JPH1157488A - Catalyst composition against bleaching action of peroxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst composition which can provide a sufficient bleaching performance even at a low temperature by activating hydrogen peroxide and inorganic peroxides of hydrogen peroxide adducts and the like of percarbonate, perborates, tripolyphosphates, diphosphates, silicate and the like. SOLUTION: A complex consists of an acyclic multidentate ligand having at least two atoms included in a molecule and capable of making coordination with a metal atom through a nitrogen atom and manganese or iron and molar ratio of the multidentate ligand to the manganese or the iron is 2 or lower. A catalyst composition consisting of an acyclic multidentate ligand of the manganese or iron and an amine having one nitrogen atom in a molecule is a catalyst for bleaching action of a peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for bleaching by activating a peroxide such as hydrogen peroxide or an adduct of hydrogen peroxide, which is used for various purposes such as domestic use and industrial use. It is about. The catalyst composition of the present invention is useful for bleaching stains and dirt attached to clothes, dirt attached to hard surfaces such as pottery, glass, plastics and dentures, various stains such as dyeing wastewater, and further mold stains. Can be used widely.

[0002]

2. Description of the Related Art Conventionally, chlorine bleaching agents such as sodium hypochlorite have been mainly used as bleaching agents. However, chlorine bleaching agents are used for discoloring and fading a material to be treated. It has drawbacks that it cannot be used for clothing, has a peculiar odor, and generates toxic chlorine gas when mixed with an acidic detergent. Therefore, safer oxygen-based bleaches are frequently used. However, among the oxygen bleaching agents, hydrogen peroxide and inorganic peroxides such as percarbonate, perborate, and hydrogen peroxide adducts such as tripolyphosphate, pyrophosphate, and silicate are chlorine. The bleaching power is inferior to that of the system bleaching agent, and does not exhibit a sufficient bleaching effect especially at low temperatures. Therefore, in order to obtain a sufficient bleaching effect even at a low temperature, for example, an organic peracid precursor such as TAED (tetraacetylethylenediamine), TAGU (tetraacetylglycoluril), or PAG (pentaacetylglucose) is added to these inorganic peroxides. Various proposals have been made to activate these inorganic peroxides in combination.

[0003] Also, various proposals have been made to use manganese or iron compounds as bleach activators. For example, Japanese Patent Publication No. 55-20520 discloses a ferric ion, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (D
TPA) or a complex with hydroxyethylethylenediaminetriacetic acid (HEEDTA) is disclosed in JP-B-60-42.
No. 280 discloses a cyanide-free manganese compound that releases manganese (II) ions in an aqueous solution, such as any manganese (II) salt such as, for example, manganous sulfate and manganous chloride. No. 241400 and Japanese Patent Publication No. 5-71298, the ratio of a water-soluble manganese (II) salt to a water-insoluble solid inorganic silicon support material is 1: 1000 to 1:10.
The catalyst consisting of a manganese (II) salt adsorbed on a support material in Japanese Patent Publication No. Hei 7-23480 includes an insoluble mixed oxide of an alkaline earth metal and manganese selected from calcium, barium and strontium. -70240
And Japanese Patent Publication No. 6-33431 include a hydroxycarboxylic acid containing at least 5 carbon atoms and a complexing agent selected from the group consisting of a salt, lactone, acid ester, ether and borate ester, and manganese (III). JP-A-2-26147 discloses a complex of water-soluble porphyrin having a certain structure with manganese (III) or iron (III). Japanese Patent Publication No. 6-99719 discloses a manganese (I
A water-soluble complex of (I), (III) or (IV) or a mixture thereof and a ligand which is a carboxylate-free polyhydroxy compound having at least three consecutive C-OH groups in its molecular structure, Tokuhei 7-65074
And JP-A-5-263098 discloses a manganese or iron complex having a macrocyclic organic molecule such as a cyclic amine as a ligand, and JP-A-6-41586 discloses a complex containing at least three nitrogen atoms. Alternatively, certain dinuclear manganese complexes having a ligand that is an organic molecule coordinated to the central manganese atom via a part thereof are disclosed in Japanese Patent Application Laid-Open No. 6-121933, in which at least three nitrogens coordinated with manganese are disclosed. Certain trialkoxy complexes of manganese in the tetravalent oxidation state with ligands selected from C3-C60 groups having atoms are each disclosed. However, even when these bleaching activators are used, the bleaching activity at a low temperature cannot be said to be sufficient yet, and the development of a complex having more excellent bleaching activity has been desired.

[0004]

SUMMARY OF THE INVENTION The present invention relates to hydrogen peroxide and percarbonate, perborate, and even tripolyphosphate,
An object of the present invention is to provide a catalyst composition which activates an inorganic peroxide such as a hydrogen peroxide adduct such as a pyrophosphate or a silicate to provide sufficient bleaching performance even at a low temperature.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the problems and as a result, have found that a manganese or iron complex having a certain acyclic nitrogen-based ligand and a certain amine can be used. In combination, the present inventors have found that the activity is dramatically improved from the bleaching activation ability of the inorganic peroxide itself, and that the inorganic peroxide has sufficient bleaching performance even at a low temperature, thereby completing the present invention.

[0006] That is, the present invention relates to a method for preparing at least two
A non-cyclic polydentate ligand having at least one nitrogen atom and capable of coordinating with a metal atom through these nitrogen atoms;
A complex with manganese or iron, wherein the molar ratio of the polydentate ligand to manganese or iron is 2 or less, and a non-cyclic polydentate complex of manganese or iron, and a nitrogen atom in the molecule. An object of the present invention is to provide a catalyst composition for bleaching action of a peroxide, which comprises one amine. Further, the present invention provides a bleaching composition comprising a peroxide and the above-mentioned catalyst composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The manganese or iron acyclic polydentate ligand complex of the present invention has an oxidation state of (II) or (II).
A complex of manganese or iron and a noncyclic polydentate ligand which can take I), (IV) or a combination thereof, which may be mononuclear or polynuclear having two or more nuclei; May be present. Further, a plurality of complexes can be used as a mixture.

An acyclic polydentate ligand is a non-cyclic polydentate ligand having at least two nitrogen atoms in a molecule and capable of coordinating with a metal atom through these nitrogen atoms. is there. The term “acyclic” means that the entire ligand molecule does not have a cyclic structure via at least two nitrogen atoms capable of coordinating with the metal, and the ligand molecule contains an aromatic or alicyclic ring. It may have a cyclic structure such as a group and a heterocyclic ring.
Further, it may contain a substituent such as a hydroxy group, an alkyl group, an aryl group, an aldehyde group, an ether group or a sugar group. Such acyclic polydentate ligands include:
For example, N, N, N ′, N′-tetramethylethylenediamine, N, N′-dimethylethylenediamine,
N, N ', N'-tetraethylethylenediamine, N,
N ', N "-trimethyldiethylenetriamine, N,
N, N ', N', N "-pentamethyldiethylenetriamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, or 1,1,2,2-tetrakis (dimethylamino) ethane Aliphatic polyalkylene polyamines such as N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, pentol,
Or polyalkanol polyalkylene polyamines such as 1,3-bis (tris (hydroxymethyl) methylamino) propane; N, N, N ′, N ′,-tetramethyl-1,2-diaminocyclohexane, or N, N ,
N ', N'-tetrakis (2-hydroxypropyl)-
Alicyclic 1,2-diamines such as 1,2-diaminocyclohexane; N, N, N ′, N′-tetramethyl-1,2;
Phenylenediamine, 2,3-diaminotoluene,
3,4-diaminotoluene, 4-methoxy-1,2-phenylenediamine, or 4,5-dichloro-1,2-
Substituted or unsubstituted phenylenediamines such as phenylenediamine; 2,2′-dipyridyl, 4,4′-dimethyl-2,2′-dipyridyl, or 2,2 ′: 6 ′,
Substituted or unsubstituted 2,2 ′ such as 2 ″ -terpyridine
-Dipyridyl derivative; 2- (2-dimethylaminoethyl) pyridine, 2- (2-piperidinoethyl) pyridine, 2-dimethylaminomethylpyridine, or 2,6
2-aminoalkyl-substituted pyridine derivatives such as -di (2-dimethylaminoethyl) pyridine; 1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, Or 1,1, such as disodium 4,7-diphenyl-1,10-phenanthroline-3,8-disulfonate
10-phenanthrolines; or N, N'-bis (salicylidene) ethylenediamine or N, N'-
And Schiff base compounds such as bis (salicylidene) -1,3-propanediamine. Of these, an acyclic bidentate ligand having two nitrogen atoms in the molecule and capable of coordinating with a metal atom through these nitrogen atoms is preferable, and more preferably 2,2 ′ -A dipyridyl derivative or a 1,10-phenanthroline derivative.

The molar ratio of manganese or iron to the polydentate ligand is not more than 2, preferably from 1: 0.1 to 1: 2.
0, more preferably 1: 0.5 to 1: 2.0
(Molar ratio).

The amine having one nitrogen atom in the molecule, which is the other component of the present invention, refers to an unsubstituted or alkyl, aryl, hydroxy or alkoxy substituted primary, secondary or tertiary amine. And those having only one nitrogen atom in the molecule. Among them, trimethylamine, triethylamine, tri-n
Trialkylamines such as -propylamine, tri-n-butylamine or triisopropylamine; triarylamines such as triphenylamine; or trialkanolamines such as triethanolamine, triisopropanolamine or trimethanolamine. Tertiary amines are preferred.

The amount of amines used is such that the molar ratio of amines to manganese or iron is from 1: 0.1 to 1: 2.
0.0, preferably 1: 0.5 to 1:10
And more preferably 1: 1.0 to 1:10.

The catalyst composition of the present invention has a function of further activating the bleaching action of the peroxide. The present invention also provides a bleach composition containing the above catalyst composition and a peroxide. The peroxide in this case is a peroxide that releases hydrogen peroxide in an aqueous solution, and examples thereof include, in addition to hydrogen peroxide, an inorganic hydrogen peroxide adduct, or an organic hydrogen peroxide adduct. Can be Examples of the inorganic hydrogen peroxide adduct include, for example, hydrogen peroxide adducts of inorganic salts such as alkali metal perborate, percarbonate, perphosphate or persulfate, and organic hydrogen peroxide adducts. Examples include hydrogen peroxide adducts such as pyrophosphate, citrate and urea. Preferred are hydrogen peroxide, sodium percarbonate or sodium perborate, with sodium percarbonate being particularly preferred. The content of peroxide in the bleaching composition is preferably 1 to 30% by weight, and the content of manganese or iron is preferably 0.0001 to 1.0% by weight as a metal.

The bleach composition of the present invention may further contain an organic peracid precursor. The organic peracid precursor has the effect of further enhancing the bleaching action of the catalyst composition of the present invention. As the organic peracid precursor, known organic peracid precursors which have been variously studied can be used. Many organic peracid precursors have been studied, for example, JP-A-53-30485, JP-A-59-22999, JP-A-61-111400, JP-A-61-210053, JP-A-63-152696, JP-A-63-25847,
JP-A-63-315666, JP-A-1-68347, JP-A-2-3637, JP-A-4-228000, JP-A-4-232
Specific examples are described in JP-A-253947 and JP-A-5-287298.

Among them, sodium-4-benzoyloxybenzenesulfonate, N, N, N ', N'-
Tetraacetylethylenediamine, sodium-1-methyl-2-benzoyloxybenzene-4-sulfonate, sodium-4-methyl-3-benzoyloxybenzoate, trimethylammonium toluyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate and sodium-3, 5,5-Trimethylhexanoyloxybenzenesulfonate is preferred.

These organic peracid precursors are used in the bleach composition in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, more preferably 2 to 5% by weight.
In addition, the bleaching composition of the present invention preferably further contains a surfactant and / or a detergent builder. As the surfactant, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant and a mixture thereof can be used.

Examples of the anionic surfactant include a higher fatty acid salt having 10 to 22 carbon atoms, an alkylbenzene sulfonate having 10 to 22 carbon atoms, a sulfate salt of a higher alcohol having 10 to 22 carbon atoms, and a salt having 10 to 22 carbon atoms.
To 22 alkyl ether sulfates, α-olefin sulfonates having 10 to 22 carbon atoms, alkane sulfonates having 10 to 22 carbon atoms, and soaps having 8 to 24 carbon atoms. , Potassium, ammonium and substituted ammonium salts. Of these, preferably, a compound having 1 carbon atom
Sodium alkylbenzenesulfonate having 1 to 15 carbon atoms, sodium alkylsulfate having 16 to 18 carbon atoms,
And sodium alkyl ether sulfate having 16 to 18 carbon atoms.

Examples of the nonionic surfactant include higher alcohols having 8 to 24 carbon atoms and 8 to 2 carbon atoms.
4 fatty acids, ethers of polyethylene glycol or polypropylene glycol having a degree of polymerization of 3 to 100 and alcohols or phenols having 6 to 22 carbon atoms, and polyethylene glycol or polypropylene glycol having a degree of polymerization of 3 to 100 and carboxylic acids having 10 to 22 carbon atoms. And the like.

Examples of the cationic surfactant include a quaternary ammonium compound having 8 to 32 carbon atoms. Specific examples thereof include cetyltrimethylammonium bromide or chloride, distearyldimethylammonium bromide or chloride, and a fatty acid. Group alkylamines. Examples of the zwitterionic surfactant include aliphatic quaternary surfactants having 8 to 32 carbon atoms.
Water soluble derivatives of quaternary ammonium, phosphonium and sulfonium cationic compounds. These surfactants are usually incorporated in the bleach composition in an amount of 50% by weight or less, preferably 1 to 40% by weight, more preferably 5 to 30% by weight.

Detergent builders include calcium ion sequestrants, sedimentants, calcium ion exchangers, and mixtures thereof. Specific examples of the calcium ion sequestering agent include, for example, alkali metal borates such as sodium tripolyphosphate, nitrilotriacetic acid or a water-soluble salt thereof, for example, carboxymethyloxysuccinic acid,
Examples include alkali metal salts of ether polycarboxylic acids such as oxydisuccinic acid or melitic acid, and alkali metal salts of ethylenediaminetetraacetic acid, benzenepolycarboxylic acid or citric acid, and polyacetal carboxylate.

Precipitants include, for example, sodium orthophosphate, sodium carbonate and sodium carbonate / calcite. Examples of the calcium ion exchanger include amorphous and water-insoluble crystalline aluminosilicates such as zeolite. Among these, sodium carbonate, sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate, and water-insoluble crystalline or amorphous aluminosilicate are preferred. The amount of these detergent builders is usually 5 to 80% by weight, preferably 1 to 80% by weight.
0 to 60% by weight.

The bleaching composition of the present invention may also contain other additives commonly used in laundry laundry detergent compositions and mold stain cleaning compositions. Specific examples of such additives include foaming agents such as alkanolamides; antifoaming agents such as alkyl phosphates or silicones; buffering agents such as carbonates such as sodium carboxymethyl cellulose or alkyl or substituted alkyl cellulose. Anti-redeposition agent such as ether,
For example, soil suspending agents / deposits such as carboxymethylcellulose, carboxyhydroxymethylcellulose, maleic anhydride / vinyl ether copolymer, maleic anhydride / (meth) acrylic acid copolymer, and water-soluble salts such as polyacrylate or polyethylene glycol. Inhibitors, for example, fabric softeners such as bentonite, and inorganic salts such as sodium sulfate and the like, and further, a fluorescent agent, a fragrance,
Examples include enzymes such as protease, cellulase, lipase or amylase, bactericides, and coloring agents such as dyes or pigments.

These bleach compositions may be in the form of a solution such as an aqueous solution or a powdery or granular solid mixture with an inert salt such as sodium carbonate. The bleaching composition of the present invention can be used as it is as an aqueous solution for washing laundry and the like, but can also be used as an additive or an auxiliary agent together with a normal detergent. Bleaching or the like of a hard surface such as a mold stain can also be performed by directly spraying or applying a bleaching agent composition to a stained portion.

Further, the catalyst composition of the present invention and the peroxide are
As a bleaching agent composition, a mixture may be used, but upon bleaching, it may be used after being mixed and / or dissolved in a solution. Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[0024]

【Example】

[Preparation of black tea-contaminated cloth] 1.5 liters of ion-exchanged water is boiled in a 3 liter stainless steel container, and 7.5 g of black tea (Twining Orange Peco) is put therein, and the mixture is boiled for 5 minutes with occasional stirring. After the black tea was filtered off with gauze, the filtrate was boiled again and cotton broad (# 100, 30)
5 pieces (30 cm square) were immersed for 30 minutes, quenched with ice, and air-dried. 5 * after drying
It was cut into 5 cm squares and used as a test cloth (cloth stained with black tea).

Examples 1-7 and Comparative Example 1-3 [Preparation of Bleach Composition] A bleach prepared by mixing sodium percarbonate and the catalyst composition components shown in Table 1 in a weight ratio shown in Table 1 After each composition was prepared, the following bleaching effect test was performed using these bleaching agent compositions. [Bleaching effect test] Calcium chloride dihydrate was added to a 2 liter separable flask equipped with a stirrer to give a hardness of 5
One liter of ion-exchanged water adjusted to 0 ppm and 5 g of a commercially available detergent (Lion Top) were inserted, and the mixture was kept at 25 ° C. while stirring. Here, after adding 500 mg of the bleaching agent composition shown in Table 1, the stirring was stopped, and 10 test cloths prepared by the above method were inserted.
Dipped for 0 minutes. After immersion, the test cloth is made of ion-exchanged water 60
After washing with water three times with 0 ml, it was air-dried. The reflectance of the test cloth thus treated was measured with a colorimeter (SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the following formula (1) was obtained.
The bleaching rate of each test cloth was determined by using the above formula, and the average value of 10 sheets was defined as the bleaching effect.

[0026]

## EQU1 ## Bleaching rate (%) = 100 × (reflection of test cloth after bleaching−reflection of test cloth before processing) / (reflection of white cloth−reflection of test cloth before processing) (1) Results The results are shown in Table 1.

Example 8 Sodium percarbonate 100, bipyridyl manganese dichloride 0.1, triisopropanolamine 0.5, and sodium nonanoyloxybenzenesulfonate
A bleach composition having a blending ratio of 0 was prepared. Using this, the above-mentioned bleaching effect test was carried out.
2%, indicating the effect of the organic peracid precursor.

[0028]

[Table 1]

[0029]

According to the present invention, when a manganese or iron complex having a certain acyclic nitrogen-based ligand is combined with a certain amine, the bleaching activation ability of the inorganic peroxide itself is reduced. The present invention provides a catalyst composition whose activity is dramatically improved and which provides sufficient bleaching performance even at a low temperature.

Claims (8)

[Claims] 1. A complex of manganese or iron with an acyclic polydentate ligand having at least two nitrogen atoms in a molecule and capable of coordinating with a metal atom through these nitrogen atoms. The manganese or iron acyclic polydentate ligand complex having a molar ratio of the polydentate ligand to manganese or iron of 2 or less, and amines having one nitrogen atom in the molecule. A catalyst composition for the bleaching action of a peroxide, characterized by the fact that: 2. A non-cyclic polydentate ligand having two nitrogen atoms in a molecule and capable of coordinating a metal atom through these nitrogen atoms. The catalyst composition according to claim 1, which is 3. The catalyst composition according to claim 1, wherein the acyclic polydentate ligand is a 2,2′-dipyridyl derivative or a 1,10-phenanthroline derivative. 4. The catalyst composition according to claim 1, wherein the amine is a tertiary amine. 5. A bleaching composition comprising a peroxide and the catalyst composition according to any one of claims 1 to 4. 6. The bleaching composition according to claim 5, wherein the peroxide is hydrogen peroxide, sodium percarbonate or sodium perborate. 7. The bleaching composition according to claim 5, further comprising an organic peracid precursor. 8. The bleaching composition according to claim 5, further comprising a surfactant and / or a detergent builder.