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Publication numberUS3855156 A
Publication typeGrant
Publication dateDec 17, 1974
Filing dateMay 5, 1972
Priority dateAug 4, 1970
Also published asDE2139074A1, DE2139074B2, DE2222899A1, DE2222899B2, DE2222899C3, US3719613, US3850853
Publication numberUS 3855156 A, US 3855156A, US-A-3855156, US3855156 A, US3855156A
InventorsH Marumo
Original AssigneeH Marumo
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
New detergent composition
US 3855156 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

United States Patent [151 Marumo Dec. 17, 1974 [76] Inventor:

[ NEW DETERGENT COMPOSITION Hideo Marumo, 5-4 Nishikubo, 3 Chome, Tokyo, Japan 22 Filed: May 5,1972

21 App]. No.: 250,653

[30] Foreign Application Priority Data May 10, 1971 Japan 46-30391 Jan. 26, 1972 Japan 47-9019 [52] US. Cl 252/547, 252/DlG. 7, 252/DIG. 13, 252/546, 252/548, 260/534 E [51] Int. Cl. ..C1ld 1/18, Cl 1d 3/26 [58] Field of Search 252/546, 548, 547, DIG. l3, 252/DIG. 7; 260/534 E, 534 M [56] References Cited UNITED STATES PATENTS 3,555,079 l/l97l Marumo et al. ZOO/501.13

Primary Examiner-Leon D. Rosdol Assistant [imminer-Edith L. Rollins Allorncy, Agent, or FirmCushman, Darby & C ushman [57] ABSTRACT A new detergent composition comprising at least one of surface active agents represented by the'general formula (I), its organic amine salts, ammonium salts,v

alkali metal salts and non-alkali metal salts, or their acid complex salts, and/or an amphoteric surfactant derived from a compound of the general formula (II) by treatment with an amphoterizing agent, its organic amine salts, ammonium salts, alkali metal salts, nonalkali metal salts or their acid complex salts, as an active component:

N-C-rCOOH ......(1- R R CHY- CH2 NX(CH2) N I m n w.'. (11

8 Claims, N0 Drawings NEW DETERGENT COMPOSITION BACKGROUND OF THE INVENTION a. Field of the Invention This invention relates to a new detergent composi- I ,tion, and more particularly toa new detergent compoagents derived from a compound having the general coon (I) wherein A andB represent hydrogen atoms or groups R-CH-Cl-hor (CH CHRO) H, (wherein R is a hydrocarbon group having2 to 28 carbonatoms and R is a hydrogen atom or a group CH' X represents a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms, Y represents a hydrogenatom, a group CH -CH CH(CH )CH I -(CH ),,COOH, (wherein n is an integer from Ho (wherein D and E are hydrogen atoms or groups n-cu-cmor -(CH CHR'O)},H), p and q are integers-from 0 to 50, and when X is a hydrogen atom, at-least one of A; I B, D and E is agroup or when A, B and Y are all hydrogen atoms, X is the. hydrocarbon group'having 2 to 28 carbon atoms, or

R CH-CHZ n wherein R represents a hydrocarbon group of 4 to 30 carbon atoms, Z represents a hydrogen atom or a group (CH CHR'O),,H, (wherein R-' is a hydrogen atom or a group --CH and p is an integer from 1 to X, Y, and W represents hydrogen atoms or groups or (CH CHR'O),,H), m is an integer from 2 to 10, n

is an integer from 0 to 5, and X, Y, Z and W cantake groups different from one another at the same time.

b. Description of the Prior Art Generally, an ionic surface active agents such as linear alkylbenzenesulfonates, sodium salts of saturated linear alcohol sulfates or the like, and non-ionic surface active agents such as nonylphenol ethylene oxide adduct or the like, as used in washing of natural fibers and synthetic fibers. However, when such detergents are used, the fibers cleansed with such detergents have a deteriorated hand feel and the antistatic property of the fibers-is-lost. Therefore, it has been the usual practice to give the washed fibers an additional treatment with a soft-finishing agent or an antistatic agent. However, these properties which are thus added to the fibers disappear when the fibers are washed again. On the other hand, when the fibers are washed with a known detergent mixed with a soft-finishing agent and an antistatic agent, the individual effects of these mixed agents are not exhibited clearly, but rather they serve, in many cases, only to lower the activity of the detergent per se. Therefore, when the soft-finishing agent, antistatic agent or the like, are used, it is necessary to add these agents into a rinsing solution after cleansing or to subject the washed fibers to a separate treatment with these agents, and thus a great inconvenience is experienced,

Further, detergents prepared from petroleum or alcohol base used as a detergent for food ware or vegetable have an excellent detergency but have a property to damageskins. Thus, the use of the synthetic detergents has recently become a great problem. Furthermore, the biodegradability of a surface active agent blended in the synthetic detergent for washing, and the pollution by condensed phosphates have been recently regarded as the public pollution problems.

SUMMARY OF THE INVENTION novel detergent composition having less skin irritativeness, and moreover a good biodegradability, and further the present detergent composition does not re quire so much builders such as condensed phosphates.

in the prior patent application of the present inventor for a detergent composition U.S. Ser. No. 168,413, now U.S. Pat. No. 3,719,613, it was disclosed that a water-insoluble metal salt of the amphoteric surface active agent of a long-chain imidazoline type was dis- 7 persed and solubilized in a water system with an effective dispersant, and the resulting transparent solution was externally deposited and absorbed on the surfaces of the fibers. As a result of further studies, the present inventors have found that the similar effect can be attained by the present novel compounds.

The novel compounds of the present invention can be used alone as a detergent, or added to the known detergent as an additive to improve detergency, bubble formability and bubble durability and endow an antistatic property, resistibility to resoiling and soil releasability to a material to be washed. The present detergent composition can be regarded as a kind of polymeric electrolytes or polymeric surface active agent. Therefore; its critical micelle formation concentration is very low, for example, about one one-hundredth to one onethousandth of that of alkylbenzenesulfonates. That is,

the present detergent composition can exhibit a good surface activity at a very low concentration and shows a good detergency. Furthermore, a strong monolayer is formed on the surfaces of material to be washed through absorption, and can be stably retained on the surface even in the cleansing step or even after drying. Thus, the antistatic property and soil releasability can be endowed thereby to the materials to be washed for a considerably prolonged period of time. That is to say, the present detergent composition can be used alone in the antistatic, anti-redeposition and soil release treatments.

As described above, the feature of the present detergent composition can be obtained without any failure even if it is added to the other conventional detergent composition, but particularly when the present composition is added to the conventional carpetshampoo consisting mainly of sodium alkylsulfates ester, very stable bubbles can be obtained. Furthermore, the carpet surface is not so much wetted as necessary, and the fouling components can be effectively absorbed onto C1 H21 CH cH2 NH CH-COONa (A) CaCZ;

the bubble interfaces, whereby an excellent carpet surface having a good antistatic property, good anti-soil property and a good soil releasability can be obtained.

Moreover, the present amphoteric surface active C H -CH-CH5-NH-CHCOONa to household detergent,'industrial detergent, hair shampoo, carpet shampoo, syndet bar, soap, or the like. Furthermore, the present surface active agent can be used as an organic builder for detergents.

On the other hand, the present detergent composition has a wide use as an industrial detergent, for example, various detergents in the fiber industry, a detergent in the cleaning industry, a metal detergent, an automobile, ship or vehicle cleaner, or as a cleaner for plant or equipments in the food industry, or cleaner for food itself or as a cleaning agent and germicide for food container, or the like.

DETAILED DESCRlPTlON OF THE PREFERRED EMBODlMENTS Now, a process for producing a novel surface active agent used in the present invention will be outlined.

The compound as represented by the general formula (I) is obtained by adding 1,2-epoxyalkane or a-olefin to a natural or synthetic a-amino acid, or further by reacting ethylene oxide or propylene oxide with the resulting product. For example, a product (A) obtained by reacting disodium glutamate with 1,2- epoxydodecane in a solvent mixture of alcohol-water is double-decomposed with calcium chloride to a compound (B):

l I (A) CH CH COONa OH CH CH C'OONa C H -CHCH -NHCH-COO l l Ca (B) OH CH CH COO When 20 moles of ethylene oxide are added to one mole of the product (A), a compound (C) is obtained. When the compound (C) is double-decomposed with zinc chloride, a compound (D) is obtained:

ca CH 0) H I 2 2 q C I-l -CH-Cl-l-N-CHCOON8.

I CH CH COONa (CH CH O H decorrlposed with the corresponding inorganic metal salt, for example, magnesium chloride, a compound (E) is obtained.

peroxide ultraviolet irradiation NaOI-I The compound as represented by the general formula (II) can be obtained, for example, by. reacting 1,2- expoxyalkane with propylene diamine. The present am- 5 photeric surface active agent can be obtained by reacting an amphoterizing agent, for example, methyl acrylate, with the resulting compound of the general formula (ll). The resulting compound is further saponified 20 with sodium hydroxide thereby to obtain a sodium salt of the amphoteric surfaceactive agent, as shown below:

NHCOCH3 NHZ c ,H -ccooNa (E) R CHCH NH(CH NH2 CH2 CHCOOCHa I OH R-CHCH NH(CH 3NHCH CH COOCH NaOH RCHCHZNIHCH NHCH CH COONa CHgOH i OH 7 8 When ethylene oxide or propylene oxide is added to Examples of the amphoteric surface active agents the resulting sodium salt, adduc ts containing various having the formula (I) include the following commoles of ethylene oxide or propylene oxide can be obpounds: tained.

'c n CHCH NHCH COO I Ca 1 OH 2 C 1 H2 QCHCHZNHCHZCOO I Na (2) PC 2 5H 5 3 CHCH ZNHCHCOO l I Ca (3) OH CH 3 2 1 C H CHCH N-CHCOO Mg (4) c H cncn l CH 3 C u, CHCH;.NHCHCOO r l l ZL'L 3) OH CH CH COO "c H CH-CH N-CHCOO l (6) on icn cu coo Ca coca- 'c n cucn nncncoo i OH (CH )r,NHCH- CHC H Ba l d on 2 C10 H2 ICHCH 2 NHCHCOO I NH2(CH2CH2OH) 2 (8) OH (CH micoc n 2 'c n cucn N cacoo I I OH cri c n Ca (9) coca 2 'C H CHCH NHCHCOO l I OH (CH2)3NHCH2CH-C6H13 NH(CH2CH2OH)3 (10) CeH l I OH (CH NHcocH Ca (ll) cocH 2 Very good c H CHCH NHCH CH NH cacoo 7 I g I j mm) 2 v (55) OH CH 2 COO on Oh l l (CH7CHZO) cii cii-cii N'CH' 'CHQ'CH; 'Ni

' 3 I H,o H 2 (56) CH 2 CH 2 0 s 0 CHQCOO CHZC O( CH2CH2 Now, the present invention will be explained in de' Table l -Continued tail, referring to Examples. in the Examples, part is by weight.

. Antistatic effect E [Half time of XAMPLE l Compound No. Detergency Hand feel leakage (sec.)] Detergent compositions were prepared each from 10 i. with. parts of the present amphoteric' surface active agent, 5 x2 W 2% parts of sodium metasilicate, 8 parts of soda ash and 77 29 g g Good parts of Glaubers salt. These detergent compositions 30 Very good Good were charged each in a standard amount as the heavy 36 y good od 3.2 duty detergent (0.165% by weight) into an electric 37 very h h' fll d h l' H v I 30 38 was ing mac me i e wit acry 1c i ers onne a 40 very good Good 44 trademark of acrylic fibers made by Mitsubishi Rayon 44 Very good Good 7.6 Co., Ltd., Japan) fouled by wearing, and subjected to 46 y good Good washing according to the standard washing procedure. 2; ery good Good 5.0 On the other hand, the acrylic fibers were washed like- 49 very good Good wise with a commercially available synthetic detergent 35 50 Very good Good 3.7 and a commercially available soft-finishing agent. De- Very 52 Very good Good 2.8 tergency and hand feel of the washed fibers were deter- 53 very good Good 36 mined visually or by touch. The results are shown in 54 Very good Good 2.9 Table 1. It is evident from Table I that the present de- 55 y good- Good tergent compositions have an excellent detergency, Confirm! very even though the present detergent compositions conheavy duty Very good Poor m tain less active components than those of the commer- E ai s on cially available detergent, and contain no bu lder such. as sodium tripolyphosphate, etc.

Table 1 EXAMPLE 2 Anlistatic Five parts of the present surfactant was added to a Compound No Detergency 5 feel g z z tgf commercial heavy duty detergent composition consisting, for example, of 25 parts of sodium linear alkylben- 2 Very good Good 2- zenesulfonate (LAS), 25 parts of sodium tripolyphos- 3 3:3 5:83 phate, 5 parts of sodium metasilicate, 5 parts of soda 10 v good Good 7 ash and 40 parts of Glaubers salt, while the amount of 12 y good 600d 28 LAS was reduced to 20 parts, whereby detergent com- 13 Very good Good 3.0 14 very good Good 28 positions were prepared. Fouled polyester sheets were 15 Very good Good 3.5 washed according to the standard washing procedure, is 32 using the respective detergent composition in a stan- 18 g g Good dard amount as the heavy duty detergent (0.165% by 19 Very good Good 4.7 weight). The results are shown in Table 2. As shown in g? gm 2'? Table 2, the washed shirts had a good hand feel with an v good Good 25 excellent detergency in the case of the present deter- 23 y good Good gent compositions. Further, cleansing could be carried 24 Ve ood Good 3 5 J; g Goo-d out more easily by blending the present surfactant in 2 Good 4,0 the detergent composition.

Table 2 Table 3 Antistatic efi'ect Static friction- Bubble [Half time of Compound No. alcoefiicient Hand fecl stability Compound No. Detergency Hand feel leakage (sec.)] 5 12 202 Sofi Good 1 v Good 25 13 0.195 Soft Good 2 2% Good 2.5 14 0200 Soft Good 3 Ve d G 3 0 15 0.193 Soft Good g 19 0 199 Soft Good 4 Very good Good 3.5 2 5 Very good Good 5 1 0.210 Soft GOOd E 2s 0211 Soft Good 7 Very good Good 3.8 26 0210 Soft G 3 .Very good Good 4.0 38 0.194 Soft" Good 9 Very 8 M 46 0204 Soft Good 10 y good Good 47 0.210 Soft Good 11 y good Good 4s 0.195 Soft Good 12 y good Good 49 0.206 Soft Good 13 y good .Good 50 0202 Soft Good 14 Very good Good 51 0.200 Soft Good 15 y good Good 52 0190 Soft Good 16 .Very good Good 4.0 53 0.208 Soft Good 17 Very good Good 3.7 54 0.202 Soft Good 18 Very good Good 3.0 55 0.200 I Soft Good 19 Very good Good 4.2 20 r so 0198 Soft Good 20 Very good Good 4.0 Commercial 21 Very good Good 4.7 shampoo 0230 Ro F ir 22 Very good Good 35 (control) 23 Very good Good 4.2 24 Very good Good 2.8 25 Very good Good 5.6 32 Very gal 25 EXAMPLE 4 ery g Good 53 3:0 m 3% 0.2 parts of the present surfactant was added to a carg g Good 5 pet detergent consisting of 0.5 parts of sodium salt of 31 Very good Good 4.2 lauryl sulfate, 015 parts of ,lauroyldiethanolamide and 3% 5% 30 99.35 parts'of water, while reducing the amount of the 34 Very good Good 3 7 sodium salt of lauryl sulfate to 0.3 parts thereby to pre- 35 y good Good pare carpet detergent compositions. Fouled beige 36 Very good Good 3.6 37 very good Good 42 nylon carpets were washed w th the thus prepared de- 38 Very good 'Good 4.3 tergent compositions according to the conventional 39 Very good Good 2.8 w 40 veryvgood 4'4 35 carpet ashing procedure comprising bubblmg, brush 4] very Good mg, leaving at a standstill and suction under vacuum. 42 Very good Good I 3.7 The results are shown in Table '4. It is obvious that the 43 Verygmd carpet detergent composition has an improved deter- 44 Very good Good 7.8 45 v good Good 5. gency and bubble stab1l1ty and faster drying by blend- 46 y good Good' 40 ing the present surfactant into the conventional deter- 47 Very good Good 3.0 1 48 very good Good 3.8 gent composition, and an antlstatic property can be en- 49 Very good Good 2.8 dowed to the icarpets after washing. 50 Very good Good 3L0 5] Very good Good 4.2 Table 4 52 Very good Good 53 Very good Good 45 wemn g of g; xg m gm the c t Antistatic, effect 56 v G 1 Com- Soil right er [Halftime of Co ma] cry g 4 v pound No. releasability washing leakage (sec.)] ggg i g very good Poor m Feeling of ESS, 50 12 Good 3. dry- 0.5

Feeling of dryness, EX 3 l4 GOOd {:zter dry- 0.6 Two percent by weight of the present surfactant was Egg: added to ahair shampoo composition consisting, for 15 Good i'asterdry- 1.0 example, of 10 parts of lauryl sulfate triethanolamine, g of 2 parts of lauroyldiethanolamide, 8 parts of urea, 3 dryness, parts of sodium salt of lauryl alcohol ether sulfate (3 s?" moles) and 76 parts of water to prepare hair shampoo. 6 geeiing f r e85 Women 5 ha r was washed with the thus prepared hair 18 yg dry 15 shampoo according to the conventional procedure. ing The results are shown in Table 3. It is seen that the degeeling'of tergency and bubble stability are improved by blending 20 Good q f a 14 the present surfactant to the conventional shampoo gig f composition, and the good hand feel can be endowed V f g to the hair after washing and drying. 22 Good faster dry- 0.3

Table 4-Continued Wetting of the c t right er washing Antistatic effect [Half time of leakage (sec.)]


Soil pound No. releasability ing Feeling of faster drying Feeling of ess, faster drymg ggerliing of ess, faster dry- 8 Feeling of faster dry mg gxeyerlling of faster drying Feeling of faster dry in Feeling of dryness,

49 faster dry- 1.0

mg Feeling of dryness. faster dry ing Feeling of 555, faster drymg Feeling of ryness, 52 faster drying Feeling of faster drying Feeling of dryness, faster dryin Fe eling of 55 faster dry- 0.8


Feeling of faster drying Wettish feeling cc 56 Good Commercial carpet sham control Foulings remam EXAMPLE 5 were tested by 10 household wives for one month in the winter season (February), and it was found that the detergent compositions had a very good detergency and gave no irritation to hands, as compared with the controls.

Sodium linear alkylbenzenesulfonate (LAS) 20 parts Amisol CD (a product of Kawakami Fine Chemicals. Co., Japan) 2 parts Urea 6 parts Lanolin alcohol-ethylene oxide (50 moles) adduct 0.2 parts Water 71.8 parts EXAMPLE 6 Glass cleaners having the following composition were prepared, and glass was washed with the thus prepared compositions. In that case, the present surfactants (31), (32) and (33) were used. it was found that the compositions had a good detergency, and a lustrous glass surface was obtained after the washing.

Present surfactant 0.025% by weight Higher alcohol-ethylene oxide (9 moles) adduct 0.25 by weight Amisol CD (a product of Kawakami 7 Fine Chemicals, Co., Japan) 0.50 by weight lsopropyl alcohol 5.0 70 by weight Water 94.225% by weight EXAMPLE 7 Ten parts of the present surfactant having the general formula (I) and 3 parts of the present surfactant derived from the compounds having the general formula (ll) were melted, and 87 parts of hot water was added little by little with stirring thereto to dilute the surfactants. The resulting solution was passed through a homogenizer at C, and then to the normal temperature, whereby the detergent composition were obtained. The thus obtained detergent compositions were subjected to detergency tests in the same method as described in Example 1. The results are shown in Table 5.

The present compositions had a good detergency and endow a good hand feel and antistatic effect.

What is claimed is: v I 1. A detergent composition consisting essentially of at least one surface active agent of the formula:

wherein R is a hydrocarbon of 4 to 30 carbon atoms; Z is hydrogen or --(CH CHR'O),,H,

wherein R is hydrogen or methyl and p is an integer from 1 to 100; X, Y and W are independently hydrogen,

wherein Z and P are as defined above;

m is an integer from 2 to 10;

n is an integer from to and salts thereof.

2. A detergent composition according to claim 1, wherein the surface active agent is amphoterized with an amphoterizing agent of monochloroacetic, B-chloropropionic, -y-chlorobutyric and monochlorosuccinic acids, and their alkali metal salts or esters, maleic anhydride, acrylic or inethacrylic acid esters, and acrylonitrile.

' 3.,The detergent composition according to claim 1 wherein the surface active agent has the formula:

CHZCIHZOII I l0 2l H-CHzN-CH2-CH2N 5 H CHzCOOH CI-IzCI-IzOH CHZCOOH 4. The detergent composition according to claim 1 wherein the surface active agent has the formula:

, wherein the sum of p plus q plus r is, 9.

5. The detergent composition according to claim 1 wherein the surface active agent has the formula 6. The detergent composition according to claim 1 wherein the surface active agent has the formula CiuHaaCHCHzNOHzCHzCHzNCHzCH-CrsHaa H cmomooo OH- omomooon .7. The detergent composition according to claim 1 wherein the surface active agent has the formula:

8. A detergent composition comprising the detergent of claim 1 blended with atleast one inorganic detergent builder.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3555079 *Aug 18, 1969Jan 12, 1971Lion Fat Oil Co LtdPreparation of amphoteric surface active agents
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4107096 *Oct 11, 1977Aug 15, 1978Texaco Development Corp.Low foaming beta-amino propionic acid surface active agents
US4171278 *Nov 2, 1978Oct 16, 1979Henkel Kommanditgesellschaft Auf AktienSurface-active compound combination containing hydroxyalkylamines
US4214102 *Apr 14, 1978Jul 22, 1980Henkel Inc.Amino-ether amphoteric surface-active compounds
US4374056 *Nov 2, 1981Feb 15, 1983Kao Soap Co., Ltd.Lowly irritating detergent
US4760176 *Aug 5, 1987Jul 26, 1988Borg-Warner Chemicals, Inc.Aminocarboxylic acid-terminated polyoxy-alkylenes and process for the preparation thereof
US4914232 *Sep 28, 1987Apr 3, 1990The B. F. Goodrich CompanyPolysubstituted 2-morpholones, related compounds, processes for their preparation, and U-V light stabilized compositions
US5066425 *Jul 16, 1990Nov 19, 1991The Procter & Gamble CompanyFormation of high active detergent particles
US5089614 *Mar 29, 1990Feb 18, 1992The B. F. Goodrich CompanyPolysubstituted 2-morpholones
US5656586 *Aug 19, 1994Aug 12, 1997Rhone-Poulenc Inc.Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US5789371 *Apr 22, 1997Aug 4, 1998Rhodia Inc.Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US5846926 *Jun 9, 1997Dec 8, 1998Rhodia Inc.Nonionic gemini surfactants with three hydrophilic heads and two lipophilic tails
US6121222 *Dec 27, 1996Sep 19, 2000Rhodia Inc.Anionic surfactants having multiple hydrophobic and hydrophilic groups
US6183550Apr 16, 1999Feb 6, 2001Hercules IncorporatedPaper size dispersions
US8003089 *Mar 12, 2003Aug 23, 2011Beijing Jiankai Technology Co., Ltd.Y shape branched hydrophilic polymer derivatives, their preparation methods, conjugates of the derivatives and drug molecules, and pharmaceutical compositions comprising the conjugates
US20050180946 *Mar 12, 2003Aug 18, 2005Shishan JiHydrophilic polymer derivative with y type branch and preparation method of it medical cpmposite comprising above compund
US20100221213 *May 17, 2010Sep 2, 2010Shishan JiY-shape branched hydrophilic polymer derivatives, their preparation methods, conjugates of the derivatives and drug molecules, and pharmaceutical compositions comprising the conjugates
U.S. Classification510/480, 510/299, 510/350, 510/433, 562/564, 510/182, 510/434, 562/567, 510/235, 510/328, 510/490, 510/111, 510/499, 510/280, 510/356, 510/351, 510/128
International ClassificationC11D1/90, C11D1/88, A01N37/44, D06M13/342, C11D1/00, C07C229/24, C07D233/18, C11D1/94
Cooperative ClassificationC11D1/88, A61Q5/02, A61K8/44
European ClassificationC11D1/88, A61K8/44, A61Q5/02