Process for handwashing socks or stockings
This is a continuation of U.S. Ser. No. 756,954, filed Jan. 5, 1977, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to a new detergent composition. More specifically, it is concerned with a detergent composition suitable for use in washing socks and stockings. 
     Heretofore, conventional detergents for clothings have been used in washing socks and stockings. When the socks and stockings are washed together with other clothes in a washing machine using these detergents, many problems arise. For example, the rubbered garter section of the socks and stockings is loosened; the fiber from which the socks and stockings are made deteriorates; the fiber waste of other clothes adheres to the socks and stockings; and difficulty is encountered in rinsing the socks and stockings. In addition to these difficulties, the offensive odor inherent in the socks and stockings soaks into other clothes. 
     Further, when the socks and stockings are handwashed using the above mentioned detergents, the detergents heavily foam, so that they are unfavourable on the points of rinsability, deodorization, and prevention of hand chap. 
     In addition, detergents which are generally called detergents for wool have also been used in washing socks and stockings. In most cases, these detergents are used in washing by hand. However, these detergents have selectivity with respect to fiber materials and are not useful for a wide range of raw fiber materials. Also, unless tepid water is used, they cannot satisfactorily exhibit their detergency. Additionally, those detergents are not satisfactory as detergents for socks and stockings on the points of rinsability and deodorization. 
     SUMMARY OF THE INVENTION 
     It is an object of the present invention to provide a detergent composition particularly favorable as a detergent for use in laundering socks and stockings which overcomes the above mentioned difficulties associated with the conventional detergents for clothings. 
     The detergent composition of the present invention comprises, as effective components, an ethylene oxide adduct of a secondary alcohol, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant. 
     Generally, a fiber material for socks and stockings includes cotton, nylon, acrylic, polyurethane, polyester, acetate, rayon, wool, and silk. These fiber materials are used singly or in combination. Therefore, a detergent for socks and stockings must have excellent detergency for dirt adhering to the above mentioned fiber materials, and excellent deodorization and must be effective for all types of fiber material. Further, it is necessary that the detergent must not damage the fiber material and must be easily rinsed out. 
     The dirt of socks and stockings is generally divided into dirt arising from the interior thereof and dirt accumulated from the exterior thereof when one is wearing them. The dirt produced from the interior includes oily and greasy grime, hydrocarbon contaminants and salts, such as perspiration, sebum and skin dirt. The dirt accumulated from the exterior includes, in particular, dust and dirt. In addition to the adherence of these dirts, the smell of a shoe material, for example, the smell of rubber or leather, soaks into the socks and stockings. Thus, the dirt of the socks and stockings is considered to be a combination of these dirts and smells. Consequently, soiled socks and stockings almost always reek with the smell of sweat and a putrid and offensive ordor which promote the growth of fungi and render them unsanitary. 
     We have made many attempts to develop a detergent composition useful for removing the dirt and odor characteristic of socks and stockings. As a result, we have found that when a detergent composition comprising, as effective components, an ethylene oxide adduct of a secondary alcohol, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and an amphoteric surfactant is dissolved in water and soiled socks and stockings are immersed in the solution for a certain period of time, for example, an hour, only a subsequent slight hand washing and rinsing are necessary to produce odorless and clean socks and stockings without the aforementioned difficulties encountered in washing the socks and stockings with detergents for general clothings or for wool. On the basis of this discovery, we have developed this invention. 
     DETAILED DESCRIPTION 
     The ethylene oxide adduct of a secondary alcohol usable for the present invention is suitably a secondary alcohol having from 10 to 16 carbon atoms, for example, a mixture of secondary alcohols having from 11 to 15 carbon atoms with from 3 to 12 ethylene oxides added thereto. Examples of the adduct are a mixture of secondary alcohols having from 11 to 15 carbon atoms with 3, 5, 9 or 12 moles of ethylene oxide added thereto and a mixture of secondary alcohols having from 14 to 15 carbon atoms with 3, 5 or 10 moles of ethylene oxide added thereto. 
     The sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol usable for the present invention is suitably a salt of sulfate of a secondary alcohol having from 10 to 16 carbon atoms, such as, for example, a mixture of secondary alcohols having from 11 to 15 carbon atoms with from 1 to 8 ethylene oxides added thereto. Suitable types of the salt are sodium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts. Examples of the sulfuric ester salt are sodium, triethanolamine and ammonium salts of a mixture of C 11  -C 15  secondary alcohols ethoxysulfate having 3 moles of ethylene oxide added thereto and sodium, triethanolamine and ammonium salts of a mixture of C 14  -C 15  secondary alcohols ethoxysulfate having 3 moles of ethylene oxide added thereto. 
     Examples of suitable amphoteric surfactants usable in the present invention are alkyl glycine amphoteric surfactants wherein the alkyl has 8 to 18 carbon atoms such as alkyldiaminoethylglycines wherein the alkyl has 8 to 18 carbon atoms; betaines such as alkyldimethylbetaines wherein the alkyl has 12 to 18 carbon atoms and imidazolines such as cyclic imidinum amphoteric surfactants disclosed in U.S. Pat. No. 2,773,068 and having the formula: ##STR1## wherein R 1  is an aliphatic hydrocarbon group of 7 to 17 carbon atoms, R 2  is a member selected from the group consisting of hydroxyl, ##STR2## C 12  H 25  OSO 3  and C 13  H 27  (OC 2  H 4 ) 2  OSO 3 , R 3  is a member selected from the group consisting of CH 2  COOH, CH 2  COONa and ##STR3## and R 4  is a member selected from the group consisting of hydrogen, alkali metals, CH 2  COOH, CH 2  COONa and CH 2  COOK. 
     The particular effectiveness for washing socks and stockings of the detergent composition comprising, as effective compounds, the ethylene oxide adduct of a secondary alcohol, the sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, and the amphoteric surfactant will be illustrated by the following experimental examples and comparative experimental examples. 
     Detergency Test 1 
     The components indicated in Table 1 in the amounts of the ratio indicated in Table 1 were mixed with stirring to prepare a sample of a detergent composition. The total net content of the surfactants constituted 20 parts out of 100 parts of the composition. 
     Sample VI is a detergent composition comprising an ethylene oxide adduct of a secondary alcohol and a sulfuric ester of an ethylene oxide adduct of a secondary alcohol, and samples I through V are comparison samples. 
     
                                           TABLE 1                                 
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Sample                                                                    
Ratio                                                                     
     I        II       III     IV       V       VI                        
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33   C.sub.12 -C.sub.15 primary                                           
              C.sub.12 natural alco-                                      
                       Sodium salt of                                     
                               Linear alkyl-                              
                                        Normal paraffin                   
                                                Triethanolamine           
parts                                                                     
     alcohol ethoxy-                                                      
              hol ethoxysulfate                                           
                       C.sub.12 natural                                   
                               benzenesulfonate                           
                                        sulfonate                         
                                                salt of                   
                                                C.sub.11 -C.sub.1         
     sulfate           alcohol sulfate          secondary alcohol         
     (addition of                                                         
              (addition of 3   (C.sub.12 alkyl)                           
                                        (C.sub.14 -C.sub.16               
                                                ethoxysulfate             
     3 moles of E.O.)                                                     
              moles of E.O.)            paraffin)                         
                                                (addition of 3            
                                                moles of E.O.)            
67   Polyoxyethylene nonyl phenol ether         Ethylene oxide            
parts                                                                     
     (E.O. 10 moles)                            adduct of C.sub.11        
                                                -C.sub.15                 
                                                secondary alcohol         
                                                (addition of 9            
                                                moles of E.O.)            
Balance                                                                   
     Purified water                                                       
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 Note: E.O. = ethylene oxide                                              
 
    
     (1) Detergency test (according to reflectance measurement): 
     Socks to which natural dirts were adhering after one day&#39;s wear were immersed in an aqueous solution of each of the samples indicated in Table 1 for 1 hour, wherein the concentration was adjusted to a constant concentration (3.5 ml./l. water), and rinsed twice with water. 
     Each of the socks was evaluated for the reflectance (Rc) in percent before wearing, the reflectance (Rs) in percent after wearing and the reflectance (Rw) in percent after washing by means of a glossmeter (Model GM-24, manufactured by Murakami Color Technology Institute K.K.). The percent detergency was determined by the following equation: ##EQU1## 
     The results so obtained are shown in Table 2. With regard to the percent detergency, a higher value indicates a higher detergency of the detergent composition. 
     
                       TABLE 2                                                     
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             Sample                                                       
Fiber                                                                     
material of                                                               
socks          I      II     III  IV   V    VI                            
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Cotton mixed with                                                         
               67%    74%    70%  67%  74%  76%                           
acrylic, nylon and                                                        
polyurethane                                                              
Wool mixed with                                                           
               51     48     40   50   45   59                            
nylon and                                                                 
polyurethane                                                              
Cotton 100%    70     47     69   70   71   73                            
Nylon 100%     66     59     63   64   65   70                            
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     It is clear from Table 2 that the sample VI is superior in detergency to the samples 1 through V for all the types of fiber materials. However, it cannot be said that the detergent composition comprising only the ethylene oxide adduct of a secondary alcohol and the sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol has sufficient detergency for the socks or stockings. 
     Then, an experiment was conducted by using a detergent composition comprising each of the samples I through VI to which an amphoteric surfactant was added. 
     Detergency Test 2 
     The components indicated in Table 3 in the amounts of the ratio indicated in Table 3 were mixed together with stirring to prepare samples of detergent composition. The total net content of the surfactants constituted 20 parts out of 100 parts of the composition. 
     Sample XII is a detergent composition comprising an ethylene oxide adduct of a secondary alcohol, a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol and an amphoteric surfactant (the detergent composition of the present invention), and the samples VII through XI are comparison samples. 
     
                                           TABLE 3                                 
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Sample                                                                    
Ratio                                                                     
     VII      VIII     IX      X        XI      XII                       
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30   C.sub.12 -C.sub.15 primary                                           
              C.sub.12 natural alco-                                      
                       Sodium salt of                                     
                               Linear alkyl-                              
                                        Normal paraffin                   
                                                Triethanolamine           
parts                                                                     
     alcohol ethoxy-                                                      
              hol ethoxysulfate                                           
                       sulfuric ester                                     
                               benzenesulfonate                           
                                        sulfonate                         
                                                salt of                   
                                                C.sub.11 -C.sub.15        
     sulfate           of C.sub.12 natural      secondary alcohol         
     (addition of 3                                                       
              (addition of 3                                              
                       alcohol (C.sub.12 alkyl)                           
                                        (C.sub.14 -C.sub.16               
                                                ethoxysulfate             
     moles of E.O.)                                                       
              moles of E.O.)            paraffin)                         
                                                (addition of 3            
                                                moles of E.O.)            
65            Polyoxyethylene nonyl phenol ether                          
                                                Ethylene oxide            
parts         (E.O. 10 moles)                   adduct of C.sub.11        
                                                -C.sub.15                 
                                                secondary alcohol         
                                                (addition of 9            
                                                moles of E.O.)            
parts         Miranol C2M Conc.                                           
Balance       Purified water                                              
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 Note:                                                                    
 (1) E.O. = ethylene oxide                                                
 (2) Miranol C2M Conc. is a cyclic imidinum type amphoteric surfactant as 
 disclosed in U.S. Pat. No. 2773068.                                      
 
    
     (1) Detergency test (according to reflectance measurement): 
     Each of the samples was evaluated for detergency according to the procedure described in the detergency test of Experimental Example 1. The results are shown in Table 4. 
     
                       TABLE 4                                                     
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            Sample                                                        
                                           XII                            
Fiber                                      This                           
material of                                inven-                         
socks or stockings                         tion                           
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Cotton mixed with                                                         
              66%    71%    70%  60%  69%  78%                            
acrylic, nylon and                                                        
polyurethane                                                              
Wool mixed with                                                           
              61     54     42   50   50   73                             
nylon, and                                                                
polyurethane                                                              
Cotton 100%   80     50     75   81   81   85                             
Nylon 100%    77     66     75   75   75   85                             
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     (2) Permeability test: 
     The permeability test was conducted according to a canvas disc wetting test (Seyferth &amp; Morgan, &#34;Am. Dyestuff Reporter&#34; 27, Sept. 19, 1938). A circular piece of felt having a diameter of 10 mm was placed on the surface of each of sample solutions contained in a container. The sample solutions used were a 0.5% aqueous solution of each of the samples VII through XII indicated in Table 3. Then, the time for the felt to sink to the bottom was determined for each of the solutions. The shorter the time, the higher is the permeability of the sample. The results are shown in Table 5. 
     
                       TABLE 5                                                     
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           Sample                                                         
                                          XII                             
                                          This                            
Concentration                                                             
             VII    VIII   IX   X    XI   invention                       
______________________________________                                    
    0.5%                                                                  
    solution         30.9 76.6 15.8 8.7  10.3 7.5                         
    temperature      sec. sec. sec. sec. sec. sec.                        
    20° C.                                                         
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     (3) Rinsability, deodorization and feel tests: 
     Socks made of cotton-mixed yarns to which natural dirts were adhering after one day&#39;s wear were immersed in an aqueous solution of each of the samples VII through XII indicated in Table 3 at a temperature of 20° C. for 1 hour, wherein the concentration was adjusted to a constant concentration (3.5 ml./l.-water), and rinsed twice with water. Thereafter, the socks were dried in the sun. 
     A panel consisting of 30 persons evaluated each of the socks so treated with regard to rinsability, deodorization and feel. The results are shown in Table 6. The scores +2, +1, -1 and -2 represent &#34;very good&#34;, &#34;good&#34;, &#34;bad&#34; and &#34;very bad&#34;, resectively. 
     
                       TABLE 6                                                     
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          Sample                                                          
                                         XII                              
                                         (This                            
Item        VII    VIII   IX   X    XI   invention)                       
______________________________________                                    
Rinsability +1     -1     -1   -2   -1   +1                               
Deodorization                                                             
            -1     +1     -1   -2   -1   +2                               
Feel        -1     -1     -1   +1   +1   +1                               
Total       -1     -1     -3   -3   -1   +4                               
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     In this Detergency Test 2, the test results of each detergent composition containing the amphoteric surfactant (samples VII through XII) were obtained. From Table 4, it is apparent that the sample XII (this invention) has an extremely excellent detergency performance for a wide range of fiber materials. 
     This indicates that the addition of the amphoteric surfactant to the samples I through V (resulting in samples VII through XI) does not improve the detergency to a great extent, while in the case of the sample XII (this invention) the amphoteric surfactant in incorporated with the ethylene oxide adduct of a secondary alcohol and the sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol to provide a synergistic effect. This synergistic effect is particularly conspicuous with the socks made of the wool-mixed yarn and of the 100% nylon yarn. Further, while there is a tendency for the samples VII through XI to provide a decreased detergency due to the addition of the amphoteric surfactant for the socks made of the cotton-mixed yarn, the sample XII (this invention) exhibits no such tendency and its detergency is not dependent on the type of fiber material of the socks or stockings. 
     Additionally, in the case where clothings are immersed in an aqueous solution containing a detergent composition to remove the dirt therefrom as is the case with the use of the present detergent composition, a high permeability is required which is an important factor for the affinity for the fiber and the removal of the dirt. In this respect, it is also apparent from Table 5 that the sample XII (this invention) has an excellent permeability. From Table 6, it is also evident that the sample XII (this invention) is excellent in rinsability, deodorization and feel as compared with the samples VII through XI, and it is particularly excellent in deodorization. 
     Now, the detergent composition of the present invention can be prepared by mixing with stirring (A) an ethylene oxide adduct of a secondary alcohol, (B) a sulfuric ester salt of an ethylene oxide adduct of a secondary alcohol, (C) an amphoteric surfactant, and water. In preparing the composition, the ratio of (A) to (B) is in the range of 95:5 to 30:70, preferably 80:20 to 50:50 by weight, and the weight ratio of [(A)+(B)] to (C) is in the range of 98:2 to 80:20, preferably 97:3 to 85:15. 
     When (A) is above 95 and (B) is below 5 in the ratio of (A) to (B), the detergency and the deodorization are poor. On the other hand, in the case where (A) is below 30 and (B) is above 70, the detergent is highly sudsing, and the rinsability and the permeability are poor. 
     In the case where [(A)+(B)] is above 98 and (C) is below 2 in the ratio of [(A)+(B)] to (C), the detergency will become dependency on the types of fiber materials so that the effectiveness for a wide range of fiber materials cannot be obtained, and the feel after washing is poor. On the other hand, when [(A)+(B)] is below 80 and (C) is above 20, the permeability is reduced with the result that detergency is decreased. 
     Therefore, the preferred mixing ratio is within the above mentioned range. The particularly preferred mixing ratio is in the range of from 80:20 to 50:50 by weight for the ratio of (A) to (B) and in the range of from 97:3 to 85:15 by weight for the ratio of [(A)+(B)] to (C). 
     The detergent compositions of the present invention can contain some additives such as fluorescent dyes, perfumes, sequestering agents, soil suspending agents, fungicides, thickners, solvents and alkaline detergency builders, if necessary. In this case, these ingredients can be suitably added in the course of the preparation of the detergent composition of the present invention. 
     In use, the detergent composition of the invention in a suitable amount (about 1 to 5 ml. per liter of water) is dissolved in water to prepare an aqueous solution into which socks and stockings are immersed for an appropriate period of time. Then, the socks and stockings are removed from the solution and rinsed with water and dried. 
     When soiled socks and stockings are subjected to an immersion washing wherein the detergent composition of the invention is used, good sudsing is provided, and excellent detergency and deodorization are attained. Furthermore, the smell characteristic of the socks and stockings is removed, whereby the socks and stockings are made clean. In addition, the rinsability is good and, after washing, an excellent feel is imparted to the socks and stockings. Furthermore, the detergent composition of the invention may be used in washing socks and stockings whose materials consist of a wide range of fibers. At the same time, this detergent possesses high safety and does not cause chapping of the hands. 
     Although, as mentioned above, the detergent composition of the present invention is an excellent detergent composition for washing socks and stockings as compared with detergent compositions for general clothings, it is to be understood that it can be used as a detergent for general clothings. 
     The features and advantages of the present invention will be concretely illustrated by the following examples, which are set forth as illustrative only and are not intended to limit the scope of the present invention. 
    
    
     EXAMPLE 1 
     72.7 parts of purified water, 19.0 parts of an ethylene oxide adduct of C 11  -C 15  secondary alcohol (with the addition of 5 moles of E.O.), 5.0 parts of sodium salt of C 11  -C 15  secondary alcohol ethoxysulfate (with the addition of 3 moles of E.O.), 1.0 part of an alkyldimethylbetaine, 2.0 parts of isopropyl alcohol, 0.2 part of hexachlorophene, and 0.1 part of a fluorescent dye were added in the order stated and mixed together with stirring to prepare a homogeneous composition. 
     The detergent composition thus obtained was dissolved in water in a ratio of 3 to 5 ml. per 1 liter of water to prepare an aqueous solution. Then, soiled socks were immersed in the solution for about 1 hour and, thereafter, the socks were removed from the solution and rinsed with water. The resulting socks were odorless and clean. 
     EXAMPLE 2 
     69.1 parts of purified water, 13.0 parts of an ethylene oxide adduct of C 11  -C 15  secondary alcohol (with the addition of 9 moles of E.O.), 13.0 parts of triethanolamine salt of C 14  -C 15  secondary alcohol ethoxy sulfate (with the addition of 3 moles of E.O.), 4.0 parts of an alkyldiaminoethylglycine, 0.3 part of disodium ethylenediaminetetraacetate, 0.5 part of sodium carboxymethyl cellulose and 0.1 part of fluorescent dye were added in the order stated and mixed together to prepare a homogeneous composition. 
     The detergent composition thus obtained was dissolved in water in a ratio of 3 to 5 ml. per 1 liter of water to prepare an aqueous solution. Then, soiled socks were immersed in the solution for about 1 hour and, thereafter, the socks were removed from the solution and rinsed with water. The resulting socks were odorless and clean. 
     EXAMPLE 3 
     58.0 parts of purified water, 22.0 parts of an ethylene oxide adduct of C 14  -C 15  secondary alcohol (with the addition of 10 moles of E.O.), 15.0 parts of a sodium salt of C 11  -C 15  secondary alcohol ethoxysulfate (with the addition of 3 moles of E.O.), 3.0 parts of Miranol C2M Conc. (a cyclic imidinum type amphoteric surfactant, manufactured by Miranol Corp., United States of America) 1.0 part of triethanolamine, and 1.0 part of a perfume were added in the order named and mixed together with stirring to prepare a homogeneous composition. 
     The detergent composition thus obtained was dissolved in water in a ratio of 3 to 5 ml. per 1 liter of water to prepare an aqueous solution. Then, soiled socks were immersed in the solution for about 1 hour and, thereafter, the socks were removed from the solution and rinsed with water. The resulting socks and stockings were odorless and clean.