CA1296361C - Quaternary ammonium compounds useful in hair treating preparations - Google Patents
Quaternary ammonium compounds useful in hair treating preparationsInfo
- Publication number
- CA1296361C CA1296361C CA000541507A CA541507A CA1296361C CA 1296361 C CA1296361 C CA 1296361C CA 000541507 A CA000541507 A CA 000541507A CA 541507 A CA541507 A CA 541507A CA 1296361 C CA1296361 C CA 1296361C
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- hair
- treating
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- aqueous
- formula
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/45—Derivatives containing from 2 to 10 oxyalkylene groups
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Quaternary ammonium compounds corresponding to the formula are prepared by reaction of 1 mol of at least one tertiary ether amine in the form of its salt corresponding to the formula with about 1 mol of at least one alpha-epoxide corresponding to the formula .
They are suitable for use as conditioning and revitalizing agents in hair-cosmetic preparations.
Quaternary ammonium compounds corresponding to the formula are prepared by reaction of 1 mol of at least one tertiary ether amine in the form of its salt corresponding to the formula with about 1 mol of at least one alpha-epoxide corresponding to the formula .
They are suitable for use as conditioning and revitalizing agents in hair-cosmetic preparations.
Description
i3~
PATENT
Case D 7614 QUATERNARY AMMONIUM COMPOUNDS
USEFUL IN HAIR TREATING PREPARATIONS
BACKGROUND ON THE INVENTION
lr Field of the Invention:
This invention relates to new quaternary ammon~um compounds as well as to their use as hair-condltioning and combability-improving additives in halr-cosmet1c preparations~
PATENT
Case D 7614 QUATERNARY AMMONIUM COMPOUNDS
USEFUL IN HAIR TREATING PREPARATIONS
BACKGROUND ON THE INVENTION
lr Field of the Invention:
This invention relates to new quaternary ammon~um compounds as well as to their use as hair-condltioning and combability-improving additives in halr-cosmet1c preparations~
2. Statement`of Related Art~
Cationic surfactants of the quaternary ammonlum compound type are used~in hair cosmetics as revita~lizing and conditioning agents for improv'ng the ~combab1~1ity, body and fee1 of the hair and~
for~red~ucing its stat~c charge. The products are normally used in hair aftertreatment preparations (conditioners) which, after~wash-~ing of the hair~9 are intended to restore favorable hair-cosmetic properties~ However, such~compounds are not su~table as condi-tioner~additive~s~ n~shampoos themse~lves~,~ because most of the known quaternary~ammoni~um~comp~ound;s are incompatlble with the high-foam 15~ ~an10nic~`surfactant~s normal~ly~ u~sed 1n~ shampoos. ~ When present n ~the~ concentrations required for an adequate condlt~oning ~effect,~they~fo~rm~;substanti~ally~water-lnsoluble and cosmetically lneffectua~ deposi~ts. ~ ~Quaternary ammonium compounds . .
.
: :
which are more compatible with anionic sur~actants generally have an inadequate conditloning ef~ect.
Although water-soluble cationlc polymers are generally com-patible with anionic surfactants, they are attended by other disadvantages, such as accumulation on the hair aftPr repeated treatment resulting in dullness, and inadequate antista-tic effects on dry hair.
DESCRIPTION OF THE INVENTION
Other than in the sperating examples, or where other-wise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
The present invention provides novel quaternary ammo-nium compounds, which have strong revitalizing and conditioning properties on human hair and which may even be incorporated in shampoos based on high-foam anionic surfactants in conditioner effective concentrations, without negatiYe effects.
The novel quaternary ammonium compounds have the following 20 formul~
R ~ nH2n)x -(+) N - CH7 - CH - R3 1 A m(-) (I
I m ~ (C2H4O)y - H
wherei-n R1 ~s~a C8-22 alkyl; R2 is a C1 4 alkyl or -~C2H4O~z-H, R3 is a ~6-~0 alkyl;~x is O or a number from 1 to 10; y and z are each numbers from 1 to ~0; n is 2 or 3; A is ~he anion of an i~gm i-c- a-cid or of a C1 1g organic carboxylic or sul~oni-c acid;
and m 1~ ~he acid's valency.
The new quaternary ammonium compounds are produced from reacting at least one tertiary ether amine which is used in the ~ form of its sal~t or in stoichiometric quantities with an inorga-ic~;~acid~suitabl-e for salt formation or a C1 18 organic carboxyl~c ; ~ ; -2-:
: ~ ` : :
.
.
9~ 6~L
or sulfonic acid. The salts of the tertiary ether amines have the follow1ng formula R1 (0CnH2n)x - N (+) - H 1 A m(-) (II) ¦ m (C2H40)y - H
They are reacted with approximately an equimolar amount of at least one alpha-epoxide having the formula R3 - CH - CH~ (III) In formulae II and III, ~1, R2, R3, n, x, y, A and m are as defined for formula I.
Ether amines corresponding to formula II are known from the literature, for example from published British patent appl~cation 1,087,413 and from published European patent application 102,140.
In the process described therein, the ether amines in~question are;
prepared from primary and secondary amines by alkylation at the nitrogen atom, with alkyl polyglycol ether sulfates. Another pro-cess, which is the~subject of German patent application 35 04 242, (which~was~ published~14 August 1986, subsequent to the or19inal Germàn~p~atent application; for~the present 1nvQntion), starts out from tertiary alkanolamines~ and ~leads to ether~ amines corresponding to formula II by~alkylation at the hydroxyl group, with~alkyl~sul~fates or alkyl polyglycol ether sul~ates. The ter-tiary ether amines are converted into the salts of formula II by addltion~o~ mi~neral acids~, such as concentrated hydrochlor~c ac1d, concentrated hyd~robromic acid,~sulfur~c acid, phosphor~c ac~d or boric ~ae~id, or~ organic acids, such as form1c ac1d, acetic ac~d, ~benzoic acid, ben2ene sulfonlc acid, p-toluene sul~onlc ac1d9 ~so-:
~ 3-, , ~ .
:~ ;:
, .
, ~ 6~
nonanoic acid or lauric acid, Polybasic organic acids, such as citric acid, malic acid or tartarlc acid, maleic acid or succinic acid, may also be used.
The salts of the tertiary ether amines correspondiny to for-mula II are reacted with alpha-epoxides corresponding to formula III by methods known e~ se.
One partlcularly su~table method is descr~bed in U.S. patent 4,492,802, accordin~ to which the reaction is carried out at 40 to 100C in the presence o~ 0.3 to 10 wt.X of a quaternary ammonium compound as phase transfer catalyst.
Compounds corresponding to formula II, in which y or z has a value of greater than 1, may be obtained by a relevant known pro-cess, by reacting ether amines correspond1ng to the formula Rl - (CnH2n~x ~ N (IV) C2H4~J
wherein R1 and R2 are as previously deflned, except that R2 optionally may be -C2H4OH; with (y-1) + (z - 1) mols ethylene oxide. The hydrophilicitymof the quaternary ammonium compounds according to the invention may be increased as requ1red in this manner.
The quaternary ammonium compounds according to the invention have surface-active properties and, like all quaternary ammonium compounds, are substantive, i.e. they become attached to fiber surfaces~where they show antistatic and revitalizing properties.
In addit~on, they may be clearly solubil~zed in aqueous surfactant solutions. Most surprisingly, the quaternary ammonium compounds according to the lnventlon may even be solubllized in aqueous solutions of anionlc sur~actan~ts to form clear or only fa~nt1y opal solutlons~without any~substantially insoluble electroneutral salts~being formed. Th1s property makes any quaternary ammonium accordi~ng to the lnvention, or a combinat~on of one or more ~ ~ -4-: ~ :
:' - , :
thereof, particularly su~table for use as a condltionlng and revi-talizing agent in hair-cosmetic preparations.
In the context of the ~nvent~on, ha~r-cosmet~c preparations are understood to be any aqueous or aqueous alcoholic preparations which are suitable ~or the car~ng and decoratiYe treatment of human hair, such as hair washes, hair lotions, hair cures, hair lacquers, hair dyes, permanent waving lot~ons, ha~r aftertreatment preparations (conditioners), hair rinses and shampoos or their mixtures. The compounds of this invention are included within the foregoing preparations in respect~vely conditioner effective amounts, i.e. hair wash conditioner-effective, hair lotlon conditioner-effective, etc.
Particularly preferred embodiments of the lnvention are aqueous shampoos conta~ning from 5 to 25% by weight anionic sulfate and/or sulfonate surfactants and a conditioner/antistatic effective amount, preferably from 0.1 to 5~ by welght of at least one quaternary ammonium compound corresponding to formula I. By anionic sulfate or sulfonate surfactants are meant alkali and/or mono-, di- or tri-C2 3 alkanolamine salts, of surface-active com-pounds which contain a completely or predominantly linear C10-l6 alkyl and an anionic -S03 (~) or -OS03(-) moiety in the molecule.
Preferred examples of sulfate or sulfonate surfactants such as these are at least one of fatty alcohol sulfates, fatty alcohol polyglycol ether sulfates (containing from 1 to 12 glycol ether groups), secondary alkane sulfonates and alpha-olefin sulfonates.
The following Examples illustrate the invention wlthout limiting it in any way.
EXAMPLES
1. C12 14 (70:30) alkylpoly (2) oxyethyl di-(2-hydroxyethyl)-2-hydroxydodecyl ammonium chloride 189 9 (0.5 mol) C12 14 (70:30) alkyl poly (2) oxyethyl d~-(2-hydroxyethyl)-amine (amine number 161, prepared from C12 14 alkyl ~ 2 EO sulfdte~ Nd salt and diethanolamine) were heated with stirring to 95C wlth 331 ml (0.4 mol) concentrated hydrochloric ac~d and 94 9 (0.5 mol) 1-epoxydodecane. After ~
hours, a clear brown solutlon had formed, the course of the reac-tion being followed by determinat~on of the epoxide number.
Another 8.3 ml (0.1 mol) concentrated hydrochloric acid were then added, followed by stirring for another 30 minutes at 95C. The water was then removed in a rotary evaporator. A brown viscous substance having the following characteristic data was obtained:
Epox~de number : 0.3 (% by weight epoxide oxygen) Hydroxyl number : 267.8 (according to DGF-C-V 17a) Cationic surfactant : 163.3 mval/100 g (as determined by the two-phase ti~ration method - DIN
(German Industry Norm) IS0 2871) 2. Cocos-(C12 1g)-alkyl poly(6)oxyethyl dl-(2-hydroxy-ethyl)-2- hydroxydodecyl ammonium chloride 1000 9 (1.48 mols) cocos-(C12 1g)-alkyl poly (6) oxyethyl di-(2-hydroxyethyl)-amine (amine number 83, prepared from cocos-(C12 1g)-alkyl + 6 E0 sulfate, Na salt and diethanolamlne), 278.1 g (1.48 mol) I-epoxydodecane and 98 ml concentrated hydro-chloric acid were heated wlth stlrring to 95Co After 6 hours, another 24.5 ml concentrated hydrochloric acid were added, followed by stirring for 30 minutes at 95C. The mixture was then dried in a rotary evaporator. A clear, brown, v~scous product havlng the followlng characteristic data was obtained:
Epoxide number : 0.3 (% by weight epoxide oxygen) Hydroxyl number : 198 Cationic surfactant : 116 mval/100 9 (as determ1ned by the two-phase titrat~on method - DIN IS0 ~ 2871) 3. C12 14 (50:50)-alkyl poly (4.6) oxyethyl d~-(2-hydroxyethyl)-2- hydroxldode~yl amnon~um ~sononanoate :: :
~ :
, `
.
y~
3.1 271 kg t6.775 x 103 mols) sod~um hydrox~de (flakes), 3720 kg (5.661 x 103 mols) fatty alcohol C12_14 (50:50)-3.6 E0-sulfate, Na salt (sulfur~c acid semiester salt of the adduct of 3.6 mols ethylene ox~de w~th a fatty alcohol m~x-ture of 50% by we~ght lauryl alcohol and 50% by we~ght myristyl alcohol, 70% aqueous solut~on) and 1013 kg (6.79 x 103 mols) triethanolamine were mlxed ~n a reaction vessel and the resultlng mixture carefully dehydrated while stirring ~n a water jet vacuum by gradual heating for 8 hours to 100C
and then for another 4 hours to 160C. The reaction mixture was then heated for another 8 hours at 160C. A~ter cooling to 20C, the reaction mixture was washed once with water and twice with saturated sod~um chloride solution and then dried by heating to 90C ln a water jet vacuum. The sodium chlo-ride precipltated was off-filtered. A yellow oil having an amine number of 103 was obtained.
3.2 590 g of the reaction product obtained in accordance wlth 3.1 were mixed with 188 9 1-epoxydodecane and 128 9 isononano~c acid in a reaction vessel, heated to 95C and stlrred for 4 hours at that temperature. Another 32 9 ~sononanolc ac~d were then added and the react~on cont1nued for another 30 m~nutes. A v1scous yellow-brown product was obtained.
Epox~de number 0.3 ~% by we~ght~epoxlde oxygen) 4. Ha~r-cosmetic testing The quaternary ammonium compounds accordlng to the 1nventlon prepared ln Examples 1 and 2 were lncorporated in formulations 4.2 and 4.3 of the Table and performance-tested for the~r effeo-t~veness in improving wet combab1l~ty against (a) a standard sham-poo (formulation q.1) withou~ any quaternary ammon~um compounds and (b) a comparlson shampoo conta~n1ng cetyl tr1methyl ammonlum chlor1de (formulat1On 4.4).
~ 5. Measu~rement of wet combabil~ty (laboratory test) ~Standardi~ed strands of ha1r predamaged under dei'1ned con-:
t .
' ' , , .
~L~3~ 6~L
dit~ons by bleach~ng and cold wav~ng were used. The strands were shampooed 1n lukewarm water w~th the shampoos ~nd~cated ~n the Table ~n a quantlty of 1 g per g ha1r and r1nsed w1th clear water.
Wet combab11ity was determ1ned by measurement of the combing res1stance, ~.e. the force requ1red to draw a comb through a tuft of hair, using a modified draw test1ng mach1ne of the 1402 type manufactured by the Zw~ck company (E1ns1ngen bei Ulm/Donau, Germany)~ The test arrangement ~s described ~n "Riechstoffe, Aromen, Kosmetika" no. 12, (1977), page 325, columns 2 and 3, a lower value (% combing resistance) being preferred.
To m~nimize errors, the combing res1stance was determined 15 times with each of the shampoos to be tested and the average values formed. The measured average combing resistance values were expressed in percent of the standard. The standard was determined after shampoo~ng wlth shampoo 4.1 (free ~rom quaternary ammonium compounds) and rinsing with clear water.
The results of the test are shown in the following Table:
Table .. ~ .. _ .... _ EXAMPLE
Shampoo ingredients 4.1 4.2 4.3 4.4 (operat~ve) (~n- (~n-vention) vent~on) Fatty alcohol (C12-14~
+ 2 E0 sulfate, Na salt (28Z) 50 50 50 50 QUAT Example 1 2 QUAT Example 2 2 Cetyl trimethyl ammonium chloride 2 Water (fully delonized) 50 48 48 48 ~ _ 4- Appearance at 20C clearclear clear ment) Wet combab~llty 100 78 74 88 % comb~ng res~stance~ _ .
l~,g~
As can be seen from the above, the product of ccmparat1ve example 4.4 had a cloudy appearance and a sediment, resulting in a totally unacceptable product. Moreover, its comblng resistance was relatively high, although acceptable. Comparat~ve example 4.1, although clear, had an unacceptably high combing res1stance, indicating no hair treating qualities as desired in this inven-tion. Example 4.2 and 4.3, according to the inventlon and repre-sentative of its novel compounds, were not only clear, but also had desireably reduced combing resistance.
~9 ::: ;
' :: :
~, .
.
:, ~ .
Cationic surfactants of the quaternary ammonlum compound type are used~in hair cosmetics as revita~lizing and conditioning agents for improv'ng the ~combab1~1ity, body and fee1 of the hair and~
for~red~ucing its stat~c charge. The products are normally used in hair aftertreatment preparations (conditioners) which, after~wash-~ing of the hair~9 are intended to restore favorable hair-cosmetic properties~ However, such~compounds are not su~table as condi-tioner~additive~s~ n~shampoos themse~lves~,~ because most of the known quaternary~ammoni~um~comp~ound;s are incompatlble with the high-foam 15~ ~an10nic~`surfactant~s normal~ly~ u~sed 1n~ shampoos. ~ When present n ~the~ concentrations required for an adequate condlt~oning ~effect,~they~fo~rm~;substanti~ally~water-lnsoluble and cosmetically lneffectua~ deposi~ts. ~ ~Quaternary ammonium compounds . .
.
: :
which are more compatible with anionic sur~actants generally have an inadequate conditloning ef~ect.
Although water-soluble cationlc polymers are generally com-patible with anionic surfactants, they are attended by other disadvantages, such as accumulation on the hair aftPr repeated treatment resulting in dullness, and inadequate antista-tic effects on dry hair.
DESCRIPTION OF THE INVENTION
Other than in the sperating examples, or where other-wise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
The present invention provides novel quaternary ammo-nium compounds, which have strong revitalizing and conditioning properties on human hair and which may even be incorporated in shampoos based on high-foam anionic surfactants in conditioner effective concentrations, without negatiYe effects.
The novel quaternary ammonium compounds have the following 20 formul~
R ~ nH2n)x -(+) N - CH7 - CH - R3 1 A m(-) (I
I m ~ (C2H4O)y - H
wherei-n R1 ~s~a C8-22 alkyl; R2 is a C1 4 alkyl or -~C2H4O~z-H, R3 is a ~6-~0 alkyl;~x is O or a number from 1 to 10; y and z are each numbers from 1 to ~0; n is 2 or 3; A is ~he anion of an i~gm i-c- a-cid or of a C1 1g organic carboxylic or sul~oni-c acid;
and m 1~ ~he acid's valency.
The new quaternary ammonium compounds are produced from reacting at least one tertiary ether amine which is used in the ~ form of its sal~t or in stoichiometric quantities with an inorga-ic~;~acid~suitabl-e for salt formation or a C1 18 organic carboxyl~c ; ~ ; -2-:
: ~ ` : :
.
.
9~ 6~L
or sulfonic acid. The salts of the tertiary ether amines have the follow1ng formula R1 (0CnH2n)x - N (+) - H 1 A m(-) (II) ¦ m (C2H40)y - H
They are reacted with approximately an equimolar amount of at least one alpha-epoxide having the formula R3 - CH - CH~ (III) In formulae II and III, ~1, R2, R3, n, x, y, A and m are as defined for formula I.
Ether amines corresponding to formula II are known from the literature, for example from published British patent appl~cation 1,087,413 and from published European patent application 102,140.
In the process described therein, the ether amines in~question are;
prepared from primary and secondary amines by alkylation at the nitrogen atom, with alkyl polyglycol ether sulfates. Another pro-cess, which is the~subject of German patent application 35 04 242, (which~was~ published~14 August 1986, subsequent to the or19inal Germàn~p~atent application; for~the present 1nvQntion), starts out from tertiary alkanolamines~ and ~leads to ether~ amines corresponding to formula II by~alkylation at the hydroxyl group, with~alkyl~sul~fates or alkyl polyglycol ether sul~ates. The ter-tiary ether amines are converted into the salts of formula II by addltion~o~ mi~neral acids~, such as concentrated hydrochlor~c ac1d, concentrated hyd~robromic acid,~sulfur~c acid, phosphor~c ac~d or boric ~ae~id, or~ organic acids, such as form1c ac1d, acetic ac~d, ~benzoic acid, ben2ene sulfonlc acid, p-toluene sul~onlc ac1d9 ~so-:
~ 3-, , ~ .
:~ ;:
, .
, ~ 6~
nonanoic acid or lauric acid, Polybasic organic acids, such as citric acid, malic acid or tartarlc acid, maleic acid or succinic acid, may also be used.
The salts of the tertiary ether amines correspondiny to for-mula II are reacted with alpha-epoxides corresponding to formula III by methods known e~ se.
One partlcularly su~table method is descr~bed in U.S. patent 4,492,802, accordin~ to which the reaction is carried out at 40 to 100C in the presence o~ 0.3 to 10 wt.X of a quaternary ammonium compound as phase transfer catalyst.
Compounds corresponding to formula II, in which y or z has a value of greater than 1, may be obtained by a relevant known pro-cess, by reacting ether amines correspond1ng to the formula Rl - (CnH2n~x ~ N (IV) C2H4~J
wherein R1 and R2 are as previously deflned, except that R2 optionally may be -C2H4OH; with (y-1) + (z - 1) mols ethylene oxide. The hydrophilicitymof the quaternary ammonium compounds according to the invention may be increased as requ1red in this manner.
The quaternary ammonium compounds according to the invention have surface-active properties and, like all quaternary ammonium compounds, are substantive, i.e. they become attached to fiber surfaces~where they show antistatic and revitalizing properties.
In addit~on, they may be clearly solubil~zed in aqueous surfactant solutions. Most surprisingly, the quaternary ammonium compounds according to the lnventlon may even be solubllized in aqueous solutions of anionlc sur~actan~ts to form clear or only fa~nt1y opal solutlons~without any~substantially insoluble electroneutral salts~being formed. Th1s property makes any quaternary ammonium accordi~ng to the lnvention, or a combinat~on of one or more ~ ~ -4-: ~ :
:' - , :
thereof, particularly su~table for use as a condltionlng and revi-talizing agent in hair-cosmetic preparations.
In the context of the ~nvent~on, ha~r-cosmet~c preparations are understood to be any aqueous or aqueous alcoholic preparations which are suitable ~or the car~ng and decoratiYe treatment of human hair, such as hair washes, hair lotions, hair cures, hair lacquers, hair dyes, permanent waving lot~ons, ha~r aftertreatment preparations (conditioners), hair rinses and shampoos or their mixtures. The compounds of this invention are included within the foregoing preparations in respect~vely conditioner effective amounts, i.e. hair wash conditioner-effective, hair lotlon conditioner-effective, etc.
Particularly preferred embodiments of the lnvention are aqueous shampoos conta~ning from 5 to 25% by weight anionic sulfate and/or sulfonate surfactants and a conditioner/antistatic effective amount, preferably from 0.1 to 5~ by welght of at least one quaternary ammonium compound corresponding to formula I. By anionic sulfate or sulfonate surfactants are meant alkali and/or mono-, di- or tri-C2 3 alkanolamine salts, of surface-active com-pounds which contain a completely or predominantly linear C10-l6 alkyl and an anionic -S03 (~) or -OS03(-) moiety in the molecule.
Preferred examples of sulfate or sulfonate surfactants such as these are at least one of fatty alcohol sulfates, fatty alcohol polyglycol ether sulfates (containing from 1 to 12 glycol ether groups), secondary alkane sulfonates and alpha-olefin sulfonates.
The following Examples illustrate the invention wlthout limiting it in any way.
EXAMPLES
1. C12 14 (70:30) alkylpoly (2) oxyethyl di-(2-hydroxyethyl)-2-hydroxydodecyl ammonium chloride 189 9 (0.5 mol) C12 14 (70:30) alkyl poly (2) oxyethyl d~-(2-hydroxyethyl)-amine (amine number 161, prepared from C12 14 alkyl ~ 2 EO sulfdte~ Nd salt and diethanolamine) were heated with stirring to 95C wlth 331 ml (0.4 mol) concentrated hydrochloric ac~d and 94 9 (0.5 mol) 1-epoxydodecane. After ~
hours, a clear brown solutlon had formed, the course of the reac-tion being followed by determinat~on of the epoxide number.
Another 8.3 ml (0.1 mol) concentrated hydrochloric acid were then added, followed by stirring for another 30 minutes at 95C. The water was then removed in a rotary evaporator. A brown viscous substance having the following characteristic data was obtained:
Epox~de number : 0.3 (% by weight epoxide oxygen) Hydroxyl number : 267.8 (according to DGF-C-V 17a) Cationic surfactant : 163.3 mval/100 g (as determined by the two-phase ti~ration method - DIN
(German Industry Norm) IS0 2871) 2. Cocos-(C12 1g)-alkyl poly(6)oxyethyl dl-(2-hydroxy-ethyl)-2- hydroxydodecyl ammonium chloride 1000 9 (1.48 mols) cocos-(C12 1g)-alkyl poly (6) oxyethyl di-(2-hydroxyethyl)-amine (amine number 83, prepared from cocos-(C12 1g)-alkyl + 6 E0 sulfate, Na salt and diethanolamlne), 278.1 g (1.48 mol) I-epoxydodecane and 98 ml concentrated hydro-chloric acid were heated wlth stlrring to 95Co After 6 hours, another 24.5 ml concentrated hydrochloric acid were added, followed by stirring for 30 minutes at 95C. The mixture was then dried in a rotary evaporator. A clear, brown, v~scous product havlng the followlng characteristic data was obtained:
Epoxide number : 0.3 (% by weight epoxide oxygen) Hydroxyl number : 198 Cationic surfactant : 116 mval/100 9 (as determ1ned by the two-phase titrat~on method - DIN IS0 ~ 2871) 3. C12 14 (50:50)-alkyl poly (4.6) oxyethyl d~-(2-hydroxyethyl)-2- hydroxldode~yl amnon~um ~sononanoate :: :
~ :
, `
.
y~
3.1 271 kg t6.775 x 103 mols) sod~um hydrox~de (flakes), 3720 kg (5.661 x 103 mols) fatty alcohol C12_14 (50:50)-3.6 E0-sulfate, Na salt (sulfur~c acid semiester salt of the adduct of 3.6 mols ethylene ox~de w~th a fatty alcohol m~x-ture of 50% by we~ght lauryl alcohol and 50% by we~ght myristyl alcohol, 70% aqueous solut~on) and 1013 kg (6.79 x 103 mols) triethanolamine were mlxed ~n a reaction vessel and the resultlng mixture carefully dehydrated while stirring ~n a water jet vacuum by gradual heating for 8 hours to 100C
and then for another 4 hours to 160C. The reaction mixture was then heated for another 8 hours at 160C. A~ter cooling to 20C, the reaction mixture was washed once with water and twice with saturated sod~um chloride solution and then dried by heating to 90C ln a water jet vacuum. The sodium chlo-ride precipltated was off-filtered. A yellow oil having an amine number of 103 was obtained.
3.2 590 g of the reaction product obtained in accordance wlth 3.1 were mixed with 188 9 1-epoxydodecane and 128 9 isononano~c acid in a reaction vessel, heated to 95C and stlrred for 4 hours at that temperature. Another 32 9 ~sononanolc ac~d were then added and the react~on cont1nued for another 30 m~nutes. A v1scous yellow-brown product was obtained.
Epox~de number 0.3 ~% by we~ght~epoxlde oxygen) 4. Ha~r-cosmetic testing The quaternary ammonium compounds accordlng to the 1nventlon prepared ln Examples 1 and 2 were lncorporated in formulations 4.2 and 4.3 of the Table and performance-tested for the~r effeo-t~veness in improving wet combab1l~ty against (a) a standard sham-poo (formulation q.1) withou~ any quaternary ammon~um compounds and (b) a comparlson shampoo conta~n1ng cetyl tr1methyl ammonlum chlor1de (formulat1On 4.4).
~ 5. Measu~rement of wet combabil~ty (laboratory test) ~Standardi~ed strands of ha1r predamaged under dei'1ned con-:
t .
' ' , , .
~L~3~ 6~L
dit~ons by bleach~ng and cold wav~ng were used. The strands were shampooed 1n lukewarm water w~th the shampoos ~nd~cated ~n the Table ~n a quantlty of 1 g per g ha1r and r1nsed w1th clear water.
Wet combab11ity was determ1ned by measurement of the combing res1stance, ~.e. the force requ1red to draw a comb through a tuft of hair, using a modified draw test1ng mach1ne of the 1402 type manufactured by the Zw~ck company (E1ns1ngen bei Ulm/Donau, Germany)~ The test arrangement ~s described ~n "Riechstoffe, Aromen, Kosmetika" no. 12, (1977), page 325, columns 2 and 3, a lower value (% combing resistance) being preferred.
To m~nimize errors, the combing res1stance was determined 15 times with each of the shampoos to be tested and the average values formed. The measured average combing resistance values were expressed in percent of the standard. The standard was determined after shampoo~ng wlth shampoo 4.1 (free ~rom quaternary ammonium compounds) and rinsing with clear water.
The results of the test are shown in the following Table:
Table .. ~ .. _ .... _ EXAMPLE
Shampoo ingredients 4.1 4.2 4.3 4.4 (operat~ve) (~n- (~n-vention) vent~on) Fatty alcohol (C12-14~
+ 2 E0 sulfate, Na salt (28Z) 50 50 50 50 QUAT Example 1 2 QUAT Example 2 2 Cetyl trimethyl ammonium chloride 2 Water (fully delonized) 50 48 48 48 ~ _ 4- Appearance at 20C clearclear clear ment) Wet combab~llty 100 78 74 88 % comb~ng res~stance~ _ .
l~,g~
As can be seen from the above, the product of ccmparat1ve example 4.4 had a cloudy appearance and a sediment, resulting in a totally unacceptable product. Moreover, its comblng resistance was relatively high, although acceptable. Comparat~ve example 4.1, although clear, had an unacceptably high combing res1stance, indicating no hair treating qualities as desired in this inven-tion. Example 4.2 and 4.3, according to the inventlon and repre-sentative of its novel compounds, were not only clear, but also had desireably reduced combing resistance.
~9 ::: ;
' :: :
~, .
.
:, ~ .
Claims (22)
1. A quaternary ammonium compound of the formula:
(I) wherein:
R1 is a C8-22 alkyl;
R2 is a C1-4 alkyl or -(C2H4O)z - H;
R3 is a C6-20 alkyl;
x is 0 or a number from 1 to 10;
y and z are each a number from 1 to 10;
n is 2 or 3; and A is the anion of an inorganic acid or a C1-18 carboxylic or sulfonic acid, where m is its valency.
(I) wherein:
R1 is a C8-22 alkyl;
R2 is a C1-4 alkyl or -(C2H4O)z - H;
R3 is a C6-20 alkyl;
x is 0 or a number from 1 to 10;
y and z are each a number from 1 to 10;
n is 2 or 3; and A is the anion of an inorganic acid or a C1-18 carboxylic or sulfonic acid, where m is its valency.
2. The compound of claim 1 wherein x is a number from 2 to 10, y is 1, R2 is a 2-hydroxyl, and A is chloride.
3. The compound of claim 1 having the formula:
C12-14 (70:30) alkyl poly (2) oxyethyl di-(2-hydroxyethyl)-2-hydroxy-dodecyl ammonium chloride.
C12-14 (70:30) alkyl poly (2) oxyethyl di-(2-hydroxyethyl)-2-hydroxy-dodecyl ammonium chloride.
4. The compound of claim 1 having the formula:
cocos-(C12-18)-alkyl poly(6)oxyethyl di-(2-hydroxyethyl)-2-hydroxy-dodecyl ammonium chloride.
cocos-(C12-18)-alkyl poly(6)oxyethyl di-(2-hydroxyethyl)-2-hydroxy-dodecyl ammonium chloride.
5. The compound of claim 1 having the formula:
C12-14 (50:50)-alkyl poly (4.6) oxyethyl di-(2-hydroxyethyl)-2-hydroxydodecyl ammonium isononanoate.
C12-14 (50:50)-alkyl poly (4.6) oxyethyl di-(2-hydroxyethyl)-2-hydroxydodecyl ammonium isononanoate.
6. A method for synthesizing a compound according to claim 1 wherein:
at least one tertiary ether amine salt of the formula:
(II) is reacted in about equimolar quantities with an alpha-epoxide of the formula:
(III);
all substituents being as previously defined.
at least one tertiary ether amine salt of the formula:
(II) is reacted in about equimolar quantities with an alpha-epoxide of the formula:
(III);
all substituents being as previously defined.
7. A method for synthesizing a compound according to claim 2 wherein:
at least one tertiary ether amine salt of the formula:
(II) is reacted in about equimolar quantities with an alpha-epoxide of the formula:
(III);
all substituents being as previously defined.
at least one tertiary ether amine salt of the formula:
(II) is reacted in about equimolar quantities with an alpha-epoxide of the formula:
(III);
all substituents being as previously defined.
8. A method for treating hair comprising applying thereto a hair-treatment-effective amount of at least one compound according to claim 1.
9. A method for treating hair comprising applying thereto a hair-treatment-effective amount of at least one compound according to claim 2.
10. A method for treating hair comprising applying thereto a hair-treatment-effective amount of at least one compound according to claim 3.
11. A method for treating hair comprising applying thereto a hair-treatment-effective amount of at least one compound according to claim 4.
12. A method for treating hair comprising applying thereto a hair-treatment-effective amount of at least one compound according to claim 5.
13. A method for treating hair comprising applying thereto a composition consisting essentially of: at least one compound according to claim 1, present in a hair-treating effective amount; at least one anionic surfactant; and an aqueous or aqueous/alcoholic carrier.
14. A method for treating hair comprising applying thereto a composition consisting essentially of: at least one compound according to claim 2, present in a hair-treating effective amount; at least one anionic surfactant; and an aqueous or aqueous/alcoholic carrier.
15. A method for treating hair comprising applying thereto a composition consisting essentially of at least one compound according to claim 3, present in a hair-treating effective amount; at least one anionic surfactant; and an aqueous or aqueous/alcoholic carrier.
16. A method for treating hair comprising applying thereto a composition consisting essentially of: at least one compound according to claim 4, present in a hair-treating effective amount; at least one anionic surfactant; and an aqueous or aqueous/alcoholic carrier.
17. A method for treating hair comprising applying thereto a composition consisting essentially of: at least one compound according to claim 5, present in a hair-treating effective amount; at least one anionic surfactant; and an aqueous or aqueous/alcoholic carrier.
18. The method of claim 13 wherein said composition is a shampoo.
19. The method of claim 14 wherein said composition is a shampoo.
20. The method of claim 15 wherein said composition is a shampoo.
21. The method of claim 16 wherein said composition is a shampoo.
22. The method of claim 17 wherein said composition is a shampoo.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3623730A DE3623730A1 (en) | 1986-07-14 | 1986-07-14 | NEW QUARTERS OF AMMONIUM COMPOUNDS AND THEIR USE |
| DEP3623730.2 | 1986-07-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1296361C true CA1296361C (en) | 1992-02-25 |
Family
ID=6305154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000541507A Expired - Fee Related CA1296361C (en) | 1986-07-14 | 1987-07-07 | Quaternary ammonium compounds useful in hair treating preparations |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0253275B1 (en) |
| JP (1) | JPS6323843A (en) |
| AT (1) | ATE61338T1 (en) |
| CA (1) | CA1296361C (en) |
| DE (2) | DE3623730A1 (en) |
| ES (1) | ES2020531B3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19846538C2 (en) * | 1998-10-09 | 2003-08-14 | Cognis Deutschland Gmbh | Quaternary ammonium compounds |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA721771A (en) * | 1963-06-25 | 1965-11-16 | Marchon Products Limited | Surface-active agents and preparation and use thereof |
| DE3116087A1 (en) * | 1981-04-23 | 1982-11-11 | Degussa Ag, 6000 Frankfurt | "METHOD FOR PRODUCING QUARTERA AMMONIUM COMPOUNDS" |
| DE3345156A1 (en) * | 1983-12-14 | 1985-06-27 | Hoechst Ag, 6230 Frankfurt | QUATERNAIRE OXALKYLATED POLYESTER, METHOD FOR THE PRODUCTION AND THEIR USE |
| DE3442175A1 (en) * | 1984-11-17 | 1986-05-28 | Henkel KGaA, 4000 Düsseldorf | CONDITIONING HAIR CARE PRODUCTS |
-
1986
- 1986-07-14 DE DE3623730A patent/DE3623730A1/en not_active Withdrawn
-
1987
- 1987-07-07 EP EP87109763A patent/EP0253275B1/en not_active Expired - Lifetime
- 1987-07-07 DE DE8787109763T patent/DE3768354D1/en not_active Expired - Fee Related
- 1987-07-07 CA CA000541507A patent/CA1296361C/en not_active Expired - Fee Related
- 1987-07-07 AT AT87109763T patent/ATE61338T1/en not_active IP Right Cessation
- 1987-07-07 ES ES87109763T patent/ES2020531B3/en not_active Expired - Lifetime
- 1987-07-10 JP JP62173733A patent/JPS6323843A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3623730A1 (en) | 1988-01-21 |
| EP0253275B1 (en) | 1991-03-06 |
| ES2020531B3 (en) | 1991-08-16 |
| JPS6323843A (en) | 1988-02-01 |
| EP0253275A1 (en) | 1988-01-20 |
| DE3768354D1 (en) | 1991-04-11 |
| ATE61338T1 (en) | 1991-03-15 |
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