KR20040031426A - Use of a giant ring manganese complex compound as bleaching catalyst and bleaching detergent composition comprising these compound - Google Patents

Abstract

PURPOSE: Provided are a use of macrocyclic manganese complex compound and composition of bleaching agent containing the same compound which is advantageous in that is easily synthesized and stabilized, does not cause damage and decolorization to fabric and has high bleaching efficiency. CONSTITUTION: The bleaching agent is formed of macrocyclic manganese complex compound such as £Mn¬(III)Cl2(L)|ClO4, £Mn¬(III)(H2O2)2(L)|Cl3·2H2O·0.5HCl and £Mn¬111(N3)2(L)|N3·2H2O, here L is 3,14-dimethyl-2,6,13,17-tetraazatricyclo£14,4,01.18,07.12|docosane. The bleaching agent comprises 1 to 40 wt.% of peroxide, surfactant, builder, bleaching agent and 0.001 to 1 wt.% of bleach catalyst which is selected from a group consisted of £Mn¬(III)Cl2(L)|ClO4, £Mn¬(III)(H2O2)2(L)|Cl3·2H2O·0.5HCl and £Mn¬(III)(N3)2(L)|N3·2H2O.

Description

Use of a giant ring manganese complex compound as bleaching catalyst and bleaching detergent composition comprising these compound}

The present invention relates to a macrocyclic manganese complex compound and a bleach detergent composition containing the same, and more particularly, to a method of using a macrocyclic manganese complex compound as a bleaching catalyst or an activator for activating hydrogen peroxide generated from a peroxide of a bleach detergent and the complex compound. It relates to a composition of bleach detergent containing.

Bleach detergents can be divided into chlorine and oxygen, but chlorine bleach can be used for clothing because it can decolorize dyes or produce a characteristic irritant odor. It is common to use bleach.

As the oxygen-based bleach detergent, liquid hydrogen peroxide is used for the liquid bleach detergent, and solid peroxide (NaBO ₃ · H ₂ O, NaBO ₃ · 4H ₂ O) and sodium percarbonate (2Na ₂ CO ₃ · 3H _2). O ₂ ) has long been used in powder bleach. However, oxygen-based bleaching agents such as sodium perborate, sodium percarbonate and hydrogen peroxide have less bleaching power than chlorine-based bleaching agents, and have relatively weak bleaching performance at low temperatures, and thus a sufficient bleaching effect can be seen only at a temperature higher than 60 ° C. When washing at a temperature lower than 60 ° C, the oxidizing power of these inorganic peroxides can be increased by adding bleach activators such as acyl and ester. However, these conventional bleach activators have the disadvantage that they must typically be combined in stoichiometric amounts or in excess. Moreover, the conventional bleach activator has a disadvantage in that the efficacy of the bleach activator is significantly reduced at a washing temperature of about 20 ° C. which is the washing environment of our country.

Conventionally, it is known that common transition metal ions catalyze the decomposition of hydrogen peroxide and the peroxides that generate hydrogen peroxide in aqueous solution. Thus, there has been an effort to develop an effective bleaching activator that can solve the disadvantages of the conventional by using this to exhibit sufficient bleaching power even at low temperatures around 20 ℃. For example, US Pat. No. 4,119,557 and US Pat. No. 4,430,243 disclose methods for activating peroxides using transition metal ions with chelating agents. However, not all combinations of transition metal ions and chelating agents are effective for activating oxygen-based bleach, and in fact, many types of transition metal ions and chelating combinations are known to have no bleaching effect or adverse effects.

Therefore, in order to use the transition metal as a bleach activating catalyst in the bleach detergent composition, it is important to find a metal catalyst which does not decompose peroxides through a path not involved in bleaching and does not cause irreversible oxidation.

In recent years, attempts have been made to use transition metal complexes, especially complex compounds using manganese and cobalt, as bleaching catalysts. These are described, for example, in US Pat. No. 5246621, dinuclear manganese complexes using ligands called 1,4,7-trimethyl-1,4,7-triazacyclononane. This transition metal complex may be used to wash the fabric using a suitable inorganic peroxide. However, the complex compound is difficult to synthesize the ligand, the price is very expensive, and there is a problem that excessive bleaching such as damage to the fiber may occur when the catalyst is used in an appropriate amount. In addition, the bleach detergent may be added excessively because some specific components are ubiquitous or due to the physical properties that the bleach detergent is composed of particles, when there is excessive bleaching due to the excessive addition of the bleach catalyst, there is a fear of damage or discoloration of the fiber.

Accordingly, the present invention is to solve the above-mentioned problems, the synthesis is relatively easy, is stable to hydrolysis, oxidation, reduction, etc., does not cause damage or discoloration of the fiber, excellent bleaching effect even at low temperatures The purpose is to provide.

In addition, another object of the present invention to provide a bleach detergent composition containing the bleach catalyst.

Using: (L stands), the present inventors have the following structural formula 1 of 3,14- di methyl -2,6,13,17- tetrahydro aka tricyclo [14,4,0 ^1,18, 0 ^7,12] docosane acid The manganese complex was synthesized relatively easily, and the macrocyclic manganese complex compound was used to significantly improve the bleaching power of the peroxide, and found that excessive bleaching did not occur even when used in excess, thereby completing the present invention.

[Compound 1]

Therefore, the bleaching catalyst of the present invention for achieving the above object as a bleaching catalyst [Mn ^III Cl ₂ (L)] ClO ₄ , [Mn ^III (H ₂ O) ₂ (L)] Cl ₃ · 2H ₂ O.0.5 BCl catalyst characterized in that it is selected from macrocyclic manganese complex compounds such as HCl, [Mn ^III (N ₃ ) ₂ (L)] N ₃ .2H ₂ O.

The manganese complex bleaching catalyst described above serves to activate a peroxide oxygen-based bleaching agent that generates hydrogen peroxide. These macrocyclic manganese complexes are stable to hydrolysis, oxidation and reduction, and are excellent bleaching catalysts capable of activating bleach even at low temperatures. In addition, there is an advantage that does not cause excessive bleaching of clothing even when added excessively.

Accordingly, the present invention exhibits a beneficial effect of improving the bleaching power of the bleach detergent even in small amounts when used in combination with bleach detergents such as inorganic peroxides, peracids and salts thereof, which generate hydrogen peroxide in hydrogen peroxide or aqueous solutions.

As mentioned above, certain transition metal complexes containing manganese according to the constitution of the present invention have been studied for purposes not related to bleaching. See, eg, Ju Chang Kim, and Alan J. Lough. "Synthetic, Spectroscopic, and X-ray Crystallographic Studies on Manganese (III) Complexes with a 14-Membered Tetraaza Macrocyclic Ligand", Bull. Korean Chem. Soc., Vol. 20, No. 10, 1999, 1241] [Mn ^III Cl ₂ (L)] Cl, [Mn ^III (H ₂ O) ₂ (L)] Cl ₃ .2H ₂ O.0.5HCl, [Mn ^III (N ₃ ) ₂ ( 14-decane)] N ₃ .2H ₂ O has been described, but it was not recognized at all that the complex can act as a bleaching catalyst that is remarkably efficient against peroxides.

Bleach detergent composition according to another aspect of the present invention is a peroxide, surfactant, builder, bleach activator and bleach catalyst [Mn ^III Cl ₂ (L)] ClO ₄ , [Mn ^III (H ₂ O) ₂ (L) ] Cl ₃ · 2H ₂ O.0.5HCl, [Mn ^III (N ₃ ) ₂ (L)] N ₃ · 2H ₂ O, and the like.

In this case, as the inorganic peroxide, sodium percarbonate or soda perborate is used, and the content thereof is preferably 1 to 40% by weight, and the macrocyclic manganese complex compound may be blended at 0.001 to 1% by weight in the detergent composition. have.

In the composition, as the surfactant, anionic surfactants, nonionic surfactants, soaps, and the like may be used. As the anionic surfactant, at least one selected from alkylbenzene sulfonate, alkyl sulfonate, alkyl ether sulfonate, alkanesulfonate and olefin sulfonate can be used. As the nonionic surfactant, one or more selected from linear and branched alkylpolyethoxy alcohols, alkylpolyethoxy fatty acid esters and fatty acid alkanolamides can be used. The total content of the surfactant is suitably 1 to 50% by weight of the composition.

In addition, in the composition, the builder uses an inorganic builder and an organic builder at 1 to 90% by weight. Examples of inorganic builders include sodium carbonate, sodium tripolyphosphate, aluminosilicates such as natural and synthetic zeolites, sodium silicate and sodium sulfate, and organic builders include sodium salts of polyacrylates, polymaleates, and citrate. Can be.

The bleach detergent composition of the present invention may further contain a bleach activator other than the macrocyclic manganese complex compound, and the bleach activator may be an acyl system such as tetraacetylethylenediamine, an ester system such as alkanoyloxybenzenesulfonate, a kenon system, Amide based and nitrile based, but not limited thereto.

In addition, the bleach detergent composition of the present invention may contain auxiliary additives such as fluorescence, enzymes, fragrances, and chelating agents commonly used in powder detergents.

Hereinafter, the present invention will be described in more detail with examples and examples, but the present invention is not limited thereto.

Preparation Example 1. Synthesis of 3,14-Dimethyl-2,6,13,17-tetraazatricyclo [14,4,0 ^1,18 , 0 ^7,12 ] docoic acid (L)

Shin-Geol Kang et al., Bull. Korean Chem. Soc., Vol 12, No 5, 1991, 483] 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0 ^1,18 , 0 ^7,12 ] doco 4-2,12-dienedihydroperchlorate was synthesized and reduced with sodium borohydride to give 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0 ^1,18 , 0 ^7,12 ] docoic acid was synthesized.

Melting Point: 221 ℃

Elemental Analysis: Calcd for C ₂₀ H ₄₀ N ₄ : C, 71.4. H, 12.0; N 16.7%. Found: C, 71.5; H, 12.4; N, 16.5%

Preparation Example ₂ Synthesis of [Mn ^III Cl ₂ (L)] ClO ₄

Ju Chang Kim et al., Bull. Korean Chem. Soc., 1999, Vol 20, no. 10, 1241].

Dissolve 1.692 g of ligand L in 50 mL of methanol, add 1.2 g of MnCl ₂ · 4H ₂ O in 100 mL of methanol to this solution to obtain a dark brown solution, stir for 24 hours while injecting air into this solution, and filter. . Excess concentrated hydrochloric acid and concentrated perchloric acid were added to the filtrate to yield a yellow solid. The solid was filtered off and washed with methanol to synthesize yellow [Mn ^III Cl ₂ (L)] ClO ₄ .

IR (KBr, cm ^-1 ): 3139, 2948, 2864, 1448, 1067, 623

Elemental Analysis: Calcd for C ₂₀ H ₄₀ N ₄ MnCl ₃ O ₄ : C, 42.75; H, 7. 18; N, 9.97. Found: C, 43.03; H, 7. 19; N, 9.90.

Preparation Example ₃ Synthesis of [Mn ^III (H ₂ O) ₂ (L)] Cl ₃ · 2H 2 O.0.5HCl

Ju Chang Kim et al., Bull. Korean Chem. Soc., 1999, Vol 20, no. 10, 1241].

[Mn ^III Cl ₂ (L)] ClO ₄ is dissolved in a small amount of light aqueous hydrochloric acid solution, and is slowly evaporated at room temperature. This solution produced a dark blue solid. The obtained solid was filtered and washed with methanol to synthesize [Mn ^III (H ₂ O) ₂ (L)] Cl ₃ .2H ₂ O.0.5HCl.

Elemental Analysis: Calcd for C ₂₀ H ₄₈ Cl ₃ MnN ₄ O ₄ .0.5HCl: C, 40.95; H, 8. 19; N 9.55. Found: C, 40.81; H, 8.54; N, 9.50

Preparation Example 4 Synthesis of [Mn ^III (N ₃ ) ₂ (L)] N ₃ · 2H ₂ O

Ju Chang Kim et al., Bull. Korean Chem. Soc., 1999, Vol 20, no. 10, 1241].

[Mn ^III Cl ₂ (L)] ClO ₄ is dissolved in saturated water, and an aqueous NaN ₃ solution is added thereto to obtain a dark brown solution. The solution was stored at room temperature to give a brown solid, which was filtered and washed with methanol to synthesize [Mn ^III (N ₃ ) ₂ (L)] N ₃ .2H ₂ O.

Elemental Analysis: Calcd for C ₂₀ H ₄₄ MnN ₁₃ O ₂ : C, 43.40; H, 7.96; N 32.91. Found: C, 43.66; H, 8.50; N, 32.61

Examples 1-4, Comparative Example 1-2

As shown in Table 1 below, a commercially available concentrated detergent which does not contain a bleach and soda without any bleach activator was used as Comparative Example 1, and TAED was added to Soda percarbonate as Comparative Example 2, To prepare a bleach detergent composition according to Examples 1 to 4 to the addition of the macrocyclic manganese complex prepared in Preparation Examples 2 to 4 to the soda percarbonate, the macrocyclic ring prepared in Preparation Examples 2 to 4 in the bleach detergent composition The bleaching activating capacity of the manganese complexes was evaluated using tea, coffee, curry, and red wine contaminants.

Experimental conditions, using a Terg-O-Tometer, 0.8g / l of detergent of Example 1-4, Comparative Example 1-2 at 25 ℃, stirred for 1 minute and then put each contaminated cloth and 90ppm Wash for 10 minutes (120 rpm) at hardness (as CaCO ₃ ). The evaluation measured the whiteness of the contaminated cloth before and after washing | cleaning with the white metric, converted into the value at the time of seeing the washing degree of the comparative example 1 as 100, and the result of this evaluation is shown in Table 1 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Concentrated detergent (g) 0.8 0.8 0.8 0.8 0.8 0.8 Sodium percarbonate (g) 4.6 4.6 4.6 4.6 4.6 4.6 TAED (g) 0 0.4 0 0 0 0 Preparation Example 2 (g) 0 0 0.04 0.004 0 0 Preparation Example 3 (g) 0 0 0 0 0.04 0 Preparation Example 4 (g) 0 0 0 0 0 0.04 Detergency (%) (tea) 100 114 228 147 205 220 % Cleaning power (coffee) 100 117 186 131 172 182 Cleaning power (%) (curry) 100 105 121 97 114 119 Detergent (%) (red wine) 100 111 132 120 126 130

As can be seen from Table 1, Examples 1 to 4 including the manganese complex compound of the present invention compared to Comparative Example 1, which does not include any bleach activator in soda percarbonate and Comparative Example 2 in which TAED is added to soda percarbonate At a relatively low temperature of 25 ° C, the cleaning power was very high. In particular, [Mn ^III Cl ₂ (L)] ClO ₄ of Preparation Example 2 showed higher bleaching activation even when using 1/100 weight fold compared to TAED. Therefore, the macrocyclic manganese complex of the present invention can be seen that the ability to activate the bleach is very excellent.

Example 5, Comparative Example 3.

As shown in Table 2, TAED and [Mn ^III Cl ₂ (L)] ClO ₄ of Preparation Example 2 were added to 0.8 g of a commercially available concentrated detergent and 0.2 g of sodium percarbonate, which did not contain a bleach, and Comparative Example 3 and Examples. The detergent composition of Example 5 was produced, and the bleaching power was evaluated using the tea, coffee, and curry dirt cloth.

Experimental conditions are the same as in Examples 1 to 4 above.

Comparative Example 3 Example 5 Concentrated detergent (g) 0.8 0.8 Sodium percarbonate (g) 0.2 0.2 TAED (g) 0.05 0 Preparation Example 2 (g) 0 0.005 Detergency (%) (tea) 100 370 % Cleaning power (coffee) 100 155 Cleaning power (%) (curry) 100 140

As can be seen in Table 2, compared to Comparative Example 3, which is a conventional bleach detergent composition using both sodium percarbonate and TAED, Example 5 including the macrocyclic manganese complex compound showed a significantly higher cleaning power.

Example 6.

Bleaching power at excessive addition

Except for the excessive prescription of [Mn ^III Cl ₂ (L)] ClO ₄ content of Preparation Example 2 as shown in Table 3, under the same experimental conditions as in Example 5, the bleaching power was evaluated using a stain stain. .

Preparation Example 2 (g) 0.0002 0.0005 0.0025 0.005 0.01 0.02 Cleaning power (%) 100 107 125 164 198 185

As can be seen in Table 3, even when an excessive amount of the bleach catalyst is added, it maintains a constant bleaching power and does not cause excessive bleaching of clothes.

The macrocyclic manganese complex compound according to the present invention configured as described above is useful as a bleaching catalyst or an activator for activating hydrogen peroxide generated from the peroxide of the bleach detergent, and thus has a higher bleaching effect than the conventional bleach detergent in a small amount. Bleaching effect is excellent even at low temperatures, the bleach detergent composition containing it has an excellent bleaching effect than the conventional one.

Claims (3)

[Mn ^III Cl ₂ (L)] ClO ₄ , [Mn ^III (H ₂ O) ₂ (L)] Cl ₃ · 2H ₂ O.0.5HCl, [Mn ^III (N ₃ ) ₂ (L)] N ₃ Large such as 2H ₂ O, where L stands for 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0 ^1,18 , 0 ^7,12 ] docoic acid A bleaching catalyst characterized in that it is selected from cyclic manganese complexes. As peroxides, surfactants, builders, bleach activators and bleach catalysts [Mn ^III Cl ₂ (L)] ClO ₄ , [Mn ^III (H ₂ O) ₂ (L)] Cl ₃ .2H ₂ O.0.5HCl, [ _{^{Mn III (N 3) 2 (}} L)] N 3 · bleaching detergent composition characterized in that it contains from 0.001 to 1% by weight of the macrocyclic manganese complexes on the one selected from the group consisting of 2H ₂ O. The bleach detergent composition according to claim 2, wherein the peroxide included in the composition is sodium percarbonate or sodium perborate, the content of which is 1 to 40% by weight.