JP2006199940A - Bleach activation catalyst and bleach composition - Google Patents

Abstract

The present invention provides a bleach activation catalyst that increases the bleaching activity of a peroxy compound at a low temperature, is easy to produce and does not damage an object to be bleached, and a bleaching agent composition containing the bleach activation catalyst.
A bleach-activating catalyst comprising a ligand represented by the following structural formula (1) and the like and a metal salt.
Embedded image

In the structural formula (1), X represents a substituent selected from a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, and an alkyl group including a quaternary ammonium group.
A and B may be the same as or different from each other, and each represents a substituent having at least one heteroatom.
Note that p represents an integer of 1 or 2, and when p is 2, X may be the same or different. j and k each represents an integer of 0 or 1.
[Selection figure] None

Description

  The present invention is intended for bleaching stains, washing, mold remover, pulp bleaching, dyeing wastewater treatment, dye transfer during washing on clothes, tableware, earthenware, glass, plastic, dentures and other hard surfaces. The present invention relates to a bleach activation catalyst for peroxy compounds that can be widely used for prevention, sterilization of clothing, hard surfaces, and the like, and a bleaching composition containing the bleach activation catalyst.

Conventionally, peroxy compounds, such as hydrogen peroxide or inorganic persalts that liberate hydrogen peroxide in aqueous solution or have peracid bonds, have been widely used as active ingredients in bleaching compositions. .
Since the peroxy compound has a relatively low bleaching effect at low temperatures, various proposals have been made to obtain a sufficient bleaching effect at low temperatures. For example, a method for improving the bleaching power of a peroxy compound by using an organic peracid precursor having a bleaching activation ability or a metal complex in combination has been proposed.

However, the organic peracid precursor exhibits a bleaching effect by reacting with hydrogen peroxide in a bleaching solution to produce an organic peracid. In terms of the impact on the surface and the environment, it is not satisfactory.
The metal complex may be a combination of a cyclic, linear or branched polyamine ligand such as 1,4,7-trimethyl-1,4,7-triazacyclononane and manganese. Catalysts have been proposed but are not satisfactory in terms of performance and stability. Moreover, since it has a complicated amine structure as a central skeleton, there exists a problem that manufacture is not easy. Furthermore, in the process of bleaching, free manganese may be released due to its own stability, which may damage bleaching objects such as fibers.

Among these problems, for the purpose of preventing fiber damage, a bleaching agent composition (see Patent Document 1) combining a bleach activation catalyst and a clay mineral, or a bleach activation catalyst and a crystalline layered silicate. A combined bleaching composition (see Patent Document 2) has been proposed.
However, these bleaching compositions can prevent fiber damage, but did not consider the point of improving bleaching power. In particular, when clay minerals are combined, the bleaching power may be reduced.

On the other hand, as the metal complex, in addition to the catalyst based on the combination of the polyamine ligand and manganese, as a combination of various ligands and transition metals, for example, EDTA, NTA, pyridinecarboxylic acid and the like are usually used. A combination of a chelating agent and a transition metal such as Co or Cu has been proposed (see Patent Documents 3 to 5). However, although this proposal catalyzes the decomposition of peroxy compounds, there is a problem that it does not contribute much to the activation of bleaching itself.
Further, a manganese complex having hydroxycarboxylic acid as a ligand (see Patent Documents 6 and 7), a manganese complex having a polyhydroxy compound as a ligand (see Patent Document 8), iron having a porphyrin or phthalocyanine as a ligand. Or manganese complex (see Patent Documents 9 to 13), manganese complex having cyclic polyamine as ligand (see Patent Documents 14 to 19), manganese having Schiff base synthesized from salicylaldehyde and polyvalent amine as ligand Complexes (see Patent Document 20) and copper complexes having a substituted diamine as a ligand (see Patent Document 21) have also been proposed. However, none of these proposals satisfy the improvement of the bleaching performance, the stability of the complex, and the ease of production. In particular, the production requires a complicated process and a long reaction time, and has a problem that the yield is low.

  Therefore, a bleach activation catalyst that increases the bleaching activity of peroxy compounds at low temperatures, is easy to produce, and does not cause damage to the bleaching object has not yet been provided, and further improvement is desired. Currently.

Japanese Patent Laid-Open No. 9-25499 JP-A-9-137196 US Pat. No. 3,156,654 US Pat. No. 3,532,634 Specification for UK 984,459 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 Examined 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

An object of the present invention is to solve the above-described problems and achieve the following objects.
That is, the present invention provides a bleach activation catalyst that increases the bleaching activity of a peroxy compound at a low temperature, is easy to produce and does not damage the bleaching object, and a bleaching composition containing the bleach activation catalyst. The purpose is to do.

  In order to solve the above-mentioned problems, as a result of repeated studies by the present inventors, a bleaching activation catalyst containing a ligand having a specific structure and a metal salt is used, and if necessary, an inorganic porous material The present inventors have found that the above-mentioned problems can be solved by using at least one of inorganic layered compounds and inorganic layered compounds, and have completed the present invention.

This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is,
<1> A bleaching activation catalyst comprising a ligand represented by any one of the following structural formulas (1), (2), and (3) and a metal salt.
In the structural formula (1), X represents a substituent selected from a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, and an alkyl group including a quaternary ammonium group.
A and B may be the same as or different from each other, and each represents a substituent having at least one heteroatom.
Note that p represents an integer of 1 or 2, and when p is 2, X may be the same or different. j and k each represents an integer of 0 or 1.
In the structural formula (2), R ₁ represents a hydrocarbon group which may have a hetero atom.
In addition, l and m represent the integer of 0 or 1, and A and B represent the same meaning as structural formula (1).
In the structural formula (3), R ₂ represents a hydrocarbon group which may have a hetero atom.
In addition, n and o represent the integer of 0-2, A and B represent the same meaning as Structural formula (1).
<2> The bleaching activation catalyst according to <1>, wherein A and B are represented by any one of the following structural formulas (4) to (14).
However, expressed in the structural formula _{(4) ~ (9),} R 3 ~R 10 is hydrogen atom, or a hydrocarbon group which may have a hetero atom.
However, in the structural formulas (10) and (11), R ₁₁ and R ₁₂ represent a hydrogen atom, a hydrocarbon group which may have a hetero atom, or a salt-forming cation.
However, in the structural formulas (12) to (14), R _{13 to} R ₁₆ represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group that may have a hetero atom.
<3> The bleach activation catalyst according to <1>, wherein the ligand is represented by the following structural formula (15).
However, in the structural formula (15), A ′ represents a substituent selected from any of a hydrogen atom, a hydroxyl group, an alkyl group, and an alkyloxy group.
X and p have the same meaning as in structural formula (1).
<4> The bleach activation catalyst according to any one of <1> to <3>, which contains at least one of an inorganic porous material and an inorganic layered compound.
<5> A bleach composition comprising at least the bleach activating catalyst according to any one of <1> to <4> and a peroxy compound.
<6> The bleach composition according to <5>, which is used as a detergent.

In the bleach activation catalyst of the present invention, the metal salt contains a ligand having the specific structure, and if necessary, contains at least one of an inorganic porous body and an inorganic layered compound. When used as a bleaching composition in combination with a peroxy compound, the bleaching activity of the peroxy compound at a low temperature can be improved while suppressing damage to the bleaching target such as fibers. Moreover, if it is a ligand which has the said specific structure, since a structure is not complicated, it can manufacture easily. In particular, when the ligand represented by the structural formula (15) is contained, it can be produced in a high yield by a short time reaction without requiring a complicated process.
In the bleaching composition of the present invention, the bleaching activation catalyst of the present invention is combined with the peroxy compound, so that the bleaching activity of the peroxy compound at low temperatures is increased, the production is easy, and damage to the bleaching object is prevented. be able to.

  According to the present invention, there are provided a bleach activation catalyst that increases the bleaching activity of a peroxy compound at a low temperature, is easy to manufacture, and does not damage a bleaching object, and a bleaching composition containing the bleach activation catalyst. be able to.

(Bleaching activation catalyst)
The bleaching activation catalyst of the present invention contains a ligand having a specific structure and a metal salt, and contains at least one of an inorganic porous material and an inorganic layered compound as necessary.

-Ligand-
The ligand is represented by any of the following structural formulas (1), (2), and (3).

In the structural formula (1), X represents a substituent selected from a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, and an alkyl group including a quaternary ammonium group.
A and B may be the same as or different from each other, and each represents a substituent having at least one heteroatom.
Note that p represents an integer of 1 or 2, and is preferably 1. When p is 2, X may be the same or different. J and k each represents an integer of 0 or 1, and is preferably 0.

In the structural formula (2), R ₁ represents a hydrocarbon group which may have a hetero atom.
Note that l and m each represents an integer of 0 or 1, and is preferably 0. A and B represent the same meaning as in the structural formula (1).

In the structural formula (3), R ₂ represents a hydrocarbon group which may have a hetero atom.
In addition, n and o represent an integer of 0 to 2, and it is preferable that one is 1 and the other is 0. A and B represent the same meaning as in the structural formula (1).

--Substituent having a hetero atom--
There is no restriction | limiting in particular as a substituent which has the said hetero atom, Although it can select suitably according to the objective, For example, a hydroxyl group, an amino group, an isocyano group, a carboxyl group, a Schiff group etc. are mentioned.
Specific examples of A and B in the structural formulas (1) to (3), which are substituents having one or more heteroatoms, include, for example, at least one of the following structural formulas (4) to (14) Preferred examples include substituents represented.

However, expressed in the structural formula _{(4) ~ (9),} R 3 ~R 10 is hydrogen atom, or a hydrocarbon group which may have a hetero atom.

However, in the structural formulas (10) and (11), R ₁₁ and R ₁₂ represent a hydrogen atom, a hydrocarbon group which may have a hetero atom, or a salt-forming cation.

However, in the structural formulas (12) to (14), R _{13 to} R ₁₆ represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group that may have a hetero atom.

--Specific examples of structural formulas (1) to (3)-
The ligand represented by the structural formulas (1) to (3) is not particularly limited as long as it can be represented by these structural formulas, and can be appropriately selected depending on the purpose. A ligand represented by the structural formula shown in FIG.

  Moreover, as said ligand, what is represented by following Structural formula (15) from a viewpoint of being a high yield etc. is mentioned more suitably.

However, in the structural formula (15), A ′ represents a substituent selected from a hydrogen atom, a hydroxyl group, an alkyl group, and an alkyloxy group, and is preferably a hydroxyl group. X and p represent the same meaning as in the structural formula (1).

  The ligand represented by the structural formula (15) is not particularly limited as long as it can be represented by these structural formulas, and can be appropriately selected depending on the purpose. For example, the structural formula shown below A ligand represented by

-Metal salt-
The metal salt is not particularly limited as long as it is a metal compound capable of releasing a metal ion in an aqueous solution and forming a complex structure composed of the ligand, and can be appropriately selected according to the purpose. Examples thereof include water-soluble salts and organic solvent-soluble salts.
Examples of the water-soluble salt include nitrates, sulfates, halides, acetates, perchlorates, phosphates, tetrafluorophosphates, and the like.
There is no restriction | limiting in particular as a metal atom in the said metal salt, Although it can select suitably according to the objective, For example, manganese, copper, cobalt, iron, zinc, etc. are preferable.

The metal salt is added as a metal source of a metal complex coordinated with the ligand. In the bleaching activation catalyst of the present invention, the ligand and the metal salt may be added as separate compounds, or may be added in a complexed form in advance.
The counter ion of the metal complex may be derived from a metal compound or may be counter ion exchanged, and can be appropriately selected according to the purpose. Suitable counter ions include, for example, Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , NCS ⁻ , PF ₆ ⁻ , OAc ⁻ , BPh ₄ ⁻ , CF ₃ SO ₃ ⁻ , RSO ₃ ⁻ , RSO ₄ ^{— and the} like can be mentioned. Here, as R, a C1-C3 alkyl group is mentioned, for example.
In addition to the ligand, water, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxylic acid group, a thiol group, a halogen atom, and the like may be coordinated with the metal complex.
The metal complex may be mononuclear or polynuclear, and examples of the crosslinking species in the case of taking a polynuclear form include, for example, oxygen, sulfur, halogen atoms, acetate, butyrate, alkoxide, thiolate, amide, Examples include thiol, peroxide, and hydroxyl group.

The content of the metal salt is preferably added so as to be 0.005 to 300 ppm as a metal in the bleaching bath of the metal complex, and more preferably 0.05 to 30 ppm. If the metal content is less than 0.005 ppm, the bleaching effect may not be sufficiently improved, and if it exceeds 300 ppm, decomposition of hydrogen peroxide may be promoted and the bleaching effect may be reduced.
When the metal salt and the ligand are added separately, the amount of the ligand is preferably 1 to 30 mole equivalents relative to the metal amount, and 1 to 5 mole equivalents are preferably added. More preferred.

The complex in the case where the metal salt and the ligand are previously complexed may be a known complex or a novel complex.
The method for forming the complex is not particularly limited and may be appropriately selected. For example, (1) a complex obtained by mixing a metal salt and a ligand in water or an organic solvent and concentrating with an evaporator. (2) After mixing a metal perchlorate and a ligand in water, a peroxy compound is added, and the resulting precipitate is added. A method of forming a complex by recrystallization (see Masatatsu Suzuki et.al., Chem. Lett., 1988, 477), (3) a metal salt and a ligand are reacted, oxidized with an oxidizing agent, then alkali A method of forming a complex by oxidizing with oxygen under conditions (see JP-A-7-8801), (4) obtained by mixing a ligand and potassium permanganate in an organic solvent. Such methods which was filtered off to form a complex precipitation is preferably exemplified.

-Inorganic porous material-
The inorganic porous material is, for example, oxide particles such as silicon, aluminum, titanium, calcium, magnesium, zinc, and phosphorus, or a composite of two or more of these metal oxides, and has fine pores on the particle surface. It can be used with a catalyst supported.
Examples of the commercially available inorganic porous material include Mizuka Life manufactured by Mizusawa Chemical Co., Ltd. and Sunsphere manufactured by Asahi Glass Co., Ltd. In addition to commercially available products, a meso-type synthesized using a surfactant or a polymer as a template. A porous body or the like is also suitable.
There is no restriction | limiting in particular as a manufacturing method of the said inorganic porous body, According to the objective, it can select suitably, For example, a sol-gel method, a gaseous-phase method, a spray pyrolysis method, a hydrothermal method etc. are mentioned.
The pore diameter of the inorganic porous body is not particularly limited and may be appropriately selected according to the appropriate matter. When determined by the BET method, it is preferably 0.0005 to 1 μm, More preferably, it is 0.5 μm. If the pore diameter is less than 0.0005 μm, catalyst molecules may not enter the pores, and if it exceeds 1 μm, a sufficient supporting effect may not be obtained.

-Inorganic layered compound-
The inorganic layered compound is, for example, a hydrous silicate containing a metal such as aluminum, iron, manganese, magnesium, calcium, potassium, sodium, etc., and is composed of an aggregate of fine crystal pieces and is used with a catalyst supported thereon. Say what you can.
There are many kinds of inorganic layered compounds depending on the arrangement of crystal pieces, the granularity, etc., and there is no particular limitation on using any of these, and it can be appropriately selected according to the purpose. , Smectites, mica, vermiculite, chlorite, pyrophyllite, talc, kaolin mineral, serpentine, sepiolite, allophane, hydrotalcite and the like. Among these, smectites and water-swellable mica are particularly preferable from the viewpoint of water swellability.

Examples of the smectites include montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, and stevensite.
Examples of the mica include sericite, illite, muscovite, and phlogopite.

  The smectites include natural products and synthetic products, and any of them can be suitably used.

Specific examples of the commercially available natural products include the following.
Containing montmorillonite, Toyshun Mining Co., Ltd. Wengel, Wenger HV, Wenger A, Wenger FW, Wenger 31, Wenger W-100, Kunimine Industry Co., Ltd. Kunipia G, Kunipia F, American Bond Co., Ltd. Western Bond And Yellowstone manufactured by Dresser Minerals.
Examples of the saponite-containing material include Vegum T, Begham HV, Begham F, and Begham K manufactured by Vanderville.
Examples of those containing hectorite include Hectorite AW manufactured by American Colloid Co., Hectabilite 200, Benton EW, and Macaloid manufactured by National Reed.

  Specific commercial products of the synthetic product include, for example, Smecton SA manufactured by Kunimine Kogyo Co., Ltd., Ionite H manufactured by Mizusawa Chemical Co., Ltd., SWN, SAN manufactured by Co-op Chemical Co., Ltd., and Laponite manufactured by Lapotelte Industry Co., Ltd. It is done.

  Specific examples of commercially available products of the mica include water-swellable mica, such as swellable synthetic mica ME manufactured by Corp Chemical Co., sodium tetrasilicon mica DP-DM manufactured by Topy Industries, Ltd., and the like. .

The particle size of the inorganic layered compound is not particularly limited, and those having an appropriately selected particle size may be used, but when determined with a light scattering particle size distribution meter, it is preferably 0.1 to 500 μm. 0.5 to 50 μm is more preferable, and it is particularly preferable that a fine crystal is formed with a particle diameter in this range or that it has colloidal properties. When the particle size is less than 0.1 μm, sufficient catalyst supporting force may not be obtained. When the particle size exceeds 500 μm, the uniform dispersion in the bleaching or washing bath is inconvenient and the bleaching effect decreases. Sometimes.
The content of the inorganic layered compound is preferably added so as to be 0.003 to 8% by mass in the bleaching bath, and more preferably 0.01 to 1%. If the blending amount is less than 0.0003% by mass, sufficient catalyst supporting force may not be obtained. If the blending amount exceeds 8% by mass, the fluidity of the solution is extremely lowered, which may affect the bleaching effect. is there.

-Application-
The bleach activation catalyst of the present invention improves the bleaching activity of the peroxy compound at a low temperature while suppressing damage to an object to be bleached such as a fiber when used as a bleach composition in combination with a peroxy compound. Can do. Moreover, if it is a ligand which has the said specific structure, since a structure is not complicated, it can manufacture easily. Therefore, especially for clothes, bleaching stains on hard surfaces such as tableware, ceramics, glass, plastics, dentures, mold removers, pulp bleaching, dyeing wastewater treatment, preventing dye migration during washing, It can be widely used as a bleach activation catalyst for peroxy compounds for sterilizing clothes, hard surfaces and the like.

(Bleach composition)
The bleaching agent composition of the present invention contains at least a bleach activating catalyst and a peroxy compound, and optionally contains other components such as a surfactant.

-Bleach activation catalyst-
The bleach activation catalyst of the present invention described above is used as the bleach activation catalyst.
The bleaching activation catalyst may be added separately from the metal salt and the ligand, or may be added after complexing them in advance.
In addition, in the case where it is supported on at least one of the inorganic porous body and the inorganic layered compound, the metal salt and the ligand, or those obtained by complexing them in advance are added separately from the inorganic porous body and the like. Alternatively, they may be supported on these inorganic porous bodies in advance. The method for supporting the inorganic porous material or the like is not particularly limited. For example, a clay mineral containing at least one of the inorganic porous material and the inorganic layered compound is swollen with water, and a metal salt and a ligand are added thereto. Alternatively, a method in which water is distilled off after addition of those previously complexed with these is preferably mentioned.
In addition, the said bleach activation catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.
The blending amount of the bleach activation catalyst is, for example, preferably 0.003 to 8% by mass, more preferably 0.01 to 1% by mass, based on the total amount of the bleaching composition. If the blending amount is less than 0.003% by mass, a sufficient bleaching effect may not be obtained, and if it exceeds 8% by mass, the fluidity of the solution is extremely lowered and the bleaching effect is affected. There is.

-Peroxy compounds-
Examples of the peroxy compound include (a) hydrogen peroxide, (b) an inorganic persalt that liberates hydrogen peroxide in an aqueous solution or has a peracid bond.
Examples of the inorganic persalt of the component (b) include alkali metal percarbonates, perborates, perphosphates, persilicates, persulfates and the like. Among these, hydrogen peroxide, sodium percarbonate, sodium perborate, potassium persulfate, and hydrates thereof are particularly preferable.

  0.01-20 mass% is preferable with respect to the bleaching agent whole quantity, and, as for the compounding quantity of the said peroxy compound, 0.1-5 mass% is more preferable. If it is less than 0.01% by mass, a sufficient bleaching effect may not be obtained, and if it exceeds 20% by mass, damage to fibers and dyes may be caused.

-Other ingredients-
In the bleaching composition of the present invention, as necessary, other components such as a surfactant, a peracid precursor, a builder, an enzyme, a fragrance, a fluorescent agent, a fiber damage preventing agent, an antifoaming agent and manganese. Metal ions, pH adjusters and the like can be used in combination.

--Surfactant--
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant, nonionic surfactant, amphoteric surfactant, cationic surfactant, etc. are mentioned.
Examples of the anionic surfactant include alkylbenzene sulfonic acid, alkyl sulfuric acid, alkyl polyethoxy ether sulfuric acid, alkyl phenyl ether sulfuric acid ester, paraffin sulfonic acid, α-olefin sulfonic acid, α-sulfocarboxylic acid, and esters thereof. Examples include water-soluble salts and soaps.
Examples of the nonionic surfactant include ethoxylated nonions (polyoxyalkyl ether, polyoxyalkylphenyl ether, etc.), sugar-based active agents (sugar ester, glucoside ester, methyl glucoside ester, ethyl glucoside ester, alkyl polyglucoxide). Etc.), amide type activators (alkyldiethanolamide, fatty acid N-alkylglucamide etc.) and the like.
Examples of the amphoteric surfactant include aminocarboxylates (alkylcarboxybetaines, alkylsulfoxybetaines, alkylamidopropylbetaines, alkylalaninates, etc.), imidazoline derivatives, alkylamine oxides, and the like.
Examples of the cationic surfactant include alkyltrimethylammonium salts and dialkyldimethylammonium salts.
The blending amount of the surfactant is preferably 0 to 40% by mass with respect to the total amount of the bleaching composition.

--Peracid precursor-
The peracid precursor is not particularly limited as long as it reacts with a peroxy compound to produce an organic peracid, and can be appropriately selected according to the purpose. For example, decanoyloxybenzoic acid, dodecanoyloxybenzene Examples thereof include sodium sulfonate, sodium nonanoyloxybenzene sulfonate, and the like.

--- Builder--
There is no restriction | limiting in particular as said builder, According to the objective, it can select suitably. For example, since the clay mineral has a function as a builder, it may be used alone or in combination with an inorganic builder or an organic builder.
Examples of the inorganic builder include aluminosilicates such as zeolite, alkali metal carbonates, hydrogen carbonates, borates, phosphates, polyphosphates, and tripolyphosphates.
Examples of the organic builder include polycarboxylic acids such as nitrilotriacetic acid, lactic acid, citric acid, glycolic acid, succinic acid, and polyacrylic acid.
The blending amount of the builder is preferably 2% by mass or less based on the total amount of the bleaching composition. In the organic builder, it is not preferable to use a large amount of an organic chelate builder such as nitrilotriacetic acid because it chelates the metal in the bleaching bath.

--Enzyme--
Examples of the enzyme include hydrolases, oxidoreductases, lyases, transferases, and isomerases from the viewpoint of enzyme reactivity, and any of them may be used. Among these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are particularly preferable, and these may be used alone or in combination of two or more.

--- Perfume ---
Examples of the fragrances include hydrocarbons, alcohols, ethers, oxides, aldehydes, ketones, acetals, ketals, phenols, phenol ethers, acids, acid amides, lactones, esters, nitromusks. , Pyridines, quinolines, synthetic fragrances, natural fragrances from animals or plants, blended fragrances of synthetic fragrances and natural fragrances, and the like. These may be used alone or in combination of two or more.
Examples of the hydrocarbons include aliphatic hydrocarbons, terpene hydrocarbons, and aromatic hydrocarbons.
Examples of the alcohols include aliphatic alcohols, terpene alcohols, and aromatic alcohols.
Examples of the ethers include aliphatic ethers and aromatic ethers.
Examples of the oxides include aliphatic oxides and terpene oxides.
Examples of the aldehydes include aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, and aromatic aldehydes.
Examples of the ketones include aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, non-benzene aromatic ketones, and aromatic ketones.
Examples of the acids include fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, and aromatic carboxylic acids.
Examples of the lactones include aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenated aromatic lactones, and aromatic lactones.
Examples of the esters include aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, and aromatic carboxylic acid esters.
Examples of the synthetic perfume include nitrogen-containing compounds such as pyrrole and indole.

--Fluorescent agent--
Examples of the fluorescent agent include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styrylphenyl). Examples thereof include naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, and bis- (triazinylaminostilbene) disulfonic acid derivatives.

--Fiber damage prevention agent--
Since the bleaching composition of the present invention itself has an effect of preventing fiber damage, it may not be particularly used, and other fiber damage preventing agents may be used in combination.
There is no restriction | limiting in particular as said fiber damage prevention agent, According to the objective, it can select suitably, For example, the polyphenol type compound, cellulose powder, etc. which have radical trap ability, such as methoxyphenol and hydroxybenzoic acid, are mentioned. Among these, cellulose powder is particularly preferable.

--- Antifoaming agent--
There is no restriction | limiting in particular as said antifoamer, According to the objective, it can select suitably, For example, a silicone, a silica type substance, etc. are mentioned suitably.

--PH adjuster--
Examples of the pH adjuster include alkaline substances and organic acid salts in the builder, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, sodium hydroxide, potassium hydroxide, and potassium dihydrogen phosphate. Examples thereof include alkali metal dihydrogen phosphate, sulfuric acid, hydrochloric acid and the like. These may be used alone or in combination of two or more.
The pH adjuster is preferably contained so that the pH at 25 ° C. in the bleaching bath is 1 to 10, and more preferably 8 to 10.

-Application-
The bleach composition of the present invention is a hard surface such as a mold remover, a strainer cleaner, a triangular corner cleaner, a kitchen bleach, a pipe clog remover, a toilet cleaner, an automatic dishwasher detergent, and a denture cleaner. It can be widely used as a washing bleach, a washing tub washing agent, a pulp bleaching agent, a dyeing waste water treatment agent, various bleaching agents for clothes, a dye transfer inhibitor during washing, a disinfectant for clothes and hard surfaces, and the like.
The bleaching object of the bleaching composition of the present invention is not particularly limited. For example, stains on clothes, stains on hard surfaces such as tableware, ceramics, glass, plastics, dentures, mold, pulp, dyeing waste water And dyes and fungi that ooze out in the washing bath. Examples of the stain include those derived from curry, wine, fruit juice, tomato ketchup, sauce, soy sauce, blood, grass juice, tea, and coffee.

  Hereinafter, although the Example of this invention is described, this invention is not limited to this Example at all.

[Experiment 1]
(Synthesis Example 1)
In 100 ml of methanol, 6.0 g (43.8 mmol) of salicylaldoxime as a ligand (see the following structural formula) and 2.9 g (14.6 mmol) of manganese (II) chloride tetrahydrate as a metal salt ) Was dissolved and 4.4 g (43.8 mmol) of triethylamine was slowly added with stirring. After stirring at room temperature for 10 minutes, the produced precipitate was filtered to obtain 5.3 g (yield 78.4%) of a salicylaldoxime manganese complex as a bleach activation catalyst.

(Synthesis Example 2)
In 50 ml of methanol, 1.6 g (11.7 mmol) of salicylaldoxime as a ligand and 1.0 g (5.9 mmol) of copper (II) chloride dihydrate as a metal salt are dissolved, and triethylamine is dissolved. 1.2 g (11.9 mmol) was added slowly with stirring. After stirring at room temperature for 10 minutes, the produced precipitate was filtered to obtain 1.8 g (yield 90.9%) of a copper complex of a complex salicylaldoxime as a bleach activation catalyst.

(Synthesis Example 3)
In 50 ml of methanol, 1.7 g (12.4 mmol) of salicylaldoxime as a ligand and 1.5 g (6.3 mmol) of cobalt (II) chloride hexahydrate as a metal salt are dissolved, and triethylamine is dissolved. 1.3 g (12.4 mmol) was added slowly with stirring. After stirring at room temperature for 10 minutes, the mixture was allowed to stand for 1 day, and the resulting precipitate was filtered to obtain 1.2 g (yield 62.3%) of a complex salicylaldoxime cobalt complex as a bleach activation catalyst. .

(Synthesis Example 4)
In 50 ml of methanol, 20.0 g (0.16 mol) of salicylaldehyde (see the following structural formula) and 15.26 g (0.20 mol) of a 40% by weight methylamine methanol solution were dissolved, and methanol was adjusted to a total volume of 100 ml. Was added to synthesize a ligand represented by the following structural formula.
30 ml was taken out from this, and 3.24 g (16.4 mmol) of manganese (II) chloride tetrahydrate as a metal salt dissolved in 20 ml of methanol was added. Further, 4.97 g (49.1 mmol) of triethylamine was slowly added with stirring, stirred for 10 minutes at room temperature, and then allowed to stand in a refrigerator for 3 days, and the resulting precipitate was filtered to obtain a bleach activation catalyst. Of manganese complex (5.42 g, yield 74.1%) was obtained.

(Synthesis Example 5)
The ligand shown in Synthesis Example 4 was synthesized in the same manner as in Synthesis Example 4.
From this, 30 ml was taken out, and 4.19 g (24.6 mmol) of copper (II) chloride dihydrate as a metal salt dissolved in 20 ml of methanol was added to obtain a brown precipitate. Further, 4.97 g (49.1 mmol) of triethylamine was slowly added with stirring, the mixture was stirred for 10 minutes at room temperature, then left in a refrigerator for 3 days, and the resulting green precipitate was filtered to activate bleaching. 7.28 g (yield 91.4%) of a copper complex as a catalyst was obtained.

(Synthesis Example 6)
The ligand shown in Synthesis Example 4 was synthesized in the same manner as in Synthesis Example 4.
30 ml was taken out of this, and 3.19 g (24.6 mmol) of anhydrous cobalt (II) chloride as a metal salt dissolved in 30 ml of methanol was added. Further, 4.97 g (49.1 mmol) of triethylamine was slowly added with stirring, stirred for 10 minutes at room temperature, then allowed to stand in a refrigerator for 5 days, and the resulting precipitate was filtered to obtain a bleach activation catalyst. As a result, 2.62 g (yield 33.4%) of the cobalt complex was obtained.

  From the above, it was found that the bleach-activated catalyst of the present invention can be produced in a high yield by a simple and short process.

[Experiment 2]
Example 1
-Preparation of bleaching solution-
From a bleach composition comprising 0.015 mmol / L of salicylaldoxime manganese complex as a bleach activation catalyst, 17.9 mmol / L of hydrogen peroxide as a peroxy compound, and 39.6 mmol / L of sodium carbonate, a pH of 10 at 25 ° C. 0.0 ml of bleach solution was prepared.

-Bleaching of test pieces-
In this bleaching solution, a curry-stained cloth (2 × 2 cm) prepared by the method described in JP-A-2004-331816 is immersed for 60 minutes at 25 ° C., then washed with water and dried to carry out a bleaching treatment. It was.

<Evaluation of bleaching rate>
The bleaching rate (%) was determined by the following mathematical formula (1) from the measurement of the reflectance before contamination, the reflectance after contamination, and the reflectance after bleaching of the test cloth.
<< Formula 1 >>
Bleaching rate (%) = 100 × (zy) / (xy)
However, in the said Numerical formula (1), x represents the reflectance of the test cloth before contamination. y represents the reflectance of the test cloth after contamination. z represents the reflectance of the test cloth after the bleaching treatment. In addition, the said reflectance was measured by Minolta Co., Ltd. product color-color difference meter CR-300. The results are shown in the graph of FIG.

(Example 2)
In Example 1, a bleaching solution was prepared in the same manner as in Example 1 except that a copper complex was added in place of the manganese complex of salicylaldoxime as a bleach activation catalyst. Then, the bleaching rate of the test cloth was evaluated. The results are shown in the graph of FIG.

(Example 3)
In Example 1, a bleaching solution was prepared in the same manner as in Example 1 except that a cobalt complex was added in place of the manganese complex of salicylaldoxime as a bleach activation catalyst. Then, the bleaching rate of the test cloth was evaluated. The results are shown in the graph of FIG.

Example 4
In Example 1, a bleaching solution was prepared in the same manner as in Example 1 except that an iron complex was added in place of the manganese complex of salicylaldoxime as a bleach activation catalyst. Then, the bleaching rate of the test cloth was evaluated. The results are shown in the graph of FIG.

(Example 5)
In Example 1, a bleaching solution was prepared in the same manner as in Example 1 except that a zinc complex was added instead of the manganese complex of salicylaldoxime as a bleach activation catalyst. Then, the bleaching rate of the test cloth was evaluated. The results are shown in the graph of FIG.

(Comparative Example 1)
In Example 1, a bleaching solution was prepared in the same manner except that the bleach activating catalyst was not added, and then the test piece was subjected to a bleaching treatment to evaluate the bleaching rate of the test cloth. The results are shown in the graphs of FIGS.

(Example 6)
Bleach composition of manganese complex 0.015 mmol / L of the ligand shown in Synthesis Example 4 as bleach activation catalyst, hydrogen peroxide 17.9 mmol / L as peroxy compound, and sodium carbonate 39.6 mmol / L Thus, 100 mL of a pH 10.0 bleach solution at 25 ° C. was prepared.
The test piece was bleached in the bleaching solution in the same manner as in Example 1, and the bleaching rate of the test cloth was evaluated. The results are shown in the graph of FIG.

(Example 7)
Salicylaldoxime 0.09 mmol / L as a ligand, manganese chloride tetrahydrate 0.03 mmol / L as a metal salt, hydrogen peroxide 17.9 mmol / L as a peroxy compound, and sodium carbonate 39.6 mmol / L 100 mL of a pH 10.0 bleach solution at 25 ° C. was prepared from the L bleach composition.
The test piece was bleached in the bleaching solution in the same manner as in Example 1, and the bleaching rate of the test cloth was evaluated. The results are shown in the graph of FIG.

As is apparent from the results of FIGS. 1 to 3, in Examples 1 to 7 using the bleaching agent composition to which the bleach activating catalyst of the present invention was added, Comparative Example 1 in which the bleach activating catalyst was not added. It was found that the bleaching rate was improved compared to
In addition, as apparent from the results of FIG. 3, the bleaching activation catalyst of the present invention improves the bleaching rate even when a ligand and a metal salt are added separately without forming a complex. I found out.

[Experiment 3]
(Example 8)
-Preparation of bleaching solution-
0.04 mmol / L of catechol as a ligand, 0.02 mmol / L of manganese chloride as a manganese salt (metal salt), and 0.005% by mass of smectite (Smecton SA manufactured by Kunimine Industries, Ltd.) as an inorganic layered compound Then, 100 ml of a bleaching solution having a pH of 10 at 25 ° C. comprising a bleaching composition containing hydrogen peroxide as a peroxy compound so as to be 30 mmol / L was prepared.

-Bleaching of test pieces-
In the bleaching solution, a cotton test cloth contaminated with curry and a cotton test cloth contaminated with red wine were immersed for 60 minutes at room temperature, washed with water and dried to carry out a bleaching treatment.

  About the said test piece, it carried out similarly to Example 1, and evaluated the bleaching rate. The results are shown in the graph of FIG. 4 for those contaminated with curry and in the graph of FIG. 5 for those contaminated with red wine.

(Reference Example 1)
In Example 8, a bleaching solution was prepared in the same manner except that the inorganic layered compound was not added, and then the test piece was bleached to evaluate the bleaching rate of the test cloth. The results are shown in the graph of FIG. 4 for those contaminated with curry and in the graph of FIG. 5 for those contaminated with red wine.

  As is clear from the results of FIG. 4 and FIG. 5, in Example 8 using the bleaching composition to which the inorganic layered compound was added, a reference example using the bleaching composition to which the inorganic layered compound was not added. It was found that the bleaching rate was improved as compared with 1.

[Experiment 4]
Example 9
-Preparation of bleaching solution-
0.04 mmol / L of salicylaldehyde as a ligand, 0.02 mmol / L of manganese chloride as a manganese salt (metal salt), and 0.005 mass of smectite (Kunimine Industry Co., Ltd. Kunipia G) as an inorganic layered compound %, 20 ml of a bleaching solution having a pH of 10 at 25 ° C. comprising a bleaching composition containing hydrogen peroxide as a peroxy compound so as to be 30 mmol / L.

-Measurement of absorbance-
In the bleaching solution, 0.2 mmol / L of pigment (orange II) was added as a model of colored stain, and after 120 minutes, the absorbance (abs) of the bleaching solution at 480 nm was measured using an absorptiometer.

(Example 10)
A bleaching solution was prepared in the same manner as in Example 9 except that the inorganic layered compound was replaced by smectite (Kunipia F manufactured by Kunimine Kogyo Co., Ltd.), the dye was added, and the absorbance was measured after 120 minutes.

(Reference Example 2)
In Example 9, a bleaching solution was prepared in the same manner except that the inorganic layered compound was not added, the dye was added, and the absorbance was measured after 120 minutes.

<Evaluation of dye residual ratio>
Based on the absorbance measured in Examples 9 and 10 and Reference Example 2, the dye residual ratio (%) with respect to Reference Example 2 of Examples 9 and 10 was determined by the following formula (2).
<< Formula 2 >>
Dye remaining rate (%) = α / β × 100
However, in said Numerical formula (2), (alpha) represents the light absorbency of an Example. β represents the absorbance of the reference example.
The results are shown in Table 1 and the graph of FIG. As is apparent from the results of FIG. 6, in Examples 9 and 10 using the bleaching composition to which the inorganic layered compound was added, Reference Example 2 using the bleaching composition to which the inorganic layered compound was not added. It was found that the dye residual ratio was less than 50% as compared to.

  The bleach activation catalyst of the present invention improves the bleaching activity of the peroxy compound at a low temperature while suppressing damage to the bleaching object such as fibers when used as a bleaching composition in combination with a peroxy compound. Can do. Moreover, if it is a ligand which has the said specific structure, since a structure is not complicated, it can manufacture easily. Therefore, especially for clothes, bleaching stains on hard surfaces such as tableware, pottery, glass, plastics, dentures, mold remover, pulp bleaching, dyeing wastewater treatment, preventing dye migration during washing, It can be widely used as a bleach activation catalyst for peroxy compounds for sterilizing clothes, hard surfaces and the like. In addition, the bleaching composition of the present invention includes a mold remover, a strainer cleaner, a triangular corner cleaner, a kitchen bleach, a pipe clog remover, a toilet cleaner, an automatic dishwasher detergent, a denture cleaner, and the like. Can be widely used as hard surface cleaning bleach, washing tub cleaning agent, pulp bleaching agent, dyeing waste water treatment agent, bleaching agent for various clothing, dye transfer prevention agent during washing, sterilizing agent for clothing and hard surface, etc. it can.

FIG. 1 is a graph showing the bleaching rates of Examples 1 to 5 and Comparative Example 1 for a cotton test cloth contaminated with curry. FIG. 2 is a graph showing the bleaching rate of the cotton test cloth contaminated with curry in Example 6 and Comparative Example 1. FIG. 3 is a graph showing the bleaching rate for the cotton test cloth contaminated with curry in Example 7 and Comparative Example 1. FIG. 4 is a graph showing the bleaching rate for the cotton test cloth contaminated with curry in Example 8 and Reference Example 1. FIG. 5 is a graph showing the bleaching rate for a cotton test cloth contaminated with red wine. FIG. 6 is a graph showing the dye residual ratio of the dye with respect to the bleaching solution.

Claims (6)

A bleaching activation catalyst comprising a ligand represented by any one of the following structural formulas (1), (2), and (3) and a metal salt.
In the structural formula (1), X represents a substituent selected from a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, and an alkyl group including a quaternary ammonium group.
A and B may be the same as or different from each other, and each represents a substituent having at least one heteroatom.
Note that p represents an integer of 1 or 2, and when p is 2, X may be the same or different. j and k each represents an integer of 0 or 1.
In the structural formula (2), R ₁ represents a hydrocarbon group which may have a hetero atom.
In addition, l and m represent the integer of 0 or 1, and A and B represent the same meaning as structural formula (1).
In the structural formula (3), R ₂ represents a hydrocarbon group which may have a hetero atom.
In addition, n and o represent the integer of 0-2, A and B represent the same meaning as Structural formula (1). The bleaching activation catalyst according to claim 1, wherein A and B are represented by any one of the following structural formulas (4) to (14).
However, expressed in the structural formula _{(4) ~ (9),} R 3 ~R 10 is hydrogen atom, or a hydrocarbon group which may have a hetero atom.
However, in the structural formulas (10) and (11), R ₁₁ and R ₁₂ represent a hydrogen atom, a hydrocarbon group which may have a hetero atom, or a salt-forming cation.
However, in the structural formulas (12) to (14), R _{13 to} R ₁₆ represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group that may have a hetero atom. The bleach activation catalyst according to claim 1, wherein the ligand is represented by the following structural formula (15).
However, in the structural formula (15), A ′ represents a substituent selected from any of a hydrogen atom, a hydroxyl group, an alkyl group, and an alkyloxy group.
X and p have the same meaning as in structural formula (1).   The bleaching activation catalyst according to any one of claims 1 to 3, comprising at least one of an inorganic porous material and an inorganic layered compound.   A bleaching composition comprising at least the bleach activating catalyst according to claim 1 and a peroxy compound. The bleach composition according to claim 5, which is used as a detergent.