JPH10156188A - Bleaching activation catalyst and bleaching agent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a bleaching activation catalyst capable of improving the bleaching performance of a peroxy compound at a low temp. by forming a catalyst from a ligand expressed by a specific formula and a transition metal. SOLUTION: This catalyst is obtained by combining the ligand with the transition metal and the ligand has a specific structure formed by crosslinking 2 groups each having >=3 coordinating nitrogen atoms in the molecule with a cross-linking species. That is, the ligand expressed by formula I or formula II (in the formulas, X is expressed by formula III to formula VI, Y is expressed by formula III of formula VI, each of R1 , R2 , R3 , R4 , R5 , R15 and R16 is same as or different from each other and represents hydrogen and, in certain case, a (substituted) alkyl group, a cycloalkyl group or an aryl group, (n) is 0-2, (m) is 0-2, (p) is 0-3, (q) is 0-3, (r) is 0 or 1, S is 2-5, (t) is 0-4, (u) is 2-7, (v) is 0-7 and (w) is 0-7) is used with the transition metal in combination.

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, a ligand having a specific structure in which two groups having three or more coordinating nitrogen atoms in a molecule are bridged by a bridging species is combined with a transition metal. It has been made based on the finding that the above-mentioned problems can be efficiently achieved. That is, the present invention provides a bleach-activating catalyst comprising a ligand represented by the general formula (I) or (II) and a transition metal.

Embedded image (Where X is the following formulas (III) to (VI), Y is the following formula (III) or (VI), and A and B are the following formulas (VI
I) to (XII),

Embedded image R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₁₅ and R ₁₆ may be the same or different and each is hydrogen, optionally substituted alkyl, cycloalkyl or aryl. , R ₆ , R ₇ , R ₉ , R ₁₀ and R ₁₁ may be the same or different and each is hydrogen, hydroxyl, optionally substituted alkyl, cycloalkyl or aryl, R ₈ Is an optionally substituted alkyl or alkoxy group, halogen, cyano, NR ₁₂ R ₁₃ , N = R ₁₂ , N ⁺ R ₁₂ R
₁₃ R ₁₄ , a pyridyl group, a pyridinium group, a sulfonic acid group,
A thienyl group, a carboxylic acid group, or a hydroxyl group,
R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and each is a hydrogen, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group, and n is 0 to 2, m Is 0-2, p is 0-3, q is 0
3, r is 0 or 1, s is 2 to 5, t is 0 to 4, u is 2
7, v is 0 to 7 and w is 0 to 7. The present invention also provides a bleaching composition comprising the bleaching activation catalyst and a peroxy compound.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION It is preferable that one ligand can coordinate with two or more transition metals to form a binuclear complex. In the above formula, a plurality of R ₂ , R ₁₅ and R ₁₆ may be the same or different, but the same is preferable. or,
Although a plurality of m may be the same or different,
The same is preferred. Two A's in the molecule may be the same or different, but are preferably the same. In the above formula, the alkyl group, the alkoxy group, the cycloalkyl group, and the aryl group each have 1 to 20, 1 to 2 carbon atoms.
0, 3 to 8 and 6 to 24 are preferred. Examples of these substituents include a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, an amino group, a quaternary ammonium group, a sulfonic acid group, a thienyl group, a carboxylic acid group, and the like.

In the general formula (I), when r is 0, A and B
Is preferably represented by the formulas (VII) to (XII), and particularly preferably, both A and B are the same and represented by the formulas (VII) to (XII). m and n are preferably 0 to 1. It is preferred that the nitrogen atom in A or B is bonded through two carbon atoms to the nitrogen atom bonded to the bridging species. p
Is preferably 1 to 2, and q is preferably 1. R ₁ , R ₂ ,
R ₃ and R ₄ are preferably hydrogen and R ₆ and R ₇
Is preferably hydrogen, an alkyl group (particularly a methyl group), or an aryl group. t is preferably 0 or 1, and when it is 1, R ₈ is preferably an alkyl group (particularly a methyl group). u is preferably 4 or 5, v is 0 to 1, w is preferably 3 or 4, and R ₈ is preferably an alkyl group (methyl group).
When r is 1 in the general formula (I), R ₅ is preferably hydrogen or a methyl group. A and B are represented by formulas (VII) to
It is preferably represented by (XII), and particularly preferably, both A and B are the same and represented by formulas (VII) to (XII). It is preferred that the nitrogen atom in A or B is bonded through two carbon atoms to the nitrogen atom bonded to the bridging species. p and q are preferably ₁ to ₂ , and R ₁ , R ₂ , R ₃
And R ₄ are preferably hydrogen, and R ₆ and R ₇ are preferably hydrogen or an alkyl group (particularly a methyl group) or an aryl group. t is preferably 0 or 1, and when it is 1, R ₈ is preferably an alkyl group (particularly a methyl group). u is preferably 4 or 5, v is 0 to 1, w is preferably 3 or 4, and R ₈ is preferably an alkyl group (methyl group). In the general formula (II), s is preferably from 2 to 3, and particularly preferably 2. R ₁₅ and R ₁₆ are preferably hydrogen or an alkyl group (particularly a methyl group), particularly preferably R ₁₅ is an alkyl group (methyl group), and R ₁₆ is a hydrogen or an alkyl group (particularly a methyl group). p and q are preferably 1, and R ₃ and R
Preferably, ₄ is hydrogen. R ₅ is preferably hydrogen or an alkyl group (methyl group). Specific examples of the ligand represented by the general formulas (I) and (II) of the present invention include the following compounds.

[0006]

Embedded image

[0007]

Embedded image

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, the synthesis of ligand (1) is based on the reaction of ethylenediamine with 2-chloromethylpyridine hydrochloride (Hsiu-Rong
et.al., J. Am. Chem. Soc., 1990 , 112, 6814), and the synthesis of ligand (3) can be carried out using 1,3-diamino-2-propanol and 2-chloromethyl. Reaction with pyridine hydrochloride or 1,3-diamino-2-propanol with pyridine-2-aldehyde (Masa
tatsu Suzuki et. al., Chem. Lett , 1989 , 1094). 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. As the transition metal used in combination with the ligand represented by the general formula (I) in the present invention, Mn, F
e, Cu, Ni, Co, Cr, V, Ru, Rh, Pd,
Examples thereof include Re, W, and Mo, but Mn, Fe, and Cu are preferable in consideration of environmental safety. These metals can be used as one kind or as a mixture of two or more kinds. In the present invention, a mixture of the ligand represented by the general formula (I) or (II) and the transition metal may be used as separate compounds, or the ligand and the transition metal ion may be bonded to each other. It may be used as a complex. 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, the counter ion of the complex may be derived from the used transition metal salt, or may be counter ion-exchanged according to the purpose. Preferred counter ions include Cl ⁻ , B
_{^{r -, I -, NO 3}} -, ClO 4 -, NCS -, PF 6
_{^{-, OAc -, BPh 4 -}} , CF 3 SO 3 -, RSO 3
^- and RSO ₄ ^-, and the like, such as. Here, R is an alkyl group having 1 to 3 carbon atoms.

When used as a complex in which a ligand and a transition metal ion are bonded, the above-mentioned water-soluble salt is preferably used 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. Since the ligand used in the present invention is composed of two groups having three or more coordinating nitrogen atoms, a dinuclear or polynuclear complex containing two or more transition metals per ligand and a cluster. It is preferred that 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) to 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.

[0013] The bleaching composition of the present invention is characterized by containing the bleaching activation 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).

The organic peracid precursor used together with hydrogen peroxide or an inorganic peracid that releases hydrogen peroxide in an aqueous solution and used to generate an organic peracid in a bleaching bath is, for example, acyl phenol. 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 mixed together in a bleaching composition containing a peroxy compound, or may be separately added and adjusted to the concentration in a bleaching bath. 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 alkylbenzenesulfonic acid, alkylsulfuric acid, alkylpolyethoxyethersulfuric acid, alkylphenylethersulfuric acid ester, paraffinsulfonic acid, α-olefinsulfonic acid, α-sulfocarboxylic acid and esters thereof, Anionic surfactants such as water-soluble salts, soaps, etc .; ethoxylated nonions, such as polyoxyalkyl ethers, polyoxyalkylphenyl 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 builders include aluminosilicates such as zeolite, layered silicates, inorganic builders such as alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, tripolyphosphates, 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 especially 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.

[0019]

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.

[0020]

【Example】

Reference Example 1 9.84 g (60 mmol) of 2- (chloromethyl) pyridine hydrochloride and 0.90 g (15 mmol) of ethylenediamine in 50 ml of deionized water
Is dissolved, and a 5.4N aqueous sodium hydroxide solution is added dropwise.
The pH was set to 8. The operations up to this point were carried out at 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, the pH of the reaction solution was set to 8 to
In order to keep the temperature in the range of 9, a 5.4 N aqueous sodium hydroxide solution was dropped at any time. The target substance was extracted from the reaction solution three times with 50 ml of diethyl ether, and left in a refrigerator to precipitate yellow crystals. The crystals are recrystallized again in diethyl ether to give the desired ligand N, N, N ', N'-tetrakis ((2
White needle crystals of (pyridyl) methyl) ethylenediamine (1) were obtained.

REFERENCE EXAMPLE 2 In 50 ml of deionized water, 9.84 g (60 mmol) of 2- (chloromethyl) pyridine hydrochloride and 1.35 g (15 mmol) of 1,3-diamino-2-propanol were dissolved, and 5.4N hydroxide was added. The pH was adjusted to 8 by dropwise addition of aqueous sodium solution. The operations up to this point were carried out at 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. that time,
In order to maintain 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 organic phase was extracted from the reaction solution three times with 50 ml of diethyl ether, and the diethyl ether solution was dried over magnesium sulfate. Diethyl ether was distilled off under reduced pressure, and the obtained oily product was separated by a silica gel column to give the desired ligand N, N, N ', N'-tetrakis ((2-pyridyl) Methyl) -1,3-diamino-2-propanol (3) was obtained.

Example 1 Hydrogen peroxide 0.43%, manganese chloride tetrahydrate 2.0 ppm, N,
N, N ', N'-tetrakis ((2-pyridyl) methyl) -1,3-diamino-2-propanol (3) 182
An aqueous solution was prepared so as to have a concentration of ppm, and a bleached aqueous solution having a pH of 10 was prepared using sodium hydrogen carbonate and sodium carbonate as pH adjusters. 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.

[0023]

[Table 1] Table-1 Stain Comparative Example 1 Mn ligand of the present invention Not added Added curry 5.1 48.6 Red wine 49.2 80.3 Black tea 30.2 44.0

Example 2 Hydrogen peroxide, Mn salt, ligand N, N, N ', N'-tetrakis ((2-pyridyl) methyl) -1,3-diamino-
A predetermined amount of 2-propanol (3) was prepared, and the same bleaching test as in Example 1 was performed at pH 10 using curry spots. Table 2 shows the results.

[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 - 182 26.0 present invention 0.43 2.0 182 48.6 table 2 - 9.8 Comparative example 4 0.43 As is evident from the results, the bleaching rate was improved by the coexistence of the two components of hydrogen peroxide and the ligand, but the system containing the three components of hydrogen peroxide, Mn ion and the ligand had the highest bleaching. Rate.

Example 3 0.43% of hydrogen peroxide and a predetermined amount of ligands N, N, N ', N'
A solution containing tetrakis ((2-pyridyl) methyl) -1,3-diamino-2-propanol (3) and manganese chloride tetrahydrate was prepared, and the same method as in Example 1 was carried out using curry spots. Bleaching tests were performed at pH 10. Table 3 shows the results.
Shown in

[Table 3] Table-3 Comparative Example 5 MnCl ₂ .4H ₂ O concentration (ppm) of the present invention 0 0.5 2.0 5.0 20.0 Ligand concentration (ppm) 0 90 182 540 720 Bleaching rate (%) 5.1 38.2 48.6 49.0 47.0 Thus, a high bleaching ratio was obtained even when the concentrations of the manganese salt and the ligand were changed.

Continuation of 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) or (II) and a transition metal. Embedded image (Where X is the following formulas (III) to (VI), Y is the following formula (III) or (VI), and A and B are the following formulas (VI
Represented by I) to (XII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₁₅ and R ₁₆ may be the same or different and each is hydrogen, optionally substituted alkyl, cycloalkyl or aryl. , R ₆ , R ₇ , R ₉ , R ₁₀ and R ₁₁ may be the same or different and each is hydrogen, hydroxyl, optionally substituted alkyl, cycloalkyl or aryl, R ₈ Is an optionally substituted alkyl or alkoxy group, halogen, cyano, NR ₁₂ R ₁₃ , N = R ₁₂ , N ⁺ R ₁₂ R
₁₃ R ₁₄ , a pyridyl group, a pyridinium group, a sulfonic acid group,
A thienyl group, a carboxylic acid group, or a hydroxyl group,
R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and each is a hydrogen, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group, and n is 0 to 2, m Is 0-2, p is 0-3, q is 0
3, r is 0 or 1, s is 2 to 5, t is 0 to 4, u is 2
7, v is 0 to 7 and w is 0 to 7. ) 2. A bleaching composition comprising the bleaching activation catalyst according to claim 1 and a peroxy compound.