JP2002121597A - Bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleaching agent compound which decomposes coloring matters and limits damage on fabrics, which has been a problem in a bleaching system using a peroxide compound and an extremely active metal catalyst. SOLUTION: The detergent contains a peroxide compound, a metal catalyst shown in the general formula I and a radical scavenger. With this composition, coloring matters can be decomposed with limited damage on fabrics. [LnMmXp]qYr (I) (wherein M is a metal, m is an integer of 2-8, X is a ligand or crosslinking group, p is an integer of 0-32, Y is a counter ion whose electric charge depends on the electric charge q of the complex, r is equivalent with q, L is an organic molecular ligand containing two or more hetero atoms selected from the group consisting of N, P, O and S, and n is an integer of 2-8).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to bleaching agents, particularly oxidizing bleaching compositions.

[0002]

2. Description of the Related Art A peroxide compound which releases hydrogen peroxide in a solution has a poor bleaching power and cannot achieve a sufficient bleaching effect by a short bleaching treatment. It has the disadvantage that it takes a long time to obtain it.

Various proposals have been made to activate peroxide compounds in order to make bleaches usable at low temperatures. One proposal is a so-called organic bleach activator which reacts with a peroxide compound such as sodium perborate or sodium percarbonate in a solution to form an organic peroxy acid having high bleaching activity at low temperatures. This usually uses organic compounds having one or more reactive acyl residues (Detergent Age, (6) 18-20, 1976. Ibid., (7) 2
6-27, 1976. Ibid., (8) 67 1976.). However, since these organic bleach activators do not regenerate catalytically, there is a problem that the amount added to the detergent is large and a problem that the fat-soluble dye is decomposed but the water-soluble dye is insufficiently decomposed.

Another approach is to use transition series heavy metal ions, which catalyze the decomposition of peroxide compounds, with a particular type of chelating agent for the heavy metal (US Pat. No. 31,566).
No. 54, No. 3,532,634, No. 4,119,557, No. 3,372,125, and British Patent No. 984459). However, the problem with these methods is that the results, especially when used for washing fabrics at low temperatures, are often inconsistent and unsatisfactory.

[0005] Another attempt is to use an extremely active metal catalyst which catalyzes the decomposition of peroxide compounds, and has the disadvantages of low or inconsistent bleaching activity at low temperatures and too much bleach activator, which has been a conventional problem. There has been a method for solving the problem of the amount added, the bleaching property of a water-soluble dye, etc. at once (European Patent No. 458).
397, 458398). In this method, the addition amount of a metal catalyst was as small as about 100 ppm, and the bleaching activity at a low temperature and the activity against a water-soluble dye were very good. There was a problem that there is.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems with the conventional bleaching compositions, and has as its object to provide a more improved bleaching composition.

[0007]

SUMMARY OF THE INVENTION The present inventors have developed a bleaching system using a peroxide compound and a highly active metal catalyst.
Various investigations and investigations were made as to whether pigments could be decomposed by coexisting additives for controlling oxidizing power and damage to fibers could be suppressed. As a result, they have found that the coexistence of a radical scavenger can decompose a dye in the bleaching system and suppress damage to fibers. This is because it captures highly reactive radicals such as hydroxyl radicals, which are thought to be the cause of fiber damage, and suppresses damage to the fiber, while the reaction product of the metal catalyst and peroxide compound helps to decompose the dye. I have.

That is, the present invention relates to (1) a peroxide compound,
A bleaching composition comprising a metal catalyst and a radical scavenger, wherein (2) the metal catalyst has a general formula (I)
[Formula 3]

[0009]

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Wherein M is a metal, m is an integer from 2 to 8. X is a coordination or bridging species, p is an integer from 0 to 32. Y is a counter ion and Type is positive,
Depending on the charge q of the complex, which is zero or negative, r is q (Y
Charge). L is a ligand which is an organic molecule containing a plurality of heteroatoms selected from N, P, O or S, and n is an integer of 2 to 8. 2. The bleaching composition according to claim 1, wherein the bleaching composition comprises a peroxide compound, a precursor of a metal catalyst, and a radical scavenger. (4) The radical scavenger has the general formula (II)

[0011]

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Wherein R ¹ and R ² are the same or different and each represents a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aryl group, acyl group or aroyl group. A bleaching composition characterized by being a compound capable of deriving a nitroxyl radical represented by the general formula (II) in the presence of a xyl radical or a peroxide compound and a metal catalyst.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the first aspect, the metal catalyst may be any catalyst capable of decomposing and activating a peroxide compound containing a metal.

A metal catalyst represented by the general formula (I) [LnM
In [mXp] ^q Yr, M may be any metal as long as it is a metal, but a metal having a strong oxidizing power and a small environmental load, such as Mn and Fe, is preferable.

As a ligand represented by X or a bridging species
Is, for example, H_TwoO, OH^-, O_Two ^-, HO _Two ^-, SH^-, S_Two ^-,
-SO-, NR_Two ^-, RCOO^-, NR_Three(R is hydrogen source
A substituted or unsubstituted alkyl group or a substituted or unsubstituted
Substituted aryl group), Cl^-, N_Three ^-, SCN^-Or or
Represent their combination.

Y represents a counter ion having a property based on the charge q of the complex. When q is positive, Y represents an anion such as Cl ⁻ , B
_{^{r -, I -, NO 3}} -, ClO 4 -, NCS -, PF 6 -, RS
O ₃ ⁻ , RSO ₄ ⁻ , CF ₃ SO ₃ ⁻ , BPh ₄ ⁻ , AcO ^{− and the} like. When q is negative, Y is a common cation such as an alkali metal, an alkaline earth metal or (alkyl) ammonium. Indicates a cation.

L is a ligand which is an organic molecule containing a plurality of heteroatoms selected from N, P, O or S;
For example, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-trimethyl-1,4,7-triazacyclodecane, 1,4,8
-Trimethyl-1,4,8-triazacycloundecane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, tris (pyridin-2-yl) methane,
Tris (pyrazol-1-yl) methane, tris (imidazol-1-yl) methane, tris (triazole-
1-yl) methane, tris (pyridin-2-yl) borate, tris (triazol-1-yl) borate, tris (imidazol-1-yl) phosphine, tris (imidazol-1-yl) borate, 1,3,3 5-trisaminocyclohexane, 1,1,1-tris (methylamino) ethane, bis (pyridin-2-ylmethyl)
Examples include amines. All ligands which are, between the carbon atoms and / or direction of a nitrogen atom and / or CH ₂ amine may be optionally substituted.

An example of the most preferred catalyst is [Mn ₂ (μ-
O) ₃ (Me-TACN) ₂ ] (Y) ₂

[0019]

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[Fe ₂ (μ-O) ₃ (Me-TAC)
N) ₂ ] (Y) ₂ [Formula 6]

[0021]

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Examples of the precursor of the active catalyst include [Mn ₂ (μ-
O) (μ-OAc) ₂ (Me-TACN) ₂ ] (Y)
₃ [Formula 7]

[0023]

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[Fe ₂ (μ-O) (μ-OAc) ₂ (Me
-TACN) ₂ ] (Y) ₃ [Formula 8]

[0025]

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## EQU1 ## These precursors are activated catalytic cations [Mn ₂ (μ-O) ₃ (Me-TACN) ₂ ] ²⁺ [Fe ₂ (μ-O) ₃ (Me-TACN) ₂ ] ^{2 in} the presence of a peroxide compound. Converted to ⁺ .

In the general formula (I), R and
A substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aryl group, acyl group or aroyl group in R ¹ and R ² of the general formula (II) is an unsubstituted alkyl group, alkenyl group, aralkyl group, An aryl group, an acyl group, an aroyl group, or a residue thereof has a substituent.

The unsubstituted alkyl group is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl group, sec-butyl group, tert-
Butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Also, R ¹
And R ² is bonded at a methylene chain, including the nitrogen atom 5-8
A member ring may be formed.

The unsubstituted alkenyl group is a linear or branched alkenyl group having 2 to 6 carbon atoms.
Examples include a vinyl group, an allyl group, an isopropenyl group, a 4-pentenyl group, and a 5-hexenyl group.

As the unsubstituted aralkyl group, for example,
Examples include a benzyl group, a phenethyl group, a benzhydryl group, and a phenylpropyl group.

Examples of the unsubstituted aryl group and the aryl moiety of the aroyl group include a phenyl group and a naphthyl group.

Examples of the unsubstituted acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valyl group and a pivaloyl group.

As the substituent, a hydroxyl group, a halogen group, an alkoxy group, a carbonyl group, an alkyl group, an alkenyl group,
An aralkyl group, an aryl group, an acyl group and the like can be mentioned, and the number of substitution and the position of substitution are not particularly specified. Here, the halogen group is fluorine, chlorine, bromine or iodine. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an iso-butoxy group, and t.
ert-butoxy group, n-pentyl group, phenoxy group,
A benzyloxy group and the like can be mentioned. As the carbonyl group, a carboxyl group, an ethoxycarbonyl group, n
-Butoxycarbonyl group and the like. The alkyl group, alkenyl group, aralkyl group, aryl group, and acyl group are as described above.

In the first aspect, the radical scavenger may be a compound capable of scavenging radicals or a compound capable of scavenging radicals in the presence of a peroxide compound and a metal catalyst. For example, nitrobenzene, p
-Dinitrobenzene, 1,3,5-trinitrobenzene, phenol, 2,4-dinitrophenol, 2,4
-Dinitro-6-sec-butylphenol, p-nitrophenol, 2,6-dinitro-p-cresol,
4,6-dinitro-o-cresol, hydroquinone,
1,2,3-trihydroxybenzene, 4-methylphenol, 2,4,6-trimethylphenol, 4-te
In the presence of rt-butylcatechol, chloranil, diphenylpicrylhydrazine, a compound represented by the general formula (II) or a peroxide compound, and a metal catalyst,
Compounds which can be converted into I), for example N-hydroxypiperidine-2,6-dione, 3-carboxyproxyl, 3
-Carbamoylproxil, 2,2,5,5-tetramethyl-3-pyrroline-1-oxyl-3-carboxamide, di-tert-butyl nitroxide, methyl-5
-Doxyl stearate free radical, bis (trifluoromethyl) nitroxide, N, N-diethylhydroxylamine, N, N-dibenzylhydroxylamine, and tetramethylpiperidine N-oxyl derivative or peroxide compound in the presence of a metal catalyst A compound that can be converted to a tetramethylpiperidine N-oxyl derivative;
For example, 2,2,6,6-tetramethylpiperidine N-
Oxyl (TEMPO), 4-hydroxy-2,2,
6,6-tetramethylpiperidine N-oxyl (hydroxy TEMPO), 4-amino-2,2,6,6-tetramethylpiperidine N-oxyl (amino TEMPO)
O), 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl, 4-methoxy-2,2,6,6
-Tetramethylpiperidine N-oxyl, 4-acetamido-2,2,6,6-tetramethylpiperidine N
-Oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine N-oxyl, 4-phosphonooxy-2,2,6,6-tetramethylpiperidine N-oxyl, 4-diano-2,2,6 , 6-Tetramethylpiperidine N-oxyl, 4-methylsulfonyloxy-
2,2,6,6-tetramethylpiperidine N-oxyl, 4-hydrazono-2,2,6,6-tetramethylpiperidine N-oxyl, 4-isothiocyanato-2,
2,6,6-tetramethylpiperidine N-oxyl,
2,2,6,6-tetramethylpiperidin N-oxyl-4-yl benzoate, (1-hydroxy-2,
2,6,6-tetramethylpiperidin-4-yl) urea, 4-amino-1-hydroxy-2,2,6,6-tetramethylpiperidine-4-carboxylic acid, N- (1-oxyl-2, 2,6,6-tetramethylpiperidinyl)
Maleimide, 4-acetylamino-2,2,6,6-tetramethylpiperidine N-oxyl and the like can be mentioned.

The peroxide compounds which can be used in the present invention include hydrogen peroxide, hydrogen peroxide releasing compounds, hydrogen peroxide generating systems, peracids and salts thereof, peracid bleach precursors, and mixtures thereof. . Hydrogen peroxide sources are well known to those skilled in the art, such as alkali metal peroxide compounds, organic peroxide compound bleaching compounds such as urea peroxide, inorganic peroxide bleaching compounds such as alkali metal perborates, peroxides, etc. Carbonates, perphosphates and persulfates can be mentioned. These compounds may be used as a mixture of two or more kinds.
Preferred are sodium percarbonate and sodium perborate. These bleach compounds may be used alone or in combination with a peracid bleach precursor.

The peracid bleach precursors include esters such as acyl phenol sulfonates and acyl alkyl phenol sulfonates, acyl amides, and quaternary ammonium substituted peracid precursors.

The bleaching compositions of the present invention can contain most of the known general surfactants and detergency builders.

[0038]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples.

Example 1 A 0.42 mM orange II aqueous solution (using ion-exchanged water)
[Mn ₂ (μ-O) (μ
_{-OAc) 2 (Me-TACN)} 2] (PF 6) 2 of 20
0.5 M aqueous solution, 3 ml of sodium bicarbonate-sodium hydroxide buffer solution (pH 10.6), 4-hydroxy-
0.1 ml of a 3.15 mM aqueous solution of 2,2,6,6-tetramethylpiperidine N-oxyl, 0.434 ml of a 35 wt% aqueous hydrogen peroxide solution and water so that the total amount becomes 5 ml, and the reaction solution is stirred at room temperature. The bleaching activity was observed over time. The results are shown in FIG. 1 [FIG. 1]. The bleaching activity was represented by (absorbance before bleaching-absorbance after bleaching) / (absorbance before bleaching-blank absorbance) × 100. The absorbance at 485 nm was used.

Example 2 The same operation as in Example 1 was performed except that the amount of the 3.15 mM aqueous solution of 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl was changed to 0.2 ml. Was. The results are shown in FIG. 1 [FIG. 2].

Comparative Example 1 The same operation as in Example 1 was carried out except that 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl was not added. The results are shown in FIG. 1 [FIG. 1].

Comparative Example 2 [Mn ₂ (μ-O) (μ-OAc) ₂ (Me-TACN)
₂ ] (PF ₆ ) ₂ and 4-hydroxy-2,2,6,6-tetramethylpiperidine The same operation as in Example 1 was performed except that N-oxyl was not added. The results are shown in FIG. 1 [FIG. 1].

Comparative Example 3 [Mn ₂ (μ-O) (μ-OAc) ₂ (Me-TACN)
₂ ] The same operation as in Example 1 was performed except that (PF ₆ ) ₂ was not added. The results are shown in FIG. 1 [FIG. 1].

Example 3 [Mn ₂ (μ-O) (μ-OAc) ₂ (Me-TACN)
_{2] [Fe 2 (μ-} O) in place of _{(PF 6) 2 (μ-} OA
c) The same operation as in Example 1 was performed, except that ₂ (Me-TACN) ₂ ] (PF ₆ ) ₂ was used. The results are shown in FIG. 2 [FIG. 2].

Example 4 The same operation as in Example 3 was performed except that the amount of the 3.15 mM aqueous solution of 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl was changed to 0.2 ml. Was. The results are shown in FIG. 2 [FIG. 2].

Comparative Example 4 The same operation as in Example 3 was carried out except that 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl was not added. The results are shown in FIG. 2 [FIG. 2].

Comparative Example 5 [Fe ₂ (μ-O) (μ-OAc) ₂ (Me-TACN)
₂ ] (PF ₆ ) ₂ and 4-hydroxy-2,2,6,6-tetramethylpiperidine The same operation as in Example 3 was performed except that N-oxyl was not added. The results are shown in FIG. 2 [FIG. 2].

Comparative Example 6 [Fe ₂ (μ-O) (μ-OAc) ₂ (Me-TACN)
₂ ] The same operation as in Example 3 was performed except that (PF ₆ ) ₂ was not added. The results are shown in FIG. 2 [FIG. 2].

Example 5 (Model reaction for measuring damage to fiber) A 30% excess solution was prepared by dispersing 1 g of cellulose (Aldrich, powder, ２０20 μm) in 50 ml of a sodium hydrogen carbonate-sodium hydroxide buffer (pH 11). 0.27 g of hydrogen oxide (23.9 mmo
l), [Mn ₂ (μ-O) (μ-OAc) ₂ (Me-TAC
N) ₂ ] (PF ₆ ) ₂ 2.5 mg (2.87 μmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine
31 mg (0.181 mmol) of N-oxyl was added, and the mixture was stirred at 80 ° C for 30 minutes. Then 30% hydrogen peroxide 0.27
g, [Mn ₂ (μ-O) (μ-OAc) ₂ (Me-TAC
_{N) 2] (PF 6)} 2 2.5mg, 4- hydroxy -
The operation of adding 2,2,6,6-tetramethylpiperidine N-oxyl 31 mg and stirring at 80 ° C. for 30 minutes was repeated twice. After cooling to room temperature, the cellulose was filtered and dried, and the molecular weight distribution was measured by GPC. The results are shown in Table 1 [Table 1].

[Table 1]

Comparative Example 7 The molecular weight distribution of untreated cellulose was measured by GPC, and the results are shown in Table 1 [Table 1].

Comparative Example 8 The same operation was carried out in Example 1 without using 4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl, and the molecular weight distribution was measured by GPC. Table 1 shows the results
The results are shown in [Table 1].

[0052]

According to the present invention, in a bleaching system using a peroxide compound and a metal catalyst having extremely high activity, a bleaching agent composition which suppresses damage to fibers and decomposes a dye, which has been conventionally regarded as a problem, is provided. We were able to.

[Brief description of the drawings]

FIG. 1 [Mn ₂ (μ-O) (μ-OAc) ₂ (Me-T
ACN) ₂ ] (PF ₆ ) ₂ catalyst system with 4-hydroxy-
It is a figure which shows the addition effect of 2,2,6,6-tetramethylpiperidine N-oxyl.

FIG. 2 [Fe ₂ (μ-O) (μ-OAc) ₂ (Me-T
ACN) ₂ ] (PF ₆ ) ₂ catalyst system with 4-hydroxy-
It is a figure which shows the addition effect of 2,2,6,6-tetramethylpiperidine N-oxyl.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C11D 7/34 C11D 7/34 7/36 7/36

Claims (7)

[Claims] 1. A bleaching composition comprising a peroxide compound, a metal catalyst and a radical scavenger. 2. The method according to claim 1, wherein the metal catalyst is of the general formula (I) Wherein M is a metal and m is an integer from 2 to 8.
X is a coordinating or bridging species, and p is an integer from 0 to 32. Y is a counter ion whose type depends on the charge q of the complex, which is positive, zero or negative, and r is equal to q (the charge of Y). L is a ligand which is an organic molecule containing a plurality of heteroatoms selected from N, P, O or S, and n is an integer of 2 to 8. 2. The bleaching composition according to claim 1, wherein 3. The bleaching composition according to claim 2, wherein M is Mn or Fe. 4. The bleaching composition according to claim 2, wherein p is 3, n is 2, and m is 2. 5. The bleaching composition according to claim 1, comprising a precursor of the catalyst according to claim 2 instead of the metal catalyst. 6. The radical scavenger of the general formula (II) (Wherein, R ¹ and R ² are the same or different and represent a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, aryl group, acyl group or aroyl group). The bleaching composition according to claim 1, which is a compound capable of deriving a nitroxyl radical represented by the general formula (II) in the presence of a peroxide compound and a metal catalyst. 7. The method according to claim 1, wherein the radical scavenger is a tetramethylpiperidine N-oxyl derivative or a compound which can be derived into a tetramethylpiperidine N-oxyl derivative in the presence of a peroxide compound and a metal catalyst.
The bleaching composition according to any one of the preceding claims.