain a negative electrode having a thickness of 0.5 mm. Then, as a nickel oxide positive electrode, a sintered nickel positive electrode manufactured by a known method is used, a polypropylene nonwoven fabric is used as a separator, a 6N aqueous potassium hydroxide solution is used as an electrolyte, and the negative electrode is opened in combination with the negative electrode. A nickel-hydrogen secondary battery was manufactured, and the initial activity and the initial capacity were measured as described below.

Evaluation of Initial Activity and Initial Capacity These batteries were charged at 180 mA for 5 hours at a constant temperature of 20 ° C., and the battery was charged for 1 hour until the battery voltage reached 1.0 V.
The cycle of discharging with a current of 20 mA was repeated, the capacity of the first cycle was measured to evaluate the initial activity, and the results of the evaluation of the capacity at the tenth cycle as the initial capacity are shown in Tables 1 and 2 together with the conditions of each treatment. Show. In addition, Tables 3 and 4 show the results of completely the same evaluation using the hydrogen storage alloy powder stored for two months after the treatment. In addition, the experimental NO. Is a comparative example.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

Experiment NO. 0, 1, 3, 13, 16, 2
From the results of Nos. 3, 28 and 33, it can be seen that the treatment according to the present invention improves the initial activity and the initial capacity. In addition, according to the results of the examples, when the treatment is performed with an alkali of 1 to 10 N, and then the solution is treated with a solution containing a highly conjugated unsaturated compound containing 5 or more conjugated π electrons in one molecule and having a molecular weight of 100 or more. Shows that the expected effect can be sufficiently obtained.

That is, the concentration of the alkali used is 1 to 10
N is effective (Experiment Nos. 10 to 15), and the discharge capacity is reduced when the alkali treatment temperature is higher than 150 ° C. (Experiment Nos. 2 to 6). Further, potassium hydroxide, sodium hydroxide and lithium hydroxide can be used as the alkali.
NO. 16-19).

The amount of the highly conjugated unsaturated compound used is effective in the range of 0.01 to 10% by weight, and is most effective in the range of 0.1 to 1% by weight (Experiment No. 2).
6-30). Further, the treatment temperature is ineffective when the processing temperature is higher than 130 ° C. (Experiment Nos. 4, 7 to 9), which is presumed to be due to the decomposition of the highly conjugated unsaturated compound at a high temperature.

Further, regarding the storage characteristics, from the results of Tables 3 and 4, it can be seen that both the initial activity and the initial capacity are lower in the case where the treatment of the present invention is performed than in the case of the comparative example. It can be seen that good characteristics are maintained.
As described above, the hydrogen storage alloy powder is treated with an alkali,
Then, with a solution containing a highly conjugated unsaturated compound,
When the treatment is performed at a treatment temperature of 30 ° C. at a concentration of 0.01 to 10% by weight, a hydrogen storage alloy powder having particularly high initial activity and excellent storage characteristics can be obtained.

Continued on the front page (72) Inventor Masanobu Uchida 2-5-1-5 Kitafu, Takefu-shi, Fukui Shin-Etsu Chemical Co., Ltd. Magnetic Materials Research Laboratories Shin-Etsu Chemical Co., Ltd. PVC Research Laboratory (56) References JP-A-3-233868 (JP, A) JP-A-61-287553 (JP, A) JP-A-61-208754 (JP, A) JP JP-A-5-13096 (JP, A) JP-A-61-16470 (JP, A) JP-A-5-3031 (JP, A) JP-A-59-110783 (JP, A) (58) Fields studied (Int .Cl. ⁷ , DB name) H01M 4/24-4/26 H01M 4/38 B22F 1/00-1/02

Claims (8)

(57) [Claims] (1) a step of treating a pulverized hydrogen storage alloy with an alkali, followed by a treatment with a solution containing a conjugated unsaturated compound having at least 5 conjugated π bonds in one molecule and having a molecular weight of 100 or more. A method for producing a hydrogen storage alloy powder, which is characterized by the following. 2. The method according to claim 1, wherein the hydrogen storage alloy is (La) _X R _1-X (Ni
M) The method for producing a hydrogen storage alloy powder according to claim 1, represented by _Y. However, in the formula, R is Ce, Pr, Nd
At least one selected from the group consisting of Mn, Al, Co,
At least one selected from Ti, Fe, and Zr;
x is 0.2-1 and Y is 4.0-6.0. 3. The method for producing a hydrogen-absorbing alloy powder according to claim 1 or 2 molecular weight of 200 or more compounds of the conjugated unsaturated compound having a conjugated π bond 5 or more in one molecule. Is wherein the alkali, lithium hydroxide, sodium hydroxide, is at least one selected from potassium hydroxide, a method of manufacturing a hydrogen-absorbing alloy powder described in any one of claims 1 to 3 . Wherein the concentration of the alkali, process for the preparation of hydrogen-absorbing alloy powder according to any one of claims 1-4 is 1.0 to 10.0 provisions. 6. Treatment with a solution containing a conjugated unsaturated compound
Kino temperature, any claim 1-5 is a normal temperature to 130 DEG ° C.
Process for the preparation of hydrogen-absorbing alloy powder according to any. The amount of 7. conjugated unsaturated compounds having a conjugated π bond 5 or more in one molecule, from 0.01 to 10 parts by weight per 100 parts by weight of the hydrogen storage alloy of claim 1-6 of
A method for producing a hydrogen storage alloy powder according to any of the above. 8. The manufacturing method according to claim 1,
An electrode using the hydrogen storage alloy powder obtained by the method.