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Publication numberUS3874870 A
Publication typeGrant
Publication dateApr 1, 1975
Filing dateDec 18, 1973
Priority dateDec 18, 1973
Publication numberUS 3874870 A, US 3874870A, US-A-3874870, US3874870 A, US3874870A
InventorsGreen Harold A, Merianos John J, Petrocci Alfonso N
Original AssigneeMill Master Onyx Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Microbiocidal polymeric quarternary ammonium compounds
US 3874870 A
Abstract
The use of polymeric quaternary ammonium compounds prepared by the condensation of 1,4-dihalo-2-butene and 1,4-bis-dimethylamino-2-butene as microbiocidal agents in aqueous systems.
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United States Patent [11] 3,874,870 Green et al. Apr. 1, 1975 MICROBIOCIDAL POLYMERIC [56] References Cited QUARTERNARY AMMONIUM UNITED STATES PATENTS COMPOUNDS 3,140,976 7/1964 Berenschot et a1. 424/329 [75] Inventors; Harold A, Green, Havertown P3; 3,539,684 11/1970 Hoover 424/78 J Mel-ianos Jersey Ci 3,771,989 11/1973 Pera et al 424/329 Alfonso N. Petrocci, Glen Rock7 3,778,283 12/1973 Freyhold 106/84 both of FOREIGN PATENTS OR APPLICATIONS [73] Assignee: Mill Master Onyx Corporation, New 69-8949 7/1970 South rica York, N.Y.

Primary Examiner-Albert T. Meyers [22] Flled' 1973 Assistant Examiner-Douglas W. Robinson [21] App]. No.: 425,931 Attorney, Agent, or FirmArthur A. Jacobs, Esq.

52 U.S. Cl 71/67, 260/875 R, 424/78, ABSTRACT 424/329 The use of polymeric quaternary ammonium com- 1 AOIN AOlN A61K 0 pounds prepared by the condensation of 1,4-diha1o-2- A61K 17/00 butene and l,4-bis-dimethylamino-Z-butene as micro- Fleld of Search biocidal agents in aqueQuS Systems,

8 Claims, N0 Drawings MlCROBIOClDAL POLYMERIC QUARTERNARY AMMONIUM COMPOUNDS This invention relates to microbiocidal agents, and it particularly relates to microbiocidal agents comprising polymeric quaternary ammonium compounds.

It is known that many quaternary ammonium compounds have biocidal or inhibitory effects on microorganisms. However, few such compounds, or indeed few biocidal compounds of any type, have been found to have all the necessary characteristics required for the biocidal treatment of aqueous systems of the recirculated type such as industrial or process waters of the type used in paper manufacturing, cooling towers, air conditioners, humidifiers and the like. Even relatively standing waters such as swimming pools have been problems insofar as maintaining them substantially free of bacteria, fungi and algae,

The control of microorganisms in aqueous systems of the aforesaid type has long been recognized as a particularly burdensome problem since the environment of the aqueous medium itselfis often extremely conducive to rapid multiplication and growth of these undesirable organisms. Only through the rise of carefully tailored microbiocidal agents can this growth and reproduction be reliably controlled without detriment to the process in which the water is used. For example, many times a n X-CH biocidal compound is rendered completely inactive by the particular surrounding media containing the undesirable microorganisms. A particular problem in recirculated waters is that the recirculation causes many difficult problems, among which is the gradual build-up and accumulation of undesirable microorganisms in the aqueous fluid. Various bacteria, fungi and algae are favorably produced in such recirculated waters.

Another common feature of quaternary ammonium biocides is that their biocidal effectiveness is diminished in the presence of non-ionic emulsifiers, often to the point where they no longer function as acceptable biocides. This has significantly reduced their possible use in cosmetics and similar preparations that require the inclusion of non-ionic emulsifiers.

An additional problem in the use of most microbiocidal agents in aqueous systems is the formation of large amounts of foam. This foam is generally highly undesirable and the formation thereof by these agents often makes them useless for particular applications.

In accordance with the present invention, it has now been discovered that certain polymeric quaternary ammonium compounds and, particularly, the product made by the condensation of 1,4-dihalo-2-butene and l,4-bis-dimethylamino-2-butene is not only a highly effective microbiocidal agent in aqueous systems, including recirculating waters, industrial waters, cosmetics and other emulsions containing non-ionic emulsifiers, as well as in general usage, but also effects such purpose without causing undue foaming.

It is to be noted that a particular aspect of the present invention is that the quaternary ammonium moieties of -CH=CH-CH X n (CH the present compounds are part of a long chain rather than being on branches that are bonded to the long chain.

The aforesaid compounds are active against Pseudomonas aeruginosa at a concentration relative to the total composition as low as 25 ppm, although the preferred concentration is about 150 ppm. Against Aerohacter acrogenes, they are active at a concentration as low as ppm, although the preferred concentration is about 100 ppm. Against algae, such as Chlorella pyrenoidosa, they are active at a concentration at least as low as 1 ppm and probably even much below that concentration according to present indications.

Insofar as concerns upper limits, the concentration may apparently be increased indefinitely without deleteriously affecting the biocidal activity.

More specifically with regard to cosmetic compositions. the products of this invention are effective at a concentration at least as low as about 500 ppm relative to the total composition, and probably at even lower concentrations, according to present indications. The preferred range, however, is about I ,000 to 2,000 ppm.

There is no absolute certainty of the actual structure of the product of the condensation reaction because isomerizations are possible. However, ideally, the reaction would appear to be as follows:

wherein X is a halogen such as chlorine or bromine and n is an integer from about 2 to 30.

The following examples illustrate the present invention with no intent to be limited thereby, however, except as claimed:

EXAMPLE 1 14.2 grams of l,4-bis-dimethylamino-Z-butene (0.1 mole) was dissolved in grams of water, and to it was added 12.5 grams (0.] mole) of l,4-dicholoro-2- butene over a period of 15 to minutes while maintaining constant stirring. The reaction was exothermic so that the temperature rose to about 7()C. The reaction mixture was then warmed on a steam bath at a temperature of about C. for about 1 hour, after which the reaction was considered complete. Titration of ionized chlorine was used as a measure of the extent of the reaction and indicated between 98 and 10071 completeness. The reaction product was a viscous material containing about 50% active material.

It was found that when a significant excess of the dichlorobutene was used, a second phase separated out of the final reaction product. Analysis indicated this second phase to contain primarily unreacted dichlorobutene.

Quite surprisingly, the compounds of this invention may be obtained directly as crystalline-like solids when the reaction is carried out in certain organic solvents such isopropanol, acetone and inert halogenated solvents. This is illustrated as follows:

EXAMPLEZ 14.2 grams of l,4-bis-dimethylamino-2-butene were mixed with 25 grams of isopropanol, and to it was added, with stirring. 12.5 grams of 1.4-dichloro-2- butene over a period of about minutes (or at a rate which keeps the solvent gently refluxing). After the exothermic reaction subsided, the mixture was warmed on a ateam bath to reflux temperature and maintained at such temperature for about 1 hour. It was then cooled, to room temperature, whereby a precipitate was formed. The precipitate was then separated out by filtration as the final product. The precipitate weighed 18.7 grams. This product is substantially free from impurities caused by side reactions or due to absorption of unreactcd starting materials, thereby making it easier to purify for use in cosmetics or cosmetic emulsions.

Solid products of the above type have the commercial advantage over aqueous solutions or dispersions because they have less bulk on a pound for pound active ingredient basis.

EXAMPLE 3 The same reactants and procedures were used as in Example 2.except that instead of the isopropanol,

grams of acetone was used. It yielded 21.4 grams of a solid product.

The same procedures may be used except that 1,4- dibromo-2-butene is substituted for the 1,4-dichloro-2- butene, with equivalent mol ratios. The product is substantially similar in all essential characteristics.

EXAMPLE 4 142 grams of l,4'bis-dimethylamino-2-butcne were dissolved in 300 ml. of 1,1 ,l-trichloroethane and to it was added slowly, with constant stirring, 125 grams of l ,4-dichloro-2-butenc at a rate which kept the reaction mixture at a temperature between 45 and 60C., and stirring was continued at 45 to 60C. for 1 hour after an almost-white precipitate was first deposited. After cooling, the precipitate wascollected by filtration and dried in a vacuum desiccator. ltwcighed 245 grams.

Various changes in relative proportions were made to determine whether any significant variations occurred. These as illustrated as follows:

EXAMPLE 5 14.2 grams of l,4-bis-dimethylamino-2-butenc (0.1

mole) was dissolved in grams of water, and to it was added 25.0 grams of 1,4-dichloro-2-butene (0.2 moles) over a period of 15-30 minutes, maintaining constant stirring. The reaction was exothermic. After 1 hour analysis for ionic chloride showed that the reaction was about 98% complete.

EXAMPLE 6 The same reactants and procedures were used as in Example 5, but the solvent was 35 grams of isopropyl alcohol instead of water. After about 1 hour, the solid polymeric product was filtered off. It weighed about 18.7 grams. I

EXAMPLE 7 The same reactants and procedures as used in Example 5, but using 35 grams of acetone as a solvent instead of water, gave a solid product which weighed 21.4 grams after filtration.

EXAMPLE 8 14.2 grams of 1,4-bis-dimethylamino-2-butene (0. 1 mole) was dissolved in grams of water, and wit was added 37.5 grams of 1,4-dichloro-2-butene over a period of 1530 minutes, maintaining constant stirring.

The reaction was exothermic. After one hour, analysis for ionic chloride showed that the reaction was about 9894 complete.

EXAMPLE 9 EXAMPLE 10 The same reactants and procedures as used in Example 8, but using 45 grams of aceton'einstead of water gave a solid product which weighed 21.4 grams after filtration.

EXAMPLE 1 1 14.2 grams of bis-dimethylamino-Z-butene (0.1 mole) was dissolved in 20 grams of water and to it was added 6.3 grams of 1,4-dichloro-2-butene (0.05 mole) over a period of 15-30 minutes. The reaction was exothermic. After 1 hour, analysis for ionic chloride,

showed that the reaction was about 98% complete' EXAMPLE 12 The same reactants and procedures used in Example 1 1 were used with 20 grams of isopropyl alcohol as sol vent instead of water. After about 1 hour, the. solid f polymeric product was filtered off. It weighed. 9.4

grams.

EXAMPLE 13 The same reactants and procedures as used in Exam ple 1 1 were used, except that 20 grams of acetone replaced water as solvent. After about 1 hour, the product weighed about 10.7 grams.

EXAMPLE 14 21.3 grams of 1,4-bis-dimethylamino-2-butene was (0.15 moles) dissolved in 25 grams of water, and to it was added 6.3 grams of 1,4-dichloro-2-butene (0.05 moles) over a period of 15-30 minutes, maintaining constant stirring. After 1 hour, analysis for ionic ch1o-- ride showed about 9871 completion.

EXAMPLE 15 The same reactants used in Example l4,but with 25 grams of isopropyl alcohol replacing water as solvent,

produced 9.4 grams of solid polymeric product after filtration.

EXAMPLE 16 The same reactants used in Example 14, but with 25 1 grams of acetone replacing water as solvent, produced about 10.7 grams of solid polymeric product.

EXAMPLE '17 In order to determine the microbiocidal effectiveness of the present compound, the following test procedures were used:

Bactericidal Tests l. ml. volume of the product of Example 1 (here? inafter referred to as product A) was diluted in distilled water to the test concentration, and was added asceptically to previously sterilized cotton-stoppered 125 ml. Erlenmeyer flasks. For comparative purposes, the same test concentration was prepared using another known microbiocidal polymeric quaternary ammonium compound, namely a product produced by the reaction of bis(2-chlorocthyl) ether and tetramethyl ethylenediamine (hereinafter referred to as Product B").

2. One set of test flasks were each inoculated with 0.5 ml. of a 1/10 nutrient broth dilution of a 24-hour nutrient broth culture of Aerobactcr aerogenes and another set of test flasks were each inoculated with 0.5 ml. of a one-tenth nutrient broth dilution of a 24-hour nutri ent broth culture of Pseudomonas aeruginosa.

3. At 30 and 60, minutes following inoculation, a 1 ml. aliquot of each product was removed rrom each flask and added to 9 ml. of sterile azolectin/Tween 80" neutralizer from which additional fold serial dilutions were prepared in the sterile neutralizer solution.

4. Agar plate counts were prepared from 10 and 10 dilutions.

5. A control of sterile distilled water was similarly inoculated and aliquots were made at the same intervals and plates at 10*, 10", and 10 dilutions.

6. A comparison of the surviving organisms for various concentrations of test materials, at the different time periods was made. The results were as follows:

Table l AGAINST PSI-IUDUMONAS AEROGINOSA Cone. No. of Bacteria Surviving After Sample in ppm. 30 min. 60 min.

Product A 75 29,600 18,500

Product B" 150 26.000 6,800

-Untretlted 8,500,000 12,500,000

(Control) Table 2 AGAlNST AEROBACI'IJR AERUGl-INLZS Cone. No. of Bacteria Surviving After Sample in ppm. 30 min. 60 min.

Product A" 20 5,600 4,300 50 3,000 1 ,1 100 "Product 13" 100 30,000 30,000

Untreated (Control) 10,500,000 1 1,000,000

Table 3 The following 'l'ahlc comprises a comparison of Product A" and "Product B" at identical concentrations:

AGAINST AI-[ROIMCI'l-JR AEROGENl-IS' Algaestatie Tests 1. 24 ml. volumes of Product A and Product B were prepared in sterile Erlenmeyer flasks at various test concentrations.

2. 1 ml. of 5-7 days Allen's liquid medium growth of Chlorella pyrenoidosa (Wise. strain) was added to each flask (Allens liquid medium is a standard test composition comprising mg. NH,C1, 1000 mg. NaNo 250 mg. K HPO 3 mg. FcCl 513 mg. MgSO 50 mg. CaCl and 1000 mil. distilled water).

3. The inoculated flasks. plus untreated inoculated control flasks, were incubated at room temperature (about 25C.) under continuous artificial illumination.

4. Following 5 to 7 days incubation, observation was made for macroscopic growth to determine the minimum inhibitory level for each test material.

The results were as follows:

Table 4 Sample Minimum effective concentration in ppm.

Product A" 1.0 "Product 13" 1.5

A graduated blender cylinder is rinsed with distilled water. ml, of aqueous test solution is added downthe walls of the blender so as to cause no foam. the blender is turned to high speed for exactly 5 seconds, and upon turning the blades off, timing is started with a stop watch, and at the same time the foam height read in mm. from the 100 ml. mark. The foam half-life is defined as the time it takes for liquid to drain out of the foam and reach the 50 ml. mark.

A further test was made using the Cylinder Shake Test procedure which is as follows:

CYLINDER SHAKE TEST I ml. of test solution is gently poured down the walls of a 250 ml. graduated cylinder that has a glass stopper. The cylinder is stoppered and inverted times in 15 seconds, finally resting it in an upright position. The foam height is read in cc. from the base of the foam.

Table 6 Foam Height in cc. Sample ppm. Initial l min. 5 min.

B'I'C 77(1" 50 45 34 Product A" St) (I (l "BTC 2l25" 5U 50 (i 4 Another test used was .the standard Ross-Miles Test using the procedure reported in "ASTM Standards, Designation 1175-53, Part X, 1958, page 878," which is the ASTM test for foaming properties of surface active material. The results were as follows;

Table 7 Foam Height in cc. Sample ppm. Initial I min. 5 min.

BTC 776' 50 30 20 Product A" 50 0 t) I) BTC 2l25" 5O 35 I5 I() The above results clearly show not only that the product of this invention is highly biocidal but that it is non-foaming, whcreasother quaternary ammonium bi ocides cause a relatively large amount of foaming in aqueous composition.

The following examples illustrate various cosmetic compositions using the product of the present invention:

Example I8 Components 71 by Wt. I by by Wt. "/r by Wt.

Mineral oil (65/75 VisC.) 35.0 35.0 35.0 35.0

Lanolin (Cosmetic Grade) l.() 1.0 1.0 l.()

Celyl alcohol I.() l.() l.() 1.!)

'IWEEN 8t)" (Atlas Powder Co.) (non-ionic "SPAN Rt) (Atlas Powder Co.) (non-ionic emulsifier) "Product A Water (Distilled) 55.0

In the case of the first formulation, without Product A A, the mineral oil, lanolin, cetyl alcohol, Tween 80, and Span 80 were combined and heated to about (157()C. The water was heated to about 7()C. and added slowly to the hot non-aqucousphase while stirring the mixture until it emulsified completely. The emulsion was cooled to room temperatureusing con-. tinued agitation.

In each formulation when Product A was incorporated. the mineral oil, lanolin, cetyl alcohol,Twee n.8(), and Span were combined and heated to about 657()C. The water and Product A were combined and heated to about 6570C. Then the hot aqueous solution was added slowly to the hot non-aqueous phase while stirring, and agitation was maintained until emulsification was effected. Then the emulsion was cooled with continued stirring to room temperature. The resultant product was an oil-in-water emulsion.

These compositions are utilizable as hand creams and baby lotions.

These compositions were tested in thefollowing manner:

50 gm. samples from each composition were aseptieally transferred to sterile 8 02. wide mouth jars. Two replicate jars were prepared in everyinstance, includ; ing an untreated control. Each jar was inoculated with 2.5 ml. of a one-ten sterile nutrient heated dilution of pooled 24 hour broth cultures of Staphylococcus aureus. Pseudomonas aeruginosa, Escherichia coli, Enterobacteraerogenes, proteus species and Bacillus spe cies. In this manner a bacterial challenge load of l-l OX 1 O bacteria/nil. ofjar content was obtained. All. the inoculated jars were stored at 2527C. At weekly intervals following inoculation, 1 ml. aliquots of jar content were removed from each jar and tenfold serial dilutions were prepared therefrom in stcrile A zalectin/- Tween 80 neutralizer solution which wereplated into TGE a jar. In this manner the number of surviving viable bacteria in each jar was determined. In those instances where no viable surviving bacteria lO bac.teria) were observed at four weeks following inoculation,

the jar contents were reinoculated exactly as previously and IOXIO bacteria/ml. The. variation around the mean of the inoculum concentration is of little importance when a reduction to less than lO/ml. ofviable l bacteria is observed.

Table 8 INOCULATION at 6 X It) organisms/nth ol'jar content for each of the four formulations of Example 18.

From a statistical point of view, there is no significant difference between an initial inoculum load of IX I 0 Week Count Count Count Count I (19 X H)" l5.()(l() II) 10' 2 71 X [0" 74,000 H) l() 3 54 X It) 1.400 l(). [0 4 XI II) II) 10 In order to double'check the validity of this test showing less than 10 organisms/ml. after four weeks,

the samples were rcinoculat cd and the weekly counts Table 10 after reinoculation were:

INOCULATION at 3.8X10 organisms/ml. of jar content for each o1- the four formulations o1- Example 20:

Week Count Count Count Count 5 Count Count Count Count eek 5 10K X10" 10 10 10 6 169 X 10" 10 10 10 I [8x100 ISXIOIF RXXIUH 7 180x10" 10 10 10 2 23x1 :lxloli IZXIU ()IZXHW 8 209 X 10' 10 10 10 3 87x10 7 84x10" sfixloli 4 l()(t l0' 50x10" 70x10" 80x10" 10 5 109x10" 114x10" 50x10" 20x10" UZXIU 7'JXI1)" 45Xl0" 36 l0' The followmg example were prepared in the same 4X10 89x10" 67x10 750x10" manner as Example 18, but substnutmg other well- 8 fi mzxmfi xlxm" known, highly active biocidal quaternary ammonium compounds for Product A. They were then similarly evaluated.

Ex'tm 1e 19 p Example 21 I" F I/ I" Componuns h W1. 1 h Wt. by Wt. h Wt. Comlmmms (/1 by wt. by wt WL Mimml *1" Mineral 011 55.0 55.0 55.0 55.0 105/75 VISC.) 35.0 35.0 35.0 55.0 (65/75 visa) Lanolin Lanolin (Cosmetic Grade) 1.0 1.0 (Cosmetic Cetyl Alcohol 1.0 1.0 1.0 1 0 Grade) 1.0 1.0 1.0 1.0 TWEEN 150" 5.4 .1 5.4 Cetyl alcohol 1.0 1.0 1.0 1.0 SPAN 110 2.0 2.0 2.0 2.0 E 80' 5.4 .4 5.4 5.4 BTC snr SPAN 80 2.6 .0 2.6 2.6 (On\'x (711001.01) 0 0.1 0.2 04 HYAMINE 1633 Water (507') (131511110111 55.0 54.0 54.1: 54.0

Table 9 lNOCULATlON at 4.7 X 1()orgnnisn1s/ml. o1 jar content for each of the lour formulations of Example 19.

. Table 1 1 Count Count Count Count cck INOCULATION at 3.1"1 l0 organisms/ml. ot' jar content for each i 40 of the four formulations of Example 21: 1 10x10- 10x10" 10x10" 4x10" 3 98x10" 13x10" 1 1X10" 5X10" Count Count Count Count 1 07x10" 40x10 24x10 10x10" COR 4 142x10" lt)2 84x10" 01x10" 5 167Xl0" l19 l0 X4Xl0" (17 l0 l ZZXIU 19X 10 l7 l0"' l5 l0 6 180x10" l 14 10 32x11)" 44x11)" 2 P.4Xl0 21x11)" 19 l0 l -l l0 7 140x10" 95x10 82x10" 70x10" 3 80x10" 71x10" 94x10" 111x10" 8 4 0" 2 1 0 54 4 94x10 80x10 72Xl0 92X10" 5 106 l0 74 10" 67 l0 x10" 6 l loXlt) 91x10 84x10 X10 7 '-)Z l() 74 l0' 4ZX10 ZXXH)" 8 94X10" 82x10" 56 10' 43Xl0" 50 Example 20 Components "/1 by Wt. 71 hy Wt. 71 by Wt. by Wt.

Mineral oil gs (65/75 \-1se.) 35.0 35.0 35.0 35.0 Example 22 Lanolin (Cosmetic (irade) 1.0 1.0 1.0 1.0 Components "/1 by Wt. '/r by Wt. by Wt. 71 by Wt.

Cetyl alcohol 1.0 1.0 1.0 1.0 Mineral oil 0 (65/75 Vise.) 35.0 35.0 35.0 35.0 TWEEN 110" 5.4 5.4 5.4 0 5.4 Lwmlin (Cosmetic (irade) 1.0 1.0 1.0 1.0

. Z. 2. 2. 2X 51 AN 6 Cetyl 111001101 1.0 1.0 1.0 1.0 TWEEN 5.4 5.4 5.4 5.4 i 3135M "SPAN 2.0 2.0 2.0 2.0 HYAMINE 23110" (Onyx henLC o.) 0 0.1 0.2 0.4 1

(Robin & Haas) 0 0.1 0.2 0.4 Water Water (Distilled) 5540 54.) 54.1 5 (Distilled) 55.0 54.9 54.8 54.6

Table 12 INOCULATION at 4.l'l l() organisms/ml. of jar content for each of the four fornnilations of Example 22:

Although oil-in-water emulsions have been described above, it is within the scope of the present invention to use water-in-oil emulsions for the same purposes.

The invention claimed is:

l. A method of controlling the proliferation of deleterious microorganisms selected from the group consisting of bacteria and algae in an aqueous system, which comprises applying to said microorganisms a hacteriacidally or algaecidally effective amount of a condensation product formed'by mixing l,4-bisdimethylamino-Z-butene dissolved in a solvent with 1,4- dihalo-Z-butene at room temperature whereby an exothermic reaction is obtained causing the temperature of the mixture to rise, then maintaining the mixture at no higher than reflux temperature until the reaction is LII complete, wherein these reactants arepresent ina molar proportion of between about 1:3 and about 321 relative to each other.

2. The method of claim 1 wherein the dihalo is dichloro.

3. The method of claim 1 wherein the dihalo. is dibromo.

4. The method of claim 1 wherein the aqueousmedia is recirculated water.

5. An aqueous composition containing, as a biocidal agent, the condensation product formed by mixing] ,4- a

bis-dimethylamino-Z-butene dissolved in a solvent with l,4-dihalo-2-butene at room temperature whereby an .exothcrmicreaction is obtained causing the temperature of the mixture to rise, then maintaining the mixture at no higher than reflux temperature until the reaction is complete, wherein these reactants are in a molar proportion of between about about 1:3 and about 3:]

relative to each other, said agent being present in a bacteriacidally or algaecidally effective amount.

6. The composition of claim 5 wherein said aqueous media comprises recirculating water.

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Classifications
U.S. Classification504/158, 526/294, 424/78.35, 514/642
International ClassificationA61K8/04, C08G73/00, C02F1/50, A61K8/30, A61K8/72, A61K8/06, A61K8/84, A61Q17/00, A61K8/40, C08G73/02
Cooperative ClassificationC02F1/50, C08G73/0226, A61K8/06, A61K8/40, A61Q17/005, C08G73/0213, A61K8/84
European ClassificationA61K8/40, C02F1/50, A61K8/84, A61Q17/00F, C08G73/02A9, C08G73/02A9C, A61K8/06
Legal Events
DateCodeEventDescription
Jun 16, 1993ASAssignment
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Oct 25, 1988ASAssignment
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