JPH11349991A - Bleaching composition containing alpha-alkoxy hydroperoxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a bleaching agent exhibiting excellent bleaching effect without using an organic peracid precursor together with the agent, having excellent storage stability and excellent usability under the condition from neutrality to weak acidity and being useful for various kinds of detergents by including a specific α-alkoxy hydroperoxide. SOLUTION: This bleaching composition is prepared by including (A) (e.g. >=0.01 wt.%) compound of the formula R<1> and R<2> are each H, a (substituted with formyl, OH, (hydro)peroxyl, or the like) 1-50C alkyl or alkenyl, a (substituted with 1-20C alkyl, an alkenyl, or the like) aryl; X is H, a 1-20C hydrocarbon moiety, a (substituted with a 1-20C hydrocarbon moiety) acyl, or the like; A is a 2-3C alkylene; (n) is 0-50} and optionally (B) a transition metal-containing compound in a quantity of 0.001-50 wt.% based on the content of constituent A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bleaching composition containing an α-alkoxy hydroperoxide.

[0002]

2. Description of the Related Art Bleaching agents include oxygen bleaching agents and chlorine bleaching agents. Chlorine bleach uses hypochlorite and has high bleaching performance, but there is a danger to the body and a unique odor,
Further, there is a problem that chlorine is generated when an acid coexists. Further, in the bleaching of clothing, the range of use is limited because the fibers are embrittled or the color and pattern are discolored.

[0003] As the oxygen-based bleach, inorganic persalts such as hydrogen peroxide and percarbonate are used, but these have weak bleaching power and cannot obtain a sufficient bleaching effect. Therefore, Japanese Patent Application Laid-Open
As disclosed in JP-A-216396, for these bleaching bases, a means of using a bleaching activator in combination is used. A bleach activator is a precursor that reacts with hydrogen peroxide or an inorganic persalt under alkaline conditions to generate an organic peracid having a higher bleaching effect.

[0004] However, these organic peracid precursors have a problem in storage stability. In particular, a bleaching activator dispersed as a liquid bleaching composition in a solution in which hydrogen peroxide coexists uses a stabilizing agent to suppress the reaction to hydrogen peroxide or the decomposition of the bleaching activator itself. It is difficult to ensure sufficient storage stability even after taking such measures.

Another problem is that the generated organic peracid is not sufficiently stable, and the decomposition proceeds before it acts on the substance to be bleached. Therefore, an excessive amount of the organic peracid is required to obtain the bleaching effect. In addition, when an organic peracid is generated, there is a problem that hydrolysis of the organic peracid precursor occurs competitively, and in order to obtain a required amount of the organic peracid, a further excess amount of hydrogen peroxide or the organic peracid precursor is required. You need to throw in your body.

In addition, a smooth reaction of organic peracid generation does not occur under alkaline conditions, and its use is limited to alkaline conditions.

Further, when an organic peracid is generated, by-products are eliminated from the bleach activator, which are unnecessary compounds that do not contribute to bleaching at all, and may reduce the bleaching activity.

Another problem is that when the bleaching activator is introduced into the bleaching solution, the state of dispersion of the bleaching activator in the solution becomes non-uniform, and the bleaching activator in the bleached material is high. In the case of coagulation at a concentration, there is a problem that generation of an organic peracid occurs locally at a high concentration and causes discoloration of a color pattern.

[0009]

An object of the present invention is to provide a sufficient bleaching effect even when a bleaching activator is not used,
It is still another object of the present invention to provide a bleaching composition using a completely novel bleaching base, which can be sufficiently used under neutral to weak acid conditions and has excellent storage stability.

[0010]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, a specific α-alkoxy hydroperoxide has a bleaching base which can solve the above-mentioned problems. And found that the present invention was completed.

That is, the present invention provides a bleaching composition containing an α-alkoxy hydroperoxide represented by the following general formula (I).

[0012]

[0013] ^{(wherein, R 1, R 2, X} , A and n .R ^1, R ² indicating the following structure represents one of the substituents selected from the following [a group], R ¹ and R ² may be the same or different or either.

[Group a]: hydrogen atom formyl group, hydroxyl group, hydroperoxyl group, peroxyl group, carbonyl group, carboxyl group,
Amino group, amide group, ester group, ether group, R ^1-
(AO) a linear or branched carbon atom having 1 or more carbon atoms which may be substituted with at least one group selected from _n -groups and aryl groups;
To 20 alkyl or alkenyl groups. An aryl group which may be substituted with a linear or branched C1-C50 alkyl, alkenyl or alkoxyl group;

X represents a substituent selected from the following [group b]. [Group b]:-hydrogen atom-straight-chain or branched-chain hydrocarbon group having 1 to 20 carbon atoms-straight-chain or branched-chain acyl group or amide optionally substituted by hydrocarbon having 1 to 20 carbon atoms Base.

A represents an alkylene group having 2 to 3 carbon atoms.
n shows the number of 0-50)

Further, the present invention provides the above bleaching composition containing 0.01% by weight or more (0.01 to 100% by weight) of the α-alkoxy hydroperoxide represented by the general formula (I). I do.

Further, the present invention provides a method for adding 0.001 to 50% by weight of a compound containing at least one transition metal to an α-alkoxy hydroperoxide represented by the general formula (I). A bleaching composition as described above is provided.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The α-alkoxy hydroperoxide represented by the general formula (I) in the present invention will be described in more detail.

In the general formula (I), the amino group for R ¹ and R ² is a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, a dimethylamino group, a diethylamino group, a dipropyl group. Examples include an amino group, a diisopropylamino group, a dibutylamino group, a trimethylamino group, a triethylamino group, a tripropylamino group, a triisopropylamino group, and a tributylamino group.

The amide group in R ¹ and R ² includes
Formamide group, acetamido group, propanamide group,
Pentanamide group, hexaneamide group, heptaneamide group, octanamido group, nonanamido group, decanamido group, dodecanamido group, tetradecanamido group, hexadecanamide group, octadecanamide group, eicosanamide group, N-methylformamide group, N -Methylacetamide group, N-methylpentanamide group, N-methylhexanamide group, N-methyloctaneamide group, N-methyldecaneamide group, N-methyldodecaneamide group, N
-Methyltetradecanamido group, N-methylhexadecanamido group, N-methyloctadecanamido group, N-methyleicosanamide group and the like.

Examples of the ester group for R ¹ and R ² include acetoxyl, propionyloxyl, butyryloxyl, isobutyryloxyl, valeryloxyl, isovaleryloxyl, pivaloyloxyl, lauroyloxyl, and myristoyl. Oxyl group,
Palmitoyloxyl group, stearoyloxyl group and the like can be mentioned.

The ether group represented by R ¹ and R ² is dimethyl ether group, diethyl ether group, dipropyl ether group, dibutyl ether group, dipentyl ether group, dihexyl ether group, dioctyl ether group, didecyl ether group, didodecyl ether. Group, ditetradecyl ether group, dihexadecyl ether group, dioctadecyl ether group, methyl ethyl ether group, methyl propyl ether group, methyl butyl ether group, methyl hexyl ether group, methyl octyl ether group,
Methyl decyl ether group, ethyl methyl ether group, ethyl propyl ether group, ethyl butyl ether group, ethyl hexyl ether group, ethyl octyl ether group,
And an ethyldecyl ether group.

The straight-chain or branched-chain alkyl group having 1 to 50 carbon atoms or the alkenyl group having 1 to 20 carbon atoms in R ¹ and R ² includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group,
Examples include an octadecyl group, an eicosyl group and an isostearyl group.

The linear or branched alkoxyl group having 1 to 20 carbon atoms in R ¹ and R ² includes methoxyl, ethoxyl, propoxyl, butoxyl, pentyloxyl, hexyloxyl and heptyloxyl. Octyloxyl, nonyloxyl, decyloxyl, undecyloxyl, dodecyloxyl, tridecyloxyl, tetradecyloxyl, hexadecyloxyl, octadecyloxyl, eicosyloxyl, isostearyloxyl, etc. No.

The aryl group represented by R ¹ and R ² includes a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group.

In the general formula (I), examples of the straight-chain or branched-chain hydrocarbon group having 1 to 20 carbon atoms in X include an alkyl group, an alkenyl group and an aryl group, such as a methyl group and an ethyl group. , Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples include tetradecyl, hexadecyl, octadecyl, eicosyl, isostearyl, phenyl, tolyl, xylyl, biphenyl, naphthyl, anthryl, phenanthryl and the like.

Examples of the acyl group for X include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group and an isovaleryl group.

Examples of the amide group in X include a formamide group, an acetamido group, a propanamide group, a pentanamido group, a hexaneamide group, a heptanamid group, an octanamido group, a nonanamido group, a decanamido group, a dodecanamido group, a tetradecanamido group, Hexadecaneamide group, octadecanamido group, eicosanamide group, N
-Methylformamide group, N-methylacetamido group,
N-methylpentanamide group, N-methylhexanamide group, N-methyloctaneamide group, N-methyldecaneamide group, N-methyldodecanamido group, N-methyltetradecanamido group, N-methylhexadecanamido group, N -Methyloctadecaneamide group, N-methyleicosanamide group and the like.

The α-alkoxy hydride represented by the general formula (I)
In dro peroxide, R¹ And R ^Two As bleached
From the viewpoint of producing an effective hydrophobic interaction with a substance, R¹ 
And R^Two One of them is a hydrogen atom or a methyl group and the other is
One is a hydrocarbon group having 4 to 12 carbon atoms or a phenyl group.
Preferably.

In particular, when a bleaching agent is used as an aqueous solution, X is preferably a hydrogen atom, a methyl group, or an acetyl group from the viewpoint of enhancing the water solubility, and n is a number of 2 to 14. preferable. In addition, in the α-alkoxy hydroperoxide represented by the general formula (I), the bleaching composition of the present invention can be bleached in either liquid or powder by appropriately changing the number of moles of alkylene oxide added, n. It can also be used as an agent.

In the present invention, α represented by the general formula (I)
As shown in the following reaction formula, the alkoxyhydroperoxide is a compound represented by the general formula (III) with respect to at least one mol selected from the compounds represented by the general formula (II). It can be produced by adding at least one or more selected from 0.1 to 2,000 mol, and then contacting with ozone-containing air or oxygen gas.

[0033]

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(Wherein, n, X, A, R ¹ and R ² are the same as described above, and R ³ and R ⁴ are any substituents selected from the above [Group A], —OR ⁵ , and —OR ⁵ . OCOR ⁶ , -COOR
_{^{7, -CN, -CH 2 CN,}} -CH 2 CF 3, -CH 2 F,
_{-CH 2 Br, -CH 2 Cl,} -CHSO 2 CH 3, -CH
Cl _2, shows a -CHF ₂ or -CCl ₃ groups. R ⁵ , R ⁶ and R ⁷ are a formyl group, a hydroxyl group, a carbonyl group,
A linear or branched C1-C20 alkyl, alkenyl, or aryl group which may be substituted with one or more groups selected from a carboxyl group, an amino group, an amide group, an ester group and an ether group. Represents a group. Note that R ³ and R
⁴ may be the same or different.

In the above production method, a solvent is not necessarily required for the reaction, but may be used. The solvent used here may be any solvent as long as it is inert to the raw materials and the reaction products. Such solvents include dichloromethane, chloroform, n-hexane, cyclohexane, benzene, toluene, xylene, diethyl ether, ethyl acetate, acetonitrile,
A solvent such as acetone can be used. A single substance or a mixture of these solvents is used in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, more preferably 1 to 1 part by weight of at least one compound selected from the compounds represented by formula (II). 0
Use up to 30 parts by weight.

In addition, one or more compounds selected from the compounds represented by the general formula (III) are used in an amount of 0.1 mol per mol of one or more compounds selected from the compounds represented by the general formula (II). ~ 20
00 mol, preferably 0.5 to 100 mol, more preferably 1 to 20 mol.

In the reaction, the ozone concentration in the mixed gas is set to 0.1.
01 to 10 vol%, preferably 0.05 to 7.0 vo
1%, more preferably 0.1 to 5.0 vol% of a mixed gas with oxygen or air,
° C, preferably -70 to 40 ° C, more preferably 0 to
Under a temperature condition of 25 ° C., for 1 to 200 minutes, preferably 5 minutes
The reaction is carried out for 100 minutes, more preferably 10 minutes to 60 minutes. The amount of ozone introduced is 0.1 to 20 per mol of at least one selected from the compounds represented by the general formula (II).
Mol, preferably 0.5 to 10 mol, more preferably 1.0 to 5.0 mol.

Next, the bleaching composition of the present invention containing the above α-alkoxy hydroperoxide as a bleaching base will be described. In the bleaching composition, it is preferable that the α-alkoxy hydroperoxide is incorporated in an amount of 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more. 0.01% by weight in the composition
If less than this, the bleaching effect is reduced.

The bleaching composition of the present invention has a sufficient bleaching effect even with the above-mentioned α-alkoxy hydroperoxide alone as a bleaching agent. By using in combination with bleach activator
Further, the bleaching power can be increased.

In the bleaching composition of the present invention, for example, a compound containing one or more transition metals can be used in combination.
The transition metal-containing compound includes a complex, a salt, a heteropoly acid, and the like, and 0.001 to 50% by weight, preferably 0.1 to 10% by weight based on the α-alkoxyhydroperoxide.
Preferably, it is added by weight.

The transition metal contained is specifically M
n, Fe, Cu, Ni, Co, Cr, V, Mo, W, T
i, Zn, Pd, Ru, Rh, Nb, Tc, Ag, C
d, Re, Os, Ir, Pt, Hg and the like.

Among the transition metal-containing compounds, the complex may be mononuclear, dinuclear or cluster. Examples of the ligand of the complex include ligands having a coordinating nitrogen atom to the central transition metal represented by the following general formulas (IV) to (VII).

[0043]

[Wherein Y ² is a nitrogen atom, a phosphorus atom or a C
And a group represented by (R ¹⁰ ). R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents hydrogen, an optionally substituted alkyl group, cycloalkyl group or aryl group. m1 represents an integer of 0 to 2, and m2 represents an integer of 0 to 2. Y ¹ and Y ³ may be the same or different, and each of the following general formulas (A) to (E)

Embedded image (In the formula, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents a hydrogen, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group. R ¹³ is hydrogen, optionally substituted alkyl, alkoxyl, halogen, cyano, NR ¹⁷ R ¹⁸ , N ＝ R ¹⁷ , N ⁺ R
¹⁷ R ¹⁸ R ^{19 represents} a pyridyl group, a pyridinium group, a sulfonic acid group, a thienyl group, a carboxylic acid group, or a hydroxyl group;
Here, R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen, a hydroxyl group, or an optionally substituted alkyl group, cycloalkyl group or aryl group. m3 represents a number of 0 to 4 and m4 represents a number of 2 to 7).

[0045]

Embedded image

[Wherein Y ⁵ is a group represented by the following general formula (F):
(I) and Y ⁷ are represented by the following general formulas (F) or (I), and Y ⁴ and Y ⁶ are represented by the following general formulas (J) to (O);

Embedded image R ^{20 to} R ²⁶ may be the same or different and each is hydrogen, an optionally substituted alkyl group,
A cycloalkyl group or an aryl group, R ²⁷ , R ²⁸ , R ³⁰ ,
R ³¹ and R ³² may be the same or different, and each is hydrogen, a hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group, R ²⁹ is
An optionally substituted alkoxyl group,
Halogen atom, cyano group, NR ³³ R ³⁴ , N = R ³³ , N ⁺
R ³³ R ³⁴ R ^{35 represents} a pyridyl group, a pyridinium group, a sulfonic acid group, a thienyl group, a carboxylic acid group, or a hydroxyl group, wherein R ³³ , R ³⁴ and R ³⁵ may be the same or different; A hydroxyl group, an optionally substituted alkyl group, a cycloalkyl group or an aryl group, m5 is 0 to 2, m6 is 0 to 2, m7 is 0 to 3, m8 is 0 to 3, m9 Is 0 or 1, m10 is 2
5, m11 is 0-4, m12 is 2-7, m13 is 0-7, m14
Represents a number from 0 to 7]

[0047]

[In the formula, R ³⁶ and R ³⁷ may be the same or different and each represents hydrogen or a hydrocarbon group which may be substituted, m 15 represents a number of 0 to 3, m 16 represents a number of 0 to 3,
3 represents a number, R ³⁸ represents a hydrocarbon group which may be substituted or an ether-containing hydrocarbon group, and Y ⁸ and Y ⁹ may be the same or different, and each has the following general formula (P)
~ (T)

Embedded image (Wherein R ³⁹ , R ⁴⁰ , R ⁴² , R ⁴³ and R ⁴⁴ may be the same or different and represent hydrogen, a hydroxyl group or a hydrocarbon group which may be substituted, and R ⁴¹ represents hydrogen or a substituted An optionally substituted hydrocarbon group, an optionally substituted hydrocarbon oxy group, a halogen atom, a cyano group, an amino group, a substituted amino group, an ammonium group, a substituted ammonium group, a heterocyclic group,
Represents an anionic group or a hydroxyl group, m17 represents a number of 1 to 4, and m18 represents a number of 2 to 7).

Specific structural examples of the ligand represented by the general formula (IV) are shown in the following (1) to (20).

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

Specific structural examples of the ligand represented by the general formula (V) or (VI) are shown in the following (21) to (30).

[0055]

Embedded image

[0056]

Embedded image

Specific structural examples of the ligand represented by the general formula (VII) are shown in the following (31) to (56).

[0058]

Embedded image

[0059]

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[0060]

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In addition to the ligands represented by the general formulas (IV) to (VII), sodium ethylenediaminetetraacetate (EDTA), polyol, gluconate, polyhydroxy compound, porphyrin, Phthalocyanine, water, a hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a thiol group, a halogen atom and the like may be coordinated. Further, as the crosslinking species of the polynuclear complex, oxygen,
Examples thereof include a sulfur atom and a halogen atom.

Further, the counter ion of the complex may be one derived from the used transition metal or one subjected to counter ion exchange according to the purpose. Preferred examples of the counter ion include Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , and C ₃ .
10 ₄ ⁻ , NCS ⁻ , PF ₆ ⁻ , OAc ⁻ , BPh ₄ ⁻ , CF
₃ SO ₃ ⁻ , RSO ₃ ⁻ , RSO ₄ ^{− and the} like. Here, R represents an alkyl group having 1 to 3 carbon atoms.

Examples of the salts among the transition metal-containing compounds include hydrochlorides, nitrates and sulfates of transition metals.

Among the transition metal-containing compounds, the heteropolyacid is
It contains at least one or more transition metals in the central element or polyacid group. Particularly preferably, B, S
i, P, S, Nb, Ta, Cr and the like. Mo, W, V and the like are particularly preferable as the metal of the polyacid group. Specific examples of the heteropolyacid include phosphomolybdic acid, silicomolybdic acid, silicotungstic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, phosphovanadotungstic acid, and sodium salts or ammonium salts thereof.

In the bleaching composition of the present invention, various nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants can be used in combination. The surfactant used in the bleaching composition is preferably 5 to 75% by weight, more preferably 10 to 40% by weight.

Specifically, as the nonionic surfactant, higher alcohols having about 8 to 24 carbon atoms, polyhydric alcohols, fatty acids, fatty acid amides, fatty amines, alkylphenols, n-paraffins and α-olefins can be oxidized. And the like. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like.

Examples of the anionic surfactant include linear or branched alkyl (average carbon chain length of 8 to 18) benzene sulfonate, long chain alkyl (average carbon chain length of 10 to 20) sulfonate, long chain olefin ( Average carbon chain length 10-20) sulfonate, long-chain monoalkyl (average carbon chain length 10-2)
0) Sulfate ester salt, α-sulfo fatty acid ester salt, polyoxyethylene long chain alkyl (average carbon chain length 10 to 1)
6) ether sulfate, polyoxyethylene alkyl (average carbon chain length 6 to 12) phenyl ether sulfate, long chain monoalkyl, dialkyl or sesquialkyl phosphate, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphorus Acid salts and the like.

Examples of the cationic surfactant include an alkyl trimethyl ammonium salt and a dialkyl dimethyl ammonium salt.

Examples of the amphoteric surfactant include aminocarboxylates such as alkylcarboxybetaines, alkylsulfoxybetaines, alkylamidopropylbetaines, and alkylalaninates, imidazoline derivatives, and alkylamine oxides.

The bleaching composition of the present invention may contain other peroxy compounds. Other peroxy compounds include hydrogen peroxide, inorganic persalt which releases hydrogen peroxide in an aqueous solution or has a peracid bond itself, and organic peracids. And an organic peracid precursor which generates an organic peracid by reacting with the above.

Examples of the inorganic persalt include alkali metal percarbonate, perborate, perphosphate, persilicate, persulfate and the like.

Examples of the organic peracid include peroxybenzoic acid and ring-substituted peroxybenzoic acid (peroxy-α
-Naphtholic acid) or monoperoxy acids such as aliphatic, substituted aliphatic and arylalkyl monoperoxy acids (peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid), and alkyl diperoxy acids and Aryl diperoxy acids (1,12-diperoxidedecandioic acid, 1,9-
Diperoxyazelaic acid, diperoxybrasilic acid,
Diperoxysebacic acid, diperoxyisophthalic acid,
2-decyldiperoxybutane-1,4-dioic acid,
Diperoxy acids such as 4,4-sulfonylbisperoxybenzoic acid).

Examples of the organic peracid precursor include, for example,
Acyl phenol sulfonate, acyl alkyl phenol sulfonate, acyl phenol carboxylate, acylated citrate, acyl alkyl phenol carboxylate, esters such as esters of aromatic divalent carboxylic acid and alcohol having a quaternized amine, and the like, Specifically, sodium-4benzoyloxybenzenesulfonate, sodium-1-methyl-2benzoyloxybenzene-4-sulfonate, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, sodium -3,5,5-trimethylhexanoyloxybenzenesulfonate, sodium octanoylcarboxylate, sodium Nonanoyloxybenzenecarboxylate, sodium dodecanoyloxybenzenecarboxylate, sodium-3,5,5-trimethylhexanoyloxybenzenecarboxylate, acetyltriethyl citrate, 2- (4-methoxycarbonylbenzoyloxy) -N, N , N-trimethylethane aluminum methosulfate and the like. Also,
Acylamides, specifically, N, N, N
', N'-tetraacetylethylenediamine and the like. Further, quaternary ammonium-substituted peroxyacid precursors are mentioned, and specifically, N, N, N-trimethylammonium toluyloxybenzenesulfonate,
2- (N, N, N-trimethylammonium) ethyl-
4-sulfophenyl carbonate and the like.

Further, the bleaching composition of the present invention can be used in combination with components contained in a usual washing and bleaching composition. Specifically, aluminosilicates such as zeolite, layered silicates, alkali metal carbonates, borates,
Inorganic builders such as phosphate, polyphosphate, and tripolyphosphate; organic builders such as nitrilotriacetic acid, lactic acid, citric acid, glycolic acid, succinic acid, and polyacrylic acid; chelating agents such as sodium ethylenediaminetetraacetate; proteases and lipases , Cellulase, amylase and other enzymes; 2,6-di-tert-butyl-methylphenol and other peroxide stabilizers; polyvinyl alcohol and carboxymethylcellulose and other anti-staining agents; fluorescent agents; hydrotropes; Agents, foam inhibitors, coloring agents, fragrances and the like.

[0075]

EXAMPLES Preparation of α-Alkoxy Hydroperoxide Synthesis of C ₉ α-Alkoxy Hydroperoxide Tetraethylene Glycol: 1-decene (1.030 g) was placed in a 50 ml two-necked flask equipped with an inlet tube. Then, tetraethylene glycol (9.556 g) and 15 ml of methylene chloride were added, and 1.3 vol% ozone was blown at -70 ° C. as a mixed gas of oxygen for 30 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to give the following structural formula (VII
A C ₉ α-alkoxy hydroperoxide tetraethylene glycol derivative (a) represented by I) was obtained.

[0076]

The ¹ H-NMR of the product (a) (270 MH
z, CDCl ₃ ) were as follows. δ 0.88 (t, 3H), l. 26-1.43 (m,
12H), 1.54-1.74 (m, 2H), 2.62.
(Br, s, 1H), 3.58-3.90 (m, 16
H), 4.83 (t, 1H), 10.74 (s, 1H)

The α-alkoxy peroxide Nos. The structures of (a) to (d) are shown in Table 1 below.
Shown in

[0079]

[Table 1]

Examples 1 to 4 and Comparative Example 1 Bleaching test of alizarin red S aqueous solution: each of α-alkoxy hydroperoxides (a) to (d) was 4.2 m
An aqueous solution of bleach was prepared as an aqueous solution of M. This aqueous solution was adjusted to pH 11.2 by adding 24 mM sodium bicarbonate and 25 mM sodium hydroxide. To each bleach aqueous solution, 0.1 mM of alizarin red S was added as a model dye, and the change in the absorbance of alizarin red S at a wavelength of 510 nm was measured over time to determine the bleaching rate of the dye 30 minutes after the start of bleaching. I asked. Also,
The same bleaching test was performed for the case where 4.2 mM hydrogen peroxide was used as the bleaching agent, and the bleaching rates were compared. The resulting bleaching rates are shown in Table 2 below.

[0081]

[Table 2]

Examples 5 to 6 and Comparative Example 2 Bleaching test of alizarin red S aqueous solution: For α-alkoxy hydroperoxides (a) and (b), α-alkoxy hydroperoxide was 10 mM, and IX) An aqueous bleach solution containing 50 ppm of the Mn complex represented by the formula was prepared. The pH of this aqueous solution was 5.5. Alizarin Red S as a model dye is added to this bleach solution in 1 m.
The change in the absorbance of Alizarin Red S at a wavelength of 510 nm when M was added was measured over time, and 1 hour after the start of bleaching.
The bleaching rate of the dye over time was determined. A similar bleaching test was also performed for the case where 10 mM hydrogen peroxide was used as the bleaching agent, and the bleaching rates were compared. The resulting bleaching rates are shown in Table 3 below.

[0083]

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[0084]

[Table 3]

Examples 7 to 14 Comparative Examples 3 to 6 Bleaching power test of stained cloth: aqueous solutions of α-alkoxy hydroperoxides (a) to (d) were prepared as 8.8 mM aqueous solutions, respectively. . This aqueous solution was added with 8 mM sodium bicarbonate and 32 mM sodium carbonate,
The pH was 10.8. A cotton test cloth contaminated with spinach or black tea stain was immersed in the aqueous bleach solution at room temperature for 30 minutes at a bath ratio of 30 times. Thereafter, it was washed with water and dried. The bleaching rate of the stained cloth was obtained from the following equation by measuring the reflectance of the cloth. As a comparison, a blank solution containing no bleaching agent and 8.8 mM as a bleaching agent were used.
A similar bleaching test was also performed on a solution using hydrogen peroxide. The obtained bleaching rates are shown in Tables 4 and 5 below.

[0086]

(Equation 1)

[0087]

[Table 4]

[0088]

[Table 5]

Examples 15 to 16 Storage stability test: For α-alkoxyhydroperoxides (a) and (b), 50 ml of an aqueous bleach solution containing 6.3 mM of α-alkoxyhydroperoxide was prepared. . The pH of this aqueous solution was 5. A 20 ml portion of this aqueous bleach solution was pipetted off, and the change in the absorbance of alizarin red S at a wavelength of 510 nm was measured over time when 0.1 mM of alizarin red S was added as a model dye. Was determined. After the bleaching test of the dye, the remaining bleaching aqueous solution 3
0 ml was stored at 25 ° C. for 3 months. A 20 ml portion of the solution after storage was separated with a pipette, and a bleaching test of the dye was performed in the same manner as before storage to compare the bleaching rates. The resulting bleaching rates are shown in Table 6 below.

[0090]

Table 6 Bleaching rate (%) Bleach Before storage 3 months after storage Example 15 (a) 92 97 Example 16 (b) 89 87

[0091]

The α-alkoxy hydroperoxide of the present invention has excellent bleaching power as a bleaching base, and the bleaching composition of the present invention containing it has an organic peroxide for converting to an organic peracid. The acid precursor can be used without being used together, and a sufficient bleaching effect can be obtained. In addition, the bleaching composition of the present invention has excellent storage stability and can exhibit a useful bleaching effect even under neutral to weakly acidic conditions. Further, the α-alkoxy hydroperoxide in the present invention is
Since the bleaching composition of the present invention can be used both as a liquid composition and a solid composition, the bleaching agent for garments, kitchen bleaches, bleaches such as home bleaches, bleach detergents, mold removers It is useful as a cleaning agent for bathtubs, a cleaning agent for water pipes, a cleaning agent for toilets, a cleaning agent for washing tubs, a slimming agent, a cleaning agent for kitchen and the like.

 ──────────────────────────────────────────────────の Continuation of the front page (72) Inventor Takeo Inagaki 1-7-3 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (3)

[Claims] 1. A bleaching composition comprising an α-alkoxy hydroperoxide represented by the following general formula (I). (In the formula, R ¹ , R ² , X, A and n have the following structures.
R ¹ and R ² each represent a substituent selected from the following [Group a], and R ¹ and R ² may be the same or different and may be either. [Group a]: hydrogen atom formyl group, hydroxyl group, hydroperoxyl group, peroxyl group, carbonyl group, carboxyl group,
Amino group, amide group, ester group, ether group, R ^1-
(AO) a linear or branched carbon atom having 1 or more carbon atoms which may be substituted with at least one group selected from _n -groups and aryl groups;
~ 50 alkyl or alkenyl groups. An aryl group which may be substituted with a linear or branched C1-C20 alkyl, alkenyl or alkoxyl group; X represents any substituent selected from the following [group b]. [Group b]: hydrogen atom linear or branched hydrocarbon group having 1 to 20 carbon atoms linear or branched acyl group optionally substituted with a hydrocarbon group having 1 to 20 carbon atoms or Amide group. A has 2 carbon atoms
Represents alkylene groups of 1 to 3. n shows the number of 0-50) 2. The composition according to claim 1, which contains 0.01% by weight or more of the α-alkoxy hydroperoxide represented by the general formula (I).
A bleaching composition according to claim 1. 3. A compound containing at least one transition metal,
The bleaching composition according to claim 1, wherein the bleaching composition is added in an amount of 0.001 to 50% by weight based on the α-alkoxyhydroperoxide represented by the general formula (I).