United States Patent Office Patented Dec
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3,707,505 United States Patent Office Patented Dec. 26, 1972 1. In respective control tests, no N-higher acyl amino acid 3,707,505 was added. ENZYME-CONTAINING DETERGENT COMPOSTON As is evident from Table 1, the stabilizing agents of the Itsutoshi Maeda, Yasuichi Nomura, Kohei Hashimoto, invention sharply reduce the loss of enzyme activity under Akira Shimizu, Koji Mitsugi, and Ryonosuke Yoshida, the test conditions. Kanagawa-ken, Japan, assignors to Ajinomoto Co., Inc., TABLE 1. Toyko, Japan Rate of residual No Drawing. Filed Dec. 28, 1970, Ser. No. 102,182 activity, percent Claims priority, application Japan, Dec. 30, 1969, Deter- Deters 45/1,752 O gent gent nt. C. C11d 3/04 Expt. ad base base U.S. C. 252-136 7 Claims No. N-higher acy amino acid A. B 1--------- None.------------------------------------ 10 20 2--------- N-caproyl-L-valine.-- 28 25 8--------- N-capryl-L-valine----- 43 40 ABSTRACT OF THE DSCLOSURE 4. -- N-lauroylglycine.------ 36 38 5 5 ... N-lauroyl-D-alanine- 26 41 The enzymes present in an enzyme-bearing detergent 6 -- N-laturoylsarcosine- 64 39 cornposition are stabilized by small amounts of N-acyl 7 ... N-lauroyl-L-leucine. 28 31 8 N-lauroyl-L-threonine 32 29 amino acids whose acyl groups are derived from saturated 9--------- N-auroy-DL-methionine..... 3. 35 10-------- N-lauroyl-e-aminocaproic acid--- 32 30 or unsaturated fatty acids having 6 to 20 carbon atoms, 1l-------- N-auroyl-S-benzyl-L-cysteine. 32 28 and the enzymes are also stable in detergents in which the 20 12 N-myristoyl-L-waine.-- 30 39 13-- N-palmitoyl-L-valine. 55 3. N-acyl amino acids are the primary surfactant ingredients. 14-- -- N-palmitoylglycine.-- 30 39 15.-- -- N-palmitoyl-DL-alanine 35 40 a-sa 16-- N-palmitoylsarcosine- 34 45 17-------- N-palmitoyl-L-leucine.-- 35 32 18-------- N-palmitoyl-L-threonine--------- 33 30 This invention relates to detergent compositions, and 19-------- N-palmitoyl-L-phenylalanine.--- 32 43 particularly to improved enzyme-bearing detergent com 25 20- -- N-stearoyl-L-valine----- 3. 35 2.-- -- N-undecylenoyl-L-valine 35 28 positions. 22.-- -- N-auroyl-L-aspartic acid- 26 40 Enzyme-bearing detergent compositions have recently 23- -- N-palmitoyl-L-aspartic aci 33 35 24- -- N-palmitoyl-L-asparagine.-------------- 37 45 found wide application. In addition to the enzyme, such 25-------- N-palmitoyl-D-homocysteic acid.------ 29 30 compositions may typically contain an anionic surfactant 26-------- N-hydrogenated tallowyl-glutamic acidi- 32 3. 30 27-- -- N-lauroyl-L-arginine.------------------- 36 35 as the primary active ingredient, such builders as sodium 28-- -- N-palmitoyl-L-arginine----------------- 48 55 tripolyphosphate, sodium silicate, Glauber's salt, and 29 -- N-hydrogenated tallowyl-L-arginine 38 58 30- - N-auroyl-L-arginine methyl ester. 50 36 addition agents such as carboxymethylcellulose, optical 31-- -- N-lauroyl-L-ornithine methyl este 25 38 brightening agents, dyes, perfumes, etc. 32. -- N,N-dimethyl-N-auroyl-L-ornithine.... 49 62 33-------- N-palmitoyl-L-lysine methyl ester----- 55 65 The known compositions suffer from the fact that 34-------- N-hydrogenated tallowyl-L-arginine----- 54 60 the anionic surfactants make the enzymes unstable. The 35 35-------- N-pairnitoyl-L-lysine methyl ester----- 54 55 alkaline builders inactivate the enzymes at temperatures 36-------- N-Stearoyl-L-serine---------------------- 37 43 of 40 C. or more. The enzymes are even less stable in aqueous solutions having a pH of 10-11 as normally Detergent bases A and B were modified to contain caused by the other ingredients of the conventional com 40 0.4% protease, and batches of the modified bases were positions. further mixed with the stabilizing agents of the invention A practically useful detergent composition in which the listed in Table 2 in amounts of 0.8%. The powder com enzyme component is not significantly inactivated has positions so obtained were stored at 84% relative humid not been available heretofore, and it is an object of this ity and 37 C. in a desiccator over saturated aqueous am invention to provide an enzyme-bearing detergent com monium chloride solution for 7 and 14 days together position wherein the enzyme is relatively stable. 45 with controls free from the N-higher acyl amino acids, It has now been found that the stability of the enzyme and the residual enzyme activity was determined in per in detergent compositions of the type described is en cent of the initial value. The improved shelf life of the hanced by the presence of an N-acyl amino acid, and its compositions according to this invention is evident from salts and esters, the N-acyl group being the radical of a Table 2. fatty acid having 6-20 carbon atoms. The stabilizing 50 agents of the invention are effective both in aqueous TABLE 2 solutions and in dry detergent powders. The stabilizing Rate of residual activity, agents of the invention will be referred to hereinafter as percent “N-higher acyl amino acids” for the sake of brevity. Detergent Detergent To demonstrate the effectiveness of the stabilizing 55 base A base B agents, two detergent bases were prepared. Base A con Expt. 7 4. 7 14 sisted of 25% sodium n-dodecylbenzene sulfonate, 30% No. N-higher acy amino acid days days days days sodium tripolyphosphate, 5% sodium metasilicate, 37% 87------ None.------------------------- 62 40 85 65 Glauber's salt, and 3% carboxymethylcellulose together 38------ N-lauroyl-L-arginine methyl 84 64 94 82 60 ester hydrochloride. with 0.1% protease (60,000 units/g. as determined by 39------ Sodium N-hydrogenated 100 O 98 95 the modified Anson method described hereinbelow). Base tallowyl-L-glutamate. B differed from Base A by substitution of sodium lauryl 40------ N-palmitoyl-L-Waline.--------- 94. 90 100 92 sulfate for the sodium n-dodecylbenzene sulfonate. Aqueous 2% solutions of the bases having a pH of 10 The N-higher acyl amino acids of the invention also were mixed with the N-higher acyl amino acids listed in 65 favorably affect the cleaning efficiency of detergent con Table 1 in a concentration of 0.2%, each mixture was positions containing enzymes. heated to 50° C. for 30 minutes, and the residual enzyme Samples of cotton fabric artificially soiled (Empa 116) activity was measured. The term "hydrogenated tallowyl' were soaked in a liquor ratio of 1:50 in aqueous 0.2% is used in this specification for brevity's sake for the acyl solutions of detergent base A without protease, with radicals of the fatty acids in hydrogenated beef tallow. 70 0.001% protease (60,000 u./g.) but without N-higher The term "cocoyl” will be used in an analogous manner. acyl amino acid and with 0.001% protease and varying 3,707,505 3. 4 amounts of N-palmitoyl valine (P-V) or sodium N-hydro was determined by the method of Yamada et al. J. Agric. genated tallowyl-L-glutamate (HGS). After 10 minutes Chem. Soc. Japan 36 (1962) 860), one unit being the agitation at 100 r.p.m. at 30° C., the washed fabric amount of enzyme liberating 1 u, equivalent of acid per samples were dried, and the rate of reflection L after minute. washing was compared with the rate of reflection L be TABLE 5 fore washing on a color-difference meter with Hunter Cleaning Standard (91.8). Cleaning efficiency CE (percent) was efficiency Detergent composition after- Rate of calculated according to the formula residual L-L Expt. Amt., 10 30 activity, O No. Ingredient g/dl. Illin. min. percent Detergent base A--- 0.2 The results obtained with the several detergent com 57------- E.etergent base 0.0020.2 60 70 5 positions are listed in Table 3. rE, - - - -isulfate. ... 0.002 60 71 11 TABLE 3 odium laurylsulfate- 0.2 5 59------- E.“Tide' (trade name). --... o. 8330.2 67 75 Expt. No.------ 41 42 43 44 45 46, 47 48 49 60------- {E.- - - - - - - - - - - - - - - - - - 0.002 } 68 76 Disodium N-hydrogenated Protease-------- - - -- -- -- - - - - -- -- 61------- tallowy DL-glutamate. 0.2 67 75 52 P-V, percent------------ 0.01 0.001 0.0002 -------------------------- Protease--------------------- 0.002 HGS, percent-------------------------------- 0. 0.02 0.005 0, 001 Sodium N-lauroyl-DL- 0.2 CE, percent---- 60 68 71 67 69 69 67 73 73 62------ glutanate. 5. 68 48 Protease-------------------- 0.002 20 Sodium N-lauroyl-L- 0.2 The amount of N-higher acyl amino acid which sta 63------ arginine. 4. 65 30 bilizes the enzyme in a detergent composition may be 0.1 Protease. 2 to 20% based on the weight of the detergent base or 64------- 3SES .002 69 80 42 N-palmitoyl-L-phenyl- 0.2 20% to 1000% based on the enzyme. The effects of 65.------ alanine-------------------- 63 79 46 varying amounts of N-palmitoyl valine (P-V) and sodium Protease---------- 0.002 n-hydrogenated tallowyl-L-glutamate (HGS) on the re SE;odium N-hydrogenate BS A) ted 8.. 1. sidual activity of 0.01% protease in an aqueous 2% solu 66------- tallowyl-L-glutamate. 67 82 73 tion of detergent base A after 10 minutes at 50 C. is Protease-------------------- 0.002 evident from Table 4. Detergent base A wherein 0.2 sulfate was replaced by TABLE 4 30 67------- sodiumSEE EYN-hydrogenated bene 66 77 60 tallowyl-L-glutanate. Expt. No.------------------ 50 5. 52 53 54 55 56 Protease--------------------- 0, 002 Sodium N-cocoyl-L-gluta- 0.1 PV, percent---------------------- 0.1 0, 01 0.002 ------------------ mate. HGS, percent---------------------------------------- 0, 1 0, 01 0.002 68------- Sodium laurylsulfate......-- 0.1 68 8. 74 Activity, percent 41 72 62 57 74 65 60 Glauber's Salt--------- 0.