CA1131096A - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA1131096A CA1131096A CA326,453A CA326453A CA1131096A CA 1131096 A CA1131096 A CA 1131096A CA 326453 A CA326453 A CA 326453A CA 1131096 A CA1131096 A CA 1131096A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- carbon atoms
- alkyl
- formula
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- A61K8/55—Phosphorus compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- 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
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/886—Ampholytes containing P
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/74—Biological properties of particular ingredients
- A61K2800/75—Anti-irritant
Abstract
ABSTRACT OF THE DISCLOSURE
DETERGENT COMPOSITIONS
An improved cleansing, foaming and nonirritating detergent and cleansing composition for personal care use is provided containing a phosphobetaine surfactant or a phosphitaine surfactant as an active ingredient.
DETERGENT COMPOSITIONS
An improved cleansing, foaming and nonirritating detergent and cleansing composition for personal care use is provided containing a phosphobetaine surfactant or a phosphitaine surfactant as an active ingredient.
Description
3~3~
; DETERGENT COMPOSITIONS
-Background of the Invention The present invention relates to detergent and cleansing compositions, and more particularly,to those detergent and cleansing compositions which have relatively low ocular irritation and yet exhibit good foam volume and improved foam stability.
Detergent and cleansing compositions, like most types of cleaning agents, generally comprise a mixture of one or more surfactants as the active ingredient, as well as builders, perfumes, coloring agents, thickener$, and the like. The surfactant molecules have two or more different moieties comprising: ~1) a hydrophobic hydro-carbon chain miscible with organic materials and (2) a hy-drophilic moiety miscible with water. Surfactants of this type solubilize fat soluble soils via a complex adsorption/
emulsification mechanism. This process allows the efficient removal of soil from the body. The surfactants may be classified as anionic, cationic, nonionic or amphoteric depending upon the nature of the hydrophile.
It is desirable that detergent and cleansing com~ositions have good foam volume and good foam stability, particularly if they are to be used as shampoos. The amount of foam generated by a shampoo compositions has a direct bearing on the perceived efficiency with which it cleans the hair. The stability of the foam generated provides an indication to the user ' .
. ~ .
.
~, 1 ~t"~, '' .:
~3~96 as to how long it will keep the hair lathered. Generally speaking, the greater the volume of foam produced and the more stable the foam, the more efficient the perceived cleansing action of the shampoo. In addition, other detergent and cleansing com-positions, such as liquid skin cleansers and baby bath compo-sitions, are enhanced by high foam volume and good foam sta-bility.
Furthermore, it is essential that products of this type and in particular a shampoo recommended for use on infants and/or children have low ocular irritation and sting potential.
In the prior art, attempts to achieve such low ocular irritating compositions have been described such as by Masci et al. in U.S. Patent No. 3,055,836 and Bolich et al.
in U.S. Patent No. 3,928,251. Such compositions have contained either an amphoteric/anionic react:ion product or a betaine/sul-taine - anionic blend in combination with ethoxylated nonionics but such formulations, however, have generally exhibited infe-rior foam volume and stability when compared to traditional shampoo formulations.
It has now been discovered that the aforementioned deficiencies are readily and unexpectedly overcome while main-taining a low level of ocular irritancy by using a novel class of amphoteric and zwitterionic betaine surfactants, so-called "phosphobetaines" and "phosphitaines", alone or in combination with other surfactants. These phosphobetaines and phosphitaines ; are amphoteric and zwitterionic surfactants having at least one phosphorous-containing anion in the molecule as described in co-pending Canadian patent application ~o. 326,454, filed on April 26th, 1979.
It is thus an object of the present invention to prepare detergent and cleanser compositions which are effective for personal cleansing of the skin and hair.
It is another object of the present invention 3S to provide detergent and cleansing compositions which ~3~6 provide good foam volume and good foam stability.
It is yet a further object of the present inven-tion to provide detergent and cleansing compositions which while being effective cleansing agents for the skin and hair, exhibit low irritancy.
These and other objects of the present invention will become apparent to one skilled in the art from the detailed description given hereinafter.
SUMMARY OF THE_INVENTION
This invention encompasses detergent and cleans-ing compositions comprising as the active ingredient a phos-phobetaine surfactant, and preferably at least one other sur-factant selected from the group consisting of anionic, nonionic, cationic and amphoteric detergents. The balance of the compo-sitions can comprise various detergency and cleansing adjuncts, fillers, carriers and the like wel:L known in the art.
DETAILED DESCRIPTION OF THE INVENTION
The detergent and cleansing compositions of the present invention comprise as the active ingredient a phospho-betaine and preferably at least one other surfactant.
The phosphobetaines and phosphitaines which areuseful in the present invention are novel compounds described and claimed in copending Canadi~n application No. 326,454, filed on April 26th, 1979, and are characterized as amphoteric and zwitterionic betaine compounds having at least one phospho-rous-containing anion in the molecule.
The phosphobetaines are of the ~ormula ~ 6 JBP 126 (I) ~R - Y - O - P - B ¦ ~
A l Z
wherein A is selected from O , OM and -O-Y-R~
B is selected from O and OM
,_ .
X is an anion z is an integer from 0 to 2 with the proviso that only one of A and B can be O and z is of a value necessary for charge balance (i.e., when A and B are O and OM , or OM and O , respectively, z is O; when A and B are OM and OM', or -O-Y-R~ and O , 10 respectively, z is 1; when A is -O-Y-R~ and B is OM', z is 2);
R is an amidoamine reactant moiety of the formula r O R ~
IR - C ~ ~ H2~n l4 , wherein Rl is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms;
R2 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5 carbon atoms, or polyoxyalkalene of up to 10 , carbon atoms;
R3 and R4, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxy-alkyl of up .o 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms; in addition, R3 and R4 taken together with the nitrogen to which they are attached, may represent an N-heterocycle, e.g., a morpholino structure, in which the Y radical is bonded to a ring atom of said N-heterocycle other than the 113~5~'g~
nitrogen of the R moiety;
n is an integer from 2 to 12;
The term "polyoxyalkalene radical" as used above in the definition of R2, R3 and R may be of the formula (R5 - O - R5 )m~ wherein RS and RS are alkyl of from 1 to 4 carbon atoms and m is an integer from about 2 to 10 .
In addition to the foregoing definitions wherein R is amidoamine, R may be an N-heterocyclic radical which 10 may contain one additional hetero atom (e.g., oxygen sulfur or another nitrogen) and contains S to 6 total ring caxbon atoms, optionally said heterocyclic radical may be substituted with alkyl and/or hydroxyalkyl of up to 20 carbon atoms each. Typical of such N-heterocyclic 15 radicals are imidazolyl, N-alkylmorpholino, alkyl-pyrimidino, alk~loxazollnyl, and the like. Such compounds may be represented by the formula R
l6 Rl (CH ~ ~ `H2)p ` \Z
wherein Z is N, S or O;
o is an integer from 0 to 3;
p is an integer from 1 to 3;
provided that the sum of o+p is from 3 to 4;
Rl is defined as before and is linked to a ring carbon atom; and R6 is alkyl of from 2 to 6 carbon atoms which may be substituted with a hydroxyl group at the terminal or a non-terminal carbon atom;
Y may be alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms, which alkylene chain may optionally be substituted with loweralkyl, alkoxy, hydroxy or hydroxyalkyl, e.g., of not more than 10 carbon atoms each.
~3~
-- M and M', which may be the same or different, are (a) hydrogen, (b) an organic radical selected from alkyl or hydroxyalkyl of up t`o 6 carbon atoms, pilyhydroxyalkyl of up to 10 carbon atoms, glyceryl, cycloalkyl of up to 6 carbon atoms, aryl or arylalkyl of up to 10 carbon atoms, or (c) a salt radi-cal selected from alkali metals (e.g., sodium or potassium), alkaline earth metals (e.g., magnesium or calcium), and mono-, di-, or triethanolamine. With reference to formula (I) above, wherein both M and M' are contained, there is the proviso that when either M or M' is an organic radical (b), the other o~ M
and M' must be hydrogen or a salt radical (c).
The phosphitaines are of the formula ~ R~ - Y - 0 - P - H 1 wherein R and Y are as defined above.
; 20 The phosphobetaine compounds and phosphitaine compounds described above can be prepared in accordance with the processes described in copending Canadian application No 326,454, filed on April 26th, 1979.
Representati~e phosphobetaine and phosphitaine compounds useful in the present invention include compounds having the followin~ structures:
O H C~l3 Oi~
Cll~c ~ ~al2) I~+J- CH -CH-CH -O - P = O (Co~und ~) CH3 OH 0~
O- C!l 2 - ~ H -CH 2 O H C}l ¦ OH OH
Il I Ir~
Cl1-Cl.3-C-N-(~,~)3- ;I~- CH2-CH-CH2-0 - P = O. (C~ound B3) Cii3 OH C~
O li C~l3 ~ ~~
1 11 13 C N (~)3- ~ CH2-C~i-CH ~ O P O (Co~ound CC) -CH3 OH _ 2 Q~
O H CH3 ot~
1~ ~23 C ~i ~CH2)3- ~-C~i2-CH-CH2-O-P=O (Cc.. ~ 23j O H CH -CO`-~ +~2 2 C11-~23-C-N-(CH2)2 ~ ~V_ CH -CH-CH -o-p=o tCompound E~) OH ONa (CH~)2-O~
The phosphobetaine and phosphitaine compounds can . be present in the detergent and cleansing compositions of the present invention in a ranqe of f~om about 1 to 20~ by weight of the total co~position.
~: 5 Preferred embodiments of the present invention : relate to detergent and cleansing compositions containing a phosphobetaine or a pl~osphitaine and at least one `other surfactant selected from the group consisting of amphoteric, nonionic, anionic and catlonic detergents.
The amphoteric surfactants which may be used in the present invention include betaines, sultaines and ~; n-alkylamino propionates and n-alkylimino dipropionates. . .
The betaine and sultaine surfactants useful in this invention are described in U.S. Patent No. 3,950,417 issued April 13, 1976, and the n-alkylamino propionates and n-alkylimino dipropionates are sold under the trade-.
. .
~L31~6 mark DERIPHATS by General Mills.
The preferred betaine amphoteric surfactants include the alkylbetaines such as cocodimethylcarboxy-methylbetaine, lauryldimethylcarboxymethylbetaine, 5 lauryldimethyl-alpha-carboxyethylbetaine, cetyldimethyl-. carboxymethylbetaine, lauryl-bis-(2-hydroxyethyl) carboxymethylbetaine, oleyldimethyl-gamma-carboxypropyl-betaine, lauryl-bis-(2-hydroxypropyl) alpha-carboxy-ethylbetaine, and the like; the sultaines such as 10 cocodimethylpropylsultaine, stearyldimethylpropylsul-taine, lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocoamidodi-methylpropylsultaine, stearylamidodimethyl?ropylsultaine, la~lrylam-do-bis-(2-hydroxyethy1) pro?ylsultaine, and the 15 like. The preferred n-alkylamino propionates and n-alkylimino dipropionates include those of the following structures:
; DETERGENT COMPOSITIONS
-Background of the Invention The present invention relates to detergent and cleansing compositions, and more particularly,to those detergent and cleansing compositions which have relatively low ocular irritation and yet exhibit good foam volume and improved foam stability.
Detergent and cleansing compositions, like most types of cleaning agents, generally comprise a mixture of one or more surfactants as the active ingredient, as well as builders, perfumes, coloring agents, thickener$, and the like. The surfactant molecules have two or more different moieties comprising: ~1) a hydrophobic hydro-carbon chain miscible with organic materials and (2) a hy-drophilic moiety miscible with water. Surfactants of this type solubilize fat soluble soils via a complex adsorption/
emulsification mechanism. This process allows the efficient removal of soil from the body. The surfactants may be classified as anionic, cationic, nonionic or amphoteric depending upon the nature of the hydrophile.
It is desirable that detergent and cleansing com~ositions have good foam volume and good foam stability, particularly if they are to be used as shampoos. The amount of foam generated by a shampoo compositions has a direct bearing on the perceived efficiency with which it cleans the hair. The stability of the foam generated provides an indication to the user ' .
. ~ .
.
~, 1 ~t"~, '' .:
~3~96 as to how long it will keep the hair lathered. Generally speaking, the greater the volume of foam produced and the more stable the foam, the more efficient the perceived cleansing action of the shampoo. In addition, other detergent and cleansing com-positions, such as liquid skin cleansers and baby bath compo-sitions, are enhanced by high foam volume and good foam sta-bility.
Furthermore, it is essential that products of this type and in particular a shampoo recommended for use on infants and/or children have low ocular irritation and sting potential.
In the prior art, attempts to achieve such low ocular irritating compositions have been described such as by Masci et al. in U.S. Patent No. 3,055,836 and Bolich et al.
in U.S. Patent No. 3,928,251. Such compositions have contained either an amphoteric/anionic react:ion product or a betaine/sul-taine - anionic blend in combination with ethoxylated nonionics but such formulations, however, have generally exhibited infe-rior foam volume and stability when compared to traditional shampoo formulations.
It has now been discovered that the aforementioned deficiencies are readily and unexpectedly overcome while main-taining a low level of ocular irritancy by using a novel class of amphoteric and zwitterionic betaine surfactants, so-called "phosphobetaines" and "phosphitaines", alone or in combination with other surfactants. These phosphobetaines and phosphitaines ; are amphoteric and zwitterionic surfactants having at least one phosphorous-containing anion in the molecule as described in co-pending Canadian patent application ~o. 326,454, filed on April 26th, 1979.
It is thus an object of the present invention to prepare detergent and cleanser compositions which are effective for personal cleansing of the skin and hair.
It is another object of the present invention 3S to provide detergent and cleansing compositions which ~3~6 provide good foam volume and good foam stability.
It is yet a further object of the present inven-tion to provide detergent and cleansing compositions which while being effective cleansing agents for the skin and hair, exhibit low irritancy.
These and other objects of the present invention will become apparent to one skilled in the art from the detailed description given hereinafter.
SUMMARY OF THE_INVENTION
This invention encompasses detergent and cleans-ing compositions comprising as the active ingredient a phos-phobetaine surfactant, and preferably at least one other sur-factant selected from the group consisting of anionic, nonionic, cationic and amphoteric detergents. The balance of the compo-sitions can comprise various detergency and cleansing adjuncts, fillers, carriers and the like wel:L known in the art.
DETAILED DESCRIPTION OF THE INVENTION
The detergent and cleansing compositions of the present invention comprise as the active ingredient a phospho-betaine and preferably at least one other surfactant.
The phosphobetaines and phosphitaines which areuseful in the present invention are novel compounds described and claimed in copending Canadi~n application No. 326,454, filed on April 26th, 1979, and are characterized as amphoteric and zwitterionic betaine compounds having at least one phospho-rous-containing anion in the molecule.
The phosphobetaines are of the ~ormula ~ 6 JBP 126 (I) ~R - Y - O - P - B ¦ ~
A l Z
wherein A is selected from O , OM and -O-Y-R~
B is selected from O and OM
,_ .
X is an anion z is an integer from 0 to 2 with the proviso that only one of A and B can be O and z is of a value necessary for charge balance (i.e., when A and B are O and OM , or OM and O , respectively, z is O; when A and B are OM and OM', or -O-Y-R~ and O , 10 respectively, z is 1; when A is -O-Y-R~ and B is OM', z is 2);
R is an amidoamine reactant moiety of the formula r O R ~
IR - C ~ ~ H2~n l4 , wherein Rl is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms;
R2 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5 carbon atoms, or polyoxyalkalene of up to 10 , carbon atoms;
R3 and R4, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxy-alkyl of up .o 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms; in addition, R3 and R4 taken together with the nitrogen to which they are attached, may represent an N-heterocycle, e.g., a morpholino structure, in which the Y radical is bonded to a ring atom of said N-heterocycle other than the 113~5~'g~
nitrogen of the R moiety;
n is an integer from 2 to 12;
The term "polyoxyalkalene radical" as used above in the definition of R2, R3 and R may be of the formula (R5 - O - R5 )m~ wherein RS and RS are alkyl of from 1 to 4 carbon atoms and m is an integer from about 2 to 10 .
In addition to the foregoing definitions wherein R is amidoamine, R may be an N-heterocyclic radical which 10 may contain one additional hetero atom (e.g., oxygen sulfur or another nitrogen) and contains S to 6 total ring caxbon atoms, optionally said heterocyclic radical may be substituted with alkyl and/or hydroxyalkyl of up to 20 carbon atoms each. Typical of such N-heterocyclic 15 radicals are imidazolyl, N-alkylmorpholino, alkyl-pyrimidino, alk~loxazollnyl, and the like. Such compounds may be represented by the formula R
l6 Rl (CH ~ ~ `H2)p ` \Z
wherein Z is N, S or O;
o is an integer from 0 to 3;
p is an integer from 1 to 3;
provided that the sum of o+p is from 3 to 4;
Rl is defined as before and is linked to a ring carbon atom; and R6 is alkyl of from 2 to 6 carbon atoms which may be substituted with a hydroxyl group at the terminal or a non-terminal carbon atom;
Y may be alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms, which alkylene chain may optionally be substituted with loweralkyl, alkoxy, hydroxy or hydroxyalkyl, e.g., of not more than 10 carbon atoms each.
~3~
-- M and M', which may be the same or different, are (a) hydrogen, (b) an organic radical selected from alkyl or hydroxyalkyl of up t`o 6 carbon atoms, pilyhydroxyalkyl of up to 10 carbon atoms, glyceryl, cycloalkyl of up to 6 carbon atoms, aryl or arylalkyl of up to 10 carbon atoms, or (c) a salt radi-cal selected from alkali metals (e.g., sodium or potassium), alkaline earth metals (e.g., magnesium or calcium), and mono-, di-, or triethanolamine. With reference to formula (I) above, wherein both M and M' are contained, there is the proviso that when either M or M' is an organic radical (b), the other o~ M
and M' must be hydrogen or a salt radical (c).
The phosphitaines are of the formula ~ R~ - Y - 0 - P - H 1 wherein R and Y are as defined above.
; 20 The phosphobetaine compounds and phosphitaine compounds described above can be prepared in accordance with the processes described in copending Canadian application No 326,454, filed on April 26th, 1979.
Representati~e phosphobetaine and phosphitaine compounds useful in the present invention include compounds having the followin~ structures:
O H C~l3 Oi~
Cll~c ~ ~al2) I~+J- CH -CH-CH -O - P = O (Co~und ~) CH3 OH 0~
O- C!l 2 - ~ H -CH 2 O H C}l ¦ OH OH
Il I Ir~
Cl1-Cl.3-C-N-(~,~)3- ;I~- CH2-CH-CH2-0 - P = O. (C~ound B3) Cii3 OH C~
O li C~l3 ~ ~~
1 11 13 C N (~)3- ~ CH2-C~i-CH ~ O P O (Co~ound CC) -CH3 OH _ 2 Q~
O H CH3 ot~
1~ ~23 C ~i ~CH2)3- ~-C~i2-CH-CH2-O-P=O (Cc.. ~ 23j O H CH -CO`-~ +~2 2 C11-~23-C-N-(CH2)2 ~ ~V_ CH -CH-CH -o-p=o tCompound E~) OH ONa (CH~)2-O~
The phosphobetaine and phosphitaine compounds can . be present in the detergent and cleansing compositions of the present invention in a ranqe of f~om about 1 to 20~ by weight of the total co~position.
~: 5 Preferred embodiments of the present invention : relate to detergent and cleansing compositions containing a phosphobetaine or a pl~osphitaine and at least one `other surfactant selected from the group consisting of amphoteric, nonionic, anionic and catlonic detergents.
The amphoteric surfactants which may be used in the present invention include betaines, sultaines and ~; n-alkylamino propionates and n-alkylimino dipropionates. . .
The betaine and sultaine surfactants useful in this invention are described in U.S. Patent No. 3,950,417 issued April 13, 1976, and the n-alkylamino propionates and n-alkylimino dipropionates are sold under the trade-.
. .
~L31~6 mark DERIPHATS by General Mills.
The preferred betaine amphoteric surfactants include the alkylbetaines such as cocodimethylcarboxy-methylbetaine, lauryldimethylcarboxymethylbetaine, 5 lauryldimethyl-alpha-carboxyethylbetaine, cetyldimethyl-. carboxymethylbetaine, lauryl-bis-(2-hydroxyethyl) carboxymethylbetaine, oleyldimethyl-gamma-carboxypropyl-betaine, lauryl-bis-(2-hydroxypropyl) alpha-carboxy-ethylbetaine, and the like; the sultaines such as 10 cocodimethylpropylsultaine, stearyldimethylpropylsul-taine, lauryl-bis-(2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocoamidodi-methylpropylsultaine, stearylamidodimethyl?ropylsultaine, la~lrylam-do-bis-(2-hydroxyethy1) pro?ylsultaine, and the 15 like. The preferred n-alkylamino propionates and n-alkylimino dipropionates include those of the following structures:
2 CH2 - CH2 - COG( and CH - CH2 - COo R - N
H CH2 - CH2 - Coo Na : wherein R is from about 8 to 22 carbon atoms and mi~tures thereof. ~he amphoteric detergents should be present in an amount from about 1 to 20o by weight of the total : . com?osition.
It is envisioned that any anionic surfactant may be used in the compositions of the in~rention sucn as, for examDle, an alkyl sulfate of the formula R-CH2-OSO3X, an alkylether sulfate of the formula R(OCH2CH2)p OSO3X, an alkylmonoglyceryl ether sulfonate of the formula R-OCH2-CH-CII2-SO3X, an alkylmonoglyceride sulfate of the OH
formula RCOOCH2-CH-CH2OSO3X, an alkylmonoglyceride OH
~ JBP 126 sulfonate of the formula RCOOCH2CH-CH2S03X, an alkyl OH
sulfonate of the formula RS03X, an alkylaryl sulfonate of the formula O o an alkyl sulfosuccinate of the formula R-CH2~C-CH-CH2-C-OX, an alkyl sarcosinate of the formula R C-N-CH2-COOX, an acyl isothionate of the formula R-C-O-CH2CH2S03X, an alkyl :~ methyl tauride of the formula R-C-N-CH2-CH2-S03X, a fatty -O R' O R"
: acid protein condensate of the formula ~C-(I~-C~~-CH)r~X~, an alcohol ether carboxylate of the formula RO(CH2CH20~q~
15 CH2C02X and the like; wherein R is higheralkyl having from 7 to 17 carbon atoms; R' and R" are members each selected from the group cc,nsisting of hydrogen, loweralkyl, hydroxyloweralkyl, thioloweralkyl, carboxyloweralkyl, aminoloweralkyl, benzyl, and p--hydroxybenzyl; X is a 20 member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from 1 to 3 loweralkyls;
:p is an integer from about 3 to about 6, q is an integer from 2 to about 6 and r is an integer from 2 to 10.
: 25 The preferred type of anionic surfactant is an : alkyl ether sulfate, more preferably sodium tridecyl-alcohol ether sulfate in which p is 1 to 5. The anionic detergent should be present in an amount of from about 1 to 20% by weight of the total composition.
Nonionic detergents which are useful include the alkylene oxide ethers of phenols, fatty alcohols, and alkyl mercaptans; the alkylene o~ide esters of fatty acid amides; the condensation products of ethylene oYide with partial fatty acid esters, and mi~tures ~3~
thereof. The polyoxyalkylene chain in such agents may contain from 5 to 100 alkylene oxide units in which each alkylene unit has from 2 to 3 carbon atoms.
The preferred nonionic surfactant in the composi-5 tions of the invention is a water-soluble polyoxyethylene derivative of a hydrophobic base, said derivative being a member of the group consisting of the reaction products of 9~20 carbon atom fa~ty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain 10 at least 3 hydroxyls, with at least 10 moles of ethylene oxide, and preferably with from about 10 to about 100 moles of ethylene oxide.
The nonionic surfactant should be present in an amount oE from about 1 to 20~ by weight of the total 15 composition.
Cationic surfactants suitable in these composi-tions incluae mono- and bis-quaternary ammonium halides such as stearyldimethylbenzylammonium chloride, cetyl-trimethylammonium chloride, N,N-dioctadecyl-N,N,N',N'-20 tetramethyl-1,5 (3 oxapentylene)di-a~monium dibromide;
tertiary amine salts such as cocamidopropyldimethylamine hydrochloride stearylamidopropyldimethylamine citrate;
cationic polymers such as hydroxyethyl cellulose reacted with epichlorohydrin and then quaternized with 25 trimethylamine. (Polymers of this type are sold by ; Union Carbide under the trademark POLYMER JR. ) The -~ cationic surfactants should be present in an amount of .from about 1 to 5~ by weight of the total composition.
The total amount of the active surfactant 30 ingredients in the present invention should not be greater than about 35~ by weight of the total composition in order to avoid ocular irritation problems, preferably from about 8 to 15~ by weight of the total composition.
In addition, other ingredients conventionally added 35 to detergent and cleansing compositions for personal use, such as dyes, preservatives, perfumes, thickeners, opacifiers, conditioners, emollients, buffering agents, J~P 126 and the like, may be added in minor amounts.
Ingredients such as dyes, preservatives and perfumes together usually constitute less than 2% by weight of the total composition and thickeners may be added to the composition in an amount of from about 1 to about
H CH2 - CH2 - Coo Na : wherein R is from about 8 to 22 carbon atoms and mi~tures thereof. ~he amphoteric detergents should be present in an amount from about 1 to 20o by weight of the total : . com?osition.
It is envisioned that any anionic surfactant may be used in the compositions of the in~rention sucn as, for examDle, an alkyl sulfate of the formula R-CH2-OSO3X, an alkylether sulfate of the formula R(OCH2CH2)p OSO3X, an alkylmonoglyceryl ether sulfonate of the formula R-OCH2-CH-CII2-SO3X, an alkylmonoglyceride sulfate of the OH
formula RCOOCH2-CH-CH2OSO3X, an alkylmonoglyceride OH
~ JBP 126 sulfonate of the formula RCOOCH2CH-CH2S03X, an alkyl OH
sulfonate of the formula RS03X, an alkylaryl sulfonate of the formula O o an alkyl sulfosuccinate of the formula R-CH2~C-CH-CH2-C-OX, an alkyl sarcosinate of the formula R C-N-CH2-COOX, an acyl isothionate of the formula R-C-O-CH2CH2S03X, an alkyl :~ methyl tauride of the formula R-C-N-CH2-CH2-S03X, a fatty -O R' O R"
: acid protein condensate of the formula ~C-(I~-C~~-CH)r~X~, an alcohol ether carboxylate of the formula RO(CH2CH20~q~
15 CH2C02X and the like; wherein R is higheralkyl having from 7 to 17 carbon atoms; R' and R" are members each selected from the group cc,nsisting of hydrogen, loweralkyl, hydroxyloweralkyl, thioloweralkyl, carboxyloweralkyl, aminoloweralkyl, benzyl, and p--hydroxybenzyl; X is a 20 member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from 1 to 3 loweralkyls;
:p is an integer from about 3 to about 6, q is an integer from 2 to about 6 and r is an integer from 2 to 10.
: 25 The preferred type of anionic surfactant is an : alkyl ether sulfate, more preferably sodium tridecyl-alcohol ether sulfate in which p is 1 to 5. The anionic detergent should be present in an amount of from about 1 to 20% by weight of the total composition.
Nonionic detergents which are useful include the alkylene oxide ethers of phenols, fatty alcohols, and alkyl mercaptans; the alkylene o~ide esters of fatty acid amides; the condensation products of ethylene oYide with partial fatty acid esters, and mi~tures ~3~
thereof. The polyoxyalkylene chain in such agents may contain from 5 to 100 alkylene oxide units in which each alkylene unit has from 2 to 3 carbon atoms.
The preferred nonionic surfactant in the composi-5 tions of the invention is a water-soluble polyoxyethylene derivative of a hydrophobic base, said derivative being a member of the group consisting of the reaction products of 9~20 carbon atom fa~ty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain 10 at least 3 hydroxyls, with at least 10 moles of ethylene oxide, and preferably with from about 10 to about 100 moles of ethylene oxide.
The nonionic surfactant should be present in an amount oE from about 1 to 20~ by weight of the total 15 composition.
Cationic surfactants suitable in these composi-tions incluae mono- and bis-quaternary ammonium halides such as stearyldimethylbenzylammonium chloride, cetyl-trimethylammonium chloride, N,N-dioctadecyl-N,N,N',N'-20 tetramethyl-1,5 (3 oxapentylene)di-a~monium dibromide;
tertiary amine salts such as cocamidopropyldimethylamine hydrochloride stearylamidopropyldimethylamine citrate;
cationic polymers such as hydroxyethyl cellulose reacted with epichlorohydrin and then quaternized with 25 trimethylamine. (Polymers of this type are sold by ; Union Carbide under the trademark POLYMER JR. ) The -~ cationic surfactants should be present in an amount of .from about 1 to 5~ by weight of the total composition.
The total amount of the active surfactant 30 ingredients in the present invention should not be greater than about 35~ by weight of the total composition in order to avoid ocular irritation problems, preferably from about 8 to 15~ by weight of the total composition.
In addition, other ingredients conventionally added 35 to detergent and cleansing compositions for personal use, such as dyes, preservatives, perfumes, thickeners, opacifiers, conditioners, emollients, buffering agents, J~P 126 and the like, may be added in minor amounts.
Ingredients such as dyes, preservatives and perfumes together usually constitute less than 2% by weight of the total composition and thickeners may be added to the composition in an amount of from about 1 to about
3~ by weight of the total composition.
The detergent and cleansing compositions of the present invention may be concentrate compositions which are subsequently modified ~y dilution with water or other diluents to provide the ultimate compositions for use or they may be the ultimate cleansing compositions to be employed without modification. The compositions of the present invention are primarily useful in shampoo formulations where high foaming characteristics as well as low ocular and skin irritation potential are desired They may also be used as liquid soaps and cleansers such as baby bath compositions, in bubble bath compositions, as well as in compositions suitable for cleansing animals and inanimate ob~ects.
The aforementioned detergent and cleansing co~positions are prepared by admixing the phosphobetaine or phosphitaine with the other surfactant(s), if utilized, at room temperature or slightly evelated temperatures (about 50C) and then sufficient deionized water is added to bring the composition to about three-~uarters of its intended weight. The pH is adjusted to within the range o~ 5 to 8, preferably 6 to 8, by adding strong acid, e.g" HCL, or strong base, e.g., NaOH, as needed.
Other ingredients such as viscosity builders, preserva-tives, dyes, perfumes and the like are incorporatedprior to adjusting the pH and adding the remainder of 1 the water.
; The detergent and cleansing compositions of the present invention can be tested for ocular irritation by the following modified Draize Test (J.H. Draize et al., Toilet Goods Assn. No. 17, ~lay 1952, No. l.
Proc. Sci. Sect.).
~ 6 JBP 126 A 0.1 ml sample of a neutral composition under test is dropped into one eye of an albino rabbit, the other eye serving as a control. Six rabbits are employed for each composition. Observations are made 5 after l, 24, 48, 72 and 96 hours and 7 days after initial instillation; second and third instillations are made after the 24 and 48 hour readings. ~esults may vary from substantially no change or only a slight irritation in the appearance of the rabbit's eye after 7 days to 10 severe irritation and/or complete corneal opacity.
Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number indicating greater -ocular irritation and the scores are added to give a total numerical value for each reading for six rabbits 15 and averaged. The averaged score is an indication of the irritation potential of the composition under test.
Based on the averaged score, descriptive irritation evaluation may be given, e.g., none, slisht, moderate, severe, as the case may be.
The detergent and cleansing compositions of the invention provide high foam volume and moreover outstand-ing foam stabilitv as measured by an adaption of the well-known Ross-r~liles foam test principle ["Oil and Soap" 18.99-102 (19~1)]:
Lanolin, anhydrous, cosmetic grade is mixed with aioxane (technical qrade) in the proportion of 2.5 grams lanolin and 100 grams of dioxane. The lanolln is first mi~ed with 25 cc. of dioxane. This mixt~re is heated over a steam bath to 45C in order to dissolve the lanolin in the dioxane. The remainder of the dioxane is then added and mixed. This lanolin-dioxane solution, which is stored in an amber bottle, should be prepared fresh on the day tha-t the tests are run.
~_ _ _ ___ __ __ _ ____ _ __ _ __ ~ 6 JBP 126 The composition to be tested is diluted by adding 376 cc. of distilled water to 4 gra~s of the composition, and then by adding 20 cc. of the lanolin-dioxane solution described above while mixing. Heat is 5 produced when the lanolin-dioxane solution is added to the solution of the composition in water and care must be taken in adjusting the temperature of this solution to 24-25C. Both of these intermediate solutions should therefore be adjusted to 23C before mixing. The coolins 10 of the lanolin-dioxane solution should be graclual in order to avoid precip;tation of the lanolir.. This will produce a final solution with a temperature of 2~-25C.
The final solution of the composition to be tested, water, dioxane and lanolin described above, is - 15 then run in a modified Ross-~liles foam column in the usual way. A1] tests are conducted in duplicate, and the average of the two results is taken. Foam stability is determined by measuring the decay in foam height after two minutes, expressed as a percentage of 20 the original height.
Specific embodiments of the detergent and cleansing compositions prepared in accordance ~ith the present invention are illustrated b~ the following representative e~amples~ It will be understood, however, that the invention is not confined to the specific limitations set forth in the individual examples, but rather to the scope of the appended claims.
.
.:
~3~ . BP 126 E,~ PL~ I
A detergent and cleansina com~osition is prepared by charging 192.6 gra~s of a 35~ acti~e solution of Com2ound AA to a steam jack;eted vessel ;ith agitation. 225.0 grams of a 30~ active solution of a cocoamido Detaine of tne formula O H CH
(R is a mixture of C10-C18) is acded with asitation followed ~ the addi.ion of 200.0 srams of a /2~ acti~e solutior. of pol~c~:ieth~lene (S0) scrbitan monolaurate anc 50.0 sr~ s Or a YC^- active solution of t~iethanolamine lauryl sulfa~e resultins in a clear, homogenous solu'ion. 100.0 gra~s of deior.ized water is added and the mixture is hea.ec o 60~C and 10.0 ~rams of polyeth~!lene gl~col 6000 distearate are ad~ed with agitation over a r!eriod of _0 r,inltes cr un'il .he solution is clear. 100.0 gra~s Oc deioni~ed ~.ater are added and 6.72 grams of 15-c HCL .o attain a p~ of 7.0 - O.l. 0.5 grams of DOWICIL 200 (trademark) preservative and 1.0 gram of benzyl alcohol are added followed by the addition of 25.0 grams of propylene glycol and 3.0 grams of fragrance. Sufficient deionized water is then added to produce 1000 grams (1 liter) of the desired composition consisting of the following ingredients:
i ~
, ~., .
~ ~ .
:
~3~ JBP 126 wt./wt.
Compound AA 6.0 cocoamidobetaine 6.0 triethanolamine lauryl sulfate 2.0 propylene glycol 2.5 polyethylene glycol 6000 distearate 1.0 polyoxyethylene (80) sorbitan mDnolaurate 15.0 DOWICIL 200 (Dcw C~cal C~ny's ~rademarkfor the cis isomer of 1-(3-chloroa~Tl)-3,;,7-triaza-1-azon~ ~ntine chloride) .05 benzyl alcohol .10 dye and fragrance .35 deionized water q.s. to 100%
pH = 7.0 with dilute HCL.
The above composition is tested for ocular irritation in accordance with the previously described modified Draize test and found to be a slight irritant.
The above composition is tested for foam volume and stability in accordance with the previously described `I 20 modified Ross-11iles test and compared to two detersent compositions (Composition A and Composition B) prepared in accordance with the prior art teachings of U.S.
Patents ~los. 3,055,836 and 3,978,251 and yielded the following results as shown in Table I:
2S Table I
Foam Volume (l~ Deca~
..
Composition of E~ample I 205 15 Composition A 100 ~0 Composition B 130 60 As can be readily seen from the results abo~e, the detergent and cleansinq composition prepared in accor-dance ~ith the teachinus of this invention possesses sigr.ificantly higher foam volume and significantly superior foam stability ~;hen compared with compositions tausht in the prior art.
~ 96 JBP 126 EXAMPLES II -IV
The following compositions are prepared in accordance with the procedure of EXA~lPLE I:
% wt./wt.
E ~ IPLE
II III IV
30% activ2 Compound EE 33.300 -- ~~
40~ active Cbmpound BB - 8.000 --40% active Compound AA - - 14.900 28% active sodium lauryl (3) ether sulfate -- 22.200 --28% active sodium lauryl sulfate -- 11.900 77~ active polyoxyethylene (80~ sorbitan nonococoate ~20.000 15.000 polyethylene glycol 6000 distearate 2.500 -- 1.000 15% HCL 1.400 -- 1.600 10% NaOH - 5.600 --DOWICIL 200 0.100 0.050 0.100 dye 0.001 0. 002 0. 003 fragra~ce 0.350 0.200 0.100 20 deionized water q.s.to q.s.to q.s.to 100% 100~ 100%
Each of the above compositions is tested for ocular irritations in accordance with the previously described modified Draize test and found to be a slight irritant.
Each of the above compositions (EXA~LES II-IV) are tested for ~oam volume and stability in accordance with the previously described modified Ross-~iles test ~nd the results are shown below in Table II:
Table II
CompositionFoam Volume (~) ~ Decay EXA~PLE II 145 38 EXA*~LE III 130 9 As can be seen from the results in Table II, the detergent and cleansing compositions of EXAMPLES II-IV, each prepared in accordance with the teachings of the present invention, each possess good foam volume and excellent foam stability.
~' ~.
.
~L3~
EXi~5PLE V
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXP~PLE I:
wt./wt.
Compound AA 5.0 tridecyl alcohol ether (4) sulfate (TDES4) 15.0 deionized water 80.0 , .
pH adjusted to 7.0 with 10~ HCL.
This composition exhibits low irritation and excellent : foam properties.
E~A~LE VI
A liquid detergent and cleansing composition consisting of the following ingredients is prepare~ in ; accordance witn the teachings of EX.~lPLE I:
; t~t.,/t~t.
Compound AA 2.5 ; C14-C16~j-olefin sodium sulfonate 2.5 d~e .01 DOWICIL 200 .1 fragrance .2 deionized water q.s. to 100 pH adjusted to 5.0 with citric acid.
This composition exhibits low irritation and excellert foam properties.
.
,,, ~
3~ BP 126 EXAMPLE VII
A liquid detergent and cleansing composition consisting of the ~ollowing ingredients is prepared in accordance with the teachings of EXA~LE I:
S wt./~.t. %
Compound BB 15 0 sodium lauryl ether (3) sulfate 15.0 POLYMER JR 400 1.0 DOWICIL 200 .1 fragrance 3 deionized water q s. to 100C
This composition exhibits low irritation and eY~cellent foam properties.
EXAMPLE VI I I
:
A liquid detergent and cleansins composition consisting of the following ingredients is prepared in accordance with the teachings of E~YA~I~LE I:
~t./~t s~
Compound CC S.o lauryl amido propylbetaine 5 0 tridecyl ether sulfate 5.0 isoproponal .S
propylene glycol 2.0 dye .01 Z5 fragrance 7 deionized water q.sO to 100 pH aàjusted to 7.5 with 10~ HCL
~This composition exhibits low irritation and excellent foam properties.
6 ~P 1~6 E~AMPLE IX
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXAMPL~ I:
~.t./wt.
Compound AA 2.5 Compound CC 2.5 polyoxyethylene (80) sorbitan monococoate 5.0 tridecyl ether sulfate 5.0 deionized water q.s. to 100o pH adjusted yo 7.0 with H2~O4 (dilute) This composition exhibits low lrrlta~lon ana excellent foam properties.
EXAMPLE X
A liquid deterg~llL ~id ~ nsing composition consisting of the following ingredients is prepared in accordance with the teachings of EXA~lPLE I:
~It./~t.
Compound DD 5.0 lauric-mvristic-g-aminopropionic 5.0 acid sodium lauryl (3) ether sulfate 10.0 DOWICIL 200 .5 deionized water q.s. to lOOQ
: 25 pH adjusted to 6.5 with phosphoric acid This composition exhibits low irritation and excellent foam properties.
.~ , ., ~1~31~39~ JBP 12 6 .~
EXA~SPLE XI
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXAMPLE `L:
wt./wt.
Compound DD 5.0 3-(N,I~ dimethyl-~-lauryl amino)- 5.0 2-(hydroxyl propane sulfonate) cetyl trimethylammonium chloride 1.0 deionized water q.s. to 100 pH adiusted to 5.0 with dilute HCL.
This composit~on exhib~ts l~w ~rritation and excellent foam properties.
EXAMPLE XII
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXA~IPLE I:
wt./t.t. b Compound DD 2.0 sodium lauryl ether sulfate 16.0 lauric/myristic alkanolamide 4.0 deioni2ed water q.s. to 100 pH adjusted to 7.5 This composition exhibits low irritation and excellent foam propert;~es.
EXAMPLE XIII
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXAMPLE I:
t~t./wt.
Compound E~ 5.0 ethyleneoxylethylene-bis-(dimethyl- 2.0 octadecylammonium chloride) tridecyl ether sulfate 10.0 alcohol (SDA 40) 1.0 dye and fragrance .35 deionized water q.s. to 100 pH adjusted to 8.0 This composition exhibits low irritation and excellent foam properties.
EXP~IPLE IV
A li~uid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of E~ iPLE I:
wt./~t. s Compound EE 10.0 dye and fragrance .35 deionize~ water q.s. to 100%
This composition exhibits low irrltatlon ana excellent foam properties.
EXAMPLE V
A liquid detergent and cleansing com2osition consisting of the following ingredients is prepared in accordance with the teachings of E~ iPLE 1:
t /~;t.
Compound BB 5.0 amidosultaine 5.0 polyoxyethylene (80) sorbitan monolaurate 10.0 preservative .l dye and fragrance .75 deionized water q.s. to 100-~
This composition exnibits low irritation an~ excellent foam properties.
, ;~
. BP 126 EXAMPLE XVI
A liquid baby bath composition is prepared having the following formulation:
~t./~-t. %
Compound EE 2.50 stripped coconut sultaine 2.50 polyoxyethylene (80) sorbitan monolaurate 5.00 tridecylether sulfate 5.00 ~olyvinylpyrrolidine 2.00 polyethylene glycol 6000 distearate1.00 preservative .10 dye and fragrance .35 deionized water q.s. to 100 pH adjusted to 6.5 with dilute HCL.
This composition exhibits low irritation and excellent foam properties.
EXAMPLE XVII
A qel detergent composition is prepared having the following formulation:
wt./~t.
Compound EE 10.0 Compound AA 10.0 triethanolamine lauryl sulfate 5.0 polyvinylpyrrolidine 2.0 polyoxyethylene (80) sorbitan monolaurate 15.0 : polyethylene gly~ol distearate (150) 3.0 DOWICIL 200 . .1 ; dye and fragrance .35 This composition exhibits low irritation and excellent foam properties.
Various other features and embodiments of the present invention not specifically enumerated will be : obvious to those skilled in the art, all of which may be achieved without departing from the spirit and the 3S scope of the invention as defined by the following claims.
The detergent and cleansing compositions of the present invention may be concentrate compositions which are subsequently modified ~y dilution with water or other diluents to provide the ultimate compositions for use or they may be the ultimate cleansing compositions to be employed without modification. The compositions of the present invention are primarily useful in shampoo formulations where high foaming characteristics as well as low ocular and skin irritation potential are desired They may also be used as liquid soaps and cleansers such as baby bath compositions, in bubble bath compositions, as well as in compositions suitable for cleansing animals and inanimate ob~ects.
The aforementioned detergent and cleansing co~positions are prepared by admixing the phosphobetaine or phosphitaine with the other surfactant(s), if utilized, at room temperature or slightly evelated temperatures (about 50C) and then sufficient deionized water is added to bring the composition to about three-~uarters of its intended weight. The pH is adjusted to within the range o~ 5 to 8, preferably 6 to 8, by adding strong acid, e.g" HCL, or strong base, e.g., NaOH, as needed.
Other ingredients such as viscosity builders, preserva-tives, dyes, perfumes and the like are incorporatedprior to adjusting the pH and adding the remainder of 1 the water.
; The detergent and cleansing compositions of the present invention can be tested for ocular irritation by the following modified Draize Test (J.H. Draize et al., Toilet Goods Assn. No. 17, ~lay 1952, No. l.
Proc. Sci. Sect.).
~ 6 JBP 126 A 0.1 ml sample of a neutral composition under test is dropped into one eye of an albino rabbit, the other eye serving as a control. Six rabbits are employed for each composition. Observations are made 5 after l, 24, 48, 72 and 96 hours and 7 days after initial instillation; second and third instillations are made after the 24 and 48 hour readings. ~esults may vary from substantially no change or only a slight irritation in the appearance of the rabbit's eye after 7 days to 10 severe irritation and/or complete corneal opacity.
Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number indicating greater -ocular irritation and the scores are added to give a total numerical value for each reading for six rabbits 15 and averaged. The averaged score is an indication of the irritation potential of the composition under test.
Based on the averaged score, descriptive irritation evaluation may be given, e.g., none, slisht, moderate, severe, as the case may be.
The detergent and cleansing compositions of the invention provide high foam volume and moreover outstand-ing foam stabilitv as measured by an adaption of the well-known Ross-r~liles foam test principle ["Oil and Soap" 18.99-102 (19~1)]:
Lanolin, anhydrous, cosmetic grade is mixed with aioxane (technical qrade) in the proportion of 2.5 grams lanolin and 100 grams of dioxane. The lanolln is first mi~ed with 25 cc. of dioxane. This mixt~re is heated over a steam bath to 45C in order to dissolve the lanolin in the dioxane. The remainder of the dioxane is then added and mixed. This lanolin-dioxane solution, which is stored in an amber bottle, should be prepared fresh on the day tha-t the tests are run.
~_ _ _ ___ __ __ _ ____ _ __ _ __ ~ 6 JBP 126 The composition to be tested is diluted by adding 376 cc. of distilled water to 4 gra~s of the composition, and then by adding 20 cc. of the lanolin-dioxane solution described above while mixing. Heat is 5 produced when the lanolin-dioxane solution is added to the solution of the composition in water and care must be taken in adjusting the temperature of this solution to 24-25C. Both of these intermediate solutions should therefore be adjusted to 23C before mixing. The coolins 10 of the lanolin-dioxane solution should be graclual in order to avoid precip;tation of the lanolir.. This will produce a final solution with a temperature of 2~-25C.
The final solution of the composition to be tested, water, dioxane and lanolin described above, is - 15 then run in a modified Ross-~liles foam column in the usual way. A1] tests are conducted in duplicate, and the average of the two results is taken. Foam stability is determined by measuring the decay in foam height after two minutes, expressed as a percentage of 20 the original height.
Specific embodiments of the detergent and cleansing compositions prepared in accordance ~ith the present invention are illustrated b~ the following representative e~amples~ It will be understood, however, that the invention is not confined to the specific limitations set forth in the individual examples, but rather to the scope of the appended claims.
.
.:
~3~ . BP 126 E,~ PL~ I
A detergent and cleansina com~osition is prepared by charging 192.6 gra~s of a 35~ acti~e solution of Com2ound AA to a steam jack;eted vessel ;ith agitation. 225.0 grams of a 30~ active solution of a cocoamido Detaine of tne formula O H CH
(R is a mixture of C10-C18) is acded with asitation followed ~ the addi.ion of 200.0 srams of a /2~ acti~e solutior. of pol~c~:ieth~lene (S0) scrbitan monolaurate anc 50.0 sr~ s Or a YC^- active solution of t~iethanolamine lauryl sulfa~e resultins in a clear, homogenous solu'ion. 100.0 gra~s of deior.ized water is added and the mixture is hea.ec o 60~C and 10.0 ~rams of polyeth~!lene gl~col 6000 distearate are ad~ed with agitation over a r!eriod of _0 r,inltes cr un'il .he solution is clear. 100.0 gra~s Oc deioni~ed ~.ater are added and 6.72 grams of 15-c HCL .o attain a p~ of 7.0 - O.l. 0.5 grams of DOWICIL 200 (trademark) preservative and 1.0 gram of benzyl alcohol are added followed by the addition of 25.0 grams of propylene glycol and 3.0 grams of fragrance. Sufficient deionized water is then added to produce 1000 grams (1 liter) of the desired composition consisting of the following ingredients:
i ~
, ~., .
~ ~ .
:
~3~ JBP 126 wt./wt.
Compound AA 6.0 cocoamidobetaine 6.0 triethanolamine lauryl sulfate 2.0 propylene glycol 2.5 polyethylene glycol 6000 distearate 1.0 polyoxyethylene (80) sorbitan mDnolaurate 15.0 DOWICIL 200 (Dcw C~cal C~ny's ~rademarkfor the cis isomer of 1-(3-chloroa~Tl)-3,;,7-triaza-1-azon~ ~ntine chloride) .05 benzyl alcohol .10 dye and fragrance .35 deionized water q.s. to 100%
pH = 7.0 with dilute HCL.
The above composition is tested for ocular irritation in accordance with the previously described modified Draize test and found to be a slight irritant.
The above composition is tested for foam volume and stability in accordance with the previously described `I 20 modified Ross-11iles test and compared to two detersent compositions (Composition A and Composition B) prepared in accordance with the prior art teachings of U.S.
Patents ~los. 3,055,836 and 3,978,251 and yielded the following results as shown in Table I:
2S Table I
Foam Volume (l~ Deca~
..
Composition of E~ample I 205 15 Composition A 100 ~0 Composition B 130 60 As can be readily seen from the results abo~e, the detergent and cleansinq composition prepared in accor-dance ~ith the teachinus of this invention possesses sigr.ificantly higher foam volume and significantly superior foam stability ~;hen compared with compositions tausht in the prior art.
~ 96 JBP 126 EXAMPLES II -IV
The following compositions are prepared in accordance with the procedure of EXA~lPLE I:
% wt./wt.
E ~ IPLE
II III IV
30% activ2 Compound EE 33.300 -- ~~
40~ active Cbmpound BB - 8.000 --40% active Compound AA - - 14.900 28% active sodium lauryl (3) ether sulfate -- 22.200 --28% active sodium lauryl sulfate -- 11.900 77~ active polyoxyethylene (80~ sorbitan nonococoate ~20.000 15.000 polyethylene glycol 6000 distearate 2.500 -- 1.000 15% HCL 1.400 -- 1.600 10% NaOH - 5.600 --DOWICIL 200 0.100 0.050 0.100 dye 0.001 0. 002 0. 003 fragra~ce 0.350 0.200 0.100 20 deionized water q.s.to q.s.to q.s.to 100% 100~ 100%
Each of the above compositions is tested for ocular irritations in accordance with the previously described modified Draize test and found to be a slight irritant.
Each of the above compositions (EXA~LES II-IV) are tested for ~oam volume and stability in accordance with the previously described modified Ross-~iles test ~nd the results are shown below in Table II:
Table II
CompositionFoam Volume (~) ~ Decay EXA~PLE II 145 38 EXA*~LE III 130 9 As can be seen from the results in Table II, the detergent and cleansing compositions of EXAMPLES II-IV, each prepared in accordance with the teachings of the present invention, each possess good foam volume and excellent foam stability.
~' ~.
.
~L3~
EXi~5PLE V
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXP~PLE I:
wt./wt.
Compound AA 5.0 tridecyl alcohol ether (4) sulfate (TDES4) 15.0 deionized water 80.0 , .
pH adjusted to 7.0 with 10~ HCL.
This composition exhibits low irritation and excellent : foam properties.
E~A~LE VI
A liquid detergent and cleansing composition consisting of the following ingredients is prepare~ in ; accordance witn the teachings of EX.~lPLE I:
; t~t.,/t~t.
Compound AA 2.5 ; C14-C16~j-olefin sodium sulfonate 2.5 d~e .01 DOWICIL 200 .1 fragrance .2 deionized water q.s. to 100 pH adjusted to 5.0 with citric acid.
This composition exhibits low irritation and excellert foam properties.
.
,,, ~
3~ BP 126 EXAMPLE VII
A liquid detergent and cleansing composition consisting of the ~ollowing ingredients is prepared in accordance with the teachings of EXA~LE I:
S wt./~.t. %
Compound BB 15 0 sodium lauryl ether (3) sulfate 15.0 POLYMER JR 400 1.0 DOWICIL 200 .1 fragrance 3 deionized water q s. to 100C
This composition exhibits low irritation and eY~cellent foam properties.
EXAMPLE VI I I
:
A liquid detergent and cleansins composition consisting of the following ingredients is prepared in accordance with the teachings of E~YA~I~LE I:
~t./~t s~
Compound CC S.o lauryl amido propylbetaine 5 0 tridecyl ether sulfate 5.0 isoproponal .S
propylene glycol 2.0 dye .01 Z5 fragrance 7 deionized water q.sO to 100 pH aàjusted to 7.5 with 10~ HCL
~This composition exhibits low irritation and excellent foam properties.
6 ~P 1~6 E~AMPLE IX
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXAMPL~ I:
~.t./wt.
Compound AA 2.5 Compound CC 2.5 polyoxyethylene (80) sorbitan monococoate 5.0 tridecyl ether sulfate 5.0 deionized water q.s. to 100o pH adjusted yo 7.0 with H2~O4 (dilute) This composition exhibits low lrrlta~lon ana excellent foam properties.
EXAMPLE X
A liquid deterg~llL ~id ~ nsing composition consisting of the following ingredients is prepared in accordance with the teachings of EXA~lPLE I:
~It./~t.
Compound DD 5.0 lauric-mvristic-g-aminopropionic 5.0 acid sodium lauryl (3) ether sulfate 10.0 DOWICIL 200 .5 deionized water q.s. to lOOQ
: 25 pH adjusted to 6.5 with phosphoric acid This composition exhibits low irritation and excellent foam properties.
.~ , ., ~1~31~39~ JBP 12 6 .~
EXA~SPLE XI
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXAMPLE `L:
wt./wt.
Compound DD 5.0 3-(N,I~ dimethyl-~-lauryl amino)- 5.0 2-(hydroxyl propane sulfonate) cetyl trimethylammonium chloride 1.0 deionized water q.s. to 100 pH adiusted to 5.0 with dilute HCL.
This composit~on exhib~ts l~w ~rritation and excellent foam properties.
EXAMPLE XII
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXA~IPLE I:
wt./t.t. b Compound DD 2.0 sodium lauryl ether sulfate 16.0 lauric/myristic alkanolamide 4.0 deioni2ed water q.s. to 100 pH adjusted to 7.5 This composition exhibits low irritation and excellent foam propert;~es.
EXAMPLE XIII
A liquid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of EXAMPLE I:
t~t./wt.
Compound E~ 5.0 ethyleneoxylethylene-bis-(dimethyl- 2.0 octadecylammonium chloride) tridecyl ether sulfate 10.0 alcohol (SDA 40) 1.0 dye and fragrance .35 deionized water q.s. to 100 pH adjusted to 8.0 This composition exhibits low irritation and excellent foam properties.
EXP~IPLE IV
A li~uid detergent and cleansing composition consisting of the following ingredients is prepared in accordance with the teachings of E~ iPLE I:
wt./~t. s Compound EE 10.0 dye and fragrance .35 deionize~ water q.s. to 100%
This composition exhibits low irrltatlon ana excellent foam properties.
EXAMPLE V
A liquid detergent and cleansing com2osition consisting of the following ingredients is prepared in accordance with the teachings of E~ iPLE 1:
t /~;t.
Compound BB 5.0 amidosultaine 5.0 polyoxyethylene (80) sorbitan monolaurate 10.0 preservative .l dye and fragrance .75 deionized water q.s. to 100-~
This composition exnibits low irritation an~ excellent foam properties.
, ;~
. BP 126 EXAMPLE XVI
A liquid baby bath composition is prepared having the following formulation:
~t./~-t. %
Compound EE 2.50 stripped coconut sultaine 2.50 polyoxyethylene (80) sorbitan monolaurate 5.00 tridecylether sulfate 5.00 ~olyvinylpyrrolidine 2.00 polyethylene glycol 6000 distearate1.00 preservative .10 dye and fragrance .35 deionized water q.s. to 100 pH adjusted to 6.5 with dilute HCL.
This composition exhibits low irritation and excellent foam properties.
EXAMPLE XVII
A qel detergent composition is prepared having the following formulation:
wt./~t.
Compound EE 10.0 Compound AA 10.0 triethanolamine lauryl sulfate 5.0 polyvinylpyrrolidine 2.0 polyoxyethylene (80) sorbitan monolaurate 15.0 : polyethylene gly~ol distearate (150) 3.0 DOWICIL 200 . .1 ; dye and fragrance .35 This composition exhibits low irritation and excellent foam properties.
Various other features and embodiments of the present invention not specifically enumerated will be : obvious to those skilled in the art, all of which may be achieved without departing from the spirit and the 3S scope of the invention as defined by the following claims.
Claims (11)
1. A detergent and cleansing composition wherein the active ingredient consists essentially of from about 1 to 20% by weight of the total composition of a compound selected from the group consisiting of a phosphobetaine of the formula (I) wherein A is selected from O- , OM, and -O-Y-R+;
B is selected from O- and OM';
X- is an anion;
z is an integer from 0 to 2;
with the proviso that only one of A and B can be O and z is of a value necessary for charge balance, R is an amidoamine reactant moiety of the formula wherein R1 is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms, R2 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5 carbon atoms, or polyoxyalkalene of up to 10 carbon atoms;
R3 and R4, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxy-alkyl of up to 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms, in addition, R3 and R4 taken together with the nitrogen to which they are attached, may represent an N-heterocycle structure, in which the Y radical is bonded to a ring atom of said N-heterocycle other than the nitrogen of the R moiety;
n is an integer from 2 to 12;
or R is an N-heterocyclic radical of the formula wherein z is N, S or O;
o is an integer from 0 to 3;
p is an integer from 1 to 3;
provided that the sum of o+p is from 3 to 4;
R1 is defined as before and is linked to a ring carbon atom; and R6 is alkyl of from 2 to 6 carbon atoms which may be substituted with a hydroxyl group at the terminal or a non-terminal carbon atom;
Y is alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms, which alkylene chain may optionally be substituted with loweralkyl, alkoxy, hydroxy or hydroxyalkyl, contains not more than 10 carbon atoms each;
M and M', which may be the same or different, are (a) hydrogen, (b) an organic radical selected from alkyl or hydroxyalkyl of up to 6 carbon atoms, polyhydroxyalkyl of up to 10 carbon atoms, glyceryl, cycloalkyl of up to 6 carbon atoms, aryl or arylalkyl of up to 10 carbon atoms, or (c) a salt radical selected from alkali metals, alkaline earth metals, and mono-, di- or tri-ethanolamine, provided that when either M or M' is an organic radical (b), the other M and M' must be hydrogen or a salt radical (c);
or a phosphitaine of the formula wherein R and Y are as defined above.
B is selected from O- and OM';
X- is an anion;
z is an integer from 0 to 2;
with the proviso that only one of A and B can be O and z is of a value necessary for charge balance, R is an amidoamine reactant moiety of the formula wherein R1 is alkyl, alkenyl, alkoxy, or hydroxyalkyl of from 5 to 22 carbon atoms each, or aryl or alkaryl of up to 20 carbon atoms, R2 is hydrogen or alkyl, hydroxyalkyl or alkenyl of up to 6 carbon atoms each or cycloalkyl of up to 6 carbon atoms, preferably of from 2 to 5 carbon atoms, or polyoxyalkalene of up to 10 carbon atoms;
R3 and R4, which may be the same or different, are selected from alkyl, hydroxyalkyl, carboxy-alkyl of up to 6 carbon atoms in each alkyl moiety, and polyoxyalkylene of up to 10 carbon atoms, in addition, R3 and R4 taken together with the nitrogen to which they are attached, may represent an N-heterocycle structure, in which the Y radical is bonded to a ring atom of said N-heterocycle other than the nitrogen of the R moiety;
n is an integer from 2 to 12;
or R is an N-heterocyclic radical of the formula wherein z is N, S or O;
o is an integer from 0 to 3;
p is an integer from 1 to 3;
provided that the sum of o+p is from 3 to 4;
R1 is defined as before and is linked to a ring carbon atom; and R6 is alkyl of from 2 to 6 carbon atoms which may be substituted with a hydroxyl group at the terminal or a non-terminal carbon atom;
Y is alkylene, optionally interrupted by up to 3 oxygen atoms, of up to 12 carbon atoms, which alkylene chain may optionally be substituted with loweralkyl, alkoxy, hydroxy or hydroxyalkyl, contains not more than 10 carbon atoms each;
M and M', which may be the same or different, are (a) hydrogen, (b) an organic radical selected from alkyl or hydroxyalkyl of up to 6 carbon atoms, polyhydroxyalkyl of up to 10 carbon atoms, glyceryl, cycloalkyl of up to 6 carbon atoms, aryl or arylalkyl of up to 10 carbon atoms, or (c) a salt radical selected from alkali metals, alkaline earth metals, and mono-, di- or tri-ethanolamine, provided that when either M or M' is an organic radical (b), the other M and M' must be hydrogen or a salt radical (c);
or a phosphitaine of the formula wherein R and Y are as defined above.
2. The composition of claim 1 containing in addition at least one surfactant selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants wherein the total active level of surfactants shall not exceed 35% by weight of the total compositon.
3. The composition of claim 2 containing from about 1 to 20% by weight of the total composition of an anionic surfactant selected from the group consisting of alkylsulfate, alkylether sulfate, alkylmonoglyceryl ether sulfonate, alkylmonoglyceride sulfate, alkyl-monoglyceride sulfonate, alkyl sulfonate, alkylaryl sulfonate, alkyl sulfosuccinate, alkyl sarcosinate, acyl isothionate, alkyl methyl tauride, fatty acid protein condensate and an alcohol ether carboxylate.
4. The composition of claim 2 containing from about 1 to 20% by weight of the total composition of a nonionic surfactant selected from the group consisting of alkylene oxide ethers of phenols, mono- or polyhydric alcohols, and alkyl mercaptans; alkylene oxide esters of fatty acid amides; condensation products of ethylene oxide with partial fatty acid esters and mixtures thereof.
5. The composition of claim 2 containing from about 1 to 5% by weight of the total composition of a cationic surfactant selected from the group consisting of mono- and bis-quaternary ammonium halides, tertiary amine salts and cationic polymers.
6. The composition of claim 2 containing from about 1 to 20% by weight of the total composition of an amphoteric surfactant selected from the group consisting of betaines, sultaines, n-alkylaminopropionates and n-alkylimino-dipropionates.
7. The composition of claim 1 wherein the phosphobetaine compound is of the formula
8. The composition of claim 1 wherein the phosphobetaine compound is of the formula
9. The composition of claim 1 wherein the phosphobetaine compound is of the formula
10. The composition of claim 1 wherein the phosphitaine compound is of the formula
11. The composition of claim 1 wherein the phosphobetaine compound is of the formula
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/965,463 US4233192A (en) | 1978-11-30 | 1978-11-30 | Detergent compositions |
| US965,463 | 1992-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131096A true CA1131096A (en) | 1982-09-07 |
Family
ID=25509994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA326,453A Expired CA1131096A (en) | 1978-11-30 | 1979-04-26 | Detergent compositions |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4233192A (en) |
| JP (1) | JPS5575497A (en) |
| AT (1) | AT376451B (en) |
| AU (1) | AU528549B2 (en) |
| BE (1) | BE876057A (en) |
| BR (1) | BR7902727A (en) |
| CA (1) | CA1131096A (en) |
| CH (1) | CH654325A5 (en) |
| FR (1) | FR2442884A1 (en) |
| GB (1) | GB2035362B (en) |
| GR (1) | GR69968B (en) |
| IE (1) | IE48108B1 (en) |
| IT (1) | IT1116830B (en) |
| MX (1) | MX149620A (en) |
| NL (1) | NL7903527A (en) |
| NZ (1) | NZ190364A (en) |
| PH (1) | PH15903A (en) |
| PT (1) | PT69575A (en) |
| ZA (1) | ZA792158B (en) |
Families Citing this family (72)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4552685A (en) * | 1979-08-02 | 1985-11-12 | The Dow Chemical Company | Thickened amphoteric surfactant solutions |
| US4372869A (en) * | 1981-05-15 | 1983-02-08 | Johnson & Johnson Baby Products Company | Detergent compositions |
| US4948576A (en) * | 1983-02-18 | 1990-08-14 | Johnson & Johnson Consumer Products, Inc. | Detergent compositions |
| US4490355A (en) * | 1983-03-14 | 1984-12-25 | Miranol Chemical Company, Inc. | Betaine based cosmetic formulations |
| JPS60197614A (en) * | 1984-03-21 | 1985-10-07 | Shionogi & Co Ltd | Shampoo composition of low irritation |
| US4595526A (en) | 1984-09-28 | 1986-06-17 | Colgate-Palmolive Company | High foaming nonionic surfacant based liquid detergent |
| GB2181737A (en) * | 1985-08-29 | 1987-04-29 | Avent Medical Ltd | Liquid shampoo composition |
| US5300494A (en) * | 1986-06-06 | 1994-04-05 | Union Carbide Chemicals & Plastics Technology Corporation | Delivery systems for quaternary and related compounds |
| US5000868A (en) * | 1987-04-03 | 1991-03-19 | Wittpenn Jr John R | Surfactant compositions |
| US5075042A (en) * | 1989-05-01 | 1991-12-24 | Ppg Industries, Inc. | Surfactant blend containing an alkyl poly(ethyleneoxy)sulfonate to reduce dermal irritation |
| US5225112A (en) * | 1989-09-05 | 1993-07-06 | Shiseido Company, Ltd. | Shampoo composition |
| US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
| US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
| US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
| ES2121011T3 (en) * | 1991-02-15 | 1998-11-16 | Formulogics Inc | DETERMINATION OF POLLUTANTS. |
| US5286719A (en) * | 1991-10-28 | 1994-02-15 | Mona Industries, Inc. | Phospholipid virucidal compositions |
| US5648348A (en) * | 1991-10-28 | 1997-07-15 | Mona Industries, Inc. | Phospholipid antimicrobial compositions |
| US5215976A (en) * | 1991-10-28 | 1993-06-01 | Mona Industries, Inc. | Phospholipids useful as spermicidal agents |
| DE69303005T2 (en) * | 1992-01-23 | 1997-01-23 | Procter & Gamble | COMPOSITION OF LIQUID CLEANING AGENTS FOR HARD SURFACES, CONTAINING ZWITTERIONIC AND CATIONIC SURFACES AND MONOETHANOLAMINE AND / OR BETA AMINO ALKANOL |
| ZA931613B (en) * | 1992-04-15 | 1993-11-15 | Curtis Helene Ind Inc | Conditioning shampoo composition and method of preparing and using the same |
| CA2092284C (en) * | 1992-04-15 | 2003-02-11 | Wolfgang Bergmann | Conditioning shampoo composition and method of preparing and using the same |
| US5275761A (en) * | 1992-04-15 | 1994-01-04 | Helene Curtis, Inc. | Conditioning shampoo composition and method of preparing and using the same |
| US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
| AU8132894A (en) * | 1993-11-12 | 1995-05-29 | Procter & Gamble Company, The | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
| US5531933A (en) * | 1993-12-30 | 1996-07-02 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders |
| DE4416566A1 (en) * | 1994-05-11 | 1995-11-16 | Huels Chemische Werke Ag | Aqueous viscoelastic surfactant solutions for hair and skin cleansing |
| US5534198A (en) * | 1994-08-02 | 1996-07-09 | The Procter & Gamble Company | Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity |
| FR2725365B1 (en) * | 1994-10-07 | 1996-11-08 | Oreal | CLEANSING AND / OR MAKE-UP REMOVAL COMPOSITION CONTAINING AN ALCOHOL AND A PHOSPHATE COMPOUND |
| US5567427A (en) * | 1995-03-17 | 1996-10-22 | Helene Curtis, Inc. | Emulsified, low ph cosmetic compositions having improved stability |
| US6090773A (en) * | 1996-01-29 | 2000-07-18 | Johnson & Johnson Consumer Products, Inc. | Personal cleansing |
| ID18376A (en) * | 1996-01-29 | 1998-04-02 | Johnson & Johnson Consumer | DETERGENT COMPOSITIONS |
| US6258859B1 (en) * | 1997-06-10 | 2001-07-10 | Rhodia, Inc. | Viscoelastic surfactant fluids and related methods of use |
| US6531119B1 (en) * | 1998-03-05 | 2003-03-11 | Colgate-Palmolive Company | Compositions with low irritancy |
| US6524594B1 (en) | 1999-06-23 | 2003-02-25 | Johnson & Johnson Consumer Companies, Inc. | Foaming oil gel compositions |
| EP1410713B1 (en) * | 1999-07-27 | 2008-05-21 | Rhodia Inc. | Hybrid ionic phosphorus surfactant adjuvants for bioactive compositions |
| US6683032B1 (en) | 2002-05-06 | 2004-01-27 | O'lenick, Jr. Anthony J. | Multifunctional phospholipid surfactants |
| US7084104B2 (en) * | 2003-08-28 | 2006-08-01 | Johnson & Johnson Consumer Company Inc. | Mild and effective cleansing compositions |
| US7098180B2 (en) * | 2003-08-28 | 2006-08-29 | Johnson & Johnson Consumer Companies Inc. | Mild and effective cleansing compositions |
| US20050049172A1 (en) * | 2003-08-28 | 2005-03-03 | Lukenbach Elvin R. | Mild and effective cleansing compositions |
| US7119059B2 (en) * | 2003-08-28 | 2006-10-10 | Johnson & Johnson Consumer Companies, Inc. | Mild and effective cleansing compositions |
| US7157414B2 (en) * | 2003-08-28 | 2007-01-02 | J&J Consumer Companies, Inc. | Methods of reducing irritation in personal care compositions |
| US20050075256A1 (en) * | 2003-08-28 | 2005-04-07 | Joseph Librizzi | Methods of reducing irritation associated with personal care compositions |
| AU2004270669A1 (en) | 2003-08-28 | 2005-03-17 | Irina Ganopolsky | Methods of reducing irritation in personal care compositions |
| US20050070452A1 (en) * | 2003-08-28 | 2005-03-31 | Joseph Librizzi | Methods of reducing irritation in personal care compositions |
| WO2006121806A1 (en) * | 2005-05-10 | 2006-11-16 | Johnson & Johnson Consumer Companies, Inc. | Low-irritation compositions and methods of making the same |
| US7446088B2 (en) | 2006-05-05 | 2008-11-04 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising low-DP polymerized surfactants and methods of use thereof |
| US7446087B2 (en) | 2006-05-05 | 2008-11-04 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising low-DP polymerized surfactants and methods of use thereof |
| US7803403B2 (en) * | 2006-11-09 | 2010-09-28 | Johnson & Johnson Consumer Companies, Inc. | Low-irritation compositions and methods of making the same |
| US8623344B2 (en) | 2007-06-29 | 2014-01-07 | Mcneil-Ppc, Inc. | Structured depilatory compositions |
| US8518991B2 (en) * | 2007-06-29 | 2013-08-27 | Johnson & Johnson Consumer Companies, Inc. | Structured compositions comprising betaine |
| US7820608B2 (en) * | 2007-07-17 | 2010-10-26 | Johnson & Johnson Consumer Companies, Inc. | Methods of cleansing dyed hair |
| WO2009089496A2 (en) * | 2008-01-09 | 2009-07-16 | Reveal Sciences, Llc | Color-changing cleansing compositons and methods |
| US20090246376A1 (en) | 2008-03-28 | 2009-10-01 | Gunn Euen T | Methods and products for applying structured compositions to a substrate |
| US20090247966A1 (en) | 2008-03-28 | 2009-10-01 | Gunn Euen T | Methods and products for applying structured compositions to a substrate |
| AU2009248453A1 (en) | 2008-12-22 | 2010-07-08 | Johnson & Johnson Consumer Companies, Inc. | Dilute structured compositions comprising a branched fatty alcohol |
| US9060956B2 (en) | 2009-10-07 | 2015-06-23 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising a low-DP polymerized surfactant and a micellar thickener |
| US8399590B2 (en) * | 2009-10-07 | 2013-03-19 | Akzo Nobel Chemicals International B.V. | Superhydrophilic amphiphilic copolymers and processes for making the same |
| US11173106B2 (en) | 2009-10-07 | 2021-11-16 | Johnson & Johnson Consumer Inc. | Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener |
| US8258250B2 (en) | 2009-10-07 | 2012-09-04 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof |
| US20110081310A1 (en) * | 2009-10-07 | 2011-04-07 | Fevola Michael J | Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof |
| CN102574928B (en) | 2009-10-07 | 2015-04-08 | 阿克佐诺贝尔化学国际公司 | Superhydrophilic amphiphilic copolymers and processes for making the same |
| ES2745987T3 (en) | 2009-10-07 | 2020-03-04 | Johnson & Johnson Consumer Inc | Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof |
| US9266821B2 (en) * | 2009-10-16 | 2016-02-23 | Harcros Chemicals Inc. | Process for making fatty amides |
| US20110277796A1 (en) | 2010-05-13 | 2011-11-17 | Russel Walters | Method of cleansing skin having an impaired barrier |
| US8329626B2 (en) | 2010-06-24 | 2012-12-11 | Johnson & Johnson Consumer Companies, Inc. | Low-irritating, clear cleansing compositions with relatively low pH |
| US8329627B2 (en) | 2010-06-24 | 2012-12-11 | Johnson & Johnson Consumer Companies, Inc. | Low-irritating, clear cleansing compositions with relatively low pH |
| US8343902B2 (en) | 2010-06-24 | 2013-01-01 | Johnson & Johnson Consumer Companies, Inc. | Low-irritating, clear cleansing compositions with relatively low pH |
| US8338348B2 (en) | 2010-12-21 | 2012-12-25 | Johnson & Johnson Consumer Companies, Inc. | Skin cleansing compositions with polyglycerol esters and hydrophobically modified polymers |
| US9370478B2 (en) | 2012-11-09 | 2016-06-21 | Johnson & Johnson Consumer Inc. | Skin care compositions containing cotton and citrus-derived materials |
| US20140134217A1 (en) | 2012-11-09 | 2014-05-15 | Johnson & Johnson Consumer Companies, Inc. | Leave-on compositions containing cellulose materials |
| US20140134218A1 (en) | 2012-11-09 | 2014-05-15 | Johnson & Johnson Consumer Companies, Inc. | Rinse-off skin care compositions containing cellulosic materials |
| JP6645991B2 (en) | 2017-01-13 | 2020-02-14 | 株式会社東芝 | Moving blade noise reduction device, flying object and program |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2774786A (en) * | 1953-08-10 | 1956-12-18 | Gen Mills Inc | Phosphono-ammonium surface active agents |
| US2999069A (en) * | 1957-11-18 | 1961-09-05 | Johnson & Johnson | Detergent composition |
| US3055836A (en) * | 1957-12-24 | 1962-09-25 | Johnson & Johnson | Detergent composition |
| US3670230A (en) * | 1970-12-21 | 1972-06-13 | Ibm | Active filter capacitor for power supply switching regulators |
| US3928251A (en) * | 1972-12-11 | 1975-12-23 | Procter & Gamble | Mild shampoo compositions |
| FR2363627A2 (en) * | 1973-04-09 | 1978-03-31 | Gaf Corp | Quaternised, phosphated, alkoxylated fatty amine surfactants - which are biodegradable and useful e.g. as cleaning agents and emulsifiers |
| US3950417A (en) * | 1975-02-28 | 1976-04-13 | Johnson & Johnson | High-lathering non-irritating detergent compositions |
| JPS5334716A (en) * | 1976-09-10 | 1978-03-31 | Lion Corp | Preparation of amide amine amphoteric surface active agent |
-
1978
- 1978-11-30 US US05/965,463 patent/US4233192A/en not_active Expired - Lifetime
-
1979
- 1979-04-26 CA CA326,453A patent/CA1131096A/en not_active Expired
- 1979-05-03 MX MX177522A patent/MX149620A/en unknown
- 1979-05-03 NZ NZ190364A patent/NZ190364A/en unknown
- 1979-05-04 NL NL7903527A patent/NL7903527A/en not_active Application Discontinuation
- 1979-05-04 FR FR7911366A patent/FR2442884A1/en active Granted
- 1979-05-04 CH CH4223/79A patent/CH654325A5/en not_active IP Right Cessation
- 1979-05-04 AT AT0335779A patent/AT376451B/en not_active IP Right Cessation
- 1979-05-04 BR BR7902727A patent/BR7902727A/en unknown
- 1979-05-04 PT PT69575A patent/PT69575A/en unknown
- 1979-05-04 GR GR59020A patent/GR69968B/el unknown
- 1979-05-04 GB GB7915708A patent/GB2035362B/en not_active Expired
- 1979-05-04 BE BE0/195009A patent/BE876057A/en not_active IP Right Cessation
- 1979-05-04 JP JP5411779A patent/JPS5575497A/en active Granted
- 1979-05-04 ZA ZA792158A patent/ZA792158B/en unknown
- 1979-05-07 PH PH22457A patent/PH15903A/en unknown
- 1979-05-07 IT IT48957/79A patent/IT1116830B/en active
- 1979-05-11 AU AU46935/79A patent/AU528549B2/en not_active Expired
- 1979-08-08 IE IE882/79A patent/IE48108B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NZ190364A (en) | 1981-05-29 |
| BR7902727A (en) | 1980-10-07 |
| AT376451B (en) | 1984-11-26 |
| JPS5575497A (en) | 1980-06-06 |
| IE790882L (en) | 1980-05-30 |
| GR69968B (en) | 1982-07-22 |
| FR2442884B1 (en) | 1984-11-23 |
| NL7903527A (en) | 1980-06-03 |
| JPH0112800B2 (en) | 1989-03-02 |
| IE48108B1 (en) | 1984-10-03 |
| ZA792158B (en) | 1980-12-31 |
| AU4693579A (en) | 1980-06-05 |
| PH15903A (en) | 1983-04-15 |
| ATA335779A (en) | 1984-04-15 |
| IT1116830B (en) | 1986-02-10 |
| PT69575A (en) | 1979-06-01 |
| GB2035362B (en) | 1983-01-19 |
| GB2035362A (en) | 1980-06-18 |
| BE876057A (en) | 1979-11-05 |
| US4233192A (en) | 1980-11-11 |
| FR2442884A1 (en) | 1980-06-27 |
| CH654325A5 (en) | 1986-02-14 |
| AU528549B2 (en) | 1983-05-05 |
| MX149620A (en) | 1983-12-02 |
| IT7948957A0 (en) | 1979-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1131096A (en) | Detergent compositions | |
| US4372869A (en) | Detergent compositions | |
| CA1183147A (en) | Detergent compounds and compositions | |
| US4110263A (en) | Mild cleansing compositions containing alkyleneoxylated bisquaternary ammonium compounds | |
| US4181634A (en) | Mild cleansing compositions comprising an alkyleneoxylated bisquaternary ammonium compound and an anionic or amphoteric detergent such as a phosphobetaine | |
| US4186113A (en) | Low irritating detergent compositions | |
| US6329353B1 (en) | Clear personal care formulations containing quaternary ammonium compounds and other nitrogen-containing compounds | |
| US7578995B2 (en) | Pearlizer concentrate and its use in personal care compositions | |
| US4265782A (en) | Detergent composition | |
| JPH07509740A (en) | foaming detergent mixture | |
| CA1112536A (en) | Detergent compositions | |
| US4511513A (en) | Detergent compounds and compositions | |
| FI80013B (en) | TVAETTMEDELSFOERENINGAR OCH - KOMPOSITIONER. | |
| FI67723C (en) | TVAETTMEDELKOMPOSITION INNEHAOLLANDE AMPHOTERISKT FETTSYRAKOMPLEX | |
| JPH08501101A (en) | Mild and virtually colorless shampoo composition | |
| USRE30641E (en) | Low irritating detergent compositions | |
| US5075042A (en) | Surfactant blend containing an alkyl poly(ethyleneoxy)sulfonate to reduce dermal irritation | |
| US20030064083A1 (en) | Substantive hydrophobic cationic UV-absorbing compounds | |
| JPH03275800A (en) | Detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |