JP2006193593A - Bleaching activator and bleaching agent composition containing the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a bleaching activator that improves bleaching performance such as a peroxy compound, etc., and a bleaching agent composition containing the compound. <P>SOLUTION: The bleaching activator contains an oxometalate anion. The oxometalate anion is essentially represented by general formula (1): [W<SB>2</SB>O<SB>3</SB>(O<SB>2</SB>)<SB>4</SB>(H<SB>2</SB>O)<SB>2</SB>]<SP>2-</SP>. The bleaching agent composition essentially comprises the bleaching activator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a bleach activator and a bleach composition containing the compound. More specifically, the present invention relates to a bleach activator that exhibits high detergency as a commercial and household bleach activator, and a bleach composition containing the compound.

As a bleaching agent, an oxygen bleaching agent is known, and has functions such as bleaching stains on clothes and the like, and removing stains such as tea astringents on ceramics, glass and plastic tableware. Representative compounds of oxygen bleaching agents include hydrogen peroxide, organic / inorganic peracids (eg, perboric acid, percarbonate), and the like, which play a role as an oxidizing agent for soil components. Further, for the purpose of improving the efficiency of the bleaching agent, a bleaching activator such as tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS) may be used in combination. These bleach activators improve the bleaching efficiency by forming peroxides, and the peroxide formation reaction is a stoichiometric reaction. It was necessary to increase the cost, which led to an increase in cost.

With respect to conventional bleaching agents, it is disclosed that polyoxometalates having a specific structure are used as bleaching catalysts in order to activate peroxy compounds formed from bleaching agents and bleach activators (for example, (See Patent Document 1). The structure of this bleaching catalyst includes isopolyoxometalates containing metal ions and oxygen, and heteropolyoxometalates containing nonmetallic, semi-metallic and / or transition metal ions in addition to metal ions and oxygen. It is a waste. And when it has a deficient structure in which an atom that should be in the crystal structure is missing, it contains a metal element, that is, a poly atom is substituted with another metal element. This bleaching catalyst is a polyoxometalate that always contains any of 2 to 8 subgroups such as Mn, V, Ti, Fe, Co, Cu, Zn, Ni, etc. An oxometalate is disclosed. Further, an oxygen bleach bleach activator containing at least one of a water-soluble molybdenum compound or a water-soluble tungsten compound is disclosed (for example, see Patent Document 2).
However, there has been room for improvement in which the effective utilization rate of the bleaching agent is improved, ineffective decomposition of the bleaching agent is suppressed as much as possible, and the generated active species are effectively used for the oxidation of the substrate.
JP-A-9-118899 (page 2-8) JP-A-6-41593 (2nd page)

The present invention has been made in view of the above situation, and an object thereof is to provide a bleach activator capable of improving the bleaching performance of a peroxy compound and the like, and a bleach composition containing the compound. It is.

As a result of various studies on the bleach activator, the present inventors paid attention to the fact that the oxometalate anion is useful as a bleach activator, and by using an oxometalate anion having a specific stable active structure. It has been found that a bleaching effect can be exerted quickly, efficiently and with high selectivity. Further, when used together with a bleaching agent (for example, hydrogen peroxide (H ₂ O ₂ )), the ineffective decomposition of H ₂ O ₂ is suppressed as much as possible, and the generated oxidative active species is effectively used for the oxidation of the substrate. Therefore, not only can the effective utilization rate of organic peracids such as H ₂ O ₂ and inorganic peracids be increased, but also the selectivity of the oxidation reaction is increased and the bleaching effect is further increased. I found that I could do it. In addition to activating the peroxy compounds formed from bleach and bleach activators, it can also catalytically activate bleach (inorganic peroxy acid salts), etc. Compared to conventional TAED and NOBS Thus, since it is possible to reduce the amount of use, it has been found that it is simpler and more economical, and it has been conceived that the above problems can be solved brilliantly.

That is, the present invention is a bleach activator containing an oxometalate anion, wherein the oxometalate anion is represented by the following general formula (1);
[W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] ^2- (1)
It is a bleaching activator which essentially represents
The present invention is also a bleaching composition essentially comprising the above-described bleach activator.
The present invention is described in detail below.

The bleach activator of the present invention contains an oxometalate anion represented by the above general formula (1). In this specification, such oxo anions as W _2.
The above W ₂ exhibits a bleaching effect by oxidizing a compound having at least one ethylenic double bond that causes blackening or chromophore formation, alone or in combination with a bleaching agent. Is. As an example, as represented by the following reaction formula, W ₂ generates an epoxy group by oxidizing an unsaturated bond and exhibits a bleaching effect.

As the structure of the oxometalate anion (W ₂ ), as shown in the above reaction formula, two tungsten atoms are bonded through one oxygen, and each tungsten atom is an oxygen atom by a W═O bond. One, _two water molecules of W- (H ₂ O), _two oxygen atoms located at the apex of the triangle, and two tungsten atoms and two oxygen atoms forming a triangle is there. Such a structure can be identified by X-ray crystal structure analysis, elemental analysis, FT-IR (Fourier transform infrared spectroscopy) analysis, or the like of the oxometalate anion salt. Incidentally, W ₂ represented in the reaction formula (1), despite determined by X-ray crystal structure analysis are those showing the conceptual view, the present invention is not particularly limited to the three-dimensional structure of the formula (1) Absent. Thus, W ₂ has a peroxy group in the skeleton, and its structure is greatly different from the raw material of W ₂ , and this structure exhibits excellent performance as a bleach activator.

In the case where W ₂ acts as a bleach activator, for example, a form in which a necessary amount of W ₂ isolated in advance is added at the time of washing is suitable. By adopting such a form, the effect of increasing the selectivity and quickly producing a bleaching effect is exhibited. In the present invention, a tungsten species that produces W ₂ and a Keggin type heteropolyoxometalate anion coexist with a bleaching agent such as hydrogen peroxide to generate W ₂ in the system, thereby exhibiting a bleaching effect. It may be.

Tungsten acid, lithium tungstate, sodium tungstate, potassium tungstate, cesium tungstate, magnesium tungstate, calcium tungstate, barium tungstate, zinc tungstate, tungstic acid as the tungsten species for preparing W ₂ A compound having a hexavalent tungsten atom, such as aluminum, ammonium tungstate, or tungsten oxide, is preferable.

As the Keggin type heteropolyoxometalate anion for preparing W ₂ , the following general formula (2)
[XW _a (H ₂ O) _b O _c ] ^d- (2)
(In the formula, X represents a silicon atom or a phosphorus atom. A represents an integer of 9 to 11. b represents an integer of 0 to 6. c represents a positive number of 28 to 39. d Represents a valence and is a positive number).
In the Keggin heteropolyoxometalate anion represented by the general formula (2), a part or all of the constituent anions have a structure in which a part of oxygen atoms bonded to a poly atom is replaced with water molecules. It may be an anion in which oxygen atoms are bonded to all of the poly atoms. Moreover, in the bleaching activator in which the Keggin type heteropolyoxometalate anion is essential, the anion may be one kind or two or more kinds.

As the structure of the Keggin type heteropolyoxometalate anion represented by the general formula (2), a hetero atom is a silicon atom (Si) or a phosphorus atom (P), and a tungsten atom (W ) Becomes a crystal structure in which a (9 to 11) coordinates are formed via an oxygen atom, and has a deficient structure part in which 12-a poly atoms that should be in the crystal structure are missing. Among these 1, 2 and 3 defect structures, it is preferable that X is a silicon atom and has two or more defect structure sites.

As a preferred form of the structure of the Keggin type heteropolyoxometalate anion, when attention is paid to the structure of the deficient part in the Keggin type heteropolyoxometalate anion, an oxygen atom (terminal oxygen) located at the deficient site in the W = O bond ) Having W), the W═O bond is partially a W—H ₂ O bond. More preferably, two W═O bonds located diagonally out of the four W═O bonds at the two deficient sites are W—H ₂ O bonds. Such a structure can be identified from X-ray analysis, elemental analysis, and FT-IR spectroscopy.

The Keggin-type heteropolyoxometalate anion that gives W ₂ can be obtained in the form of a salt. As the preparation method, for example, Inoganic synthesis, Vol. 27, p. It is preferable that a salt of a 1-3 deficient Keggin type heteropolyoxometalate anion obtained by the method described in 71 is generated. Further, by preparing an aqueous solution of this salt and adjusting the pH of the aqueous solution, the Keggin heteropolyoxometalate anion in which the W═O bond at the defect site is converted to W—H ₂ O in the form of a salt is prepared. It can also be manufactured. In such a method for producing a Keggin-type heteropolyoxometalate anion, whether or not the oxygen atom bonded to the poly atom has a structure in which a part of the oxygen atom is replaced with water molecules is shown, and the present invention The pH of the aqueous solution is preferably −1.0 or more and 7.0 or less. More preferably, they are 0 or more and 5.0 or less, More preferably, they are 1.5 or more and 3.0 or less, Most preferably, they are 2.0 or more and 2.5 or less.

When the Keggin heteropolyoxometalate anion is in the form of a salt, the salt has a counter cation. Examples of the counter cation include protons, alkali metal cations (lithium ions, sodium ions, potassium ions). , Rubidium ion, cesium ion), alkaline earth metal cation (beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion) and quaternary ammonium salt (tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt) , Tetrabutylammonium salt, tributylmethylammonium salt, trioctylmethylammonium salt, trilaurylmethylammonium salt, benzyltrimethylammonium salt, benzyltrie Ammonium salt, benzyltributylammonium salt, cetylpyridinium salt, butylpyridinium salt, cetyltrimethylammonium salt, tetrapentylammonium salt, tetrahexylammonium salt, tetraoctylammonium salt, dimethyldioctadecylammonium salt), quaternary phosphonium Salt (tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, tetraphenylphosphonium salt, ethyltriphenylphosphonium salt, benzyltriphenylphosphonium A cation containing an organic cation such as a salt) is preferred. Preferably, proton, lithium ion, sodium ion, potassium ion, cesium ion, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, trioctylmethylammonium salt, tetramethylphosphonium salt, tetraethyl Phosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, cetylpyridinium salt, cetyltrimethylammonium salt, more preferably proton, lithium ion, sodium ion, potassium ion, cesium ion, tetramethyl Ammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, trioctylmethylammonium salt, It is a Chirupirijiniumu salt. The cation constituting the salt of the Keggin type heteropolyoxometalate anion may be one type or two or more types.

Examples of the other Keggin-type heteropolyoxometalate anion also include deficient types (4 or more deficient types) in which a in the general formula (2) is a natural number of 8 or less. Further, the Keggin type heteropolyoxometalate anion may contain other elements. The other element is at least one selected from the group of elements of groups 3 to 16 of the periodic table, and is different from the tungsten atom that is a poly atom of the Keggin heteropolyoxometalate anion of the present invention. . The type of other element may be appropriately selected according to the type of heteroatom of the Keggin type heteropolyoxometalate anion, but one or more types of atoms selected from the group of elements in groups 3 to 11 of the periodic table Is preferred. As other elements, for example, molybdenum, iron, cobalt, manganese, vanadium, chromium, ruthenium and the like are suitable.

The content of the other element is preferably 0.0001 or more, more preferably 0.01 or more with respect to one hetero atom in the Keggin heteropolyoxometalate anion. . Moreover, it is preferable that it is six or less. More preferably, it is 5 or less, and more preferably 3 or less.

As the form of the other element, the cation may be a balance between the heteropolyoxometalate anion and the charge, or may be in the form of an oxide or the like.
In this case, as the existence form of the other element and the Keggin type heteropolyoxometalate anion, the Keggin type heteropolyoxometalate anion and the other element may be present together. The bonding forms described in (i) and (ii) are preferred.

(I) Other elements are complex compounds, for example, [XW _a (H ₂ O) _b O _c ] ^d- -B- [XW _a (H ₂ O) _b O _c ] ^d- A form that exists in coordination with an oxometalate anion.
In the form (i), the structure in which the other element and the Keggin type heteropolyoxometalate anion are bonded can be determined or estimated from X-ray analysis, elemental analysis, or FT-IR spectroscopic measurement.

(Ii) A form in which other elements are present by being supported or adsorbed on the Keggin type heteropolyoxometalate anion. In this case, the site where other elements are supported or adsorbed in the Keggin heteropolyoxometalate anion is not particularly limited. Such a form is estimated from elemental analysis, FT-IR analysis, and the like.
In any of the cases (i) and (ii), the difference between the hetero atom which is a silicon atom and / or phosphorus atom in the Keggin heteropolyoxometalate and other elements is determined by X-ray analysis.・ Can confirm.

When, for example, [SiW ₁₀ O ₃₆ ] ⁸⁻ (SiW ₁₀ ) is used as the Keggin heteropolyoxometalate anion that generates W ₂ , the reaction proceeds in the presence of a bleaching agent such as hydrogen peroxide in the system. , W ₂ is generated from SiW ₁₀ , which is represented by the following reaction formula.

The above W ₂ is produced by the above reaction, and can be isolated and purified by recrystallization operation, filtration operation, washing operation, centrifugation operation or the like.

The Keggin heteropolyoxometalate anion of the present invention may contain other Keggin heteropolyoxometalate anion and other components as long as W ₂ represented by the general formula (1) is essential. Good.

Since the bleaching activator which essentially requires the oxometalate anion (W ₂ ) of the present invention is in the form of an active species, it can quickly exert a cleaning effect. Moreover, the bleaching effect can be shown by oxidizing a compound having a high selectivity at the time of washing and having at least one ethylenic double bond that causes darkening and chromophore formation. The bleach activator is capable of exerting its function and effect even in the absence of peracid as a bleaching agent, but is also useful when used in combination with a bleaching agent. When hydrogen peroxide is used as a bleaching agent, a peracid (peroxy compound) is generated on W, the oxidation reaction is accelerated, and the decomposition reaction of the peroxide is suppressed by using the bleach activator. For example, the bleaching ability is improved without damaging the clothes. As described above, the bleach activator may be used together with a bleaching agent, and a bleach activator may be used in combination as required. When a bleaching activator is used in combination, not only a peracid (peroxy compound) is generated on W, but also the oxidation reaction is further promoted by peroxidizing the bleaching activator, thereby improving the oxidizing power. It will be.

The bleach activator having the oxometalate anion (W ₂ ) as an essential component of the present invention can further exhibit the following effects (1) to (9).
That is, (1) In the ethylenic double bond, the isomerization reaction to generate aldehydes and ketones hardly occurs, and the selectivity to the epoxy compound is increased. (2) By the oxidation of the ethylenic double bond. The production amount of glycol monoalkyl ethers produced by the reaction of the resulting epoxy compound with the ring-opening with water and the compound having at least one ethylenic double bond is small. (3) Even if there is a large amount of water or alcohol in the reaction system, side reactions such as isomerization and ring-opening reactions are unlikely to occur, and the selectivity of the epoxy compound Therefore, it is possible to use a low-concentration oxidizing agent such as hydrogen peroxide. (4) When the oxidizing agent is hydrogen peroxide, there is little decomposition into oxygen. , The effective utilization rate of the oxidant to the epoxy compound is increased, and (5) the reaction activity is high even if the ratio of hydrogen peroxide used for the compound having at least one ethylenic double bond is low. (6) Because the activator has high activity, (7) Since there are few ketones such as acetone produced as a by-product, it is difficult to produce organic peroxides produced from ketones. , The risk of explosion, etc. is reduced, (8) the consumption of oxidants such as hydrogen peroxide due to the accumulation of organic peroxide during bleaching is less likely to occur, (9) biodegradable, The addition to the environment after use is small.

When the oxometalate anion (W ₂ ) of the present invention is used as a bleach activator, the pH of the bleach solution is preferably 1 or more and 14 or less. More preferably, it is 2.0 or more and 13.8 or less. More preferably, it is 2.5 or more and 13.0 or less.

The bleach activator is preferably composed of the oxometalate anion as a main component. However, as long as the effect of the present invention is exhibited, the bleach activator contains impurities or other components generated in the bleach activator preparation process. It may also be used in combination with an activator capable of bleaching activity other than the oxometalate anion.

The present invention is also a bleaching composition containing the bleach activator.
The above-mentioned bleaching composition is a so-called detergent or bleaching agent having a function of removing stains on clothes and tableware, and is usually a bleaching agent composed of a peracid (salt) in an oxygen-based bleaching agent. In addition, a bleaching activator for activating the oxidation reaction by the bleaching agent is included, or these are used in combination. Such a bleaching composition is one of the preferred forms of the present invention.
The above-mentioned bleaching agent composition usually contains a bleaching agent in addition to the bleaching activator, and the bleaching agent composition that essentially comprises the bleaching activator and the bleaching agent is also one of the preferred embodiments of the present invention. It is.
As the bleaching agent, organic and inorganic peracids (salts) and hydrogen peroxide are suitable. These can be used alone or in combination of two or more. Such a bleaching agent can be suitably used in the process of generating the W _2, also is preferred as bleaching agent used in combination when using W ₂ as bleach activators.

Examples of the organic peracid (salt) include monoperoxycarboxylic acids such as t-butyl peroxide, peracetic acid, peroxybenzoic acid, peroxynonanoic acid, peroxylauric acid and monoperoxyphthalic acid, and salts thereof; 2-alkylperoxy-1,4-butanedioic acid, 1,7-heptanediperoxycarboxylic acid, 1,9-nonanediperoxycarboxylic acid, 1,12-dodecanediperoxycarboxylic acid and diperoxy Diperoxycarboxylic acids such as phthalic acid and their salts; N-decanoylaminoperoxycaproic acid, 5- (N-nonylcarbamoyl) peroxyvaleric acid, 3- (N-nonylcarbamoyl) peroxypropionic acid, etc. Peroxycarboxylic acid having an amide bond in its hydrocarbon chain and salts thereof; 4,4′-sulfonyldiper Sulfonylperoxycarboxylic acids such as xylbenzoic acid, 3,3′-sulfonyldiperoxypropionic acid, 4-methylsulfonylperoxybenzoic acid and 3-decylsulfonylperoxypropionic acid and their salts, N, N′— Preferred are unsubstituted or mono- or polysubstituted phthaloylaminoperoxycarboxylic acids such as phthaloylaminoperoxy-n-hexanoic acid (PAP) and N, N′-phthaloylaminoperoxylauric acid. It is.

As the inorganic peracid (salt), perboric acid, percarbonate, perphosphoric acid, persulfuric acid, hydrogen peroxide, and salts thereof are preferable.
In the case where the organic and inorganic peracids are in a salt form, the counter cation is preferably a cation exemplified when the Keggin type heteropolyoxometalate anion is in a salt form.
More preferred as the bleaching agent are perboric acid, percarbonate, persulfuric acid, and hydrogen peroxide, and more preferred are perboric acid, percarbonate, and hydrogen peroxide.
When a bleach activator is used in a powdered product, a perborate such as sodium perborate monohydrate or tetrahydrate, a percarbonate such as sodium percarbonate, a percarbonate Sulfuric acid (salt) is preferred.

The bleach composition may also contain other bleach activators. By using a bleach activator in combination, the efficiency of the bleaching agent can be improved.
The bleach activator is not particularly limited as long as it has a bleaching activity effect. For example, N-acylated amine, N-acylated diamine, N-acylated amide and glycoluril, tetraacetylmethylenediamine, tetra Acetylethylenediamine (TAED), diacetylaniline, diacetyl-p-toluidine, 1,3-diacetyl-5,5-dimethylhydantoin, tetraacetyl glycoluril, tetrapropionyl glycoluril, 1,4-diacetyl-2,5-diketo Piperazine, 1,4-diacetyl-3,6-dimethyl-2,5-diketopiperazine and diacetyldioxohexahydrotriazine (DADHT), nonanoyloxybenzene sulfonate (NOBS) and benzoyloxybenzene sulfonate (BOBS) Acyloxybenzene sulfonate such as pentaacetylglucose (PAG); sugar derivatives such as sugar amides; active carboxylic acid esters; carboxylic acid anhydrides such as isatoic anhydride, maleic anhydride, succinic anhydride and anhydrous citric acid Lactones; acylals; acyllactams such as nonanoyl- and benzoylcaprolactam; alkanenitriles and arenenitriles are preferred. More preferably, they are TAED and NOBS. These bleach activators can be used alone or in combination of two or more.

The bleaching composition may further contain other additives.
Examples of the other additives include surfactant compounds such as anionic, nonionic, zwitterionic (amphoteric) or cationic surfactants, builders, cobuilders, enzymes, and other components. The surfactant may be natural or synthesized, and examples thereof include alkyl sulfate, alkyl sulfonate, alkyl aryl sulfonate, alpha-sulfo fatty acid methyl ester, soap and alkyl ether sulfonate. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.

As the builder and cobuilder, phosphates such as sodium polyphosphate, A, X and P type zeolites, alkali metal carbonates and alkali metal hydrogen carbonates, amorphous and crystalline silicates, etc. are suitable. As the silicate, phyllosilicate, disilicate and the like are more preferable. The cobuilder is preferably an organic carboxylic acid such as citric acid and amino acid; a polymer of polyacrylic acid type, and a copolymer of acrylic acid and maleic acid or derivatives thereof. Furthermore, phosphonates or other complexing agents may be added.

As the enzyme, amylase, protease, lipase, cellulase and peroxidase are suitable. Examples of other components include cellulose ether, silicon, bentonite, fluorescent brightener and fragrance.
The said other additive can be used 1 type (s) or 2 or more types.

As a ratio of the bleach activator, the bleach, and other bleach activators constituting the bleach composition of the present invention, the bleach is 0.005 to 200,000 with respect to 100 parts by mass of the bleach activator. It is preferable that it is a mass part, and it is more preferable that it is 0.5-100000 mass part. Moreover, it is preferable that another bleaching activator is 0-200000 mass parts, and it is more preferable that it is 0-100,000 mass parts. Furthermore, another additive can be added as needed, and it is preferable that it is 0-100,000 mass parts, and it is more preferable that it is 0-90000 mass parts.

The above bleach compositions are detergents and detergents, such as clothes detergents, heavy duty detergents, multi-component detergents (module systems), stain removal salts, spot pretreatment agents, automatic dishwasher cleaners, hard surface cleaners. Can be used as a cleaning agent, a disinfectant and a denture cleaning agent. In addition to the bleaching action, it also acts as a dye transfer inhibitor.

The amount used in the case of using the above-mentioned bleaching composition is 2 to 40% by mass in the case of heavy duty detergent, and 20 to 100% by mass in the case of a stain-removing salt and a pretreatment agent for washing, for dishwashers. In the case of a cleaning agent, it is 1 to 30% by mass, in the case of a cleaning agent for a hard surface and a disinfecting cleaning agent, it is 2 to 50% by mass, and in the case of a denture cleaning agent, it is 2 to 20% by mass. The above-mentioned bleaching composition can be added to detergents and cleaning agents in the form of powder materials or granules.

The bleaching activator of the present invention and the bleaching composition containing the compound have the above-mentioned constitution, and can improve the bleaching performance of a peroxy compound, etc. A bleaching activator useful for removing soils such as tea astringents from ceramics, glass and plastic tableware, and a bleaching composition containing the compound.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Synthesis of K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] 30 mL of water was added to K ₂ WO ₄ · 2H ₂ O (8 g, 22 mmol) and dissolved therein. 30 mL was added. Concentrated hydrochloric acid was immediately added to set the pH to 2.5, and the mixture was left overnight in a refrigerator. The white solid obtained by adding KCl (3 g) to the solution was filtered, washed with a small amount of cold water and ethanol, and the desired K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] ( 11.6 g, 17.6 mmol, yield 80%).

Example 1
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 40 ° C. Bleach activator _{K 2 [W 2 O 3 (} O 2) 4 (H 2 O) 2] of the present invention to this beaker was added (1.66 g), cotton cloth (5 × 4 contaminated with red wine. 5 cm) was added and stirred for 5 minutes. The rotation speed indicator value at this time was set to 100. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the whiteness increase rate is calculated from the whiteness before and after bleaching using the following formula, and the degree of bleaching Evaluated.
White increase rate (%) = (C−B) / (A−B) × 100
A: Whiteness of white cloth before red wine contamination B: Whiteness of red wine contaminated cloth C: Whiteness after bleaching test

Example 2
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 40 ° C. Bleach activator _{K 2 [W 2 O 3 (} O 2) 4 (H 2 O) 2] of the present invention to this beaker was added (1.66 g), cotton cloth (5 × 4 contaminated with red wine. 5 cm) was added and stirred for 5 minutes. The rotation speed indicator value at this time was set to 100. Subsequently, sodium percarbonate (3.5 g) was added and stirred for 1 minute. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the whiteness increase rate is calculated using the above formula from the whiteness before and after bleaching. Evaluated.

Example 3
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 40 ° C. After adding the bleach activator K ₂ [W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] (1.66 g) and sodium percarbonate (3.5 g) of the present invention to this beaker, Contaminated cotton cloth (5 × 4.5 cm) was added and stirred for 15 minutes. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the whiteness increase rate is calculated using the above formula from the whiteness before and after bleaching. Evaluated.

Example 4
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 20 ° C. Bleach activator _{K 2 [W 2 O 3 (} O 2) 4 (H 2 O) 2] of the present invention to this beaker was added (1.66 g), cotton cloth (5 × 4 contaminated with red wine. 5 cm) was added and stirred for 5 minutes. Subsequently, sodium percarbonate (3.5 g) was added and stirred for 1 minute. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluated.

Comparative Example 1
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 40 ° C. The bleach activator Na ₂ WO ₄ (1.65 g) was added to the beaker, and then cotton cloth (5 × 4.5 cm) contaminated with red wine was added and stirred for 5 minutes. The rotation speed indicator value at this time was set to 100. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the whiteness increase rate is calculated using the above formula from the whiteness before and after bleaching. Evaluated.

Comparative Example 2
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 40 ° C. The bleach activator Na ₂ WO ₄ (1.65 g) was added to the beaker, and then cotton cloth (5 × 4.5 cm) contaminated with red wine was added and stirred for 5 minutes. Subsequently, sodium percarbonate (3.5 g) was added and stirred for 1 minute. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the whiteness increase rate is calculated using the above formula from the whiteness before and after bleaching. Evaluated.

Comparative Example 3
1 L of pure water was put into a beaker of a targotometer (manufactured by Daiei Kagaku Seiki Seisakusho), and the temperature was set to 20 ° C. The bleach activator Na ₂ WO ₄ (1.65 g) was added to the beaker, and then cotton cloth (5 × 4.5 cm) contaminated with red wine was added and stirred for 5 minutes. Subsequently, sodium percarbonate (3.5 g) was added and stirred for 1 minute. Immediately after bleaching, the cotton cloth was taken out of the beaker, washed thoroughly with pure water, and then dried with an iron. After drying, the whiteness of the cotton cloth is measured using a color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluated.

Claims (2)

A bleach activator containing an oxometalate anion,
The oxometalate anion has the following general formula (1);
[W ₂ O ₃ (O ₂ ) ₄ (H ₂ O) ₂ ] ^2- (1)
A bleaching activator characterized in that it is essential to be represented by: A bleach composition comprising the bleach activator according to claim 1 as an essential component.