DE2064086A1 - Deodorizing detergent - Google Patents

Description

PATENT ADVOCATE DR.-ING. LOTTERHOS

FRANKFURT (MAIN) j. rc χ 9D6AG86

Annastrasse 19 AjinomotO Oo . , Ine . ^ UQHUUU

FcRNSPRECHER = COiH) 555061 No. 7> 1-chome, Takara-cho, Chuo-ku

t: legrammei lomosapatent (Dokvo Jat> sn

LANDESZENTRALBANK 50007149 «^ ♦ i" »"

POST CHECK ACCOUNT FfM. 1667

HI / K FRANKFURT (MAIN). 22.12.197o

Deodorizing detergent

The invention relates to a deodorizing detergent or cleaning agent, in the case of a soap or a synthetic detergent, the deodorant is one or more higher N-aliphatic Acyl basic amino acid derivatives of the following formulas (I) to (III) are incorporated:

RCO

NO"

P ^ ι TI

^Ά 3 (CH ₀ ) ,,. ^a 2 " NH

Uf R ₄ ROO-N-OHGOX

(i) Cn) '

(III)

According to the invention, salts of these compounds can also be used will. In the formulas: ROO means the remainder of a saturated or unsaturated fatty acid with 6 to 2o carbon atoms,

R ,. a hydrogen atom or a ΟΗ, group, X an NH ₃ -, OCH, -, QC ₂ H ₅ -, OC ₅ H ₇ -, OC ^ Hq- or OH ₂ O ₆ H ₅ group.

In the formulas (I) and (II), R ₂ denotes a hydrogen atom or a CH, group, R, a hydrogen atom, an OH, or OH ₂ C ₆ H ₅ group and η 2, 3 or 4.

It is the object of the invention to provide deodorants which are suitable for incorporation into a detergent, an excellent develop antibial (antimicrobial) effect, especially against microorganisms such as bacteria and fungi.

109827/1779

206A086

do not cause skin irritation and the washing or cleaning effectiveness increase.

Lately soaps or synthetic ones are becoming increasingly popular Requires detergents that contain disinfecting and deodorizing additives. As see fabrics are in practical use e.g. hexachlorophene, trichlorocarbanilide, tribromosalicylanide, tetramethylthiuram disulfide and the like. All these known deodorants, however, have the disadvantage that they cause skin irritation and are sparingly soluble in water or are insoluble. It was therefore necessary to use them in proportion to bring large quantities into the detergent in order to achieve a sufficient antibiotic effect. The application In turn, such large amounts are disadvantageous in terms of skin irritation. Especially with hexachlorophen or tetramethylthiuram disulfide detergents containing detergents have been reported to cause eczematic sensitization of the skin, if it is exposed to sunlight after use (Nobuyuki Mizuno "The Health Insurance Newspaper" July 15, 1969).

Common cationic wetting agents that have good antibial properties Have an effect, are water-soluble, but they cannot be used as deodorants for detergents, because when they are incorporated into detergents such as soaps, they form an insoluble precipitate and thereby the antibial effectiveness is reduced or eliminated and also the detergency (J is significantly reduced.

It has now been found that the compounds of the formulas (I) to (III) and their salts have excellent properties as Have deodorants for detergents, in terms of water solubility, excellent antibial activity against Microorganisms such as bacteria and fungi, good wetting agent effect and skin friendliness. When using these compounds could not find any skin disorders such as irritation, eczema or increased sensitivity

109 827/1779

be, and "when incorporating into soaps or other synthe · * - table detergents they developed an excellent antibiotic Effect without the washing or »cleaning effect to basia * · - pregnant © unfold even when incorporated into such synthetic detergents, which normally make the skin rough it has a protective effect that destroys the brittle, cracked skin «· guards "

The compounds according to the invention are easy and with to produce relatively low costs »

Among the compounds of formulas I and II are those with η equal to 2 α-γ-diaminobutyric acid derivatives and those with η equal to 3 ornithine derivatives and those with η equal to 4-lysine derivatives »The compounds of the formula (III) are arginine derivatives * All of these basic amino acid derivatives can be obtained from the corresponding basic amino acid derivatives without difficulty Amino acids are produced, e.g. © according to the method of published Japanese patent applications Fr · 11926/67 and 9529/68 "Both the optically active L ~ or D-forms as are also the racemic forms of the amino acid components effective · As salts of these compounds are for example: Salts of mineral acids, such as hydrochloride and Sulphates, salts of organic acids, such as optically active or inactive ^ pyrrolidonearboxylic acid · ,. optically active or inactive acidic amino acids (ζ · Β »glutamic acid and aspartic acid), Lactic acid, citric acid and acetic acid © The use of the hydrochloride and salts of the Dir · or L-o> »Pyrro« - Lidoncarboftäure is particularly advantageous because of the crystalline Structure"

S a
N -Cocoyl-N -methylornithine methyl ester hydrochloride "

Examples of compounds according to the invention are ι / άγ'- cocoyl * ·· - Κ ^γ , N ^ -dimethyl-DL-a-, γ-diaminobutyric acid methyl ester hydrochloride, H ^ lauroyl-N ^ i ^ 'dimethyloriiithinbenzyl ester hydro- Chloride, N ^0- PaImItoyl-S ?, N ^r _f N ^Y -a? Rimethylornithine methyl ester>. Hydrochloride,] # ^ Palmitoyl «-N ^Y , N ^Y - <Limethylornithine benzyl ester" - hydrochloride, H ^ lauroyl ^ N ^ -benzyl-lirTi-methylornithine methyl ster-hydrochloride, ^, N ^ -dimethyl ^ N ^ -hydrogen-tallowyl ** - ornithine - ethyl ester hydrochloride, I ^ -Myristoyllysinemethylester-Hydro "

109827/1779

Chloride, N ^a -Myristoyllysin-amin ^ hydrochloride, I ^ -Palmitoyl-N, Nr-Dimethyllysine methyl ester hydrochloride ₉ J ^ -Lauroyl-IJ ^ -benzyl-Ifr-methyllysine methyl ester hydrochloride, l ^ -Lauroylargininemethyl · · ester-oc- pyrrolidone carboxylate, I-hydrogenated tallowyl ** - arginine methyl ester - hydrochloride, S-semihyärogenated tallowyl - arginine butyl ester hydrochloride · The abbreviations have the following meanings: Oocoyl * * remainder of coconut oil fatty acid hydrogenated tallowyl ** «remainder of hydrogenated beef tallow fatty acid
semi-hydrogenated tallowyl *** ■ remainder of the semi-hydrogenated

Beef Tallow Fatty Acid "

It should be pointed out that the above list does not constitute a limitation of the compounds according to the invention »

It is an outstanding feature of the compounds of the invention that they have a strong antibiale activity and in particular the antibial · or "consists inhibitory effect against microorganisms which are relatively highly resistant to the known antibialen substances such" .B _e Bacillus subtilis , Candida albicans, Aspergillus niger. Staphylococcus aureuse The following table contains the results of comparative tests with compounds of the invention and N-lauroylarginine, streptomycin, sorbic acid, N-lauroylsarcosine, N-palmitoyl-L-phenylalanine, N-stearoyl-L-glutamic acid, Hexachlorophen and p-oxybenzoic acid methyl ester

10982 7/1779

Compound according to the invention 1 tribe
2 3 10-100 N ^a -Lauroyl-L-arginine methyl-
ester hydrochloride 10-1oo 10-1oo 10-1oo Il N ^a -Lauroyl-N ^, N * -dimethyls
L — ornithine methyl ester—
Hydrochloride Il It It It N ^a -Miristoyl-L-lysine methyl-
ester hydrochloride It H ti 10-1000 Ϊ «—Lauroyl — N —benzyl — N -
methyl-L-lysinamide-
Hydrochloride Il 10-1ooo 10-1ooo Ιο-loo N ^ —Lauroy 1-N ^, N; —dimethyl — L »
ornit hinme thyle st er-L <-a> »
pyrrοlidonc arboxylate ti Ιο-loo 10-100 Comparison substances N ^a -Lauroyl-L-arginine 1ooo < »Μ mm- 1ooo < Streptomycin 10-1oo - 1ooo < 1ooo < Sorbic acid 1ooo < i. ** m , j 1OOO < 1ooo <. N-Lauroylsarco sin 1oo Ι00-Ι000 1οοο <^ 1ooo- ^ Nf-palmitoyl-L-phenylalanine 1oo-1ooo 1oo * ~ »4ooo 1o-loo 1000-Q N-Ste aroy1-L-glut amic acid 1ooo < 1ooo <[1ooo < 100-1000 Hexachlorophene <1o ^ Io <1o 1000 ¹ ^ p-methyl oxybenzoate 1ooo < 1oeo {. 1οοο <

The numerical values in the table show the inhibition concentration of the compound against the growth of the microorganisms in γ / ocm »

The microorganism strains used, their cultivation and the culture medium are given in the following table »

109827/1779

No,

tribe

Cultivation (single culture medium line cultivation)

Staphylococcus aureus ATCG 65389

Bacillus subtilis ATCG 6633

Candida albicans ATCC

Aspergillus niger ATCG 9642

37 ° C, 3 days (24 hours),) bouillon

I pH 7, o

31 ⁰ C, 3 days (24 hours) I.

25 ° G, 3 days (24 hours)) glucose

L bouillon «T yeast extract

25 ° C, 3 days (48 hrs) J pH 5.8

From the table it appears that compounds with free hydroxyl groups have a lower antibiale \ w · inhibitory effect · The compounds of the invention of the amides or esters are used in the form *

These active substances are used in soaps or synthetic detergents in.Menger / vino _t 1 to 5 wt '% _s incorporated · Suitable synthetic detergents ζ · Β such _ο considered mainly consisting of: H higher-acyl glutamates, N-higher Acylasparaginate, Alkylbenzenesulfonates, higher alkylsulfonates ,. tx-olefin sulfonates and alkyl ether sulfates * The detergents can be manufactured in the form of pieces, tablets, powders or liquids as required *

The deodorants according to the invention have the following excellent ones Properties: They bring about excellent washing power and antibial or *, inhibitory activity against undesired Microorganisms and that also in mixtures with detergents * The compounds according to the invention themselves have surface activity or "wetting effect in contrast to the known de · odorants". This increases the cleaning effect * yours antibial activity lasts for many hours after application · Furthermore, they are water soluble · When the compounds themselves do not have the desired solubility in water, one uses their salts with mineral acids or organic * acids » The following table shows the solubility of various compounds in water

*) from 0.1 to 50, preferably

10 98 27/1779 - * ■.

Compound solubility __ κ / dl, 4-o ° C

N ^a ~ Lauroyl-L-arginine methyl ster-Hydro Chloride 2o

l ^ -Lauroyl-L-arginine methyl st er-DL-a-

pyrrolidone arboxylate 2.5-3jO

y-N ^, Ir «dimethyl-DL-ornithinemethyl-05_. 50

ester hydrochloride ^ * "

N ^ Palmitoyl-L-lysiiime thyle ster hydrochloride 15

li ^ -Cocoyl-L-arginine methyl ester-Ii-a-pyrrolidon- ς - 8

carboxylate. ? - ο

ester hydrochloride
N ^ -Myristoyl-Ij-lysinamide hydrochloride 55

Another advantage of the compounds is that they are non-toxic and do not cause skin irritation, ζ · Β · was found in the acute oral toxicity test in mice for. N —— Lauroyl-III-arginine ethyl ester-DL-α-pyrrolidone exn LDc ₀ ** value from 2 to $ .0 g / kg body weight. Furthermore, this amino acid derivative was mixed with polyethylene glycol and applied to the tissue of an adhesive plaster for the plaster test in a moist state and then applied to the skin for 24 hours. * This test did not reveal any skin irritation »

To further explain the invention, examples follow »

example 1

Nv-Lauroy L-L-arginine methyl Ie ster-DL-KX-pyrrolidone carboxylate (hereinafter referred to as DL-I) was in the in Table 1 specified amounts mixed with 2, ο g fatty acid soap material, and the mixture was given in 100 ecm of that in Table 2 Culture medium dissolved · Then the pH value was adjusted to 6.2 to 7 »3« Each 4 ecm of these solutions were mixed with the in Table 2 under A to H indicated microorganism strains and under the conditions also indicated in Table 2 cultivated «The growth of the microorganisms was assessed by the increasing turbidity of the culture solution and checked by taking place at certain time intervals

109827/1779

Measuring the absorbance at 56ο ΐΐιμ (optical density) by means of a spe ^ meters · The results show the curves of FIG © 1, from which it follows that the medium inoculated with DL-I culture media Kr ₀ 4 and 5, a significantly higher inhibitory effect on the growth the microorganisms exercise as the culture medium JJR «1 alone and the only fat acid is" fenmaterial offset culture medium No. ₄ 2 * the inhibitory effect was equal to that of

Table 1
Me «soap material (g); Deodorant (g)

try

1 without without

2 2 ₉ o without

3 2, o G-Tl * o, o41 g

Additions according to

Erfindu ng ■ ■

2 _f o DL-I

2, o

* G-11: hexachlorophen

109827/1779

Table 2

Microorganism strain.

Cultivation ·· culture temperature medium

pH of the culture «- cultivation medium

CD OO NJ

co

A Lactobacillus easel ATGC

B Lactobacillus ferment!

ATCG

C Staphylococcus aureus

ATGC

D Escherichia coll

ATCG

E Pseudomonas aeruginosa

ATCC

F Bacillus subtilia ATCG

G Candida albicans

ATCC

H. Aspergillus niger ATCC 9642

7469 37 9338 37 65389 ν 1o? 98 1263 3o 6633 3o 1o259 3o 9642 3o

1 1

2 2

2 3 3

7.2 - 7.3

7 * .o. - 7.2

I'6.2

fluid when standing

liquid with shaking

ti

fluid in standing

Those identified in Table 2 with the numbers 1, 2 and 3

Culture media had the following composition:

JSftp »1 amount of the complete solution

Peptone 1, above

SäSäu Ι ', ϊ 100 ml aqueous solution

Hind extract o, 2

Oas amino acid ο, 5

Glucose o, 2

Glycerin ο, 3

Magnesium sulfate o ₉ 1

Tween 8o 1 drop

No. ₈ . 2 .

fiinderextrakt 100 ml aqueous solution

Peptone 1 »o

Sodium chloride o ₉ 3

Yeast extract 0.3 100 ml aqueous solution

Malt extract o, 3

Peptone 1, o

Glucose 1 «o

Example 2

N ^a "lauroyl" L "(· hereafter referred to as LI fesw · DL *!) (Or DL) ~ argininmethylester-La ^ pyrrolidonecarboxylate was indicated in Table 3 heptene with 2 g of monosodium H *" cocoyl Ic - (or -DL) -glu.tamat (referred to below as LV-II or DL-II) mixed. With this, inhibition tests against the various microorganisms were carried out in the same way as in Example 1 *

Table 5 Np Deodorant Comparison test 1 soap material 2 g without 2 DMX 2 g ohn® 3 DB-II 2 g G-11 * o _t o41 p Additions according to the invention 4 DL-II 2 g 5 L-II 2g * S = \ «Y ^t * v- 4 * \ J & b Sf
DIi ^ l © _t 224 g * Gw11i hexachlorophene 109827/1779

The culture media showed a clear IY & ibitor effect against the microorganism strains A "to H. The results versus the strains Δ, C, E and G can be seen from Fig. 2. It can be seen that the culture medium No. 2 with DL-II A certain antibacterial effect in comparison with the culture medium Mr · 1 without additive shows «The culture media no« 4 and 5 with further additions of L-I and DL-I show an excellent, antibial activity comparable to hexachloroform »

Example ff

2 parts of H ^ i-Lauroyl-DL-arginine methyl ester-L-cx ^ pyrrolidone carboxylate were put on the roller with 100 liters of soap mixed · The mixture was warmed to 50 to 60 ° G, to ™ Seals of 25mm diameter extruded and placed in metal molds molded on an impact press machine «The appearance of the soap bars was just like the bar of soap made for comparison made of pure soap material · Likewise, both products showed no difference in solubility due to the abrasion test according to Japanese Industrial Standards K-33o4- and at disintegration in water

Of each of the two pieces (with Twr · addition of DL-I ohn) was 2 ₉ og scraped off and dissolved as in Example Λ in 1oo cc culture solution · Each 4- cc of the solution was inoculated with the given in Table 2 Microorganisms and m · cultured under the same conditions to determine the growth of the microorganisms was as described in example 1 j, the measured turbidity of the culture solutions with a spectrophotometer. "

The culture medium ait DL-I showed an inhibitory effect against ^ · all · Stäjune A to H. In Fig. 3 are only the results given for the strains A, C and G · The dashed curves relate to the experiments with the addition of DL-X and the continuous curves on the experiments without DL-I »It results that the soap with the addition of DL-X the growth Microorganisms effectively inhibited in contrast to the soap

without the addition "A particularly strong effect can be determined compared to strain A"

109827/1779

206A086

Example 4

10 parts were used to make a shampoo Sodium sulphate mixed with 90 parts of sodium dodecyl sulphate, and it became Nf'-lauroyl-N ^, NP-dimethyl-DL-ornithine methyl ester lactate added in the amounts given in table 4 »

Tabel o, 2 4th Deodorant o, o4o δ sample Ne-dodecyl sulfate Na ₉ f It 3O ₄ o, o41 S. No. W. none o, 225 S. 1 1.8 g η S. 2 It DL-III 3 Il BLJIX 4th Il

* G-1i: Hßxachlorphen

Each robe was dissolved in 100 ecm of culture medium according to Table 2, and 4 ecm of each of these solutions were inoculated and cultivated with the microorganism strains A to E. The growth of the microorganisms was determined as in Example 1. In the culture medium Ir _e 1 without DL- III, signs of growth were already observed 1 hour after the start of cultivation * In contrast, growth was inhibited for 10 to 15 hours in the case of culture media no. 3 and 4. The inhibitory effect was about the same as that of culture medium no.

Example 5

In each case 5 parts of the 11 compounds listed in Table 5 were mixed on the roller with 1 parts of soap material and 1 to 3 parts of water. The mixture was heated to 50 to 55 ° C and made into soap bars of 25 mm. Diameter extruded and pressed «The measurement of the solubility was carried out after the abrasion test according to Japanese Industrial Standards K-33o4 on samples of the soaps with the additives according to the invention and comparative samples, which consisted of pure soap material, and showed that in the samples with the Additions Measured values were found that were within 2o % of the measured values of the comparison samples There is no significant difference with regard to the dissolution in water

109327/1779

Table 5

1β N ^a -Myristoyl-L-lysine methyl ester-HydrocBbrid 2 «J ^ -Myristoyl-L-lysine amide hydrochloride

3 «y5yyyy

4 "N ^a -Lauroyl-N ^OC , H ^S , 1-trimethyl-D ^ ornithine methyl ester hydrochloride

5 «N <-cocoyl-N -methyl-DIi-oriiithine methyl ester hydrochloride

6. N ^a -palmitoyl-lTr, IP-dimethyl-DL-ornithine benzyl ester * · Hy dr ο chloride

7 «] S ^ L · a ^ iroyl-N ^
Hydrochloride

8 · N ^a -Go coyl-ilX, FT-dimethyl-DL-α, Y'-diaminobutyric acid methyl ester hydrochloride

9 · N ^ jl ^ -dimethyl-Hf-hydrogenated tallowyl-DL ^ ornithine ethyl «™

ester hydrochloride

10c ^ H ^ hydrogenated tallowylarginine methyl ester-lj-cxwpyrro- · lidone carboxylate

11 • U ^cx -'Semihydrogenated tallowyl arginine butyl ester hydrochloride "

Of the soaps ^ every sample and a comparison soap

w
Pieces without additive, 2 g each were scraped off and dissolved in 1oo ecm of the culture medium given in Table 2: ". 4 ecm (each solution was inoculated with microorganism strains A and E and cultivated microorganisms as determined in example 2 from the measured opacity ". _Ä

In the case of cultivation for 22 hours while standing, the absorption of the culture medium with the comparative soap was already o.8o * after 10 hours of cultivation for strain A, whereas the absorption of the other culture media with the additives was below o.1o, and after 12 hours of cultivation was below shaking, resulted in the strain e in the culture solution with the Vergi © .U nd ^ .ife after 8 to 1o hours absorption of o, 2o, währeüd the other culture solutions with the additives, only one value yon o _t o5 was achieved _e This is proof of the deodorizing effect »

109 8 27 Π 7 79

Claims (1)

Claim Deodorizing detergent, characterized by a Soap or a synthetic detergent with an addition of compounds of the forms X to III RCO t J, EGO-E-GHCOX. (D ¹ (II) L (III) in which RGO is a residue of a saturated or unsaturated fatty acid with 6 to 20 carbon atoms, R, j a hydrogen atom or a CH, group ^ X a HH ₂ -, OGH, - ^ ÖGgH, - «, OG, H" ~ _S OG ^ Hq- or OGH ₂ GgHt " Group, R _{2 is} a hydrogen atom or a GHz group, R, a hydrogen atom is «a GHz» or CH ₂ GgHc »group and η is 2, 3 or 4» 109827/1779 JS .. Lee rs ej te