JPH10140193A - Bleaching activating catalyst and bleaching agent composition containing the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching activating catalyst which can improve the bleaching ability of a peroxy compound at low temperature by combining a transition metal with a ligand of a specified structure having at least three coordinative nitrogen atoms in the molecule. SOLUTION: This catalyst is made from a ligand having at least three coordinative nitrogen atoms and represented by formula I [wherein X is N, P, or C(R0 ); R0 , R1 and R2 area each H, an alkyl, a cycloalkyl or an aryl; (n) and (m) are each 0 to 2; and A and B are each, e.g. a group of formula II (wherein R3 , R4 , R6 , R7 and R8 are each H, OH, an alkyl, a cycloalkyl or an aryl; R5 is H, an alkyl, an alkoxy, a halogeno, cyano, pyridyl, sulfo, carboxyl, OH, etc.; R9 , R10 and R11 are each H, OH, an alkyl, etc.; (p) is 0 to 4; and (q) is 2 to 7)] and a transition metal. The ligand used preferably comprises a ligand of which at least three nitrogen atoms can facially coordinate to a transition metal. The transition metal used preferably comprises Mn, Fe or Cu from the viewpoint of environmental safety. The ligand and transition metal used may be a mixture of different compounds or a complex made by combining them, and it is desirable to use them at a molar ratio of (1:1) to (50:1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the cleaning of clothes, tableware, pottery, glass, plastic, dentures and other hard surfaces such as dentures, fungicides, pulp bleaching, dyeing wastewater treatment, washing Prevention of dye transfer in clothing, clothing,
The present invention relates to a bleach-activating catalyst for peroxy compounds, which is widely used for sterilizing hard surfaces and the like, and to a bleaching composition containing the bleach-activating catalyst.

BACKGROUND OF THE INVENTION Hydrogen peroxide, an inorganic persalt which liberates hydrogen peroxide in aqueous solution or has a peracid bond itself,
Organic peracids (hereinafter, these compounds are abbreviated as peroxy compounds), and organic peracid precursors that generate organic peracid by reacting with hydrogen peroxide in a bleaching bath, have been widely used as an active ingredient of bleaching agents. Have been. However, inorganic peroxides which release hydrogen peroxide in an aqueous solution or have a peracid bond by themselves have a relatively low bleaching effect at low temperatures, and are therefore required to obtain a sufficient bleaching effect at low temperatures. Various proposals for activating these compounds have been made. The method for improving the bleaching power with an organic peracid precursor requires an equimolar amount of hydrogen peroxide and an organic peracid precursor, and is an economically and environmentally effective agent for improving the bleaching performance with a very small amount. Was desired.

As such compounds, combinations of various ligands and transition metals have been proposed. For example, U.S. Pat. No. 3,156,654, U.S. Pat. No. 3,532,634 and U.K. Pat.
Combinations with transition metals such as o and Cu are disclosed and catalyze the decomposition of peroxy compounds, but do not significantly contribute to substantial bleach activation. 6-33431
Japanese Patent Publication No. 6-70240 discloses a manganese complex having a hydroxycarboxylic acid as a ligand, and Japanese Patent Publication No. 6-99719 discloses a manganese complex having a polyhydroxy compound as a ligand. JP-A-52-155279, JP-A-1-97267, JP-A-2-61547, JP-A-8-503247 and JP-A-8-503248 disclose porphyrin or phthalocyanine as a ligand. Iron or manganese complex
No. 7-12437, No. 7-65074, No. 7-68543, No. 7-12076, Japanese Patent Laid-Open No. 5-263098 and No. 6-
No. 121933 discloses a manganese complex having a cyclic polyamine as a ligand, and JP-A-8-67687 discloses a manganese complex having a Schiff base synthesized from salicylaldehyde and a polyamine as a ligand. Patent No. 5,021,187 discloses a copper complex having a substituted diamine as a ligand, but none of these copper complexes satisfy the improvement of bleaching performance, stability of the complex, and ease of production. Absent.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a bleaching-activating catalyst which can improve the bleaching performance of a peroxy compound at a low temperature. The present invention
Another object of the present invention is to provide a bleaching composition which exhibits excellent bleaching performance even at low temperatures.

According to the present invention, the above object can be efficiently achieved when a ligand having a specific structure having three or more coordinating nitrogen atoms in a molecule is combined with a transition metal. It was based on knowledge. That is, the present invention provides a bleach-activating catalyst comprising a ligand represented by the general formula (I) having three or more coordinating nitrogen atoms and a transition metal.

[0004]

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(Where X is a nitrogen atom, a phosphorus atom or C
The group represented by (R ₀ ), R ₀ , R ₁ and R ₂ may be the same or different and each is hydrogen, an optionally substituted alkyl group, cycloalkyl group or aryl group, n Is 0 to 2, m is 0 to 2, A and B may be the same or different, and

[0006]

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Wherein R ₃ , R ₄ , R ₆ , R ₇ and R ₈
May be the same or different, each hydrogen, a hydroxyl group, an optionally substituted alkyl group,
A cycloalkyl group or an aryl group, R ₅ is hydrogen, an optionally substituted alkyl or alkoxy group, halogen, cyano, NR ₉ R ₁₀ , N ＝ R ₉ , N ⁺ R
₉ R ₁₀ R ₁₁ , a pyridyl group, a pyridinium group, a sulfonic acid group, a thienyl group, a carboxylic acid group, or a hydroxyl group;
R ₉ , R ₁₀ and R ₁₁ may be the same or different and are each hydrogen, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group, and p is 0 to 4, q Is 2-7. )). The present invention
The present invention also provides a bleaching composition comprising the above bleaching activation catalyst and a peroxy compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (I), an alkyl group,
As alkoxy, cycloalkyl and aryl groups
Has 1 to 20, 1 to 20, 3 to 8 and 6 carbon atoms, respectively.
~ 24 are preferred. Also, as these substituents
Represents a halogen atom, a hydroxyl group, an alkoxy group,
Ano group, amino group, quaternary ammonium group, sulfonic acid
Group, thienyl group, carboxylic acid group and the like. General
In the formula (I), X represents a nitrogen atom or C (R₀)
Groups are preferred and R ₀Is a hydrogen atom or an atom having 1 to 4 carbon atoms.
Alkyl group is preferred, and R₁And R_TwoIs a hydrogen atom
Is preferred. n is preferably from 0 to 2 and m is preferably from 0 to 1. molecule
Two A's may be the same or different, but are the same
Is preferred. For A and B, A and B
Is a group represented by the formula (III),
And when B is a group represented by the formula (II) or
When A is a group represented by the formula (III) represented by the formula (V)
Is preferred. In particular, A and B are both of the formula (II) or (III)
Particularly preferred is a group represented by the formula
The case represented by the formula (III) is preferred. R_ThreeAnd R
_FourAs a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
And aryl groups are preferred._FiveIs a hydrogen atom or
An alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a sulfonic acid group,
Rubonic acid groups are preferred, and hydrogen atoms and methyl
Group, ethyl group, isopropyl group, sec-butyl group, water
It is an acid group. R₆, R₇And R₈As a hydrogen atom or
Is preferably an alkyl group having 1 to 4 carbon atoms, more preferably
Is a hydrogen atom or a methyl group, most preferably a hydrogen atom
I am a child. p is preferably 0 or 1. The general formula (I)
Of the ligands represented by
Coordinating Nitrogen Facial to Transition Metal
Those that can coordinate (all nitrogen atoms are cis
Is preferred). The arrangement represented by the general formula (I)
As the ligand, the following general formula (Ia) or (Ib)
Those represented are preferred.

[0009]

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In the formula, R ₀ is a hydrogen atom or a group having 1 to 4 carbon atoms.
R ₁ and R ₂ are hydrogen atoms, n is 0 to 2,
m is 0 to 2 (preferably 0 to 1); A and B may be the same or different;

[0011]

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(Wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an aryl group, a hydroxyl group, a sulfonic acid group, a carboxylic acid And the group p is 0 or 1.) In the above general formula (Ia) or (Ib), when A and B are both groups represented by the formula (III), both A and B are represented by the formula (II) And the case where B is a group represented by the formula (II) or the formula (V) and A is a group represented by the formula (III). Above all, both A and B have the formula (II) or (III)
Particularly preferred is a group represented by Specific examples of the ligand represented by the general formula (I) of the present invention include the following compounds.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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Although most of these compounds are known,
New ones are also included. These compounds can be easily synthesized, for example, by the following method. For example, ligand (1) is prepared by reacting dipyridylamine with 2-bromopyridine [William R. McWhinnie, J. Chem. Soc. (A), 19
66 , 1199], and the ligand (7) reacts with 2-aminomethylpyridine and 2-chloromethylpyridine hydrochloride [Zoltan Tyeklar et.al., J. Am. Chem. Soc. , 1993, 11].
5,2677], and the ligand (13) reacts with 2-vinylpyridine with ammonium acetate [Chi-Ming Che et.al., J. Am.C.
Chem. Soc., 1990 , 112, 2284], ligand (15) reacts with 2-bromopyridine after reducing bis (2-pyridyl) ketone to bis (2-pyridyl) methane [Allan J. Canty e
t al., Aust. J. Chem., 1986 , 39, 1063 or F. Richard K.
eene et al., Inorg. Chem. 1988 , 27, 2040], and ligand (19) is 2- (hydroxymethyl) -2-methyl-
After bromination of 1,3-propanediol with phosphorus tribromide, Ga
It can be synthesized by briel synthesis [Kitajiri et al., Japan Chemical Journal , 91, 240 (1970)], and other ligands can be synthesized according to these synthesis methods.

In the present invention, the ligand represented by the general formula (I) can be used as one kind or as a mixture of two or more kinds. The transition metals used in combination with the ligand represented by the general formula (I) in the present invention include Mn, Fe, C
u, Ni, Co, Cr, V, Ru, Rh, Pd, Re,
W, Mo, etc., but considering environmental safety, M
n, Fe and Cu are preferred. These metals can be used as one kind or as a mixture of two or more kinds.
In the present invention, the ligand represented by the general formula (I) and the transition metal may be formed as separate compounds, and a mixture of both may be used. Alternatively, the ligand and the transition metal ion may be used as a complex. Is also good. Further, the amount of the transition metal or the amount of the ligand may be adjusted by adding a ligand or a transition metal ion to the complex.

When the ligand and the transition metal are used as separate compounds, the transition metal is preferably a compound that releases a transition metal ion when placed in an aqueous solution, and a water-soluble metal salt is preferred. For example, in the case of manganese, manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, manganese acetylacetonate, etc., in the case of iron, iron nitrate, iron sulfate, iron chloride, iron perchlorate, When iron acetylacetonate, iron citrate, iron ammonium citrate, iron ammonium oxalate, ammonium iron sulfate, etc. are copper, copper nitrate, copper sulfate, copper chloride, copper acetate, copper citrate, copper cyanide, and copper Copper oxide, copper ammonium chloride, copper tartrate, copper perchlorate and the like are preferred. On the other hand, examples of the ligand include those having various counter ions. Preferred counter ions include Cl ⁻ ,
_{^{Br -, I -, NO 3}} -, ClO 4 -, NCS -, PF
_{^{6 -, OAc -, BPh 4}} -, CF 3 SO 3 -, RSO
₃ ^- or RSO ₄ ^-, and the like. Here, R is an alkyl group having 1 to 3 carbon atoms.

When the complex is used as a complex of a ligand and a transition metal ion, it is preferable to use the above-mentioned water-soluble salt as a transition metal source. However, an appropriate transition metal source such as an organic solvent-soluble salt or potassium permanganate may be used. May be used. As the complex in which the ligand and the transition metal ion are used in the present invention, the number of ligands per transition metal may be one or more, and the transition metal constituting the complex may be one or more. It may be individual. Thus, the complex may be mononuclear, dinuclear, or cluster. The transition metals constituting the polynuclear complex may be the same or different. In addition to the ligand represented by the general formula (I), water, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxylic acid group, a thiol group, a halogen, and the like may be coordinated with the transition metal. Examples of the crosslinking species of the polynuclear complex include oxygen, sulfur, and halogen atoms.

The complex when synthesized in advance may be known or may be new. The complex can be synthesized, for example, by the following method. 1) A transition metal salt and a ligand are mixed in water or an organic solvent and concentrated by an evaporator to obtain a complex [WO 9
525159 and JP-A-8-67687] 2) A transition metal perchlorate and a ligand are mixed in water, hydrogen peroxide is added thereto, and the obtained precipitate is recrystallized [Ma
satatsu Suzuki et.al., Chem. Lett., 1988 , 477] 3) Reaction of a transition metal salt with a ligand, oxidation with an oxidizing agent, alkalinization, and oxygen oxidation [JP-A-7-8801] 4) The ligand and potassium permanganate are mixed in an organic solvent, and the obtained precipitate is separated by filtration [Asada et al., The 70th Chemical Society of Japan]
Proceedings of the Spring Meeting, p511 (1996)]

In the present invention, the ratio of the ligand represented by the general formula (I) and the transition metal is preferably 1: 4 to 200: 1, more preferably 1: 1 to 50: 1 in molar ratio. When a complex is formed in the bleaching solution, it is preferable to add an excess molar amount to the transition metal, but adding a larger amount than necessary is not economical. When the complex is synthesized in advance, the complex may be used in a proportion corresponding to the complex structure, or either of them may be used in an excessive amount, and after the complex is synthesized, the excess may be removed. When the ligand is used in excess, it is not always necessary to remove the ligand, and the ligand may be used as it is. The bleaching activation catalyst of the present invention is characterized by comprising the ligand represented by the general formula (I) and a transition metal. The bleach-activating catalyst has a transition metal content of 0.001 to
It is preferably added so as to be 1000 ppm, more preferably 0.005 to 200 ppm, and most preferably 0.01 to 100 ppm. The addition amount of the transition metal is preferably 0.00001% by weight (hereinafter abbreviated as%) to 10%, more preferably 0.0001% to 1%, based on the peroxy compound.

The bleach composition of the present invention is characterized by containing the bleach activating catalyst and a peroxy compound. As the peroxy compound, (a) hydrogen peroxide,
(B) an inorganic persalt which releases hydrogen peroxide in an aqueous solution or has a peracid bond itself, and (c) an organic peracid. As the inorganic persalt of (b), for example,
Examples include alkali metal percarbonates, perborates, perphosphates, persilicates, and persulfates. Of these, hydrogen peroxide, sodium percarbonate, sodium perborate, and potassium persulfate are particularly preferred. Examples of the organic peracid (c) include peroxybenzoic acid and ring-substituted peroxybenzoic acid (peroxy-α-naphthol acid), aliphatic, substituted aliphatic and arylalkyl monoperoxy acids (peroxylauric acid, peroxystearic acid, N Monoperoxy acids such as N, N-phthaloylaminoperoxycaproic acid); alkyl diperoxy acids and aryl diperoxy acids (1,12-diperoxidedecandionic acid, 1,9)
-Diperoxyazelaic acid, diperoxybrasilic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, 4,
Diperoxy acids such as 4-sulfonylbisperoxybenzoic acid).

Examples of the organic peracid precursor which is used together with hydrogen peroxide or an inorganic peracid which releases hydrogen peroxide in an aqueous solution and which generates an organic peracid in a bleaching bath include acylphenol. Esters such as sulfonates, acylalkylphenolsulfonates, acylphenolcarboxylates, acylated citrates, acylalkylphenolcarboxylates, esters of aromatic dihydric carboxylic acids with alcohols having quaternized amines, specifically sodium 4-benzoyloxybenzenesulfonate, sodium-1-methyl-2-benzoyloxybenzene-4-sulfonate, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxy Benzenesulfonate, sodium dodecanoyl oxybenzene sulfonate, sodium
-3,5,5, -trimethylhexanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenecarboxylate, sodium decanoyloxybenzenecarboxylate, sodium dodecanoyloxybenzenecarboxylate, sodium-3, 5,5, -trimethylhexanoyloxybenzenecarboxylate, acetyltriethylcitrate, 2- (4-methoxycarbonylbenzoyloxy) -N, N, N-trimethylethanaminium methosulfate; acylamides, specifically, N, N, N ', N'
-Tetraacetylethylenediamine; quaternary ammonium-substituted peroxyacid precursors, specifically N, N, N-trimethylammonium toluyloxybenzenesulfonate, 2- (N, N, N-trimethylammonium) ethyl-4-sulfo Phenyl carbonate.

A transition metal, a ligand, or a complex thereof may be incorporated together into a bleaching composition containing a peroxy compound, or may be separately added to the bleaching bath to obtain the concentration. You may. In the bleaching composition, 0.00
It is preferable to contain 5 to 10,000 ppm, 0.001 to 1000 ppm of transition metal and 0.0001 to 15% of peroxy compound. When an organic peracid precursor is used, it is preferable to use 10 to 100 parts by weight per 100 parts by weight of peroxy compound. . The bleaching composition may be granular or liquid, and the transition metal, ligand, or complex thereof may be granulated or microencapsulated as appropriate to maintain stability in the composition. The amount of the peroxy compound varies depending on the purpose of use,
It is generally preferred that the content be 0.0001 to 15% during the bleaching bath, preferably 0.001 to 10%. The bleaching composition of the present invention has a pH in the bleaching bath of 7 to 12, preferably 8 to 1.
It is preferable to include an inorganic or organic builder, a pH buffer, or the like so as to be 1. Further, it can be used in combination with various surfactants, chelating agents, enzymes, fragrances and the like.

For example, surfactants include alkyl benzene sulfonic acid, alkyl sulfuric acid, alkyl polyethoxy ether sulfuric acid, alkyl phenyl ether sulfate, paraffin sulfonic acid, α-olefin sulfonic acid, α-sulfocarboxylic acid and esters thereof, Anionic surfactants such as water-soluble salts, soaps, etc .; ethoxylated nonions, such as polyoxyalkyl ethers, polyoxyalkyl phenyl ethers, sugar esters, glucoside esters, methyl glucoside esters, ethyl glucoside esters, alkyl polyglucooxides, etc. Nonionic surfactants such as sugar-based activators, amide-based activators such as alkyldiethanolamide and fatty acid N-alkylglucamide; alkylcarboxybetaines, alkylsulfoxybetaines, and alkyls Cocamidopropyl betaine, aminocarboxylates, imidazoline derivatives such as alkyl alaninate, amphoteric surfactants such as alkyl amine oxides;
Cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts are exemplified. These surfactants are used in the bleach composition of the present invention.
The content is preferably 0 to 40%.

Examples of the builder include inorganic builder such as aluminosilicate such as zeolite, layered silicate, alkali metal carbonate, hydrogencarbonate, borate, phosphate, polyphosphate and tripolyphosphate, nitrilotriacetic acid, and lactic acid. And organic builders such as polycarboxylic acid salts such as citric acid, glycolic acid, succinic acid and polyacrylic acid. These builders are preferably contained in the bleaching composition of the present invention in an amount of 0 to 40%. Sodium ethylenediaminetetraacetate,
It is not preferable to use a large amount of a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid since the transition metal in the complex formed in the bleaching bath is chelated. Is preferred. Examples of the enzyme include alcalase and lipase. In addition, fragrances, fluorescent agents, foam inhibitors such as silicones, stabilizers for peroxides, and other metal ions, Ca, Mg, Si, A
l, Zn and the like may be contained.

The bleaching composition of the present invention exhibits an excellent bleaching effect particularly at low temperatures to about lukewarm water, for example, at 5 to 40 ° C.
Bleached materials include clothing, towels, carpets, tableware,
Stain on pottery, glass, plastic, dentures, etc., organic stains, yellowing substances, stain bleaching, curry, wine, fruit juice, tomato ketchup, sauce, especially as stains
Soy sauce, blood, grass juice, tea, coffee, etc., dyes eluted from clothes in the washing bath (prevention of dye transfer), dye waste liquid and pulp,
Examples include paper, woven fabric, and yarn.

[0036]

The use of the bleach-activating catalyst of the present invention activates the bleaching of peroxy compounds at room temperature and in a neutral to alkaline region against various stains, organic stains, yellowing, and stains on clothes, etc. Effective bleaching can be performed. Therefore, the bleaching composition containing the bleaching activation catalyst of the present invention is a bleaching agent for various kinds of clothing, a toilet cleaning agent, an automatic dishwashing agent, a hard surface cleaning bleach such as a denture cleaning agent, a fungicide, It can be widely used as a bleaching agent for pulp, a treating agent for dyeing wastewater, an agent for preventing dye transfer during washing, a disinfectant for clothes, hard surfaces and the like. Next, the present invention will be described with reference examples and examples. The numbers in parentheses for the compounds correspond to the numbers of the compounds described above.

[0037]

【Example】

Reference Example 1 In 100 ml of 1,3,5-trimethylbenzene, 10.27 g (60 mmol) of 2,2′-dipyridylamine and 9.48 g of 2-bromopyridine (60 mmo
l), 15 g of potassium carbonate, 8 g of copper powder, and 0.1 g of potassium iodide were added, and the mixture was refluxed at 150 to 160 ° C. for 12 hours. The reaction solution was filtered at 150 ° C. to remove inorganic salts and copper powder, and the filtrate was allowed to stand at room temperature to obtain green needle crystals. The crystals are washed with water and diethyl ether, and the desired ligand tris (2-pyridyl) amine
White needle crystals of (1) were obtained.

Reference Example 2 In 50 ml of deionized water, 9.84 g (60 mmol) of hydrochloride of 2- (chloromethyl) pyridine and 11.96 g of 2,2'-dipicolylamine (60 m
mol) was dissolved, and the pH was adjusted to 8 by dropwise addition of a 5.4 N aqueous sodium hydroxide solution. The operation up to this point was performed under the condition of 0 ° C. while stirring with a stirrer. When the pH reached 8, the temperature of the reaction solution was raised to 60 ° C., and the mixture was stirred for 6 hours while maintaining the temperature. At that time, in order to keep the pH of the reaction solution in the range of 8 to 9, a 5.4 N aqueous sodium hydroxide solution was added dropwise as needed. The target substance was extracted from the reaction solution using 50 × 3 ml of diethyl ether, and left as it was in a refrigerator to precipitate yellow crystals. The crystals were recrystallized again in diethyl ether to obtain white needle crystals of the objective ligand tris ((2-pyridyl) methyl) amine (7).

Reference Example 3 2-vinylpyridine (10.5 g, 100 mmol) and ammonium acetate 2.
31 g (30 mmol) were mixed and stirred in methanol and reacted at room temperature. After methanol was distilled off with an evaporator, the residue was cooled in an ice bath, and a 20% aqueous sodium hydroxide solution was added until the mixture became alkali. Solution in dichloromethane
After extracting four times with 100 ml and drying over anhydrous sodium sulfate, dichloromethane was distilled off with an evaporator. The oily residue was separated by column chromatography to obtain the desired ligand tris (2- (2-pyridyl) ethyl) amine (13).

Reference Example 4 3.6% potassium hydroxide-diethylene glycol solution 10
5.0 g of bis- (2-pyridyl) ketone was dissolved in 0 ml.
Hydrazine monohydrate (4.0 ml) was added, and the mixture was heated under reflux at 150 ° C. for 4 hours. After cooling, 150 ml of deionized water was added and extracted six times with 60 ml of benzene. The benzene layer was washed three times with 100 ml of water and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue (liquid) was distilled under reduced pressure at 110 ° C. and 0-5 mmHg to obtain a ligand precursor bis- (2-pyridyl) methane shown in (9).

[0041]

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2.2 g of bis- (2-pyridyl) methane was dissolved in 25 ml of dry diethyl ether, and cooled to -60 ° C. in 6.3 ml of a 15% n-butyllithium / hexane solution.
It was added dropwise over 15 minutes. In a reaction solution maintained at a temperature of −60 ° C., 2.0 g of 2-bromopyridine distilled at the time of use was dissolved in 25 ml of dry diethyl ether and added dropwise over 90 minutes. The reaction solution was cooled at −60 ° C. for 30 minutes, at −20 ° C. for 60 minutes, at 0 ° C. for 30 minutes, and then returned to room temperature.
0 ml was added. 60 ° C of diethyl ether from the reaction solution
Then, the mixture was refluxed for 10 hours. The operations so far were performed in a nitrogen atmosphere. After cooling, 60 ml of deionized water was added and the benzene layer was separated. Water layer 3 with 25 ml of benzene
It was re-extracted once, combined with this benzene layer and the previous benzene layer, and dehydrated with magnesium sulfate. After evaporating the solvent under reduced pressure,
The residue (liquid) was extracted with 100 ml of petroleum ether. The solution was boiled with activated carbon, filtered hot and the total amount reduced to about 40
After concentrating under reduced pressure to ml, the precipitated colorless crystals were collected by filtration to obtain the target ligand tris- (2-pyridyl) methane (15) shown below.

Example 1 An aqueous solution was prepared so as to contain 0.43% of hydrogen peroxide, 2.0 ppm of manganese chloride tetrahydrate, and 116 ppm of tris ((2-pyridyl) methyl) amine (7). An aqueous bleaching solution having a pH of 10 was prepared using sodium and sodium carbonate. Immediately after the preparation, a cotton test cloth contaminated with various stains was immersed at room temperature for 30 minutes. After 30 minutes, the product was washed with water and dried. From the measurement of the reflectance of the cloth, the bleaching ratio was determined using the following equation. Bleachability: 100 × (CB) / (AB) A; reflectance of test cloth before stain contamination B: reflectance of test cloth before stain contamination C: reflectance of test cloth after bleach test Table 1 shows the bleaching ratio.

[0044]

[Table 1] Table-1 Kinds of spots Comparative example 1 Spinach of the present invention 9.0 32.0 Curry 5.1 45.8 Red wine 49.2 82.1 Coffee 28.2 55.3 Black tea 30.2 48.2

Example 2 Predetermined amounts of hydrogen peroxide, Mn salt and ligand tris ((2-pyridyl) methyl) amine (7) were prepared, and the same bleaching test as in Example 1 was carried out using curry spots at pH10. I went in. Table 2 shows the obtained bleaching rates.

[Table 2] Table-2 ────────────────────────────────── No H ₂ O ₂ (%) MnCl ₂ · 4H ₂ O (ppm) ligand (ppm) bleach rate (%) Comparative example 2 0.43 - - 5.1 Comparative example 3 0.43 2.0 - 116 6.8 present invention 0.43 2.0 116 45.8 table 2 - 9.8 Comparative example 4 0.43 From the results, hydrogen peroxide, Mn ion and ligand 3
It can be seen that only the bleaching compositions of the present invention, including those of the present invention, exhibit high bleaching rates.

Example 3 A solution containing 0.43% of hydrogen peroxide, 116 ppm of a ligand, tris ((2-pyridyl) methyl) amine (7), and predetermined amounts of various Mn salts was prepared. The same bleaching test as in Example 1 was performed at pH 10. The concentration of each Mn salt is 0.01 mM in terms of mol.
It was prepared so that Table 3 shows the obtained bleaching rates.

[Table 3] Table-3 Mn salt concentration (ppm) bleach rate _{(%) MnCl 2 · 4H 2} O 2.0 45.8 Mn (NO 3) 2 · 6H 2 O 2.9 47.2 MnSO 4 · 5H 2 O 2.4 45.0 Mn (CH 3 COO) 2 · 4H 2 O 2.5 43.0 From the results shown in Table 3, it can be seen that the same bleaching effect as in the case of using manganese chloride can be obtained using any of the Mn salts.

Example 4 A solution containing 0.43% of hydrogen peroxide, 116 ppm of ligand tris ((2-pyridyl) methyl) amine (7) and a predetermined amount of manganese chloride tetrahydrate was prepared, and the black tea stain was removed. Example 1 using
The same bleaching test was carried out at pH 10. Table 4 shows the obtained bleaching rates.

TABLE 4 TABLE -4 ────────────────────────────────── Comparative Example The present invention MnCl ₂ · 4H ₂ O concentration (ppm) 0 0.1 0.5 2.0 10.0 20.0 Bleaching rate (%) 31.1 37.3 44.4 48.2 46.6 47.0 From the results in Table 4, the effect was already recognized at 0.1 ppm of Mn salt, and was excellent at 2.0 ppm or more. It can be seen that the effect can be obtained.

Example 5 0.43% of hydrogen peroxide, 2.0 ppm of manganese chloride tetrahydrate and a predetermined amount of ligand tris ((2-pyridyl) methyl) amine
Example 1 was prepared by preparing a solution containing (7) and using a black tea stain.
The same bleaching test was carried out at pH 10. Table 5 shows the obtained bleaching rates.

Table 5 Comparative Example 6 MnCl ₂ .4H ₂ O of the present invention Concentration (ppm) 0 11.6 58 116 132 Bleaching rate (%) 33.2 36.0 42.0 48.2 49.0 From the results in Table 5, it can be seen that the effect increases as the ligand concentration increases with respect to the Mn salt concentration.

Example 6 0.17% of hydrogen peroxide, 37.2 ppm of manganese chloride tetrahydrate, 58.1 pp of ligand tris ((2-pyridyl) methyl) amine (7)
A predetermined amount of various dyes was added to a bleaching solution containing m as a model of a dye waste liquid, and a bleaching test was performed. This bleaching solution was prepared using sodium carbonate and sodium bicarbonate at pH 10
Was adjusted. The bleaching rate of the dye one minute after the start of bleaching was determined by measuring the change over time of the specific wavelength of each dye with an absorbance meter. Table 6 shows the obtained bleaching rates.

[Table 6] Table 6 色素 Dye Measurement Wavelength Concentration Comparative Example This Invention (nm) (ppm) Alizarin Red S 520 27.4 0.33 93.0 Orange I 516 28.0 0 75.1 Orange II 486 28.0 0.26 21.0 As is clear from the results in Table-6, the bleaching of any dyes compared to the comparative example It can be seen that the invention has very good effects. This result indicates that the catalyst of the present invention has an excellent effect as an agent for preventing color transfer during the treatment of waste dye liquor and washing.

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[Procedure amendment]

[Submission date] December 4, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

When the ligand and the transition metal are used as separate compounds, the transition metal is preferably a compound that releases a transition metal ion when placed in an aqueous solution, and a water-soluble metal salt is preferred. For example, in the case of manganese, manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, manganese acetylacetonate, etc., in the case of iron, iron nitrate, iron sulfate, iron chloride, iron perchlorate, When iron acetylacetonate, iron citrate, iron ammonium citrate, iron ammonium oxalate, ammonium iron sulfate, etc. are copper, copper nitrate, copper sulfate, copper chloride, copper acetate, copper citrate, copper cyanide, and copper Copper oxide, copper ammonium chloride, copper tartrate, copper perchlorate and the like are preferred. On the other hand, examples of the counter ion of the complex include those having various counter ions. Preferred counterions include
Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , NCS
⁻ , PF ₆ ⁻ , OAc ⁻ , BPh ₄ ⁻ , CF ₃ S
O ₃ ⁻ , RSO ₃ ⁻ and RSO ₄ ⁻ are exemplified. Here, R is an alkyl group having 1 to 3 carbon atoms.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yutaka Fukuda 3-3-6 Kashimashiya, Setagaya-ku, Tokyo

Claims (2)

[Claims] 1. A bleach-activating catalyst comprising a ligand represented by the general formula (I) having three or more coordinating nitrogen atoms and a transition metal. Embedded image (In the formula, X is a nitrogen atom, a phosphorus atom or a group represented by C (R ₀ ), R ₀ , R ₁ and R ₂ may be the same or different, and each is hydrogen, optionally substituted An alkyl group, a cycloalkyl group or an aryl group,
n is 0 to 2, m is 0 to 2, A and B may be the same or different, and each has the following groups: (Wherein, R ₃ , R ₄ , R ₆ , R ₇ and R ₈ may be the same or different and each represents a hydrogen, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group , R ₅ are hydrogen, optionally substituted alkyl or alkoxy groups, halogen,
Cyano, NR ₉ R ₁₀ , N = R ₉ , N ⁺ R ₉ R ₁₀ R ₁₁ , a pyridyl group, a pyridinium group, a sulfonic acid group, a thienyl group, a carboxylic acid group, or a hydroxyl group, and R ₉ , R ₁₀ and R ₁₁ may be the same or different and each represents hydrogen,
A hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group;
4, q is 2-7. )). 2. A bleaching composition comprising the bleaching activation catalyst according to claim 1 and a peroxy compound.