Patent Publication Number: US-7906472-B2

Title: Bleaching and detergent compositions comprising manganese complex prepared from tetra-aza macrocyclic ligands through a convenient synthesis

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     The present application is a continuation of pending International patent application PCT/KR2005/001267, filed May 2, 2005, which designates the United States and claims priority from Korean patent application no. 10-2004-0030923, filed May 3, 2004, the content of which is incorporated herein by reference. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to a tetra-aza macrocyclic ligand for use in preparing a bleach activator, a method for the convenient synthesis of the ligand, and a bleaching composition and bleaching detergent composition comprising a manganese complex prepared by the ligand. More particularly, the present invention relates to a macrocyclic manganese complex as a bleach activator for activating hydrogen peroxide and hydrogen peroxide generated by a peroxide in an aqueous solution, and to a method for the convenient synthesis of a tetra-aza microcyclic ligand for use in preparing the macrocyclic manganese complex, as well as the use of the synthesized complex, i.e., a bleaching composition and bleaching detergent composition comprising the macrocyclic manganese complex. 
     BACKGROUND OF THE INVENTION 
     Generally, bleaches are classified into chlorine-based bleaches and oxygen-based bleaches. The chlorine-based bleaches have limitations in the use thereof since they decolorize the dyes of clothes or have a unique irritating odor. Thus, the oxygen-based bleaches without such drawbacks are generally used as bleaches or detergents for clothes. 
     For the oxygen-based bleaches, liquid hydrogen peroxide has long been used in liquid bleaches, and solid sodium perborate (NaBO3.H2O, NaBO3.4H2O) and sodium percarbonate (2Na2CO3.3H2O2) have long been used in powder bleaches or detergents. However, oxygen-based bleaches, such as sodium perborate, sodium percarbonate and hydrogen peroxide, are inferior in bleaching ability to the chlorine-based bleaches and have relatively low bleaching performance at low temperature, and thus, can exhibit a sufficient bleaching effect only at a temperature of more than 60° C. If these inorganic peroxides are used at a lower temperature than 60° C., their oxidizing ability can be enhanced by the addition of bleach activators, such as acyls or esters. However, such prior bleach activators are disadvantageous in that they should be generally compounded in stoichiometrically equal or greater amounts. Furthermore, the prior bleach activators have a disadvantage in that their efficiency is remarkably reduced at a washing temperature of about 20° C., which is the washing environment in Korea. 
     It has been known in the prior art that general transition metal ions catalyze the decomposition of hydrogen peroxide and a peroxide generating hydrogen peroxide in an aqueous solution. In view of this fact, there have been efforts to solve the problem of the prior bleach activators and to develop effective bleach activators which can show sufficient bleaching ability even at a low temperature of about 20° C. U.S. Pat. Nos. 4,119,557 and 4,430,243 disclose methods of using transition metal ions together with chelating agents, to activate peroxide. However, all combinations of transition metal ions and chelating agents are not regarded to be effective in activating the oxygen-based bleaches. It is known in fact that many combinations of transition metal ions and chelates have no bleaching effects or show adverse effects. 
     Accordingly, in order to use transition metals as activating catalysts in bleaching compositions and bleaching detergent compositions, it is particularly important to find out metal catalysts which do not cause irreversible oxidations and decompose peroxides in only a pathway of bleaching. 
     In this viewpoint, attempts to use transition metal compounds, particularly complexes comprising manganese and cobalt, as bleaching catalysts, are recently made. For example, U.S. Pat. No. 5,246,621 discloses a binuclear manganese complex with a 1,4,7-trimethyl-1,4,7-triazacyclononane ligand. This transition metal complex can be used to wash fabrics using suitable inorganic peroxides. However, this complex has problems in that it is very expensive due to a difficult synthesis thereof, and causes excessive bleaching to damage fibers or to decolorize dyes, when the catalyst is used in an excessive amount. In the usual laundry practice of customers, a detergent is put onto the laundry to which water is then added. Thus, an excessive amount of the detergent component can exist on a portion of clothes, in which case if an excessive amount of the bleaching catalyst exists to cause excessive bleaching, fiber damage or dye fading can occur. 
     SUMMARY OF THE INVENTION 
     Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art. The present invention provides a bleach activator which is synthesized in a relatively easy and inexpensive manner, is stable to hydrolysis, oxidation, reduction and the like, does not cause fiber damage or dye decolorization, and has an excellent bleaching effect even at low temperature, as well as a preparation method thereof. 
     The present invention also provides a bleaching composition and bleaching detergent composition comprising said bleach activator. 
     The present inventors have synthesized racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hereinafter, referred to as “rac-14-decane”) of Formula 4 and meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hereinafter, referred to as “mes-14-decane”) of Formula 5 at high yields, and found that the use of said compounds as ligands allows relatively easy synthesis of manganese complexes of Formulas 1-3, and the use of such macrocyclic manganese complexes provides a remarkable improvement in the bleaching ability of peroxides and does not cause excessive bleaching even when used in an excessive amount. On the basis of these findings, the present invention has been completed. 
     Accordingly, the present invention discloses the inventive bleach activator that is an manganese complex for activating hydrogen peroxide and hydrogen peroxide generated from a peroxide, the bleach activator being selected from macrocyclic manganese complexes, including [Mn III (rac-14-decane)X 2 ]Y, [Mn III (mes-14-decane)X 2 ]Y.H 2 O, and [Mn III (mes-14-decane)X 2 ]Y represented by Formulas 1-3, respectively: 
     
       
         
         
             
             
         
       
     
     wherein X is at least one selected from chlorine (—Cl) and acetate (—OOCCH 3 ), Y is an anion selected from Cl—, Br—, F—, NO 3 —, ClO 4 —, OH—, NCS—, N 3 —, and PF 6 —. 
     The present invention also discloses a bleaching composition comprising 1-99% by weight of peroxide and an effective amount of the macrocyclic manganese complex as a bleach activator. 
     The present invention also discloses a bleaching detergent composition comprising 0.001-5% by weight of the macrocyclic manganese complex as a bleach activator. 
     The bleach activator according to the present invention is preferably granulated in view of stability and utility, and the detergent composition preferably comprises 1-40% by weight of sodium percarbonate or sodium perborate as inorganic peroxide. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Hereinafter, the action and effect of the inventive macrocyclic manganese complexes as bleach activators will be described in detail. 
     The present invention provides macrocyclic manganese complexes as bleach activators, such as [Mn III (rac-14-decane)X 2 ]Y, [Mn III (mes-14-decane)X 2 ]Y.H 2 O and [Mn III (mes-14-decane)X 2 ]Y represented by Formulas 1-3, respectively. 
     The above-described manganese complexes as bleach activators act to activate oxygen-based bleaches generating hydrogen peroxide. These macrocyclic manganese complexes are bleach activators which are stable to hydrolysis, oxidation and reduction and have an excellent ability to activate bleaching agents even at low temperature. Also, they have an advantage in that they do not cause excessive bleaching even when added in an excessive amount. 
     Thus, the bleach activators of the present invention show a beneficial effect of improving the bleaching ability of bleaches and bleaching detergents even when they are used in a small amount together with bleaches, such as hydrogen peroxide, inorganic peroxides generating hydrogen peroxide in an aqueous solution, peracids and their salts. 
     As described above, manganese-containing transition metal complexes according to the present invention have been studied for purposes having no connection with bleaching. For example, a synthesis method of [Mn III Cl 2 (14-decane)]X(X═PF 6 —, BF 4 —) is described in the literature (Philip S. Bryan et al., “Synthesis and Characterization of Manganese complexes Containing a synthetic macrocyclic Ligand”, Inorganic Chemistry, Vol. 14, No. 2, 1975, 296), but this complex is difficult to synthesize and also there was no recognition that this complex can act as a remarkably efficient bleach activator for peroxide. 
     Also, the literature (N. F. Curtis and R. W. Hay, Chem. Comm., 1966, No. 15, 524-525) or the literature (R. W. Hay and G. A. Lawrance, Journal of Chemical Society Perkin 1, 1975, 591-593) suggests methods for synthesizing ligands of Formulas 4 and 5. However, the former case has significant risk and low yield due to the use of perchloric acid (HClO 4 ) in a step of ligand synthesis, and the latter case provides an improvement in yield by the use of bromic acid (HBr) but also involves troublesomeness and significant risk due to direct reaction of sodium borohydride (NaBH 4 ) into methanol solution. 
     Accordingly, the present invention provides a method capable of reducing ligands at high yield in a safer manner, the method comprising the steps of: suspending 14-deca-4,11-diene of Formula 6 in water and adding dropwise to the suspension an aqueous alkaline solution of sodium borohydride of pH 9 or higher, at a temperature of 0° C. to 10° C. with stirring; maintaining the stirred solution at more than 50° C. for at least 30 minutes; and cooling the heated solution to ambient temperature and then adding an aqueous alkaline solution of pH 9 or higher to the cooled solution again so as to precipitate the product. 
     In another aspect, the present invention provides a bleaching composition comprising 1-99% by weight of peroxide and, as a bleach activator, an effective amount of at least one macrocyclic manganese complex selected from the group consisting of [Mn III (rac-14-decane)X 2 ]Y, [Mn III (mes-14-decane)X 2 ]Y.H2O and [Mn III (mes-14-decane)X 2 ]Y represented by Formulas 1-3, respectively. 
     In this respect, the macrocyclic manganese complex is preferably used in a granulated form rather than using it as it is. Thus, the granulated bleach activator is prepared by mixing the following components: a) 1-30% by weight of a binder; b) 10-90% by weight of a filler; c) 10-60% by weight of a disintegrant; and d) 0.01-50% by weight (preferably 1-30% by weight) of the macrocyclic manganese complex. Also, the granulated bleach activator is prepared by coating with post-coating powder and the like. The post-coating powder is used in an amount of 1-20% by weight. 
     The binder may be at least one selected from polyethyleneglycol (PEG), polyvinylpyrrolidone (PVP), and ethyleneoxide nonionic surfactants, and the filler may be at least one selected from inorganic salts, such as sodium carbonate (Na 2 CO 3 ), sodium chloride (NaCl), sodium sulfate (Na 2 SO 4 ), and the like. Also, the disintegrant may be at least one selected from silica, sodium carboxylmethylcellulose (SCMC), and hydroxypropylmethylcellulose (HPMC). Finally, the post-coating agent may be at least one selected from zeolite-4A, titanium dioxide (TiO 2 ) and the like. The diameter of final dried granules passed through a fluidized bed dryer is 100-2000 μm, and preferably 300-1500 μm. 
     The peroxides generating hydrogen peroxide include inorganic peroxides, such as alkali metal perborate, percarbonate and persulfate, and organic peroxides, such as urea peroxide. Organic peracids and their salts may also be used as the peroxides, but sodium percarbonate, sodium perborate monohydrate and sodium perborate tetrahydrate are preferred in terms of cost, performance and safety. These peroxides may also be used in a mixture of two or more of the above-listed peroxides. 
     In another aspect, the present invention provides a bleaching detergent composition comprising a peroxide, a surfactant, a builder and a bleach activator, the bleach activator being at least one macrocyclic manganese complex selected from the group consisting of [Mn III (rac-14-decane)X 2 ]Y, [Mn III (mes-14-decane)X 2 ]Y.H 2 O and [Mn III (mes-14-decane)X 2 ]Y represented by Formulas 1-3, respectively. 
     The bleaching detergent composition preferably comprises 1-40% by weight of sodium percarbonate or sodium perborate as inorganic peroxide, and the macrocyclic manganese complex may be compounded in an amount of 0.001-5% by weight based on the detergent composition. 
     Examples of surfactants which can be used in the composition include an anionic surfactant, a nonionic surfactant and soap. The anionic surfactant may be at least one selected from alkylbenzene sulfonate, alkyl sulfonate, alkyl ether sulfonate, alkane sulfonate, and olefin sulfonate. The nonionic surfactant may be at least one selected from straight chain and branched chain alkylpolyethoxy alcohols, alkylpolyethoxy fatty acid ester, and fatty acid alkanolamides. The total content of the surfactants is preferably 1-50% by weight based on the composition. 
     Examples of the builder used in the composition include inorganic builders and organic builders, and are used in an amount of 1-90% by weight. Examples of the inorganic builders include sodium carbonate, sodium tripolyphosphate, aluminosilicates such as natural or synthetic zeolites, sodium silicate and sodium sulfate, and examples of the inorganic builders include sodium polyacrylate, polymaleate and citrate. 
     The inventive bleaching detergent composition may comprise an additional bleach activator in addition to the macrocyclic manganese complex, and examples of the additional bleach activator include, but are not limited to, acyls such as tetraacetylethylenediamine (hereinafter, referred to as “TAED”), esters such as sodium alkanoyloxybenzenesulfonate, kenones, amides, and nitriles. 
     In addition, the inventive bleaching detergent composition may comprise additives generally used in powder detergents, such as fluorescents, enzymes, perfumes, and chelating agents. 
     In the present invention, tetra-aza macrocyclic ligands represented by Formulas 4 and 5, which are the ligands of the macrocyclic manganese complexes represented by Formulas 1-3, may first be prepared. 
     
       
         
         
             
             
         
       
     
     Preparation 1: Synthesis of 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diendihydrobromide dihydrate(14-deca-4,11-diene) 
     According to the method described in the literature (R. W. Hay, G. A. Lawrance, Journal of Chemical Society Perkin I, 1975, 591-593), 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diendihydrobromide dihydrate(14-deca-4,11-diene) was synthesized. 
     Elemental analysis for C 16 H 36 N 4 .2HBr.2H 2 O: 
     Calculated: C, 40.2; H, 8.0; N, 11.7. 
     Found: C, 40.3; H, 7.8; N, 11.9. 
     [Formula 6] 14-deca-4,11-diene 
     
       
         
           
               
            
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
           
               
               
               
            
               
                 Compound 
                 R 
                 R′ 
               
               
                   
               
               
                 A 
                 2HBr 
                   
               
               
                 B 
                 2HBr 
                 2H 2 O 
               
               
                 C 
                 2HClO 4   
               
               
                 D 
                 2HClO 4   
                 2H 2 O 
               
               
                   
               
            
           
         
       
     
     Preparation 2: Synthesis of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane(14-decane) 
     18 g of 14-deca-4,11-diene was suspended in 60 ml of H 2 O, and 3 g of sodium borohydride (NaBH 4 ) and 0.06 g of NaOH were dissolved in 20 ml of H 2 O. Then, the solution was added dropwise to the suspension at a temperature of 0° C. to 10° C. while stirring for one hour. Here, bubbles generated at this time was controlled using an antifoaming agent. The stirred solution was heated above 50° C. for 30 minutes and cooled to ambient temperature. To the cooled mixture, a solution of 8 g of NaOH in 20 ml of H 2 O was added, followed by stirring for about 1 hour. The stirred solution was cooled to 0° C. so as to produce a white solid, and this precipitate was filtered followed by washing, thus synthesizing white crystalline 14-decane. 
     Elemental analysis for C 16 H 36 N 4 : 
     Calculated: C, 67.55; H, 12.75; N, 19.69. 
     Found: C, 68.10; H, 12.55; N, 19.35. 
     Preparation 3: Separation of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane(14-decane) 
     28 g of 14-decane was dissolved in 400 ml of MeOH and hot filtered to remove impurities. The filtrate was added with 300 ml of distilled water, followed by cooling to ambient temperature. The produced solid was filtered and sufficiently washed with cold distilled water to obtain mes-14-decane. 10 g of KOH was added into the filtrate so as to precipitate a solid which was then filtered, thus obtaining rac-14-decane. 
     Preparation 4: Synthesis of [Mn III (rac-14-decane)Cl 2 ]ClO 4    
     1.692 g of rac-14-decane was dissolved in 50 ml of methanol, and to this solution, an addition of 1.2 g of MnCl 2 .4H 2 O in 100 ml of methanol gave rise to a dark brown solution. The formed solution was stirred for 24 hours with the injection of air, followed by filtration. To this filtrate, concentrated hydrochloric acid and concentrated perchloric acid were added to form a greenish solid. The solid was filtered and washed with methanol, thus synthesizing greenish [Mn III (rac-14-decane)Cl 2 ]ClO 4 . 
     IR (KBr, cm −1 ): 3157, 2971, 1629, 1172, 1104, 1000, 624 
     Elemental analysis for C 16 H 36 N 4 MnCl 3 O 4 : 
     Calculated: C, 37.70; H, 7.12; N, 10.99. 
     Found: C, 37.83; H, 7.44; N, 10.89. 
     Preparation 5: Synthesis of [Mn III (mes-14-decane)Cl 2 ]ClO 4 .H 2 O 
     1.692 g of mes-14-decane was dissolved in 50 ml of methanol, and to the solution, an addition of 1.482 g of Mn(CH 3 COO) 2 .4H 2 O in 50 ml of methanol gave rise to a dark brown solution. This solution was stirred for 24 hours with the injection of air. To the stirred solution, concentrated hydrochloric acid and concentrated perchloric acid were added to produce a greenish solid. The solid was filtered and washed with methanol, thus synthesizing greenish [Mn III (mes-14-decane)Cl 2 ]ClO 4 .H 2 O. 
     IR (KBr, cm-1): 3587, 3144, 2973, 1424, 1104, 1000, 624 
     Elemental analysis for C 16 H 36 N 4 MnCl 3 O 4 H 2 O: 
     Calculated: C, 36.41; H, 7.25; N, 10.61. 
     Found: C, 36.56; H, 7.03; N, 10.57. 
     Preparation 6: Synthesis of [Mn III (mes-14-decane)Cl 2 ]NO 3 .H 2 O 
     1.692 g of mes-14-decane was dissolved in 50 ml of ethanol, and to this solution, an addition of 1.482 g of Mn(CH 3 COO) 2 .4H 2 O in 50 ml of ethanol gave rise to a thick brown solution. The formed solution was stirred for 24 hours with the injection of air. To the stirred solution, concentrated hydrochloric acid and concentrated nitric acid were added to produce a yellow greenish solid. The solid was filtered and washed with ethanol, thus synthesizing yellow greenish [Mn III (mes-14-decane)Cl 2 ]NO 3 .H 2 O. 
     IR (KBr, cm-1): 3423, 3175, 3128, 2977, 1416, 1384. 
     Elemental analysis for C 16 H 36 N 5 MnCl 2 O 3 H 2 O: 
     Calculated: C, 39.19; H, 7.81; N, 14.28. 
     Found: C, 39.25; H, 7.99; N, 14.29. 
     Examples 1-5 And Comparative Examples 1-2 
     As set forth in Table 1 below, a bleach composition having no bleach activator added to sodium percarbonate was used as Comparative Example 1, and a composition having sodium percarbonate and tetraacetylethylenediamine as a bleach activator was used as Comparative Example 2. Also, bleach compositions having sodium percarbonate and each of the macrocyclic manganese complexes prepared in Preparations 4-6 were used as Examples 1-5. The bleaching activities of the macrocyclic manganese complexes prepared according to Preparations 4-6 in the bleach compositions were measured on tea, coffee, sugar beet, and red wine-stained fabrics. The measurement conditions are as follows: 
     Measurement device: Terg-O-Tometer 
     Washing temperature: 25° C.; 
     Washing water: distilled water containing CaCO3 in an amount to corresponding to a hardness of 90 ppm; 
     Washing time: 10 min (120 rpm) 
     Evaluation: The whiteness of the stained fabrics was measured with a specto color meter before and after the washing and expressed as a percentage based upon the washing ability of Comparative Example 1 taken as 100. The results are shown in Table 1 below. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Comparative 
                 Comparative 
                   
                   
                   
                   
                   
               
               
                   
                 Example 1 
                 Example 2 
                 Example 1 
                 Example 2 
                 Example 3 
                 Example 4 
                 Example 5 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Sodium 
                 4.6 
                 4.6 
                 4.6 
                 4.6 
                 4.6 
                 4.6 
                 4.6 
               
               
                 percarbonate (g) 
                   
                   
                   
                   
                   
                   
                   
               
               
                 TAED (g) 
                 0 
                 0.4 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Manganese 
                 0 
                 0 
                 0.04 
                 0.004 
                 0 
                 0 
                 0 
               
               
                 complex (g) of 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Preparation 4 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Manganese 
                 0 
                 0 
                 0 
                 0 
                 0.04 
                 0.004 
                 0 
               
               
                 complex (g) of 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Preparation 5 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Manganese 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0.04 
               
               
                 complex (g) of 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Preparation6 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability 
                 100 
                 123 
                 213 
                 136 
                 262 
                 161 
                 243 
               
               
                 (%) (tea) 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability 
                 100 
                 128 
                 178 
                 134 
                 210 
                 147 
                 197 
               
               
                 (%) (coffee) 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability 
                 100 
                 110 
                 142 
                 119 
                 148 
                 127 
                 150 
               
               
                 (%) (sugar beet) 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability 
                 100 
                 110 
                 138 
                 116 
                 150 
                 127 
                 131 
               
               
                 (%) (red wine) 
               
               
                   
               
            
           
         
       
     
     As can be seen in Table 1 above, Examples 1-5 comprising the inventive manganese complex showed a significantly high washing activity as compared to Comparative 1 having no bleach activator added to sodium percarbonate and Comparative Example 2 having TAED added to sodium percarbonate, even when the inventive manganese complex was used at a low temperature of 25° C. in amounts of 1/10- 1/100 times the weight of TAED. This suggests that the macrocyclic manganese complexes of the present invention have a very excellent ability to activate bleaches. 
     Examples 6-8 and Comparative Example 3 
     As shown in Table 2 below, detergent compositions of Comparative Example 3 and Examples 6-8 were prepared by adding TAED and the macrocyclic manganese complexes prepared in Preparations 4-6, respectively, to 0.8 g of a commercially available concentrated detergent having no bleach and 0.15 g of sodium percarbonate. Then, the bleaching activities of the detergent compositions were evaluated on tea, coffee, sugar beet and curry-stained fabrics. 
     The test conditions are the same as in Examples 1-4. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Comparative Example 3 
                 Example 6 
                 Example 7 
                 Example 8 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Concentrated detergent (g) 
                 0.8 
                 0.8 
                 0.8 
                 0.8 
               
               
                 Sodium percarbonate (g) 
                 0.15 
                 0.15 
                 0.15 
                 0.15 
               
               
                 TAED (g) 
                 0.05 
                 0 
                 0 
                 0 
               
               
                 Manganese complex (g) of 
                 0 
                 0.00125 
                 0 
                 0 
               
               
                 Preparation 4 
               
               
                 Manganese complex (g) of 
                 0 
                 0 
                 0.00125 
                 0 
               
               
                 Preparation 5 
               
               
                 Manganese complex (g) of 
                 0 
                 0 
                 0 
                 0.00125 
               
               
                 Preparation 6 
               
               
                 Washing ability (%) (tea) 
                 100 
                 119 
                 133 
                 132 
               
               
                 Washing ability (%) (coffee) 
                 100 
                 119 
                 121 
                 124 
               
               
                 Washing ability (%) (sugar beet) 
                 100 
                 117 
                 121 
                 119 
               
               
                 Washing ability (%) (curry) 
                 100 
                 107 
                 110 
                 106 
               
               
                   
               
            
           
         
       
     
     As can be seen in Table 2 above, Examples 6-8 comprising the macrocyclic manganese complex of the present invention showed a significantly high washing as compared to Comparative Example 3, that is the prior bleaching detergent composition containing sodium percarbonate and TAED, even though the macrocyclic manganese complexes were used in only 1/40 times the weight of TAED. 
     Example 9 
     Evaluation of Bleaching Ability in the Case of Excessive Addition 
     Compositions were prepared by adding [Mn III (rac-14-decane)Cl 2 ]ClO 4  or [Mn III (mes-14-decane)Cl 2 ]ClO 4 .H 2 O prepared in Preparations 4-5 to 0.8 g of a commercially available concentrated detergent and 0.15 g of sodium percarbonate at varying concentrations as shown in Table 3 below. The washing abilities of the compositions were evaluated on tea-stained fabrics. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
             
            
               
                 Manganese complex 
                 0.0002 
                 0.0005 
                 0.0025 
                 0.005 
                 0.001 
                 0.002 
                 0.003 
                 0.004 
                 0.005 
               
               
                 (g) of Preparation 4 or 5 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability (%) 
                 100 
                 99 
                 132 
                 179 
                 201 
                 224 
                 231 
                 251 
                 250 
               
               
                 of manganese 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 complex of 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Preparation 4 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability (%) 
                 100 
                 129 
                 229 
                 251 
                 281 
                 263 
                 240 
                 189 
                 180 
               
               
                 of manganese 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 complex of 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Preparation 5 
               
               
                   
               
            
           
         
       
     
     As can be seen in Table 3 above, [Mn III (rac-14-decane)Cl 2 ]ClO 4  of Preparation 4 maintained almost constant bleaching ability with an increase in concentration, and [Mn III (mes-14-decane)Cl 2 ]ClO 4 .H 2 O of Preparation 5 showed a decrease in bleaching activity at more than a given concentration. This indicates that the bleach activators according to the present invention do not cause the excessive bleaching of fabrics even when they are added in an excessive amount. Thus, the inventive bleach activators do not cause damage to the dyes or fibers of clothes. 
     Preparations 7-10: Granulation of Bleach Activators 
     The granulation of bleach activators can be achieved by the use of a Lödige mixer™ or an extruder. Granulation in Preparations 7 and 8 were performed using the Lödige mixer™, and granulation in Preparations 9 and 10 was performed using the extruder. First, the manganese complexes prepared in Preparations 4 and 5 together with a disintegrant and a filler were placed and mixed in Lödige mixer™. When the components were mixed homogeneously, the upper lid of the mixer was opened and an aqueous binder solution was added into the mixer while operating only a main blade. The chopper was rotated to perform the granulation of the bleach activators. As particles with a suitable size are formed, a post-coating agent was added and the main blade and the chopper were operated to complete the granulation. In this respect, the compositions and concentrations of the disintegrant, filler and binder used in the granulation process, and other detail test conditions, are shown in Table 4 below. In Preparation Examples 9 and 10 conducted using the extruder, the corresponding raw materials including the manganese complexes of Preparations 4 and 5 were mixed homogeneously, to which an aqueous binder solution was then added. Then, granules with the same diameter were prepared by the extruder and formed to a given diameter by a Spheronizer. The prepared granules were dried to hot air drying using a fluid bed dryer. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Granulation conditions 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Preparation 
               
               
                   
                 Preparation 7 
                 Preparation 8 
                 Preparation 9 
                 10 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                 Manganese 
                 300, 
                 200 g, 
                 200 g, 
                 300 g, 
               
               
                 complex (g) 
                 Preparation 4 
                 Preparation 5 
                 Preparation 4 
                 Preparation 5 
               
               
                 Filler (g) 
                 Na 2 SO 4  500 
                 NaCl 400 
                 NaCl 300 
                 Na 2 SO 4   
               
               
                   
                   
                   
                   
                 300 
               
               
                 Binder (g) 
                 PEG 120 
                 PVP K-30 
                 PVP K-30 
                 PEG 120 
               
               
                   
                   
                 120 
                 120 
               
               
                 Disintegrant 
                 SCMC 250 
                 Silica 250 
                 Silica 400 
                 SCMC 500 
               
               
                 (g) 
               
               
                 Post-coating 
                 TiO 2  70 
                 Zeolite-4A 
               
               
                 agent (g) 
                   
                 70 
               
               
                 Revolution 
                 140 
                 140 
               
               
                 speed (rpm) of 
               
               
                 main blade 
               
               
                 Revolution 
                 3000 
                 3000 
               
               
                 speed (rpm) of 
               
               
                 chopper 
               
               
                   
               
            
           
         
       
     
     Examples 10-11 and Comparative Examples 4-5 
     Evaluation of Storage Stability 
     In order to use the manganese complex granules of Examples 7-10 in bleach and detergent compositions, the complex granules were placed in vials and stored at 45° C. and 75% RH for 5 weeks. Then, the granules of the complexes in the vials were tested for long-term storage stability by the titration of active oxygen as compared with TAED. The test conditions are as follows and active oxygen was calculated according to the following equation. 
     Reagent 1: 55 ml of concentrated sulfuric acid was added to 500 ml of distilled water, and 100 g of Al 2 (SO 4 )3.18H 2 O and 1.6 g of Bi(NO 3 ) 3 .5H 2 O were dissolved to prepare I liter of a solution. 
     Reagent 2: 1N KMnO 4  solution 
     Test conditions: the sample was precisely taken and placed in a 500 ml beaker. To the beaker, 100 ml of the reagent 1 and 300 ml of distilled water were added, followed by stirring. The reagent 2 was titrated to an end point to which a pale pink color lasted for 30 minutes. The amount of active oxygen was calculated according to the following equation 1:
 
Amount of active oxygen (%)=4×volume of KMnO 4  (ml)×concentration of KMnO 4  (N)/5×amount of sample (g)  [Equation 1]
 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                   
                   
                 Manganese complex 
                   
                 Sodium 
                   
               
               
                   
                 TAED 
                 (as actives, g) 
                 Concentrated 
                 percarbonate 
                 Active 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 (g) 
                 Preparation 7 
                 Preparation 9 
                 detergent (g) 
                 (g) 
                 oxygen 
               
               
                   
               
               
                 Comparative 
                   
                   
                   
                 2.1 
                 0.9 
                 13.44 
               
               
                 Example 4 
                   
                   
                   
                   
                   
                   
               
               
                 Comparative 
                 0.15 
                   
                   
                 2.1 
                 0.9 
                 12.30 
               
               
                 Example 5 
                   
                   
                   
                   
                   
                   
               
               
                 Example 10 
                   
                 0.00375 
                   
                 2.1 
                 0.9 
                 12.27 
               
               
                 Example 11 
                   
                   
                 0.00375 
                 2.1 
                 0.9 
                 12.63 
               
               
                   
               
            
           
         
       
     
     Examples 12-13 and Comparative Example 6 
     Evaluation of Long-Term Storage Stability 
     In order to use the dried manganese complex granules of Preparations 7-9 in bleaching and detergent compositions, the granules were formulated as shown in Table 6 below and stored at 45° C. and 70% RH for 5 weeks. Then, the long-term storage stability of bleach activators in the formulations was tested on various stained fabrics to be bleached, as compared with TAED. The test conditions were the same as in Examples 1-4, and the amount of manganese complexes was based on active components. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
             
            
               
                   
                 Comparative 
                   
                   
               
               
                   
                 Example 6 
                 Example 12 
                 Example 13 
               
               
                   
               
               
                 Concentrated detergent 
                 0.67 
                 0.67 
                 0.67 
               
               
                 (g) 
                   
                   
                   
               
               
                 Sodium percarbonate 
                 0.28 
                 0.28 
                 0.28 
               
               
                 (g) 
                   
                   
                   
               
               
                 TAED(g) 
                 0.05 
                   
                   
               
               
                 Manganese complex 
                   
                 0.00125 
                   
               
               
                 (g) of Preparation 7 
                   
                   
                   
               
               
                 Manganese complex 
                   
                   
                 0.00125 
               
               
                 (g) of Preparation 9 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Stained fabrics to be 
                   
                 After 
                   
                 After 
                   
                 After 
               
               
                 bleached 
                 Initial 
                 storage 
                 Initial 
                 storage 
                 Initial 
                 storage 
               
               
                   
               
               
                 Washing ability (tea) 
                 100 
                 100 
                 101 
                 133 
                  98 
                 134 
               
               
                 Washing ability 
                 100 
                 100 
                 117 
                 100 
                 112 
                 112 
               
               
                 (coffee) 
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability (sugar 
                 100 
                 100 
                 110 
                 116 
                 107 
                 121 
               
               
                 beet) 
                   
                   
                   
                   
                   
                   
               
               
                 Washing ability 
                 100 
                 100 
                 105 
                 111 
                 102 
                 109 
               
               
                 (curry) 
               
               
                   
               
            
           
         
       
     
     As can be seen in Table 6 above, similarly to Comparative Example 5 or 6, that is the prior bleaching detergent composition containing sodium percarbonate and TAED, Examples 10 and 11 comprising the macrocyclic manganese complex of the present invention showed a slight decrease in the amount of initial active oxygen as compared with Comparative Example 4. However, as can be seen in Table 6 above, Examples 12 and 13 showed the equal or higher washing ability after 5 weeks as compared to Comparative Example 6, even when the bleach activator of the present invention was used in only 1/40 times the weight of TAED. This suggests that the compositions of Examples 12 and 13 have long-term storage stability. 
     Examples 14-15 and Comparative Example 7 
     Evaluation of Fabric Damage 
     Bleach activator-containing concentrated detergents were formulated at composition ratios as shown in Table 7 below. In accordance with a standard usage of the formulated detergents, color fabrics with various colors were washed 30 times in a top-loading washing machine (10 kg capacity) with 40° C. tap water. A change in the surface reflectivity of the dyed fabrics as compared a color difference with the initial state measured, and from the measurement results, the relative fading difference of each fabric was calculated according to the following equation 2. Also, the loss of warp and weft tensile strengths of each of the dyed fabrics were determined according to KS methods and averaged to evaluate the extent of fiber damage.
 
Δ E =√(Δ L   2   +Δa   2   +Δb   2 )  (Equation 2)
 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Evaluation of dye damage by 
               
               
                 calculation of decoloration of fibers 
               
            
           
           
               
               
               
               
            
               
                   
                 Comparative 
                   
                   
               
               
                   
                 Example 7 
                 Example 14 
                 Example 15 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                 Concentrated 
                 80% 
                 80% 
                 80% 
               
               
                 detergent 
               
               
                 Sodium percarbonate 
                 15% 
                 15% 
                 15% 
               
               
                 TAED 
                  5% 
               
               
                 Bleach activator of 
                   
                  5% 
               
               
                 Preparation 7 
               
               
                 Bleach activator of 
                   
                   
                  5% 
               
               
                 Preparation 9 
               
            
           
           
               
               
            
               
                 Dyed fabric 
                 Total color difference (   E) 
               
            
           
           
               
               
               
               
            
               
                 Reactive Red 158 
                 14.00 
                 6.33 
                 6.43 
               
               
                 Sulfur Blue 19 
                 32.56 
                 28.83 
                 28.66 
               
               
                 Reactive Blue 225 
                 17.32 
                 10.14 
                 10.37 
               
               
                 Direct Blue 71 
                 5.39 
                 5.18 
                 4.98 
               
               
                 Direct Black 22 
                 31.05 
                 10.35 
                 10.80 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Measurement of extent of fiber damage 
               
               
                 by measurement of tensile strength (unit: kgf/cm 2 ) 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Comparative 
                   
                   
               
               
                 Dyed fabric 
                 Initial 
                 Example 7 
                 Example 14 
                 Example 15 
               
               
                   
               
               
                 Reactive Red 158 
                 20.6 
                 18.6 
                 20.5 
                 19.7 
               
               
                 Sulfur Blue 19 
                 21.2 
                 17.0 
                 19.6 
                 20.3 
               
               
                 Reactive Blue 
                 20.9 
                 18.0 
                 19.5 
                 18.8 
               
               
                 225 
               
               
                 Direct Blue 71 
                 21.4 
                 17.4 
                 19.6 
                 20.2 
               
               
                 Direct Black 22 
                 22.0 
                 17.7 
                 20.4 
                 21.0 
               
               
                 EMPA 116 
                 31.8 
                 28.8 
                 30.2 
                 30.7 
               
               
                   
               
            
           
         
       
     
     As shown in Tables 7 and 8, the results of recycled washing using Examples 14-15 with the same bleach activator concentration as TAED of Comparative Example 7 showed that Examples 14-15 had very good properties with respect to the dye fading and the fiber damage as compared with Comparative Example 7. In view of the fact that the bleach activators of the present invention actually show the equal or higher bleaching activity and storage stability at an amount of about 1/40 as compared with TAED, the inventive bleaching activators do not cause damage to the dyes or fibers of fabrics in commercial applications. 
     As described above, the macrocyclic manganese complexes according to the present invention are easily synthesized and have an excellent bleaching performance even in a low amount as compared with the prior bleaching activators. Also, the inventive bleaching activators are safer with respect to fabric damage and have a bleaching performance even at low temperature. Thus, the bleaching compositions and bleaching detergent compositions comprising the inventive bleach activators have a superior bleaching performance to that of the prior compositions. 
     It will be apparent to those skilled in the art that various modifications and variation can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided that they come within the scope of the appended claims and their equivalents.