JP2008104920A - Oxidation catalyst, bleaching detergent composition containing the same, and disinfecting / sterilizing detergent composition - Google Patents

Abstract

【選択図】なしThe present invention provides a novel oxidation catalyst which has an excellent oxidation promoting effect and is suitably used for a bleaching detergent composition, a sterilizing / sterilizing detergent composition and the like.
An oxidation catalyst comprising a compound represented by the following general formula (1) and / or an anion generated from the compound and a transition metal. In the formula, A represents an imino group or an oxygen atom, and X ^{1 to} X ⁴ may be the same or different and are each selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, and an ammonia base. R represents a hydrogen atom or a hydroxyl group, and n is 0 or 1. According to the bleaching detergent composition and the disinfecting / sterilizing detergent composition containing this, a very high bleaching effect and disinfecting / disinfecting effect can be obtained.
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to an oxidation catalyst, a bleaching detergent composition and a disinfecting / sterilizing detergent composition containing the same, and a production method for industrially producing an oxidation catalyst.

Conventionally, bleaching detergent compositions have been used for washing clothes, homes and the like. In recent years, awareness of keeping clothes and living spaces clean has increased, and not only washing but also sterilization and sterilization using a sterilization / sterilization detergent composition is increasing.
The bleaching effect and the sterilizing / sterilizing effect of these compositions are usually exhibited by an oxidation reaction. The oxidation reaction component responsible for such an oxidation reaction includes a hydrogen peroxide compound (hydrogen peroxide, a peroxide that dissolves in water to generate hydrogen peroxide), and a chlorine compound ( In some cases, sodium hypochlorite is used. Among these, hydrogen peroxide compounds have attracted attention recently because they can be used easily.

And, in the bleaching detergent composition and the sterilizing / sterilizing detergent composition, such an oxidation reaction component alone may be insufficient in the bleaching effect and the sterilizing / sterilizing effect under low temperature conditions, for example. It has been proposed to use an oxidation catalyst such as an organic peracid precursor or a metal complex having characteristics that promote the oxidation reaction together with the oxidation reaction component (see, for example, Patent Documents 1 to 16).
Japanese Patent Publication No. 6-33431 Japanese Examined Patent Publication No. 6-70240 Japanese Patent Publication No. 6-99719 JP-A-52-155279 JP-A-1-97267 JP-A-2-261547 Japanese National Patent Publication No. 8-503247 JP-T 8-503248 Japanese Examined Patent Publication No. 7-12437 Japanese Patent Publication No. 7-65074 Japanese Patent Publication No. 7-68543, Japanese Patent Publication No.7-12276 JP-A-5-263098 JP-A-6-121933 JP-A-8-67687 US Pat. No. 5,021,187

  However, conventional oxidation catalysts sometimes have insufficient effects for promoting oxidation of oxidation reaction components (hereinafter referred to as oxidation promotion effects), and new oxidation catalysts with higher effects are being demanded.

  The present invention has been made in view of the above circumstances, has an excellent oxidation promotion effect, and a novel oxidation catalyst suitably used for a bleach detergent composition or a disinfecting / sterilizing detergent composition, and a bleach containing the same. It is an object of the present invention to provide a cleaning composition, a disinfecting / sterilizing cleaning composition, and a production method for industrially producing the oxidation catalyst.

（式中、Ａはイミノ基または酸素原子を表し、Ｘ^１〜Ｘ^４は同一でも異なっていてもよく、それぞれ水素原子、アルカリ金属、アルカリ土類金属、カチオン性アンモニウム基からなる群より選ばれる１種を表し、Ｒは水素原子または水酸基を表し、ｎは０または１である。）
本発明の酸化触媒においては、前記Ａがイミノ基であることが好ましい。
また、前記Ｒが水酸基であることが好ましい。
また、前記遷移金属がマンガンおよび／または銅を含むことが好ましい。
本発明の酸化触媒においては、前記遷移金属の少なくとも一部に前記陰イオンの少なくとも一部が配位し、錯形成していることが好ましい。
このような形態の酸化触媒は、前記遷移金属のイオンを発生する遷移金属イオン源と前記一般式（１）で示される化合物とを溶媒中で混合し、反応させる反応工程と、該反応工程で得られた反応液から前記溶媒を留去して、前記反応により生成した酸化触媒と副生塩とを回収する回収工程を有する製造方法により製造できる。
前記溶媒は水、エタノール、メタノールからなる群より選ばれる１種以上の極性溶媒であることが好ましい。 The present inventor has shown that a specific compound and / or an anion generated from the compound and a transition metal exhibit a high function as an oxidation catalyst, and further, at least a part of the transition metal contains the specific compound. When at least a part of the anion is coordinated and complexed, it has been found that a higher function is exhibited, and the present invention has been completed.
The oxidation catalyst of the present invention comprises a compound represented by the following general formula (1) and / or an anion generated from the compound, and a transition metal.

(In the formula, A represents an imino group or an oxygen atom, and X ^{1 to} X ⁴ may be the same or different and are each selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, and a cationic ammonium group. 1 type is represented, R represents a hydrogen atom or a hydroxyl group, and n is 0 or 1.)
In the oxidation catalyst of the present invention, the A is preferably an imino group.
The R is preferably a hydroxyl group.
The transition metal preferably contains manganese and / or copper.
In the oxidation catalyst of the present invention, it is preferable that at least a part of the anion is coordinated to at least a part of the transition metal to form a complex.
The oxidation catalyst in such a form includes a reaction step in which a transition metal ion source that generates ions of the transition metal and a compound represented by the general formula (1) are mixed and reacted in a solvent, and the reaction step The solvent can be distilled off from the obtained reaction solution, and the production can be performed by a production method having a recovery step of recovering the oxidation catalyst and by-product salt generated by the reaction.
The solvent is preferably at least one polar solvent selected from the group consisting of water, ethanol and methanol.

The bleaching detergent composition of the present invention comprises any one of the oxidation catalysts described above and an oxidation reaction component.
The disinfecting / sterilizing detergent composition of the present invention is characterized by containing any one of the oxidation catalysts described above and an oxidation reaction component.
In the disinfecting / sterilizing detergent composition of the present invention, the transition metal is preferably copper.

  According to the present invention, the oxidation promoting effect of promoting oxidation of oxidation reaction components is excellent, and includes a novel oxidation catalyst suitably used for a bleaching detergent composition, a sterilizing / sterilizing detergent composition, and the like. A bleaching detergent composition, a disinfecting / sterilizing detergent composition, and a production method for industrially producing the oxidation catalyst can be provided.

The present invention will be described in detail below.
[Oxidation catalyst]
The oxidation catalyst of the present invention exhibits an oxidation promotion effect by being used together with an oxidation reaction component having a bleaching effect or a sterilizing / sterilizing effect in, for example, a bleaching detergent composition or a sterilizing / sterilizing detergent composition. And comprising a compound represented by the following general formula (1) (hereinafter referred to as compound (1)) and / or an anion generated from the compound (1) and a transition metal. .
In the present specification, the “bleaching effect” means an effect capable of thinning or removing a stain formed by deposition of a pigment such as curry, for example. The effect that can be removed or killed.

  The oxidation catalyst of the present invention only needs to contain at least one of the above-mentioned compound (1) or at least one anion generated from this compound (1) and a transition metal, and may be a simple mixture containing these. Alternatively, the complex may be a complex in which an anion generated from the compound (1) is coordinated as a ligand to the transition metal. Moreover, the thing of the state in which these were mixed may be sufficient.

That is, specific forms of the oxidation catalyst include, for example, the following forms (i) to (iii).
(I) A solid mixture in which the compound (1) and a compound capable of generating a transition metal ion, that is, a transition metal ion source are mixed.
(Ii) A liquid mixture in which the compound (1) and the transition metal ion source are put into a solvent such as water. In this liquid mixture, at least a part of the transition metal becomes a transition metal ion, and at least a part of the anion generated from the compound (1) is complexed as a ligand.
(Iii) The compound (1) is reacted with the transition metal ion source in a solvent such as water and then removed, and the anion generated from the compound (1) is coordinated to the transition metal. A solid complex which is coordinated and bonded as a child to form a complex, or a mixture containing this solid complex.

(Compound (1))
The compound (1) is represented by the following general formula (1).

  In the formula, A represents an imino group (—NH—) or an oxygen atom (—O—), and R represents a hydrogen atom (—H) or a hydroxyl group (—OH), but a higher oxidation promoting effect can be obtained. A is preferably an imino group and R is preferably a hydroxyl group. n is 0 or 1, but is preferably 1.

X ^{1 to} X ⁴ may be the same or different, and each represents one selected from the group consisting of a hydrogen atom, an alkali metal such as sodium and potassium, an alkaline earth metal such as calcium, and a cationic ammonium group. When X ^{1 to} X ⁴ are these, in the production of the oxidation catalyst of the above forms (ii) and (iii), when this compound (1) is introduced into a solvent such as water, —COOX ¹ , —COOX ² , —COOX ³ , and —COOX ⁴ are each ionized to be —COO ^— to generate an anion of the following formula (2). Then, the anionic -COO ^- moiety becomes possible transition metal and complexing of. Preferably, X ^{1 to} X ⁴ are all sodium or potassium. When one or more of X ^{1 to} X ⁴ are the alkaline earth metal M, the portion is indicated as —COOM _1/2 .

Specific examples of the compound (1) include those represented by the following formulas (3) to (6). In these chemical formulas (3) to (6), as representative examples, X ^{1 to} X ⁴ are all sodium, but the compound (1) is not limited thereto, and the purpose is You can select the right one according to your needs.

(Transition metal)
The transition metal is not particularly limited, and examples thereof include zinc, manganese, iron, copper, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, and molybdenum, and one or more of these can be used. . Among these, when an oxidation catalyst is used in the bleaching detergent composition, manganese and / or copper are preferable from the viewpoint of obtaining an excellent bleaching effect and a washing effect, and particularly in a sterilizing / sterilizing detergent composition. When used, it is preferable to use copper. Further, when manganese and copper are used in combination as transition metals, these synergistic effects are exhibited, and a higher oxidation promoting effect tends to be obtained.

[Production method of oxidation catalyst]
The oxidation catalyst of the present invention only needs to contain at least the above-described compound (1) or an anion generated from this compound (1) and a transition metal. The specific method is not particularly limited, but in the case of producing the oxidation catalyst of the form (i) described above, the solid compound (1) and the solid transition metal ion source are simply mixed. Good. Moreover, when manufacturing the oxidation catalyst of the above-mentioned form (ii), the compound (1) and the transition metal ion source may be added to a solvent such as water, respectively. These oxidation catalysts in the forms (i) and (ii) are preferable in that they can be produced very easily.
In addition, when the oxidation catalyst in the form of (i) and (ii) is used in a bleaching detergent composition or a disinfecting / sterilizing detergent composition to be described later, it is preliminarily made in the form of (i) or (ii). However, in the step of producing these compositions, the compound (1) and the transition metal ion source may be mixed with other components such as an oxidation reaction component and a solvent such as water, respectively.

  As a transition metal ion source, water is often used as a solvent for a bleaching detergent composition or a disinfecting / sterilizing detergent composition, and therefore, those that generate transition metal ions when injected into water are preferable. Water-soluble metal salts of transition metals are preferred. Examples of water-soluble metal salts include nitrates, sulfates, chlorides, acetates, perchlorates, acetylacetonates, citrates, cyanides, oxalates, ammonium chlorides of the transition metals exemplified above. And tartrate. When the transition metal is manganese, manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, manganese acetylacetonate, etc. are preferable. When the transition metal is copper, copper nitrate, copper sulfide, sulfuric acid Copper, copper chloride, copper acetate, copper citrate, copper cyanide, copper oxalate, ammonium copper chloride, copper tartrate, copper perchlorate and the like are preferable.

  In the production of the oxidation catalyst of the forms (i) and (ii), the amount of the compound (1) used relative to the transition metal ion source is preferably 1 to 20 molar equivalents, and more preferably 1 to 5 molar equivalents. In the case of the oxidation catalyst in the form of (i) and (ii), it is preferable that the compound (1) is excessive with respect to the transition metal from the viewpoint of the bleaching effect, but is preferably 20 molar equivalents or less from the viewpoint of economy. It is.

The oxidation catalyst of the form (iii) is preferable in that a higher oxidation promoting effect is obtained than the oxidation catalysts of the forms (i) and (ii).
As a specific method for producing the oxidation catalyst of the form (iii), first, a transition metal ion source and the compound (1) serving as a ligand are added and dissolved in a solvent, and further, an alkali is added if necessary. An agent is added, and the mixture is preferably stirred at room temperature to about 100 ° C., more preferably about 25 ° C. to react them (reaction step). The stirring time is preferably 1 minute or more, more preferably 1 minute to 5 hours, and more preferably about 10 minutes. Immediately after the completion of the reaction step, the solvent is distilled off from the reaction solution under reduced pressure, and the oxidation catalyst composed of the solid complex produced in the reaction step and the by-product salt are recovered in the form of a mixture (recovery step).

Such a production method is preferable in terms of an excellent balance in production time, complex yield, simplicity, etc., and advantageous in industrial production. Further, the mixture obtained in the recovery step can be used as it is as an oxidation catalyst without separating the by-product salt. However, when it is necessary to obtain an oxidation catalyst as a higher-purity complex, the reaction solution obtained in the reaction step is allowed to stand in a cool dark place for 1 hour to 1 week, and the generated precipitate, that is, the solid complex is filtered off. You may employ | adopt the collection | recovery method obtained by these.
In addition, the oxidation catalyst thus obtained may be used after appropriately adjusting the amount of transition metal and the amount of ligand, for example, by adding a compound (1) and / or a transition metal ion source.

As the solvent used in the production of the oxidation catalyst of the form (iii), a polar solvent is preferable, and the compound (1) can be dissolved at room temperature, and further, a solvent that can be distilled off under reduced pressure at 200 ° C. or lower. preferable. Specific examples include water, ethanol, methanol, isopropanol, acetonitrile, acetone, dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide, and the like. One or more of water, ethanol, and methanol are preferable from the viewpoint of safety, easiness of distillation, and water is particularly preferable.
As the alkali agent, triethylamine, sodium hydroxide, sodium carbonate and the like can be used.
The transition metal ion source may be any source that can be dissolved in a solvent to generate a transition metal ion. In addition to the various water-soluble metal salts exemplified above, other salts soluble in the solvent to be used (for example, , Organic solvent soluble salts, etc.), potassium permanganate and the like can also be used. As described above, since water is preferably used as the solvent, it is preferable to use a water-soluble metal salt as the transition metal ion source.

  In the production of the oxidation catalyst in the form of (iii), the amount of the compound (1) used relative to the transition metal ion source is preferably set to a proportion corresponding to the complex structure to be formed. The usage-amount of the compound (1) with respect to an ion source should just be 1 molar equivalent or more, Preferably it is 1-2 molar equivalent, Especially preferably, it is 1 molar equivalent. Within this range, the balance between the amount of compound (1) (ligand amount) and the amount of transition metal becomes appropriate, and a higher oxidation promoting effect is likely to be obtained. However, either one may be used in excess, and the excess may be removed after complex synthesis. Moreover, when compound (1) is used in excess, it is not always necessary to remove the excess, and it may be used as it is as an oxidation catalyst.

  The complex structure formed here is not particularly limited, and the number of ligands per transition metal may be one or more, and one or more transition metals constituting one complex may be used. Good. That is, the complex may be mononuclear, binuclear, or cluster. Moreover, when it is a polynuclear complex, the transition metal contained in this may be only 1 type, and multiple types may be sufficient, for example, when manganese and copper coexist. Furthermore, in the case of a polynuclear complex, it may be crosslinked by a crosslinking species such as oxygen, sulfur, halogen atom and the like.

  Further, in such a complex, if at least one anion generated from the compound (1) is coordinated to the transition metal, another ligand is further coordinated during actual use of the oxidation catalyst. You may be ranked. As such other ligands, an oxidation catalyst in the form of (i) to (iii) is mixed with an oxidation reaction component or the like to produce a bleach detergent composition or a disinfecting / sterilizing detergent composition. Various functional groups and atoms (for example, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxylic acid group, a thiol group, a halogen atom, etc.) in an optional component described later are used, and water as a solvent.

[Bleaching detergent composition]
The bleaching detergent composition of the present invention contains the above-described oxidation catalyst and an oxidation reaction component that produces at least a bleaching effect by an oxidation reaction, and may further contain a solvent such as water or an optional component. Good.
Examples of the oxidation reaction component include hydrogen peroxide and hydrogen peroxide-based compounds such as peroxide that dissolves in water to generate hydrogen peroxide. Depending on the application, chlorine dioxide or the like may be used as the oxidation reaction component, but the use of a hydrogen peroxide-based compound is preferred.
Examples of peroxides that dissolve in water to generate hydrogen peroxide include alkali metal percarbonates, perborates, perphosphates, persilicates, persulfates, and hydrates thereof. And inorganic materials. The salt is preferably an alkali metal salt such as sodium salt or potassium salt. More preferred are sodium perborate, sodium percarbonate and hydrates thereof, and one or more of these can be used.

The bleaching detergent composition may be liquid or solid. Examples of the method for producing the liquid bleaching detergent composition include a compound (1) constituting an oxidation catalyst and a transition metal ion source together with an oxidation reaction component and water. The method of throwing in in the solvent of this is mentioned. Alternatively, the oxidation catalyst of the form (iii) described above may be prepared in advance, and both the oxidation catalyst and the oxidation reaction component may be put into a solvent such as water.
On the other hand, in the case of a solid bleaching detergent composition, a solid material such as powder is mixed, that is, a compound (1) constituting an oxidation catalyst, a transition metal ion source, an oxidation reaction component, and the like. And an oxidation catalyst in the form of (iii) described above is prepared in advance, and this oxidation catalyst and a solid oxidation reaction component are mixed in solid.
When producing a liquid bleach detergent composition, hydrogen peroxide is preferably used as the oxidation reaction component, and when producing a solid bleach detergent composition, it is dissolved in water and peroxidized. The above-described peroxide (solid form) that generates hydrogen is preferably used.

The bleaching detergent composition is usually used by dissolving in water during washing and bleaching. The bleaching detergent composition is preferably used so that the amount of transition metal in the oxidation catalyst is 0.001 to 300 ppm in an aqueous solution (bleaching bath) in which it is dissolved, and further 0.005 to 30 ppm. It is preferable to become. When the amount of the transition metal is within such a range, a high bleaching effect can be obtained and decomposition of the oxidation reaction component can be suppressed.
On the other hand, the amount of the oxidation reaction component in the bleaching bath is preferably 0.0001 to 20% by mass, more preferably 0.0005 to 5% by mass, as the hydrogen peroxide concentration. When the amount of the oxidation reaction component is within such a range, a high bleaching effect can be obtained, and damage can be suppressed even when the object to be bleached is a delicate fiber or dye.
When expressed in terms of mass ratio between the oxidation catalyst and the oxidation reaction component (converted to hydrogen peroxide) in the bleaching detergent composition, the oxidation catalyst: oxidation reaction component is preferably 1: 1 to 10,000, more preferably 1: 5. 200.

In the bleaching detergent composition, as optional components, for example, various surfactants, peracid precursors, builders, enzymes, fragrances, fluorescent agents, fiber damage inhibitors, antifoaming agents, pH adjusting agents, pH buffering agents, Transition metals other than manganese, copper, and the like (for example, cobalt and zinc salts) can be blended.
Among these optional components, in particular, a pH adjusting agent or a pH buffering agent may be added to the bleaching detergent composition so that the pH of the bleaching bath at 25 ° C. is 1 to 12, preferably pH 8 to 11. A pH buffering agent is preferably added, particularly preferably.
Hereinafter, the exemplified components will be specifically described. Moreover, the component shown below can be used individually or in mixture of 2 or more types, respectively.

(Surfactant)
There is no restriction | limiting in particular as surfactant, According to the objective, it can select suitably.
For example, water-soluble salts such as alkylbenzenesulfonic acid, alkylsulfuric acid, alkylpolyethoxyethersulfuric acid, alkylphenylethersulfuric acid ester, paraffinsulfonic acid, α-olefinsulfonic acid, α-sulfocarboxylic acid and esters thereof (sodium as a salt) Salt, potassium salt, etc.), anionic surfactants such as soaps; ethoxylated nonions such as polyoxyalkyl ethers and polyoxyalkylphenyl ethers, sugar esters, glucoside esters, methyl glucoside esters, ethyl glucoside esters, alkyls Nonionic surfactants such as sugar active agents such as polyglucooxide, amide active agents such as alkyldiethanolamides and fatty acid N-alkylglucamides; alkylcarboxybetaines, alkyls Such as aminocarboxylates such as sulfuloxybetaine, alkylamidopropylbetaine and alkylalaninate, amphoteric surfactants such as imidazoline derivatives and alkylamine oxides; cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts Can be mentioned.

(Peracid precursor)
The peracid precursor is not particularly limited as long as it reacts with hydrogen peroxide to produce a peroxo compound, and can be appropriately selected according to the purpose.
Examples include decanoyloxybenzoic acid, sodium decanoyloxybenzene sulfonate, sodium dodecanoyloxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate, and the like. Among these, 4-decanoyloxybenzoic acid and sodium 4-nonanoyloxybenzenesulfonate are preferable from the viewpoint of bleaching effect, and 4-decanoyloxybenzoic acid and 4-dodecanoyloxybenzene are preferable from the viewpoint of fading inhibiting effect. Sodium sulfonate is preferred.

(builder)
There is no restriction | limiting in particular as a builder, According to the objective, it can select suitably.
For example, inorganic builders such as aluminosilicates such as zeolite, alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, and tripolyphosphates, nitrilotriacetic acid, lactic acid, citric acid, glycolic acid And organic builder such as polycarboxylic acid such as succinic acid and polyacrylic acid (for example, socaran CP5, socaran CP7 (manufactured by BASF)). In addition, compound (1) may act as a builder.

(enzyme)
There is no restriction | limiting in particular as an enzyme, According to the objective, it can select suitably.
Classification from enzyme reactivity includes hydrolases, oxidoreductases, lyases, transferases and isomerases, among which proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases, etc. Use is preferred.
Specific examples of proteases include Novozyme Savinase, Alcalase, Everase, Cannase, Esperase, Showa Denko Co. API21, Genencor Maxantase (Maxase), Maxacal, Purefect, Maxapem, KAP manufactured by Kao Corporation, Proteases K-14 and K-16 described in JP-A-5-25492, and the like. Specific examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase. Specific examples of the lipase include commercially available lipases such as Lipolase manufactured by Novozyme, Lipolase Ultra, Lipex, Liposome manufactured by Showa Denko K.K. Examples of the cellulase include commercially available cellozymes manufactured by Novozyme, Carezyme, KAC500 manufactured by Kao Corporation, and cellulase described in claim 4 of JP-A-63-264699.

(Fragrance)
There is no restriction | limiting in particular as a fragrance | flavor, According to the objective, it can select suitably.
For example, hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, terpene alcohols, alcohols such as aromatic alcohols, aliphatic ethers, ethers such as aromatic ethers, aliphatic Oxides such as oxides, oxides of terpenes, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, fats Aromatic cyclic ketones, non-benzene aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids Acids such as acid amides, aliphatic lactones Macrocyclic lactone, terpene lactone, hydrogenated aromatic lactone, lactone such as aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid Esters such as esters, aromatic carboxylic esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, synthetic compounds such as nitrogen-containing compounds such as indole, natural fragrances from animals and plants, natural fragrances and / or Or the compound fragrance | flavor containing a synthetic | combination fragrance | flavor etc. are mentioned.

(Fluorescent agent)
The fluorescent agent is not particularly limited and can be appropriately selected according to the purpose.
For example, 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, Examples include 4,4′-bis (triazol-2-yl) stilbene derivatives and bis- (triazinylaminostilbene) disulfonic acid derivatives.

(Fiber damage prevention agent)
There is no restriction | limiting in particular as a fiber damage prevention agent, According to the objective, it can select suitably.
Examples of the fiber damage preventing agent include polyphenol compounds having radical trapping ability such as methoxyphenol and hydroxybenzoic acid, clay minerals, crystalline layered silicate, cellulose powder, and the like, and cellulose powder is preferable.

(Defoamer)
The antifoaming agent is not particularly limited and can be appropriately selected according to the purpose, but a silicone / silica type is preferable.

(PH adjuster, pH buffer)
There is no restriction | limiting in particular as a pH adjuster, According to the objective, an alkali agent and an acid can be selected suitably. Examples of the alkali agent include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, sodium hydroxide, potassium hydroxide, and the like in addition to the above-described alkali agents. As the acid, in addition to the organic acids described in the builder, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, sulfuric acid, hydrochloric acid, and the like can be used.
As the pH buffer, carbonates such as sodium carbonate and potassium carbonate are preferable, and sodium carbonate is preferable. As described above, the pH buffering agent may be blended so that the pH of the bleaching bath at 25 ° C. is 1 to 12, preferably pH 8 to 11.

The bleach detergent composition of the present invention includes, for example, a mold remover, a strainer cleaner, a triangular corner cleaner, a kitchen bleach cleaner, a pipe clog remover, a toilet cleaner, an automatic dishwasher detergent, and a denture cleaner. Can be widely used as a hard surface washing bleach, washing tub cleaner, pulp bleach cleaner, dye wastewater treatment agent, various clothing bleach cleaner, bleach clothing detergent, dye transfer inhibitor during washing, etc. .
Examples of the object include stains and stains on the surface of clothes, tableware, ceramics, glass, plastics, dentures, mold, pulp, dye drainage, dyes and fungi oozing out in the washing bath. There are no particular restrictions, and the types of stains include those derived from curry, wine, fruit juice, tomato ketchup, sauce, soy sauce, blood, grass juice, tea, coffee, etc. In particular, it has a high bleaching effect on stains that easily cause dyes such as curry.

[Sterilization and disinfectant cleaning composition]
The disinfecting / sterilizing detergent composition of the present invention contains the above-described oxidation catalyst and an oxidation reaction component that produces at least a bleaching effect by an oxidation reaction, and further contains a solvent such as water and an optional component. You may go out. In addition, it is preferable that the oxidation catalyst used for a disinfection and disinfection cleaning composition contains copper as a transition metal from the point of the disinfection and disinfection effect as mentioned above.
Specific examples of the oxidation reaction component can be appropriately selected from those exemplified above for the bleaching detergent composition. The sterilizing / sterilizing detergent composition may be liquid or solid, and the production method thereof is the same as the above-described method for producing a liquid or solid bleach detergent composition.

If the sterilization / sterilization cleaning composition is liquid, it can be sprayed or applied directly to the object, or used by immersing the object. Used after dissolving in solvent.
In that case, it is preferable to use so that the quantity of the transition metal in the oxidation catalyst in the liquid used (henceforth use liquid) may be 0.001-300 ppm, Furthermore, 0.005-30 ppm and It is preferable to be used. When the amount of the transition metal is within such a range, a high sterilization / bactericidal effect can be obtained, and decomposition of the oxidation reaction component can be suppressed.
On the other hand, the amount of the oxidation reaction component in the working solution is preferably 0.0001 to 20% by mass, more preferably 0.0005 to 5% by mass, as the hydrogen peroxide concentration. When the amount of the oxidation reaction component is within such a range, a high sterilization / sterilization effect can be obtained, and even when the sterilization / sterilization target is a delicate fiber or dye, the damage is suppressed. Can do.
In terms of mass ratio between the oxidation catalyst and the oxidation reaction component (in terms of hydrogen peroxide) in the sterilization / sterilization cleaning composition, oxidation catalyst: oxidation reaction component = 1: 1 to 10,000 is preferable, more preferably 1. : 5-200.

  As an optional component, for example, a surfactant, a lower alcohol having 5 or less carbon atoms (preferably ethanol), a fragrance, a pH adjuster, a pH buffer, etc. can do. The surfactant, fragrance, pH adjusting agent, and pH buffering agent can be appropriately selected from those exemplified above for the bleaching detergent composition. Among these optional components, a pH adjusting agent and a pH buffering agent are blended in the disinfecting / sterilizing detergent composition so that the pH of the used solution is 1 to 12, preferably 8 to 11. It is preferable to add a pH buffering agent, particularly preferably.

  The disinfecting / sterilizing detergent composition of the present invention can be used in a wide range of applications for various hard surfaces and clothing, like the bleach detergent composition.

  According to the oxidation catalyst described above, since the oxidation promotion effect is excellent, a high bleaching effect, sterilization / sterilization effect can be obtained by using it together with an oxidation reaction component in a bleach detergent composition or a sterilization / sterilization detergent composition. Can be expressed. In addition, since this oxidation catalyst exhibits a high effect even under relatively low temperature conditions, it can be used for selecting use conditions, and a state in which a complex is formed as in the form (iii) described above. The stability at is also good. Furthermore, since this oxidation catalyst is easy to manufacture, it has the advantage of being industrially advantageous. That is, if it is an oxidation catalyst of the form (i) described above, it is only necessary to mix the compound (1) and the transition metal ion source, and if it is an oxidation catalyst of the form (ii) described above, the compound By simply putting (1) and the transition metal ion source into a solvent such as water, at least a part of them forms a complex and exhibits a high effect. Further, even when the oxidation catalyst of the form (iii) is produced in advance, a complicated process is not necessary for the production, the reaction time is relatively short, and the complex can be obtained in a high yield.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this Example at all. “%” Means “% by mass” unless otherwise specified.

(Synthesis Example 1) Synthesis of copper complex In 20 ml of ion-exchanged water, a compound represented by the above formula (3), that is, 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt (manufactured by Nippon Shokubai Co., Ltd., 1.5 g of purity (about 80%) and 0.84 g of copper (II) sulfate pentahydrate (manufactured by Kanto Chemical Co., Ltd.), which is a transition metal ion source, are added and stirred at room temperature for 10 minutes to react. It was. Thereafter, water was distilled off from the reaction solution at 150 ° C. under reduced pressure, whereby a copper complex (oxidation catalyst) in which an anion generated from 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt was coordinated to copper. ) And sodium sulfate (by-product salt) was obtained.
In this case, the usage-amount of the compound shown by the said Formula (3) with respect to a transition metal ion source is 1 molar equivalent (equal molar equivalent).

(Synthesis Example 2) Synthesis of Manganese Complex Except for using 0.82 g of manganese (II) sulfate pentahydrate (manufactured by Kanto Chemical Co., Inc.) instead of 0.84 g of copper (II) sulfate pentahydrate. In the same manner as in Synthesis Example 1, a manganese complex (oxidation catalyst) in which an anion produced from 3-hydroxy-2,2′-iminodisuccinic acid tetrasodium salt is coordinated to manganese and sodium sulfate (by-product salt) are included. A mixture was obtained.
In this case, the usage-amount of the compound shown by the said Formula (3) with respect to a transition metal ion source is 1 molar equivalent.

  From these synthesis examples 1 and 2, it was shown that the oxidation catalyst of each synthesis example can be produced in a high yield by a simple and short process.

(Example 1)
Sodium percarbonate (2Na ₂ CO ₃ .3H ₂ O ₂ , Mitsubishi Gas Chemical Co., Ltd. SPC-Z), sodium carbonate (Asahi Glass Co., Ltd. soda ash), and copper obtained in Synthesis Example (1) A mixture containing the complex and sodium sulfate was added to ion-exchanged water to prepare a liquid test solution. Sodium percarbonate and sodium carbonate are blended so that both are 2500 ppm in the test solution, and the mixture is prepared so that the concentration of the copper complex contained therein is 12 ppm in the test solution (the amount of copper is 2 0.1 ppm).
Immediately after the preparation of the test solution, curcumin, which is one of the coloring components of curry, was added to this so as to be 37 ppm, and the decomposition rate of curcumin after 60 minutes was determined as an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. It calculated | required from the light absorbency measured in MultiSpec-1500. The decomposition rate can be obtained by the following formula.
Degradation rate (%) = [absorbance of test liquid immediately after addition of curcumin (480 nm) −absorbance of test liquid 60 minutes after addition of curcumin (480 nm)] × 100 / absorbance of test liquid immediately after addition of curcumin (480 nm)

(Example 2)
Instead of the mixture obtained in Synthesis Example (1), the decomposition rate of curcumin was determined in the same manner as in Example 1 except that the mixture containing the manganese complex obtained in Synthesis Example (2) and sodium sulfate was used. Asked. The manganese complex concentration was 12 ppm in the test solution (1.8 ppm as the amount of manganese).

(Comparative Example 1)
The decomposition rate of curcumin was determined in the same manner as in Example 1 except that the mixture obtained in Synthesis Example (1) was not blended with the test solution.

(Comparative Example 2)
Instead of the mixture obtained in Synthesis Example (1), the decomposition rate of curcumin was determined in the same manner as in Example 1 except that 12 ppm of the compound of formula (3) was added to the test solution.

  The results of Examples 1-2 and Comparative Examples 1-2 are shown in the graph of FIG.

(Example 3)
Sodium percarbonate (SPC-Z manufactured by Mitsubishi Gas Chemical Co., Inc.), sodium carbonate (soda ash manufactured by Asahi Glass Co., Ltd.), and a mixture containing the manganese complex and sodium sulfate obtained in Synthesis Example (2) were ionized. In addition to the exchange water, a liquid test solution was prepared. Sodium percarbonate and sodium carbonate were blended so that both were 2500 ppm in the test solution, and the mixture was adjusted so that the concentration of manganese complex contained therein was 6 ppm in the test solution (the amount of manganese was 0). .91 ppm).
Immediately after the preparation of the test solution, purpurogallin, which is one of the coloring components of black tea, was added to 110 ppm, and the degradation rate of purpurogallin after 120 minutes was determined in the same manner as in Example 1.

(Comparative Example 3)
The decomposition rate of curcumin was determined in the same manner as in Example 3 except that the mixture obtained in Synthesis Example (2) was not blended in the test solution.

(Comparative Example 4)
Instead of the mixture obtained in Synthesis Example (2), the decomposition rate of curcumin was determined in the same manner as in Example 3 except that 6 ppm of the compound of formula (3) was added to the test solution.

  The results of Example 3 and Comparative Examples 3 to 4 are shown in the graph of FIG.

Example 4
Sodium percarbonate (SPC-Z manufactured by Mitsubishi Gas Chemical Co., Inc.), sodium carbonate (soda ash manufactured by Asahi Glass Co., Ltd.), and a mixture containing the copper complex and sodium sulfate obtained in Synthesis Example (1) were ionized. In addition to the exchange water, a liquid test solution was prepared. Sodium percarbonate and sodium carbonate are blended so that both are 2500 ppm in the test solution, and the mixture is prepared so that the concentration of the copper complex contained therein is 6 ppm in the test solution (the amount of copper is 1). 0.0 ppm).
Immediately after the preparation of the test solution, a curry-stained cloth (2 × 2 cm) prepared by the method described in JP-A-2004-331816 was soaked at 25 ° C. for 60 minutes. After 60 minutes, it was washed with water and dried. The bleaching rate was calculated | required using the following formula from the measurement of the reflectance of cloth. The reflectance before and after bleaching was measured with a color difference meter CR-300 (trade name) manufactured by Minolta.

Bleaching rate = 100 × (C−B) / (A−B)
A: Reflectance of test cloth before stain contamination B: Reflectance of stain contamination test cloth C: Reflectivity of test cloth after bleaching test

(Example 5)
The bleaching rate was determined in the same manner as in Example 4 except that instead of the mixture obtained in Synthesis Example (1), a mixture containing the manganese complex obtained in Synthesis Example (2) and sodium sulfate was used. .

(Comparative Example 5)
The bleaching rate was determined in the same manner as in Example 4 except that the mixture obtained in Synthesis Example (1) was not added to the test solution.

(Comparative Example 6)
The bleaching rate was determined in the same manner as in Example 4 except that 6 ppm of the compound of the above formula (3) was added to the test solution instead of the mixture obtained in Synthesis Example (1).

  The results of Examples 4 to 5 and Comparative Examples 5 to 6 are shown in the graph of FIG.

  As is clear from the results shown in FIGS. 1 to 3, by using a manganese complex and a copper complex in which the compound of the above formula (3) is coordinated as a ligand as an oxidation catalyst, A high bleaching effect (coloring component decomposition effect) was obtained.

(Example 6)
A commercially available detergent Blue Diamond (manufactured by Lion Corporation, containing sodium percarbonate) and a mixture containing the copper complex obtained in Synthesis Example (1) and sodium sulfate are added to ion-exchanged water, and 9.9 mL of a liquid test solution Was prepared. In addition, a commercially available detergent is blended so as to be 667 ppm in the test solution (20 ppm as sodium percarbonate), and the mixture is adjusted so that the concentration of the copper complex contained therein is 0.3 ppm in the test solution (amount of copper). As 0.05 ppm).
0.1 mL of Staphylococcus aureus mother liquid (IFO12732) adjusted so that the number of bacteria was 10 ⁸ / mL was added to the test solution, and the mixture was stirred uniformly. Ten minutes later, 1 mL was collected and added to 9 mL of SCDLP medium (Soybean-Casein Digest Broth With Lectin & Polysorbate 80: Wako Pure Chemical Industries, Ltd.) to give a 10-fold dilution. The operation of further diluting the obtained diluted solution 10 times was repeated 4 times to obtain 10 times to 100,000 times dilution. 1.0 mL was collected from each of these dilutions in a petri dish, added with 15 mL of SCDLP agar medium (Soybean-Casein Digest Age with Lectin & Polysorbate 80: Wako Pure Chemical Industries, Ltd.) and homogenized at 37 ° C. for 2 days. After culturing, those in the range of 70 to 300 colonies were selected and the number of colonies was counted to determine the number of viable bacteria.

(Comparative Example 7)
The number of viable bacteria was determined in the same manner as in Example 6 except that ion-exchanged water was used instead of the test solution.

(Comparative Example 8)
The number of viable bacteria was determined in the same manner as in Example 6 except that the mixture obtained in Synthesis Example (1) was not added to the test solution.

(Comparative Example 9)
Instead of the mixture obtained in Synthesis Example (1), the number of viable bacteria was determined in the same manner as in Example 6 except that 0.3 ppm of the compound of formula (3) was added to the test solution.

(Example 7, Comparative Examples 10-12)
Except for using Escherichia coli mother liquor (IFO 3972) instead of S. aureus mother liquor (IFO12732), Example 7 is similar to Example 6, Comparative Example 10 is similar to Comparative Example 7, and Comparative Example 11 is Comparative Example 8. In the same manner as in Comparative Example 12, the number of viable bacteria was determined in the same manner as in Comparative Example 9.

  The results of Example 6 and Comparative Examples 7-9 are shown in FIG. 4, and the results of Example 7 and Comparative Examples 10-12 are shown in FIG.

  As is apparent from the results shown in FIGS. 4 and 5, by using a manganese complex and a copper complex in which the compound of the above formula (3) is coordinated as a ligand as an oxidation catalyst, High sterilization and bactericidal effects were obtained.

It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example. It is a graph which shows the result of an Example and a comparative example.

Claims (10)

An oxidation catalyst comprising: a compound represented by the following general formula (1) and / or an anion generated from the compound; and a transition metal.

(In the formula, A represents an imino group or an oxygen atom, and X ^{1 to} X ⁴ may be the same or different and are each selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, and a cationic ammonium group. 1 type is represented, R represents a hydrogen atom or a hydroxyl group, and n is 0 or 1.)   The oxidation catalyst according to claim 1, wherein A is an imino group.   The oxidation catalyst according to claim 1 or 2, wherein the R is a hydroxyl group.   The oxidation catalyst according to any one of claims 1 to 3, wherein the transition metal contains manganese and / or copper.   The oxidation catalyst according to claim 1, wherein at least a part of the anion is coordinated to at least a part of the transition metal to form a complex. A method for producing an oxidation catalyst according to claim 5,
A reaction step of mixing and reacting a transition metal ion source that generates ions of the transition metal and the compound represented by the general formula (1) in a solvent;
The manufacturing method of the oxidation catalyst characterized by having the collection | recovery process of distilling off the said solvent from the reaction liquid obtained at this reaction process, and collect | recovering the oxidation catalyst and byproduct salt which were produced | generated by the said reaction.   The method for producing an oxidation catalyst according to claim 6, wherein the solvent is at least one polar solvent selected from the group consisting of water, ethanol, and methanol.   A bleaching detergent composition comprising the oxidation catalyst according to any one of claims 1 to 5 and an oxidation reaction component.   A disinfecting / sterilizing detergent composition comprising the oxidation catalyst according to any one of claims 1 to 5 and an oxidation reaction component.   The disinfecting / sterilizing detergent composition according to claim 9, wherein the transition metal is copper.

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