CA1164470A - Tertiary amine salts of long-chain acids compositions and methods utilizing the same - Google Patents
Tertiary amine salts of long-chain acids compositions and methods utilizing the sameInfo
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- CA1164470A CA1164470A CA000344156A CA344156A CA1164470A CA 1164470 A CA1164470 A CA 1164470A CA 000344156 A CA000344156 A CA 000344156A CA 344156 A CA344156 A CA 344156A CA 1164470 A CA1164470 A CA 1164470A
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Abstract
ABSTRACT OF THE DISCLOSURE
Compositions obtained by reacting a tertiary amine hav-ing at least one long-chain group with d long-chain acid are dis-closed. The compositions are useful in non-irritating skin or hair-contacting compositions, such as shaving creams, hair condi-tioners, skin conditioners, and aftershave. The compositions are also useful in non-irritating soap and dishwashing compositions.
The compositions provide a combination of properties such as long-lasting slip, lubrication, emolliency. softening, and condi-tioning.
Compositions obtained by reacting a tertiary amine hav-ing at least one long-chain group with d long-chain acid are dis-closed. The compositions are useful in non-irritating skin or hair-contacting compositions, such as shaving creams, hair condi-tioners, skin conditioners, and aftershave. The compositions are also useful in non-irritating soap and dishwashing compositions.
The compositions provide a combination of properties such as long-lasting slip, lubrication, emolliency. softening, and condi-tioning.
Description
;
4fl7 ~ BACKGROUND OF THE INVENTION
., .
This invention re?at~s t~ the s~smetic, toiletry, hand soap, detergent and fabric softening area. More particularly, this invention relates to additives for use in cosmetic, toiletry hand soap, detergent and fabric softening formulations.
: SUMMARY OF THE INVENTION
! .
j It has been surprisingly discovered that tertiary amine ''I salts of the formula 1 > ~ ~ l wherein R1 is selected from the group consisting of saturated ` and unsaturated aliphatic groups containing from about 8 to about 1' 0 0 22 carbon atoms, RCNHCH2CH2CH2-, RlONHCH2CH2-, RN(CH3)CH2CH2CH2-, ` ;l RN(cH2cH~o)l-5Hc~2cH2cH2-~ RCOCH2CH2-, CH30[CH2CH(C~13)]l_~jCH2CH2 .l 2 3) 2]3-8~ H[O(CH3)CHCH3]3 80Ctl2CH2-, RCHOHCH -f I IR 5 ROCH2CH2CH2-, (HOCI~CH2)2NCH2CH2CH2-, H[ocH(cH3)cH2]~ H[OCH2CH2]y\
! , / N(CH2)3-, and ,~. / ( 2)3 ~, H[ocH(cH3)cH2~x H[ 2 2]x 1~ R3 is selected from the group consisting of aliphatic groups
4fl7 ~ BACKGROUND OF THE INVENTION
., .
This invention re?at~s t~ the s~smetic, toiletry, hand soap, detergent and fabric softening area. More particularly, this invention relates to additives for use in cosmetic, toiletry hand soap, detergent and fabric softening formulations.
: SUMMARY OF THE INVENTION
! .
j It has been surprisingly discovered that tertiary amine ''I salts of the formula 1 > ~ ~ l wherein R1 is selected from the group consisting of saturated ` and unsaturated aliphatic groups containing from about 8 to about 1' 0 0 22 carbon atoms, RCNHCH2CH2CH2-, RlONHCH2CH2-, RN(CH3)CH2CH2CH2-, ` ;l RN(cH2cH~o)l-5Hc~2cH2cH2-~ RCOCH2CH2-, CH30[CH2CH(C~13)]l_~jCH2CH2 .l 2 3) 2]3-8~ H[O(CH3)CHCH3]3 80Ctl2CH2-, RCHOHCH -f I IR 5 ROCH2CH2CH2-, (HOCI~CH2)2NCH2CH2CH2-, H[ocH(cH3)cH2]~ H[OCH2CH2]y\
! , / N(CH2)3-, and ,~. / ( 2)3 ~, H[ocH(cH3)cH2~x H[ 2 2]x 1~ R3 is selected from the group consisting of aliphatic groups
2~ containing from one to about two carbon atoms, H[O(CH3)CHCH2]1 15 and H(OCH2CH2)1_15, R2 is selected from the group consisting of I, satùrated and unsaturated aliphatic groups containing from about 3 Il O O
li 11 11 f¦ to about 22 carbon atoms, RCNHCH2CH2CH2-, RCONHCH2CH2-, Il .
~' ~
I ~6~7~
R(OCH CH CH ) N(C~3)CH2C~I2CH2-, R(CH2C~2C 2)z ( 2 2 1 5 . O
CH -, RC0C~I2CH2-~ CH3o[cH2cH(c~33o]l-scH2cH?cH2 ' H[0(CH3)CHCH2]3_8, H[O(CI13)C~-ICH2]3 8 OCH2CH2-, RCHOHCH2-, R0CH2rH2 CH2-, aliphatic groups containing from one to about two carbon atoms and H[0(CH3)CHcH2]r_l5 H(ocH2c~2)~-l5~ 4 ,ifrom O
the group consisting of R-C-0-, RCH=CH2S03-, RCONHCH(CH3)C02-,
li 11 11 f¦ to about 22 carbon atoms, RCNHCH2CH2CH2-, RCONHCH2CH2-, Il .
~' ~
I ~6~7~
R(OCH CH CH ) N(C~3)CH2C~I2CH2-, R(CH2C~2C 2)z ( 2 2 1 5 . O
CH -, RC0C~I2CH2-~ CH3o[cH2cH(c~33o]l-scH2cH?cH2 ' H[0(CH3)CHCH2]3_8, H[O(CI13)C~-ICH2]3 8 OCH2CH2-, RCHOHCH2-, R0CH2rH2 CH2-, aliphatic groups containing from one to about two carbon atoms and H[0(CH3)CHcH2]r_l5 H(ocH2c~2)~-l5~ 4 ,ifrom O
the group consisting of R-C-0-, RCH=CH2S03-, RCONHCH(CH3)C02-,
3 , RC6H5S3 , R[CH2CH2]1-10CH2C2-~ RNHCOCH=CHC02-' isostearic acid residue, ricinoleic acid residue, hydroxystearic acid residue, phen~lstearic acid residue and residues of di-basic acids containing from about 6 to about 36 carbon atoms, wherein in all instances R represents a saturated or unsaturated aliphatic ' group containing from about 8 to about 18 carbon atoms, R5 is an ;aliphatic group containing from about 8 to about 22 carbon atoms, x and y are integers from l to 9, the sum of x + y is an integer from 2 to 10, and z is 0 or 1 are useful as additives in cosmetic, toiletry soap, detergent, and fabric softening formulations.
l' The foregoing is especially surprising in view of the fact that tertiary amines are in general considered to be primary skin irritants. The tertiary amine salts of the present inven-tion, however, when utilized at the recommended levels, are not ,1~ ,.
primary'skin irritants. As far as is presently known, the only ~5 !~ somewhat similar types of salt which have been suggested in the art are the propionate, lactate, and tartrate salts of a tertiary O
,amine of the formula R C NH(CH2)3N(CII3)2 which have been ' suggested for use in applications such as hair shampoos. As far as ;s known such usage has never been developed cominercially.
~ , .
I' -2-!
~ ~8~
;, .
As the compositions useful in the present invention may be derived from the reaction of less than stoichiometric ratios of the tertiary amine and the acid, the compositions may be ~described as the product formed by reacting a tertiary amine of the formula:
~N
with an acid of the formula:
wherein Rl, R2, R3, and R4 have the meanings defined above, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
, The composition which is useful in providing the desired characteristics may be described as the product formed by mixing water, a tertiary amine of the formula:
!l IRl -~ R2 R3 and an acid of the formula:
wherein Rl, R2, R3, and R4 have the meanings defined above, in a molar ratio of amine:acid from about 0.3:1 to about '3.3:1. ~
The present invention thus provides non-irritating skin or hair-contacting formulations comprising a tertiary amine salt as defined above. The non-irritating skin or hair contacting formulations may also comprise the reaction product formed from the tertiary amine and the acid as described hereinabove, and/or may comprise the product formed by mixing water with the tertiary Iliamine and the acid.
I;
i ; -3-1 ~64.47~
DETAILED DESCRIPTIO~I OF TilE PREFERRED EMBODI~1ENTS
As indicated, the present invention provides unique add-itives which are useful in many application areas. The composi-"tions of the present invention may be used in a wide array of ~ applications and numerous skin and hair preparations in the cosmetic and toiletry industry. For example, the compositions may be used in aftershave lotion to provide long-lasting emolliency, in pre-electric shave lotion for reduction of friction, in shaving ' creams for lubrication and emollient'after feel, in bath oil for 'emolliency and softening of the skin, in after-bath products, in hair preparations as a sheening agent, in sunscreen preparations as a skin conditioner or potential substantlve agent, in hair formulations as a softener and conditioner, and skin and hand . . ~
' preparations as an emollient, lubricant, or protective film former, in shampoo as a conditioner and the like. The foregoing ;'are merely illustrative of the potential applications of the compositions of the present i,nvention in the area of skin and hair-contacting agents, and they are not meant as limitation on the scope of the present invention.
~l The use of salts and compositions of the present inven-;lkion and the foregoing formulations utilize the physical attri-',butes of the present salts and compositions with respect to slip, ,~,lubrication, conditioning, emolliency, and softening properties.
' Many o~ the salts and compositions of the present invention also ''possess other physical characteristics which are desirable, such as dispersabil'ity in water and broad solubility or dispersability in mineral oil, amides, esters, alcohols, glycols, natural oils, and the like.
Il The salts and compositions of the present invention may ,be prepared by any of the known methods of preparing amine salts ,,of fatty acids. A simple method is to simply mix the fatty acid _ ~ _ 1 ~4~7~11 and the amine. If stoichiometric ratios are utilized, the product will be the simple amine salt formed from the tertiary amine and the acid or, in the presence of water its hydrolvsate~
As indicated, it is possible to prepare useful products employing molar ratios of amine:acid from about 0.3:1 to about 3.3:l. Thus, ratios less that 1:1, as from about 0.3:1 to about 0.99:1 may be employed, as well as greater than one, as from about 1.01:1 to about 3.3:1.
If other than stoichiometric ratios are utilized, the product will be the aforementioned amine salt or, in the presence of ~later, its hydrolysate, in combination with the excess tertiary amine or excess acid. It is believed that the most beneficial results are achieved with the present invention when water is present, possibly resulting in some undefined complexing with water. It is not known whether the reaction product exists as a simple mixture of the tertiary amine salt or hydrolysate with the unreacted tertiary amine or ~nreacted acid, or in some undefined complex. In any event, it appedrs that even when other than stoichiometric ratios are employed, the resulting composition is non-irritating at the recommended levels of usage. For sa~e of simplicity the products of the present invention will simply be ~referred to by means of their process of manufdcture, the reactioll of the tertiary amine with the acid, optionally in the presence of water.
~ Generally, the amount of acid which is utilized is pre-ferably greater when tertiary amines which are highly basic are ~utilized, and preferably less when tertiary amines having less basic properties are employed. Also, dS the strength of the various acids vary considerably, one should understand that with ,1 .:
47~ 1 1, , stronger acids it is typically perferred to utilized less acid ¦ -than when employing a weaker acid.
As indicated, the tertiary amine salts, and/or the reac-tion products obtained from the tertiary amines and acids, and 'their hydrolysates may be incorporated into customary shaving co--positions, conventional hair and skin-contacting preparations, a d 'the like. Such skin and hair-contacting compositions include ,lcompositions such as those described in "Cosmetics Science and I,Technology", edited by Edward Sagarin, Interscience Publishers, lO i Inc., New York (1972 and 1974).
I Likewise, the aforementioned salts and reaction produc's ! may be utilized in dishwashing formulations as well as soap form~-lations, such as soap bars.
Il When the salts and reaction products of the present invention are utilized in the foregoing manner, incorporation into skin or hair-contacting preparations, dishwashing formulations, cr soaps, it is preferable to utilize the salts or reaction products of the present invention in an amount up to about 5X, by weight, Iof the total formulation. Preferably, an amount about equal to or 20 ,iless than 2%'is utilized, such as from about 0.1 to about 2.0~, b~
weight. Typically, the salt or reaction product will be utilized in an amount of about 1%, by weight, based on the total weight of ,iformulation.
', Of the possible tertiary amine salts useful in the prac-tice of the present invention, the following are included:
dimethyllaurylamine oleate, dimethyllaurylamine stearate, dimeth-I ylpalmitylamine oleate, diethyllaurylamine oleate, dimethylpal-llmitylamjne stearate, polyoxyethylene(15)tallowamine oleate, I bis(2-hydroxyethyl)tallowamine oleate, N,N-dimethylcocoamine 30 i'isostearate, and N,N-dimethyloctadecylamine oleate.
1, .
I lB~i70 Useful fabric conditioning compositions result from a reaction of the defined acids with tertiary amines such as methyl-~di~ocoamîn~ ann Illethyidi-hydrogenateuiallowdmine.
For use in the area of dandruff control, tertiary amine salts of the defined formula may be reacted with undecylenic acid.
In general, the preferred compositions of the present invention will be derived from tertiary amines of the defined formula wherein R1 is a sa-turated or unsaturated aliphatic group containing from about 8 to about 22 carbon atoms, and R2 and R3 are selected from the group consisting of methyl, ethyl, H[O(CH3)CH CH2]1_1s and H(OCH2CH2)1_1s, and R4 is a saturated or unsaturated aliphatic carboxylic acid group containing from about ' 8 to about 22 carbon atoms. Typically R2 and R3 will be methyl.
Il In some instances it may be desirable to employ dibasic 1. . .
acids containing froln about 6 to about 36 carbon atoms. Exemplary ,of such acids are the dimer acids from Emery, such as Empol 1016 Iwhich has the general formula H02C[C34H62]C02H, Westvaco Diacid ,l1550 which has the general formula H02C[C1gH34]C02H, and the typically available dibasic acids having the formula H02C(CH2~bC02 H, wherein b is from about 4 to about 20. One may refer to U.S.
Patent No. 2,664,429 and J. C. CowanJ~J. Am. Oil Chem. Soc., Vol.
',39, p. 534 et seq (1962) which are incorporated herein by refer-'ence, with respect to available types of dimer acids. Also onemay refer to U.S. Patent No~ 3,734,859, which is also incorporated ~herein by reference, which indicates that the Westvaco type of ~dimer acid is a mixture of 5-carboxy-4-hexyl-2-cyclohexene-1-octa-j~decanoic acid and Ç-carboxy-4-hexyl-2-cyclohexene-1-octadecanoic ~acid.
~I -7-~ 164d7n As previously indicated, the use~ul tertiary amines include diamine structures such as N,N',N'-trimethyl-N'alkylpro-panediamine. Thus, if the aforementioned dimer acids are reacted with appropriate diamines, it is possible that the resultant product may be polymeric. Other diamines which may be reacted with dimer acids to possibly produce polymeric products include j diamines of the structure , (HOCHCH2)2NCH2CH2cH2N(cH3)2 10 H~ocH(cH3)cH2~
N(cH2)3N(cH3)2~ or H[OCH(CH3)CH2]X
, H[OCH2CH2]~
N(CH2)3N(CH3)2 H[OCH2CH2]x where x and y are integers from 1 to 9 and the sum of x + y is from 2 to about 10, and R5 is an aliphatic group containing fror ¦ about 8 to about 22 carbon atoms.
I¦ The scope of tile present invention will be further 20 ,' illustrated by the following non-limiting examples.
' 47~
Example 1 - Dimethyllaurylamine Oleate 2,650 grams of dimethyllaurylamine, 4,450 grams of oleic acid~ 5 qrams of Ionol ar,~ 25 grams of hypophosphorous acid are reacted at a temperature not exceeding 125~C and high vacuum was 5 1 utilized to remove any volatiles. The resulting product was with-in the scope of the present invention and this procedure repre-sents the preferred process for making the salts and compositions of the present invention. The Ionol (ditertiarybutyl-para-cresol) Il and hypophosphorous acid are utilized to retard rancidification 10 ' and to bleach the reaction product.
Example 2 - Pre-shave Lotion Parts Dimethyllaurylamine oleate 0.5 Diisopropyl adipate 10.0 Ethanol 60.0 Boric acid 1.0 Perfume 0.5 Distilled water 28.0 ~l TOTAL 100.0 The lotion is applied to the bearded area of the face and allowed to dry before shaving with an electric razor. The result is an even, close shave with no pulling or nicking. The face is smooth and soft to the touch .
'I
~I _9 . .
~ ~6~?0 Example 3 - Bath Oil Parts ! Dimet~llaur~l.mine ^leatc '~ Isopropyl palmitate 45 Light mineral oil 45 . Sorbitan sesquioleate 5 .' Perfume 4 ¦I TOTAL 100 ' The bath oil provides a silky smooth feel to the skin.
Example 4 - Aerosol Shaving Cream Parts Dimethyllaurylamine oleate 1.5 ,i ...
Potassium stea~ate 5.0 Sodium stearate 1.0 15 . Mineral oil 20.0 ,I Stearic acid . 0.2 I Coconut fatty acid 0~7 ; Glycerine 3.0 Il Polyvinyl pyrrolidene 0.1 20 ,I Perfume 0.5 Water 58.0 Propellant (dichlorodifluoromethane) 10.0 . ~ TOTAL 100.0 l~ The shaving cream has excellent lathering properties and Ithe shave is smooth and close with minimal razor drag. The facial skin feels soft and velvety after shaving.
,, !l 1 ~6447~
.
Example 5 - Shampoo Parts Dimethyllaurylamine oleate 1.0 Sodium lauryl sulfate 7.0 Diethanollauramide 3.0 Triethanolamine salt of the monoester of succinic acid and coconut monoethanolamide 3.0 Water 86.0 TOTAL 100.0 Lathering and cleansing properties are excellent and the hair is left soft and shining.
Example 6 - Hand Lotion Parts Dimethyllaurylamine stearate 1.5 Mineral oil, light 70/80 15.5 Sorbitan oleate 5.5 Stearyl alcohol 2.5 Polyethyleneglycol 2000 monostearate 4.5 Methyl paraben 0.1 Propyl paraben 0.04 Deionized water q.s. 100 Hands treated with the lotion are soft, smooth and non-greasy.
7n Example 7 - After-shave Lotion Parts Dimethylpalrnitylamine oleate 3.0 Isopropyl alcohol 72.0 Glycerol p-amino benzoate 3.0 Water 22.0 TOTAL100.0 Splashing lotion on the face after a shave provides a refreshing feeling and a smooth, soft complexion.
Example 8 - Skin Cream PartS
Dimethyllaurylamine oleate 2.0 Diethanolstearamide 3.0 Stearic acid 2.0 Light mineral oil 5.0 Water 88.0 TOTAL100.0 The cream provides a soft, velvety talc feel to the skin.
Example 9` - Hair Dressing Parts Dimethylpalmitylamine stearate3.0 UconTM LB-385 (polyalkyleneglycol polymer) 97.0 TOTAL 100.0 Treatment of hair with the dressing results in soft hair.
., ~. ~ .
1 16447(~ , Example 10 - Liquid Lotion Hand Cleaner Parts Ethyleneglycolmonostearate 0.5 Natrosol~250HR 0.3 Triethanolaminelaurylsulfate (40%) 14.0 Stepanol WA Paste 14.0 Ninol 2012 Extra 2.0 , Methylparaben 0.1Polysorbate 80 2.0 Dimethyllaurylamine oleate 2.0 Perfume, color, water q.s. 100 Example 11 - Bar Soap Parts Dimethyllaurylamine oleate 2.0 Triethanolaminedodecyl sulfate 40.0 Coconut oil fatty acids 10.0 Soap of mixed tallow/coconut oil (80/20) 43.0 . Water 5.0 TOTAL 100.0 20 !! This bar soap exhibits excellent lathering and leaves hands soft and smooth.
,, ~
.
, ~ 1~4~7~
The compositions in Examples 12-18 are prepared as described:
Example 12 - Moisturizing Cream Parts Phase A
; Veegum (Complex colloidal magnesium aluminum silicate) 1~50 Water 72.80 Methyl paraben 0.10 Glycerine 4a 00 Trithanolamine 1.00 Phase B
Dimethyllaurylamine oleate 1.00 Lanolin oil 10.00 Stearic Acid, Triple-pressed 2.00 Isopropyl myristate 2.00 ~; Glycerol monostearate, S.E., Acid Stable 3.00 Cetyl alcohol 2.00 Il Propyl paraben 0.05 Perfume 0.55 TOTAL IOO.OO
In preparation of Phase A, Veegum is added to water, mixed for ten minutes and heated until the temperature reaches about 50C at which time the remaining ingredients of Phase A are added. The mixture is further heated to about 70C.
Phase B is mixed in a separate container and heated to about 75C. Phase B is then added to Phase A at about 70C.
After cooling to about 35C with slow agitation, the perfume is ,added.
, The cream is especially useful for making dried skin soft and smoottl without leaving a greasy feeling.
l' The foregoing is especially surprising in view of the fact that tertiary amines are in general considered to be primary skin irritants. The tertiary amine salts of the present inven-tion, however, when utilized at the recommended levels, are not ,1~ ,.
primary'skin irritants. As far as is presently known, the only ~5 !~ somewhat similar types of salt which have been suggested in the art are the propionate, lactate, and tartrate salts of a tertiary O
,amine of the formula R C NH(CH2)3N(CII3)2 which have been ' suggested for use in applications such as hair shampoos. As far as ;s known such usage has never been developed cominercially.
~ , .
I' -2-!
~ ~8~
;, .
As the compositions useful in the present invention may be derived from the reaction of less than stoichiometric ratios of the tertiary amine and the acid, the compositions may be ~described as the product formed by reacting a tertiary amine of the formula:
~N
with an acid of the formula:
wherein Rl, R2, R3, and R4 have the meanings defined above, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
, The composition which is useful in providing the desired characteristics may be described as the product formed by mixing water, a tertiary amine of the formula:
!l IRl -~ R2 R3 and an acid of the formula:
wherein Rl, R2, R3, and R4 have the meanings defined above, in a molar ratio of amine:acid from about 0.3:1 to about '3.3:1. ~
The present invention thus provides non-irritating skin or hair-contacting formulations comprising a tertiary amine salt as defined above. The non-irritating skin or hair contacting formulations may also comprise the reaction product formed from the tertiary amine and the acid as described hereinabove, and/or may comprise the product formed by mixing water with the tertiary Iliamine and the acid.
I;
i ; -3-1 ~64.47~
DETAILED DESCRIPTIO~I OF TilE PREFERRED EMBODI~1ENTS
As indicated, the present invention provides unique add-itives which are useful in many application areas. The composi-"tions of the present invention may be used in a wide array of ~ applications and numerous skin and hair preparations in the cosmetic and toiletry industry. For example, the compositions may be used in aftershave lotion to provide long-lasting emolliency, in pre-electric shave lotion for reduction of friction, in shaving ' creams for lubrication and emollient'after feel, in bath oil for 'emolliency and softening of the skin, in after-bath products, in hair preparations as a sheening agent, in sunscreen preparations as a skin conditioner or potential substantlve agent, in hair formulations as a softener and conditioner, and skin and hand . . ~
' preparations as an emollient, lubricant, or protective film former, in shampoo as a conditioner and the like. The foregoing ;'are merely illustrative of the potential applications of the compositions of the present i,nvention in the area of skin and hair-contacting agents, and they are not meant as limitation on the scope of the present invention.
~l The use of salts and compositions of the present inven-;lkion and the foregoing formulations utilize the physical attri-',butes of the present salts and compositions with respect to slip, ,~,lubrication, conditioning, emolliency, and softening properties.
' Many o~ the salts and compositions of the present invention also ''possess other physical characteristics which are desirable, such as dispersabil'ity in water and broad solubility or dispersability in mineral oil, amides, esters, alcohols, glycols, natural oils, and the like.
Il The salts and compositions of the present invention may ,be prepared by any of the known methods of preparing amine salts ,,of fatty acids. A simple method is to simply mix the fatty acid _ ~ _ 1 ~4~7~11 and the amine. If stoichiometric ratios are utilized, the product will be the simple amine salt formed from the tertiary amine and the acid or, in the presence of water its hydrolvsate~
As indicated, it is possible to prepare useful products employing molar ratios of amine:acid from about 0.3:1 to about 3.3:l. Thus, ratios less that 1:1, as from about 0.3:1 to about 0.99:1 may be employed, as well as greater than one, as from about 1.01:1 to about 3.3:1.
If other than stoichiometric ratios are utilized, the product will be the aforementioned amine salt or, in the presence of ~later, its hydrolysate, in combination with the excess tertiary amine or excess acid. It is believed that the most beneficial results are achieved with the present invention when water is present, possibly resulting in some undefined complexing with water. It is not known whether the reaction product exists as a simple mixture of the tertiary amine salt or hydrolysate with the unreacted tertiary amine or ~nreacted acid, or in some undefined complex. In any event, it appedrs that even when other than stoichiometric ratios are employed, the resulting composition is non-irritating at the recommended levels of usage. For sa~e of simplicity the products of the present invention will simply be ~referred to by means of their process of manufdcture, the reactioll of the tertiary amine with the acid, optionally in the presence of water.
~ Generally, the amount of acid which is utilized is pre-ferably greater when tertiary amines which are highly basic are ~utilized, and preferably less when tertiary amines having less basic properties are employed. Also, dS the strength of the various acids vary considerably, one should understand that with ,1 .:
47~ 1 1, , stronger acids it is typically perferred to utilized less acid ¦ -than when employing a weaker acid.
As indicated, the tertiary amine salts, and/or the reac-tion products obtained from the tertiary amines and acids, and 'their hydrolysates may be incorporated into customary shaving co--positions, conventional hair and skin-contacting preparations, a d 'the like. Such skin and hair-contacting compositions include ,lcompositions such as those described in "Cosmetics Science and I,Technology", edited by Edward Sagarin, Interscience Publishers, lO i Inc., New York (1972 and 1974).
I Likewise, the aforementioned salts and reaction produc's ! may be utilized in dishwashing formulations as well as soap form~-lations, such as soap bars.
Il When the salts and reaction products of the present invention are utilized in the foregoing manner, incorporation into skin or hair-contacting preparations, dishwashing formulations, cr soaps, it is preferable to utilize the salts or reaction products of the present invention in an amount up to about 5X, by weight, Iof the total formulation. Preferably, an amount about equal to or 20 ,iless than 2%'is utilized, such as from about 0.1 to about 2.0~, b~
weight. Typically, the salt or reaction product will be utilized in an amount of about 1%, by weight, based on the total weight of ,iformulation.
', Of the possible tertiary amine salts useful in the prac-tice of the present invention, the following are included:
dimethyllaurylamine oleate, dimethyllaurylamine stearate, dimeth-I ylpalmitylamine oleate, diethyllaurylamine oleate, dimethylpal-llmitylamjne stearate, polyoxyethylene(15)tallowamine oleate, I bis(2-hydroxyethyl)tallowamine oleate, N,N-dimethylcocoamine 30 i'isostearate, and N,N-dimethyloctadecylamine oleate.
1, .
I lB~i70 Useful fabric conditioning compositions result from a reaction of the defined acids with tertiary amines such as methyl-~di~ocoamîn~ ann Illethyidi-hydrogenateuiallowdmine.
For use in the area of dandruff control, tertiary amine salts of the defined formula may be reacted with undecylenic acid.
In general, the preferred compositions of the present invention will be derived from tertiary amines of the defined formula wherein R1 is a sa-turated or unsaturated aliphatic group containing from about 8 to about 22 carbon atoms, and R2 and R3 are selected from the group consisting of methyl, ethyl, H[O(CH3)CH CH2]1_1s and H(OCH2CH2)1_1s, and R4 is a saturated or unsaturated aliphatic carboxylic acid group containing from about ' 8 to about 22 carbon atoms. Typically R2 and R3 will be methyl.
Il In some instances it may be desirable to employ dibasic 1. . .
acids containing froln about 6 to about 36 carbon atoms. Exemplary ,of such acids are the dimer acids from Emery, such as Empol 1016 Iwhich has the general formula H02C[C34H62]C02H, Westvaco Diacid ,l1550 which has the general formula H02C[C1gH34]C02H, and the typically available dibasic acids having the formula H02C(CH2~bC02 H, wherein b is from about 4 to about 20. One may refer to U.S.
Patent No. 2,664,429 and J. C. CowanJ~J. Am. Oil Chem. Soc., Vol.
',39, p. 534 et seq (1962) which are incorporated herein by refer-'ence, with respect to available types of dimer acids. Also onemay refer to U.S. Patent No~ 3,734,859, which is also incorporated ~herein by reference, which indicates that the Westvaco type of ~dimer acid is a mixture of 5-carboxy-4-hexyl-2-cyclohexene-1-octa-j~decanoic acid and Ç-carboxy-4-hexyl-2-cyclohexene-1-octadecanoic ~acid.
~I -7-~ 164d7n As previously indicated, the use~ul tertiary amines include diamine structures such as N,N',N'-trimethyl-N'alkylpro-panediamine. Thus, if the aforementioned dimer acids are reacted with appropriate diamines, it is possible that the resultant product may be polymeric. Other diamines which may be reacted with dimer acids to possibly produce polymeric products include j diamines of the structure , (HOCHCH2)2NCH2CH2cH2N(cH3)2 10 H~ocH(cH3)cH2~
N(cH2)3N(cH3)2~ or H[OCH(CH3)CH2]X
, H[OCH2CH2]~
N(CH2)3N(CH3)2 H[OCH2CH2]x where x and y are integers from 1 to 9 and the sum of x + y is from 2 to about 10, and R5 is an aliphatic group containing fror ¦ about 8 to about 22 carbon atoms.
I¦ The scope of tile present invention will be further 20 ,' illustrated by the following non-limiting examples.
' 47~
Example 1 - Dimethyllaurylamine Oleate 2,650 grams of dimethyllaurylamine, 4,450 grams of oleic acid~ 5 qrams of Ionol ar,~ 25 grams of hypophosphorous acid are reacted at a temperature not exceeding 125~C and high vacuum was 5 1 utilized to remove any volatiles. The resulting product was with-in the scope of the present invention and this procedure repre-sents the preferred process for making the salts and compositions of the present invention. The Ionol (ditertiarybutyl-para-cresol) Il and hypophosphorous acid are utilized to retard rancidification 10 ' and to bleach the reaction product.
Example 2 - Pre-shave Lotion Parts Dimethyllaurylamine oleate 0.5 Diisopropyl adipate 10.0 Ethanol 60.0 Boric acid 1.0 Perfume 0.5 Distilled water 28.0 ~l TOTAL 100.0 The lotion is applied to the bearded area of the face and allowed to dry before shaving with an electric razor. The result is an even, close shave with no pulling or nicking. The face is smooth and soft to the touch .
'I
~I _9 . .
~ ~6~?0 Example 3 - Bath Oil Parts ! Dimet~llaur~l.mine ^leatc '~ Isopropyl palmitate 45 Light mineral oil 45 . Sorbitan sesquioleate 5 .' Perfume 4 ¦I TOTAL 100 ' The bath oil provides a silky smooth feel to the skin.
Example 4 - Aerosol Shaving Cream Parts Dimethyllaurylamine oleate 1.5 ,i ...
Potassium stea~ate 5.0 Sodium stearate 1.0 15 . Mineral oil 20.0 ,I Stearic acid . 0.2 I Coconut fatty acid 0~7 ; Glycerine 3.0 Il Polyvinyl pyrrolidene 0.1 20 ,I Perfume 0.5 Water 58.0 Propellant (dichlorodifluoromethane) 10.0 . ~ TOTAL 100.0 l~ The shaving cream has excellent lathering properties and Ithe shave is smooth and close with minimal razor drag. The facial skin feels soft and velvety after shaving.
,, !l 1 ~6447~
.
Example 5 - Shampoo Parts Dimethyllaurylamine oleate 1.0 Sodium lauryl sulfate 7.0 Diethanollauramide 3.0 Triethanolamine salt of the monoester of succinic acid and coconut monoethanolamide 3.0 Water 86.0 TOTAL 100.0 Lathering and cleansing properties are excellent and the hair is left soft and shining.
Example 6 - Hand Lotion Parts Dimethyllaurylamine stearate 1.5 Mineral oil, light 70/80 15.5 Sorbitan oleate 5.5 Stearyl alcohol 2.5 Polyethyleneglycol 2000 monostearate 4.5 Methyl paraben 0.1 Propyl paraben 0.04 Deionized water q.s. 100 Hands treated with the lotion are soft, smooth and non-greasy.
7n Example 7 - After-shave Lotion Parts Dimethylpalrnitylamine oleate 3.0 Isopropyl alcohol 72.0 Glycerol p-amino benzoate 3.0 Water 22.0 TOTAL100.0 Splashing lotion on the face after a shave provides a refreshing feeling and a smooth, soft complexion.
Example 8 - Skin Cream PartS
Dimethyllaurylamine oleate 2.0 Diethanolstearamide 3.0 Stearic acid 2.0 Light mineral oil 5.0 Water 88.0 TOTAL100.0 The cream provides a soft, velvety talc feel to the skin.
Example 9` - Hair Dressing Parts Dimethylpalmitylamine stearate3.0 UconTM LB-385 (polyalkyleneglycol polymer) 97.0 TOTAL 100.0 Treatment of hair with the dressing results in soft hair.
., ~. ~ .
1 16447(~ , Example 10 - Liquid Lotion Hand Cleaner Parts Ethyleneglycolmonostearate 0.5 Natrosol~250HR 0.3 Triethanolaminelaurylsulfate (40%) 14.0 Stepanol WA Paste 14.0 Ninol 2012 Extra 2.0 , Methylparaben 0.1Polysorbate 80 2.0 Dimethyllaurylamine oleate 2.0 Perfume, color, water q.s. 100 Example 11 - Bar Soap Parts Dimethyllaurylamine oleate 2.0 Triethanolaminedodecyl sulfate 40.0 Coconut oil fatty acids 10.0 Soap of mixed tallow/coconut oil (80/20) 43.0 . Water 5.0 TOTAL 100.0 20 !! This bar soap exhibits excellent lathering and leaves hands soft and smooth.
,, ~
.
, ~ 1~4~7~
The compositions in Examples 12-18 are prepared as described:
Example 12 - Moisturizing Cream Parts Phase A
; Veegum (Complex colloidal magnesium aluminum silicate) 1~50 Water 72.80 Methyl paraben 0.10 Glycerine 4a 00 Trithanolamine 1.00 Phase B
Dimethyllaurylamine oleate 1.00 Lanolin oil 10.00 Stearic Acid, Triple-pressed 2.00 Isopropyl myristate 2.00 ~; Glycerol monostearate, S.E., Acid Stable 3.00 Cetyl alcohol 2.00 Il Propyl paraben 0.05 Perfume 0.55 TOTAL IOO.OO
In preparation of Phase A, Veegum is added to water, mixed for ten minutes and heated until the temperature reaches about 50C at which time the remaining ingredients of Phase A are added. The mixture is further heated to about 70C.
Phase B is mixed in a separate container and heated to about 75C. Phase B is then added to Phase A at about 70C.
After cooling to about 35C with slow agitation, the perfume is ,added.
, The cream is especially useful for making dried skin soft and smoottl without leaving a greasy feeling.
4~7P
E mple 13 - Bubble Bath Parts Dimethyllaurylamine oleate 2.00 Water 50.90 Methyl paraben 0.10 Standapol WAQ Special (sodium lauryl ether sulfate, 50%, low salt content~ 35.00 Foamid L (diethanollauramide) 5.00 Polyethyleneglycol 6000 distearate 2.00 Ethyleneglycol monostearate 2.00 Perfume 2.00 Color _1.00 TOTAL 100.00 Methyl paraben and Standapol WAQ Special are added to water and heated to about 70C with agitation until homo-geneity is achieved.
In a separate beaker the dimethyl lauryl amine oleate is mixed with Foamid L and the mixture heated until uniform.
This mixture is slowly added to the water phase described above.
Polyethyleneglycol 6000 distearate is added and the solution mixed until thoroughly dissolved. Ethyleneglycol monostearate is then added with mixing until dissolved.
Finally, the solution is cooled to about 25C and perfume and color are added.
~.~
7~ 1 .
Example 14 - Low pH Conditioning Shampoo i: i Parts Water 63.~5 Standapol A (sodium lauryl ether sulfate, 30%) 30-00 Foamid LM (lauric/myristic diethanolamide) 3.00 Dimethyllaurylamine oleate 1.00 Methyl paraben 0.20 Citric acid 0.15 Sodium chloride 1.00 Perfume 0.20 Color 1.00 - TOTAL 100.00 Water was heated in a jacketed vessel equipped with a variable speed agitator. Citric acid was added and the solution was heated to about 60C at which time all remaining ingredients except sodium chloride and perfume were added. The mixture was heated to about 75C and held at that temperature for about 30 minutes.
The mixture was cooled and perfume and sodium chloride were added when the temperature reached about 40C. The final product was then cooled to about 25C.
Lathering, cleansing and ri,nsing properties were l excellent even in hard water. After use, it was observed that the hair has good manageability and luster.
.
1l!
Ii -16-1 164~7P
Example 15 - Lotion ; Parts phace A
~ Water 82.20 Lactic acid 88%, (10% solution) 1.00 Methyl paraben 3.00 Glycerine 3.00 Cellosize QP-300-H (cellulose ether) 2.00 Phase B
Glycerol monostearate 3.50 Foamid 0-100 (dimethylaminopropyloleamide) 0.30 Myristyl myristate 1.00 -- 2-Ethylhexyl palmitate 2.00 Cetyl alcohol 0.50 Dimethyllaurylamine oleate 1.00 Propyl paraben 0.10 Perfume ` _ 0.40 , TOTAL 100~00 Il Water, lactic acid solution and methyl paraben are mixed 20 jand heated to about 80C making certain that all ingredients are ,dissolved. Glycerine is added and then slowly Cellosize is mixed to make Phase A.
The ingredients of Phase B are mixed and heated to 85C
, until all waxes are melted~ Phases A and B are mixed, and agita-tion is continued for 15 minutes. The solution is cooled to about ',~ 35C, perfume is added, and the final product is cooled to about i! i 25C.
lj A soft, smooth feeling and pleasing sheen are imparted i¦to skin treated with the lotion.
il ' ,.
l l I~ -17-~ 154~7n xample 16 - Floating Bath Oil PartS
Solulan PB 20 (ethoxylated lanolin) 1.00 Oleyl alcohol 5.00 AcetulanTM (acetylated lanolin) 10.00 Light mineral oil 47.50 Isopropyl palmitate 28.00 Dimethyllaurylamine oleate 3.50 Perfume 5.00 TOTAL 100.00 All of the ingredients except perfume are blended to homogeneity~ Perfume is then added and the solution mixed until uniform.
After use of the bath oil, the skin feels clean and soft to the touch.
Example 17 - Suntan Oil Parts Light mineral oil 54.60 2-Ethylhexyl palmitate 33.50 Lauryl myristate 5,00 EscalolTM 507 (p-dimethylaminoamyl benzoate)1.90 Dimethyllaurylamine oleate3.50 Perfume 1.50 TOTAL 100.00 All of the ingredients except perfume are blended to homogeneity. Perfume is added and mixing is continued until a uniform product results.
When spread over the skin 9 the formulation provides a smooth, protective film effective in screening the sun's rays and moisturizing the skin.
~ - 18 -' J l6~7n Example 18 - Instant Hair Conditioner ,1 l Parts Phase A
Glycerine 5.00 EMCOL E-607S (Quaternium 7, Witco Chemical Co., Inc., Los Angeles, Ca.; antistatic agent) 0.50 Water 81.50 Il Phase B
10 l~ Glycerol monostearate 4.00 Cetyl alcohol 0.75 Stearyl alcohol 0.75 Lanolin 1.00 , Polyethylene glycol 400 monooleate5.00 Dimethyllaurylamine oleate 1.00 Phase C
¦ Perfume . 0.20 Sodium benzoate 0.10 Il Color 0.20 20 ll TOTAL 100.00 I, All of the ingredients of Phase A are mixed and heated ¦,to 80C and in a separate vessel all of Phase B ingredients are mixed and heated to 80C. These solutions are then mixed together Il with agitation and cooled to 45C wherëupon color, perfume and sodium benzoate are added. The preparation is then allowed to !~ cool to room temperature. I
i The use of this preparation on hair results in soft lustrous hair.
I In Examples 19-26 the term "dimethyl lauryl amine oleate" is utilized to refer to the product obtained by reacting oleic acid with dimethyl lauryl amine in a ratio of about 1.25:1, in a manner similar to Exanlple 1.
I' 1.
Il -19- 1 1 ~6447() Example 19 - Hdir Conditioning Rinse A useful hair conditioning rinse is as follows:
Parts 'I Dimethyllaurylamine oleate 2.0g Polyethylene glycol 6000 distearate 4.07 Glycerin 3.0%
Formaldehyde 0.1%
Deionized water q.s. 100 Example 20 - Hair Shampoo A useful hair shampoo is as follows:
Parts Sodium lauryl polyoxyethyleneglycol ,ulfate 3040%
(30~) ; Sodium lauryl sulfate (30%) 10.0%
Dimethyllaurylamine oleate 2.0%
; Ethyleneglycol monostearate 2.0%
Sodium chloride 0.5%
. Citric acid ` 0.5%
` Formaldehyde . O~l~o 20 j Diethanollauramide S.0 Deionized water q.s. 100 ;' Example 21 - Hand/Body Lotion :. A useful hand/body lotion is as follows:
Parts , . ~.
Mineral oil, light 70/80 15.0%
Sorbitan oleate 5.5%
Stearyl alcohol 2.5~
Dimethyllaurylamine oleate 2.0X
j Polyethyleneglycol 2000 monostearate 4~5%
30 ` (PEG 40 stearate) i, Methyl paraben 0.1%
Propyl paraben 0.04 Deionized water q.s. - 100 t 16467n Example 22 - Hand Creme A useful hand creme is as follows:
Parts Mineral oil light 70/80 15.0~
Sorbitan oleate 5.57, Stearyl alcohol 8.0%
Cetyl alcohol 2.0%
Dimethyllaurylamine oleate 2.0 ,I Polyethyleneglycol 2000 monostearate 4.5 (PEG 40 stearate) Methyl paraben O.lZ
Propyl paraben 0.04%
; Deionized water q.s. lO0 Example 23 - Soap Bars Soap pellets are made by adding a slight excess of 50~
caustic over stoichiometry t~ a 17:3 ratio of distilled tallow and ! coconut oil fatty acids. The mass is then dried and pelletized.
~The pellets contain approximately 12% moisture.
Il Soap Bar Formulation:
20 l Gold Bar Pink Bar , Tallow/coco soap/pellets9000 9 9000 9 , Slurry 250 9 282 9 Perfume 0.8 9 Q.8 9 ~, Dimethyllaurylamine oleate - 191. 2 25 ,, (slurry consists of water, pigments and bacteriostat) i The slurry, perfume, then other additives are added separately to the soap pellets while mixing thoroughly. This mix-ture is then passed through a three roll mill, then an extruder.
I This is repeated two or three times for thorough mixing and homo-I geneity. The extruded soap is then cut into size and formed.
l lI
, -21-~ 16447n ., ' :
50 bars of each of the gold and pink type were evalua~ed by 43 panelists and the results are as follows:
Pink Gold Equal 1. How easily it lathers 48.8 23.2 28.C
E mple 13 - Bubble Bath Parts Dimethyllaurylamine oleate 2.00 Water 50.90 Methyl paraben 0.10 Standapol WAQ Special (sodium lauryl ether sulfate, 50%, low salt content~ 35.00 Foamid L (diethanollauramide) 5.00 Polyethyleneglycol 6000 distearate 2.00 Ethyleneglycol monostearate 2.00 Perfume 2.00 Color _1.00 TOTAL 100.00 Methyl paraben and Standapol WAQ Special are added to water and heated to about 70C with agitation until homo-geneity is achieved.
In a separate beaker the dimethyl lauryl amine oleate is mixed with Foamid L and the mixture heated until uniform.
This mixture is slowly added to the water phase described above.
Polyethyleneglycol 6000 distearate is added and the solution mixed until thoroughly dissolved. Ethyleneglycol monostearate is then added with mixing until dissolved.
Finally, the solution is cooled to about 25C and perfume and color are added.
~.~
7~ 1 .
Example 14 - Low pH Conditioning Shampoo i: i Parts Water 63.~5 Standapol A (sodium lauryl ether sulfate, 30%) 30-00 Foamid LM (lauric/myristic diethanolamide) 3.00 Dimethyllaurylamine oleate 1.00 Methyl paraben 0.20 Citric acid 0.15 Sodium chloride 1.00 Perfume 0.20 Color 1.00 - TOTAL 100.00 Water was heated in a jacketed vessel equipped with a variable speed agitator. Citric acid was added and the solution was heated to about 60C at which time all remaining ingredients except sodium chloride and perfume were added. The mixture was heated to about 75C and held at that temperature for about 30 minutes.
The mixture was cooled and perfume and sodium chloride were added when the temperature reached about 40C. The final product was then cooled to about 25C.
Lathering, cleansing and ri,nsing properties were l excellent even in hard water. After use, it was observed that the hair has good manageability and luster.
.
1l!
Ii -16-1 164~7P
Example 15 - Lotion ; Parts phace A
~ Water 82.20 Lactic acid 88%, (10% solution) 1.00 Methyl paraben 3.00 Glycerine 3.00 Cellosize QP-300-H (cellulose ether) 2.00 Phase B
Glycerol monostearate 3.50 Foamid 0-100 (dimethylaminopropyloleamide) 0.30 Myristyl myristate 1.00 -- 2-Ethylhexyl palmitate 2.00 Cetyl alcohol 0.50 Dimethyllaurylamine oleate 1.00 Propyl paraben 0.10 Perfume ` _ 0.40 , TOTAL 100~00 Il Water, lactic acid solution and methyl paraben are mixed 20 jand heated to about 80C making certain that all ingredients are ,dissolved. Glycerine is added and then slowly Cellosize is mixed to make Phase A.
The ingredients of Phase B are mixed and heated to 85C
, until all waxes are melted~ Phases A and B are mixed, and agita-tion is continued for 15 minutes. The solution is cooled to about ',~ 35C, perfume is added, and the final product is cooled to about i! i 25C.
lj A soft, smooth feeling and pleasing sheen are imparted i¦to skin treated with the lotion.
il ' ,.
l l I~ -17-~ 154~7n xample 16 - Floating Bath Oil PartS
Solulan PB 20 (ethoxylated lanolin) 1.00 Oleyl alcohol 5.00 AcetulanTM (acetylated lanolin) 10.00 Light mineral oil 47.50 Isopropyl palmitate 28.00 Dimethyllaurylamine oleate 3.50 Perfume 5.00 TOTAL 100.00 All of the ingredients except perfume are blended to homogeneity~ Perfume is then added and the solution mixed until uniform.
After use of the bath oil, the skin feels clean and soft to the touch.
Example 17 - Suntan Oil Parts Light mineral oil 54.60 2-Ethylhexyl palmitate 33.50 Lauryl myristate 5,00 EscalolTM 507 (p-dimethylaminoamyl benzoate)1.90 Dimethyllaurylamine oleate3.50 Perfume 1.50 TOTAL 100.00 All of the ingredients except perfume are blended to homogeneity. Perfume is added and mixing is continued until a uniform product results.
When spread over the skin 9 the formulation provides a smooth, protective film effective in screening the sun's rays and moisturizing the skin.
~ - 18 -' J l6~7n Example 18 - Instant Hair Conditioner ,1 l Parts Phase A
Glycerine 5.00 EMCOL E-607S (Quaternium 7, Witco Chemical Co., Inc., Los Angeles, Ca.; antistatic agent) 0.50 Water 81.50 Il Phase B
10 l~ Glycerol monostearate 4.00 Cetyl alcohol 0.75 Stearyl alcohol 0.75 Lanolin 1.00 , Polyethylene glycol 400 monooleate5.00 Dimethyllaurylamine oleate 1.00 Phase C
¦ Perfume . 0.20 Sodium benzoate 0.10 Il Color 0.20 20 ll TOTAL 100.00 I, All of the ingredients of Phase A are mixed and heated ¦,to 80C and in a separate vessel all of Phase B ingredients are mixed and heated to 80C. These solutions are then mixed together Il with agitation and cooled to 45C wherëupon color, perfume and sodium benzoate are added. The preparation is then allowed to !~ cool to room temperature. I
i The use of this preparation on hair results in soft lustrous hair.
I In Examples 19-26 the term "dimethyl lauryl amine oleate" is utilized to refer to the product obtained by reacting oleic acid with dimethyl lauryl amine in a ratio of about 1.25:1, in a manner similar to Exanlple 1.
I' 1.
Il -19- 1 1 ~6447() Example 19 - Hdir Conditioning Rinse A useful hair conditioning rinse is as follows:
Parts 'I Dimethyllaurylamine oleate 2.0g Polyethylene glycol 6000 distearate 4.07 Glycerin 3.0%
Formaldehyde 0.1%
Deionized water q.s. 100 Example 20 - Hair Shampoo A useful hair shampoo is as follows:
Parts Sodium lauryl polyoxyethyleneglycol ,ulfate 3040%
(30~) ; Sodium lauryl sulfate (30%) 10.0%
Dimethyllaurylamine oleate 2.0%
; Ethyleneglycol monostearate 2.0%
Sodium chloride 0.5%
. Citric acid ` 0.5%
` Formaldehyde . O~l~o 20 j Diethanollauramide S.0 Deionized water q.s. 100 ;' Example 21 - Hand/Body Lotion :. A useful hand/body lotion is as follows:
Parts , . ~.
Mineral oil, light 70/80 15.0%
Sorbitan oleate 5.5%
Stearyl alcohol 2.5~
Dimethyllaurylamine oleate 2.0X
j Polyethyleneglycol 2000 monostearate 4~5%
30 ` (PEG 40 stearate) i, Methyl paraben 0.1%
Propyl paraben 0.04 Deionized water q.s. - 100 t 16467n Example 22 - Hand Creme A useful hand creme is as follows:
Parts Mineral oil light 70/80 15.0~
Sorbitan oleate 5.57, Stearyl alcohol 8.0%
Cetyl alcohol 2.0%
Dimethyllaurylamine oleate 2.0 ,I Polyethyleneglycol 2000 monostearate 4.5 (PEG 40 stearate) Methyl paraben O.lZ
Propyl paraben 0.04%
; Deionized water q.s. lO0 Example 23 - Soap Bars Soap pellets are made by adding a slight excess of 50~
caustic over stoichiometry t~ a 17:3 ratio of distilled tallow and ! coconut oil fatty acids. The mass is then dried and pelletized.
~The pellets contain approximately 12% moisture.
Il Soap Bar Formulation:
20 l Gold Bar Pink Bar , Tallow/coco soap/pellets9000 9 9000 9 , Slurry 250 9 282 9 Perfume 0.8 9 Q.8 9 ~, Dimethyllaurylamine oleate - 191. 2 25 ,, (slurry consists of water, pigments and bacteriostat) i The slurry, perfume, then other additives are added separately to the soap pellets while mixing thoroughly. This mix-ture is then passed through a three roll mill, then an extruder.
I This is repeated two or three times for thorough mixing and homo-I geneity. The extruded soap is then cut into size and formed.
l lI
, -21-~ 16447n ., ' :
50 bars of each of the gold and pink type were evalua~ed by 43 panelists and the results are as follows:
Pink Gold Equal 1. How easily it lathers 48.8 23.2 28.C
5 2. How easily the lather rinses 25.6 18.6 55.
3. Skin feel after towel drying (softness~ 44.8 20.9 34.5 4. Skin feel (smoothness) 32.6 16.3 51.1 Il 5. Over-all performance 37.2 25.6 37.2 The above results indicate a preference for the pink bar containing dimethyl lauryl amine oleate over the gold bar in the over-all performanc~ as well as skin feel after drying and the quality of lather during bathing.
Example 24 - Dishwashing Liquid A laboratory-made dishwashing liquid was comprisèd of the following formulation:
g by weight Sodium dodecylbenzene sulfonate 60% 26.2 ll Sodium xylene sulfonate 6070 1.3 C8- C12 linear alcohol ethoxylate (3-5 moles) 10.0 Triethanolamine laurylsulfate 60% 10.0 j Coconutalkyldiethanolamide (superamide) 4.0 Di~ethylcoconutalkylamine oxide .. 5070 2.7 I Deionized water to 100.0 One-half of the formula was evaluated without modifica-tion (Formula B) and the other half was evaluated after ha~ing 2 I percent, by weight, of dimethyllaurylamine oleate added thereto Il ~Formula A). Fifteen panelists responded with the follow;ng ¦ results: -~, I~ -22-~ l644~n Formula A Formula ~ Equal 1. Hand feel after towel drying (softness) 6 5 I 2. Hand feel after towel 5 ! drying (smoothness) 7 3 5 3. Dish Cleaning 6 4 5 4. Overall perference 5 5 5 The above results indicate a preference for Formula A in hand feel and dish cleaning.
Il.
Example 25 - Dishwashing Liquid Using commercially available dis'nwashing liquid "Joy"
and Joy plus 2%, by weight, of dimethyl lauryl amine oleate on artificially soiled 9" plates (the artificial soil consisted of 5 grams of a mixture containing 65% beef tallow, 8.7% oleic acid and 26.3% mineral oil placed on each plate), the plates were stacked and washed individually.
~ ! ~
.h Product A (Joy~ washed 9-1/2 dishes in run #1 and 9 dishes in run #2 ! Product B (Joy and dimethyl lauryl amine oleate) washed 20 . 11 dishes in run #1 and 11 dishes in run #2 The washing was discontinued when a greasy feel was ~' detectçd on the dishes after rinsing;
ii The results show that the dimethyl lauryl amine oleate 25 , improved the dishwashing performance of commercially available dishwashing liquid.
i 1~4~7n xample 26 - ~land Lotion A hand lotion was prepared in accordance with the 1: l following formulation:
I` Dimethyllaurvlamine oleate ~ by weight Polyethyleneglycol 6000 distearate 6~o Ethyl alcohol 5%
, Glycerin 5%
Distilled water 82%
~I The product was compared to a control consistins of allthe constituents listed above, except the dimethyllaurylamine oleate was omitted and an additional 2% water employed.
Two trained assessors evaluated the degree of hand dry-~ness and flaking. ~wo lotions were employed; LQtion A represented , the control and Lotion B the product containing the dimethyl-laurylamine oleate. The products were dispensed in 30 ml. amber glass dropper bottles, appropriately labeled. The 25 panelists were instructed to use the product as freely as desired both in frequency and quantity in the same manner than they would use any I commercial hand lotion. The panelist was informed to use Lotion A, firstly for one week. The panelist would report at 8 A.M. for ¦lan evaluation, taking care not to use any lotion the morning of the evaluation. This was necessary to prevent masking by heavy applications of lotion prior to examination. Also, occasionally Ijthe polyethyleneglycol ester would crystallize or powder giving a potential for misinterpretation as flakiness if readings were made, under magnification, within several hours of an applica-tion.
¦~ Panelists started with application day 1 on Sunday and ¦lexamination day 1 on the following day. The panelist was examinec ,and evaluated each morning Monday through Friday. On the follow-,ing Sunday, the panelist initiated the use of Lotion B and the panelist examined over the next two weeks Monday through Friday.
I
J 1~4~7(~
The method of evaluating skin dryness is a modifi-cation of the methods reported in J. Soc. Cosmet. Chem. 25, 519 (1974) and IBID, 24, 31 (1973). It consists of the use of a simple numerical scoring system to assess six areas of the hand according to the following scheme:
O = no visible signs o~ dryness 1 = slight dryness 2 = ~larked dryness and/or slight flaking 3 = severe dryness and/or marked flaking 4 = severe flaking and/or slight fissures
3. Skin feel after towel drying (softness~ 44.8 20.9 34.5 4. Skin feel (smoothness) 32.6 16.3 51.1 Il 5. Over-all performance 37.2 25.6 37.2 The above results indicate a preference for the pink bar containing dimethyl lauryl amine oleate over the gold bar in the over-all performanc~ as well as skin feel after drying and the quality of lather during bathing.
Example 24 - Dishwashing Liquid A laboratory-made dishwashing liquid was comprisèd of the following formulation:
g by weight Sodium dodecylbenzene sulfonate 60% 26.2 ll Sodium xylene sulfonate 6070 1.3 C8- C12 linear alcohol ethoxylate (3-5 moles) 10.0 Triethanolamine laurylsulfate 60% 10.0 j Coconutalkyldiethanolamide (superamide) 4.0 Di~ethylcoconutalkylamine oxide .. 5070 2.7 I Deionized water to 100.0 One-half of the formula was evaluated without modifica-tion (Formula B) and the other half was evaluated after ha~ing 2 I percent, by weight, of dimethyllaurylamine oleate added thereto Il ~Formula A). Fifteen panelists responded with the follow;ng ¦ results: -~, I~ -22-~ l644~n Formula A Formula ~ Equal 1. Hand feel after towel drying (softness) 6 5 I 2. Hand feel after towel 5 ! drying (smoothness) 7 3 5 3. Dish Cleaning 6 4 5 4. Overall perference 5 5 5 The above results indicate a preference for Formula A in hand feel and dish cleaning.
Il.
Example 25 - Dishwashing Liquid Using commercially available dis'nwashing liquid "Joy"
and Joy plus 2%, by weight, of dimethyl lauryl amine oleate on artificially soiled 9" plates (the artificial soil consisted of 5 grams of a mixture containing 65% beef tallow, 8.7% oleic acid and 26.3% mineral oil placed on each plate), the plates were stacked and washed individually.
~ ! ~
.h Product A (Joy~ washed 9-1/2 dishes in run #1 and 9 dishes in run #2 ! Product B (Joy and dimethyl lauryl amine oleate) washed 20 . 11 dishes in run #1 and 11 dishes in run #2 The washing was discontinued when a greasy feel was ~' detectçd on the dishes after rinsing;
ii The results show that the dimethyl lauryl amine oleate 25 , improved the dishwashing performance of commercially available dishwashing liquid.
i 1~4~7n xample 26 - ~land Lotion A hand lotion was prepared in accordance with the 1: l following formulation:
I` Dimethyllaurvlamine oleate ~ by weight Polyethyleneglycol 6000 distearate 6~o Ethyl alcohol 5%
, Glycerin 5%
Distilled water 82%
~I The product was compared to a control consistins of allthe constituents listed above, except the dimethyllaurylamine oleate was omitted and an additional 2% water employed.
Two trained assessors evaluated the degree of hand dry-~ness and flaking. ~wo lotions were employed; LQtion A represented , the control and Lotion B the product containing the dimethyl-laurylamine oleate. The products were dispensed in 30 ml. amber glass dropper bottles, appropriately labeled. The 25 panelists were instructed to use the product as freely as desired both in frequency and quantity in the same manner than they would use any I commercial hand lotion. The panelist was informed to use Lotion A, firstly for one week. The panelist would report at 8 A.M. for ¦lan evaluation, taking care not to use any lotion the morning of the evaluation. This was necessary to prevent masking by heavy applications of lotion prior to examination. Also, occasionally Ijthe polyethyleneglycol ester would crystallize or powder giving a potential for misinterpretation as flakiness if readings were made, under magnification, within several hours of an applica-tion.
¦~ Panelists started with application day 1 on Sunday and ¦lexamination day 1 on the following day. The panelist was examinec ,and evaluated each morning Monday through Friday. On the follow-,ing Sunday, the panelist initiated the use of Lotion B and the panelist examined over the next two weeks Monday through Friday.
I
J 1~4~7(~
The method of evaluating skin dryness is a modifi-cation of the methods reported in J. Soc. Cosmet. Chem. 25, 519 (1974) and IBID, 24, 31 (1973). It consists of the use of a simple numerical scoring system to assess six areas of the hand according to the following scheme:
O = no visible signs o~ dryness 1 = slight dryness 2 = ~larked dryness and/or slight flaking 3 = severe dryness and/or marked flaking 4 = severe flaking and/or slight fissures
6 = severe fissures The areas of the hand assessed were: back of hand, thumb web, other webs, front of fingers, back of fingers. The twelve areas (6 on each hand) were summed to give a total score.
Panelists were initially selected on the basis of an evalua-tion of widespread severe dryness, severe flaking or/and fissuring.
After the end of the trial, results were examined for statistically significant differences between A and B
2~ lotions. secause the trial was initiated with "initial" hand scores (untreated), it was possible to calculate mean changes from the previous hand scores. These changes were calculated and used as data for the analysis of variance. The results for each assessor were calculated separately and then combined to give an overall mean.
The results were as follows:
Mean Total Hand Scores Lotion A 14.6 Lotion B 11.9 Initial pre-test 14.8 ~ - 25 -1 16447(~
Lotion A produced no significant differences from the initial evaluation or pre-test conditions, while B
demonstrated a moderately but significant change from both pre-test and Lotion A mean values.
Example 27 - Evaluation of Skin Irritation A solution, in propylene glycol, IJSP, of one per-cent, by weight, of the product obtained by reacting oleic acid with dimethyllaurylamine in a ratio of about 1.25:1 in a manner similar to Example 1, was evaluated for skin irrita-tion. The method employed was that described in the HazardousSubstances Labeling Act Regulations, Code of Federal Regula-tions 16, Part 1500.41, U.S.A. A dosage of 0.5 ml per patch with four patches per rabbit was utillzed, on each of six rabbits. The skin irritation index was determined to be 0Ø
The raw data are as follows:
~ l6447n ji ' ~IJ U:
L
, O C ~- ~ O O O O O O O O O O O
~ ~ rr~ _ X
.
',OCr~~ OOOOO OOOOOO
X
`'i 1, li I ! ~ ~ aJ ~
. o ~ o O o O o o O o O o o Q~ ~.Q
X ~ ~
1. .
. . .
3 ~ aJ~
O C r~ .~ O O O O O O O O O O O
Cl. =) 0~ ~1 X ~ ~
O C. ~ O O O O O O O O O O O
a ~ 0~) X
. I
;, ~ aJ~
' I O C r .~ O O O O O O O O O O O
I' x ~ ~
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I
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o ., o ~C~l d' N 1~ N r~
, j X ,,.:
i l ll ~' O ~ '~ C ~ '~
, i ,, .~ V o ~. .
i ' C E O ~ O ~J ~ O ~ O ~i ~
I i o O ~ O L L) -a O LLJ
li 0 ~ ~ ~S ~) o ra ~ ~ :~
E ~ L D ~ L 5:1 C ~ ~ C D
!j 1'' 1.
~ l6447n Example 28 - Evaluation of Skin Irritation A solution in propylene glycol, USP, of five percent, by weight, of the product obtained by reactiny olelc acid wlth di-methyllaurylamine in a ratio of about 1.25:1 in a manner similar to Example 1, was prepared and evaluated in the same manner as outlined in Example 27. The primary skin irritation index number was determined to be 5.1, showing that at the hi gh active concen-` tration of 5 weight percent, the solution is still considered tobe only a mode ate skin irritant. The raw data are dS follows :
,1, '; .
"
~ ~ .
--l l 28- ~
~ ~447~
~o L
J
o c ~ n ~ ~ ~ ~ o C~J c~ > oo u~
X ~ ~
. ~
L
~ ~ ~ ~c~ O ~ n X ~ ~
~ N
3 a~ ~ , ~ c ~ n ~ N ~ ~> ~( ~ C~J ~) (`~ ~1 C~J U~
n X ~, L~ C~
L
O C ~ J ~) ~) ~ N
n X
L
o c ~ n C~ ~ ~ o ~ co ~ ~ oo u~
~ ~n X ~ a o c ~ n c~ N ~) ~ O C~ r) O o U) . c.~ ~n X
L.
a~
L t~
~ ~ L
o., O d' ,_ N
, X ,,.,~.
'i .
,!
:, C
I o C ,~ o ~
c- E O :/ O 1~ o O o L~ o , .
I!
11 1~4~70 ' Examples 29 through 66 - Preparation of Various Products In the following examples various tertiary amines were reacted with various acids, in a variety of equivalent ratios to . yield compositions within the scope of the present invention. ~e typical preparation procedure is to add the amine to the acid an~
to heat the mixture to about 130C for about 1.5 hours. Subse quently, the reaction mixture is allowed to cool under vacuum to rrom temperature, the vacuum released and the product removed.
;
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I
1 16447(~ ~
!
1. 1 a~ D OO~ ~~nco o oLt-u >~ ~ o ~n E OO O OC~ OO O O O O O O O ON O
~D O0~ n a) O d'D OU> C~JO N 0 E . . .. . . . . . . . ..
ro N1~ t~ c~) _r.~ Dr.~~ ~ N~70 ~) CJ~
q) ~ , ro ~) OO ~ ~ O o CO~r~oI O o~ D 1~ O
_ aJN C~ N t~ J N.~ N C~JN r,~J ~ r,~J N
~ 3 ~ !
_~ ~ ro o ~ _ O r~ ~ ~ ~
0 I01 ~1 ~ Or-- ~ ~O O O -- ~vl ~ O r~
o ~ r.~ o ~ ~ o .~ o , v) o oa~ ~ o v~o ~ ~ t 1: v~ O ~~ v~
t.) L _ ~E ~ .~ E ~ _ E ~~
E o ~D ~. ~ ILL o ,x~ ô I w o , I LIJ
-- 1~ I r~C:l I O -- O. ~ OO r.~J O --Cl r ) Cl O
r~ r~ ~O ~ ~ E s_ o. ~;~ ~) W ' ~ --~ro ~ ~--ro r ~ rr~ U -- ~
aJ ~ ~~ ra ~ r~o"~ o o a~ r,~ ~ r.~l ~ O ~ v) ~o-- ~. oa~ o E oo ~ CE o uo c~ - ~C E oa~ ~ ~C
r-- ~ r~ 3 o r-- ~ ~ 3 ~ o.-- ~ .-3 o ,--~11 N N ~ C~.l Ll~ IS~ N d- N ~ .lN N C~l N
E o o o o o oo o o o o o o O oc~.i o .. V~ ~~ ~ oo l_I~ o o o Oo O ':t ro~D ~ ~ ~ ~ ~CO _ CO ~~r ~ ~
'7 r~r.~ ~)N C~l _ C~ r__I ~ ~ ~~ ~Y) d' N
i . ~ i ~ !
I ~ s o oO ~ og "~
~3 W
, ~ = N
; 1--C~ ~ , ~ O
E ~ - = ~ = = - = '` ~ ~ = - : = c ! ~ ~ c sE
I' E = _ = : = ~ _ _ = _ ¢
~u s _ _ _ -'., ro ~
~ r-- c E
c ~ E C '~
ra , a~ ~ . = = = c = S = = ~ = O
r j l s ~ E >~
,~ O
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r- ~ _ O _~ C~J (~ d' U~ ~ 1~ COa~ O r-l N ~ ~ ~
. I
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8 o o o o o o o o o o o o o o o v~ o ~ o ~ o o u~ O n~O O O
L u~ ~ u~ u~~ CO ~ ~ ~ ~ ~ ~t u~ O U:
~1 N ~1 L~) ~`J N ~'.~1 N N C~J C~J ~ C~l , ~3:
C~
!:
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; o . ,~ , o ~' _ o U~
ID ~ ~ O ~ ~ ~ C O r-- ~ Ul r- O aJ~ L I U- V C ~ O aJ
E --rrJ ~) O--~ ~)o ~ ~ ~ E --' j O , X o ~ W '~ ~ 0-- L~
: ~ Q ~ C~ O ~ 1 0 0 -- Q ~ C~ O O
W L O --O ~ 0 L ~ Z O W L O Z Z
L ~ > ~ O . O r~ OS_ O O .--C~ ~ ~ . -~ ~ o ~ ~--~ L-- ~ ~ ~-- ~ ~ V~ QJ r~ --~ 3 t_~ -- o .-- ~ ~ 3 0 0 ~1) ~ ~t N O LC-I10 0~ l ~ N ~ N O Cl E o o o o o o o o o o o O o o o E N c~ d- O O o .o;~
' loIS) O ~D N ~D D d 1~ 1~ C~i CO a~ 1~ CO O
., jL ~ ~ N C~l L~Lf~ 0~ N~r) C`J t~l ~1 ~;t C~l;
, i ~C
j a~ ~ i ~ r--S o o o o,o~oot~ o o o o o LO ~
N N ~J N N N N N C`~ l N '.~J ~
I;W '~ = = = j;
ii -- ici i j N
. -- E ~ E
¦ E ~ I ~_) ~
>, c -- L _ '~ ~ --O '- E
!i E = = = E = = = = o C
.j ' Il i ~ ~6447() , " o 1: E O O O O O O
il i' U~ ~ _ 0 0 0 0 d- ~) . N
i o 1 i ~_ aJ N N N N~) ~
~3 ~lJ
i;
ii li ~ ~ ~ ~ o 1: o o o o u~
.~ 0 aL, ~ 0 0 i l oo o o ~ C, ~. ZZ Z Z V~ O
>
~r~r~r ~j-- O ~
O Oo O o 3 ~ J CO O O
o ~ L~) N
I E o o o o o o . .
.
O OO ~ U~ ~
i! ~
I j C
S ~ !; O O
:~ 3 !: .
l. ~ !
I ! r~ a1 C aJ
E -- =
tl~ 3 ' 'O,_ o i i C11 ~ ,_ i~ Ec_) ~
~ ! ai '~N ~1 ,_ C a~ oI a~ N ~ C
CJ r-i E 1~ r~ r--j ~ X ~ Z r ,, ~` O S
jl . S~ S aJ ~ -~ E ~ O
S E -- ~ rsl O
~ I o ~ N
j, ~ 2 ~ L" v) g ~ ~.3 0 'r- - I
n c~ c~ m N
li ' ,i . .
~ '3 - 3 3 -~ lB447~ , , Examples 67 & 6~ - Preparation Two moles ofoC-olefin oxides of the general formula RCHCH2C ;equiv~l~nt ntight 206) were r~ac~ù w,ti, one mole of N,N-dimethyl-1,3-diaminopropane to yield a product of the formula (HOCl~cH2)2~c~2cH2cH2N(cl~3)2~ having an equivalent weight of 673. One mole of the product was reacted with one mole of oleic acid (Example 67) and one mole of the product was reacted with two moles of oleic acid (Example 68) to yield compositions ; within the scope of the present invention.
Examples 69 throu~h 74 - Preparation Two moles of propylene oxide were reacted with one mole of N,N-dimethyl-1,3-diaminopropane to yield a product of the formula [HocH(cH3)cH2]2 N(CH2)3 N(CH3)2 One mole of the product was reacted with one mole of oleic acid (Example 69) and with two moles of oleic acid (Example 70) to yield compositions within the scope of the invention.
In the same manner as above, five moles of propylene oxide were utilized to yield a mixture containing products of the ll~ formula:
H[OCH(CH3)CH2] ~
(CH2)3N(CH3)2, where x+y=5 I, H[OCH(CH3)CH2]x ' ., j One mole of the product mixture was reacted with one mole of oleic 1 acid (Example 71) and with two moles of oleic acid (Example 72) to yield compositions within the scope o~ the invention.
Again, similar to the above procedure, ten moles of pro-pylene oxide were reacted to yield a mixture containing products of the formula:
!
.j , .
~ 16447~ ;
,; HLOCH(C~l3)cH2]~\
` ~ N(C~lz)3N(CH3) where x+y=10 . ~[nCH(CH3)C~12]y : One mole of the product mixture was reacted with one mole oleic acid (Example 73) and with two moles of oleic acid (Example 74) to yield compositions within the scope of the invention.
; Examples 67-74 represent alternative embodiments to the general tertiary amines disclosed hereinbefore. In the embodiment represented by Examples 67 and 68 the tertiary amine utilized in the production of the salt and other product has the general formula ~- /N
R2 \ R3 wherein R1 is (HOCHCH2)2 NCH2CH2CH - R5 representing an aliphatic group containing from about 8 to about 22 carbon atoms . and R2 and R3 are CH3-.
In the embodiment represented by Examples 69-73 the tertiary amine utilized in the production of the salt and other products has the general formula ; N
wherein R1 has the formula H[OCH(CH3)cH2]
~
" NCH2CH2CH2 ` H[OCH(CH3)CH2]y l l ~ -35-4 ~ 7(~
wherein x and y are integers from 1 to 9 and the sum of x and y is from 2 to about 10 and R2 and R3 are Cl~3-.
i In either of the ab~P embodiments, the tertiary amine , may be reacted with any of the acids represented by the formula 5 . R4-H as defined hereinabove, in any molar ratio of amine:acid . from about 0.3:1 to about 3.3:1.
The resulting salts and products may be utilized in the same manner as the other salts and products of this invention, , such as, in making skin and hair contacting formulations, dish-washing formulations, and soap bars.
.
I~ .
. I .
. . -ll !1l -36-
Panelists were initially selected on the basis of an evalua-tion of widespread severe dryness, severe flaking or/and fissuring.
After the end of the trial, results were examined for statistically significant differences between A and B
2~ lotions. secause the trial was initiated with "initial" hand scores (untreated), it was possible to calculate mean changes from the previous hand scores. These changes were calculated and used as data for the analysis of variance. The results for each assessor were calculated separately and then combined to give an overall mean.
The results were as follows:
Mean Total Hand Scores Lotion A 14.6 Lotion B 11.9 Initial pre-test 14.8 ~ - 25 -1 16447(~
Lotion A produced no significant differences from the initial evaluation or pre-test conditions, while B
demonstrated a moderately but significant change from both pre-test and Lotion A mean values.
Example 27 - Evaluation of Skin Irritation A solution, in propylene glycol, IJSP, of one per-cent, by weight, of the product obtained by reacting oleic acid with dimethyllaurylamine in a ratio of about 1.25:1 in a manner similar to Example 1, was evaluated for skin irrita-tion. The method employed was that described in the HazardousSubstances Labeling Act Regulations, Code of Federal Regula-tions 16, Part 1500.41, U.S.A. A dosage of 0.5 ml per patch with four patches per rabbit was utillzed, on each of six rabbits. The skin irritation index was determined to be 0Ø
The raw data are as follows:
~ l6447n ji ' ~IJ U:
L
, O C ~- ~ O O O O O O O O O O O
~ ~ rr~ _ X
.
',OCr~~ OOOOO OOOOOO
X
`'i 1, li I ! ~ ~ aJ ~
. o ~ o O o O o o O o O o o Q~ ~.Q
X ~ ~
1. .
. . .
3 ~ aJ~
O C r~ .~ O O O O O O O O O O O
Cl. =) 0~ ~1 X ~ ~
O C. ~ O O O O O O O O O O O
a ~ 0~) X
. I
;, ~ aJ~
' I O C r .~ O O O O O O O O O O O
I' x ~ ~
!` "' ": .
I
Vl E ~
o ., o ~C~l d' N 1~ N r~
, j X ,,.:
i l ll ~' O ~ '~ C ~ '~
, i ,, .~ V o ~. .
i ' C E O ~ O ~J ~ O ~ O ~i ~
I i o O ~ O L L) -a O LLJ
li 0 ~ ~ ~S ~) o ra ~ ~ :~
E ~ L D ~ L 5:1 C ~ ~ C D
!j 1'' 1.
~ l6447n Example 28 - Evaluation of Skin Irritation A solution in propylene glycol, USP, of five percent, by weight, of the product obtained by reactiny olelc acid wlth di-methyllaurylamine in a ratio of about 1.25:1 in a manner similar to Example 1, was prepared and evaluated in the same manner as outlined in Example 27. The primary skin irritation index number was determined to be 5.1, showing that at the hi gh active concen-` tration of 5 weight percent, the solution is still considered tobe only a mode ate skin irritant. The raw data are dS follows :
,1, '; .
"
~ ~ .
--l l 28- ~
~ ~447~
~o L
J
o c ~ n ~ ~ ~ ~ o C~J c~ > oo u~
X ~ ~
. ~
L
~ ~ ~ ~c~ O ~ n X ~ ~
~ N
3 a~ ~ , ~ c ~ n ~ N ~ ~> ~( ~ C~J ~) (`~ ~1 C~J U~
n X ~, L~ C~
L
O C ~ J ~) ~) ~ N
n X
L
o c ~ n C~ ~ ~ o ~ co ~ ~ oo u~
~ ~n X ~ a o c ~ n c~ N ~) ~ O C~ r) O o U) . c.~ ~n X
L.
a~
L t~
~ ~ L
o., O d' ,_ N
, X ,,.,~.
'i .
,!
:, C
I o C ,~ o ~
c- E O :/ O 1~ o O o L~ o , .
I!
11 1~4~70 ' Examples 29 through 66 - Preparation of Various Products In the following examples various tertiary amines were reacted with various acids, in a variety of equivalent ratios to . yield compositions within the scope of the present invention. ~e typical preparation procedure is to add the amine to the acid an~
to heat the mixture to about 130C for about 1.5 hours. Subse quently, the reaction mixture is allowed to cool under vacuum to rrom temperature, the vacuum released and the product removed.
;
', li ,, .
I
1 16447(~ ~
!
1. 1 a~ D OO~ ~~nco o oLt-u >~ ~ o ~n E OO O OC~ OO O O O O O O O ON O
~D O0~ n a) O d'D OU> C~JO N 0 E . . .. . . . . . . . ..
ro N1~ t~ c~) _r.~ Dr.~~ ~ N~70 ~) CJ~
q) ~ , ro ~) OO ~ ~ O o CO~r~oI O o~ D 1~ O
_ aJN C~ N t~ J N.~ N C~JN r,~J ~ r,~J N
~ 3 ~ !
_~ ~ ro o ~ _ O r~ ~ ~ ~
0 I01 ~1 ~ Or-- ~ ~O O O -- ~vl ~ O r~
o ~ r.~ o ~ ~ o .~ o , v) o oa~ ~ o v~o ~ ~ t 1: v~ O ~~ v~
t.) L _ ~E ~ .~ E ~ _ E ~~
E o ~D ~. ~ ILL o ,x~ ô I w o , I LIJ
-- 1~ I r~C:l I O -- O. ~ OO r.~J O --Cl r ) Cl O
r~ r~ ~O ~ ~ E s_ o. ~;~ ~) W ' ~ --~ro ~ ~--ro r ~ rr~ U -- ~
aJ ~ ~~ ra ~ r~o"~ o o a~ r,~ ~ r.~l ~ O ~ v) ~o-- ~. oa~ o E oo ~ CE o uo c~ - ~C E oa~ ~ ~C
r-- ~ r~ 3 o r-- ~ ~ 3 ~ o.-- ~ .-3 o ,--~11 N N ~ C~.l Ll~ IS~ N d- N ~ .lN N C~l N
E o o o o o oo o o o o o o O oc~.i o .. V~ ~~ ~ oo l_I~ o o o Oo O ':t ro~D ~ ~ ~ ~ ~CO _ CO ~~r ~ ~
'7 r~r.~ ~)N C~l _ C~ r__I ~ ~ ~~ ~Y) d' N
i . ~ i ~ !
I ~ s o oO ~ og "~
~3 W
, ~ = N
; 1--C~ ~ , ~ O
E ~ - = ~ = = - = '` ~ ~ = - : = c ! ~ ~ c sE
I' E = _ = : = ~ _ _ = _ ¢
~u s _ _ _ -'., ro ~
~ r-- c E
c ~ E C '~
ra , a~ ~ . = = = c = S = = ~ = O
r j l s ~ E >~
,~ O
!; r E ~ E
r- ~ _ O _~ C~J (~ d' U~ ~ 1~ COa~ O r-l N ~ ~ ~
. I
1~ ~ -31-~ 16~47(!
. .
, O~ ~ O O C~l ~) ~ O Lf~ CO Lt~ lD O N O
8 o o o o o o o o o o o o o o o v~ o ~ o ~ o o u~ O n~O O O
L u~ ~ u~ u~~ CO ~ ~ ~ ~ ~ ~t u~ O U:
~1 N ~1 L~) ~`J N ~'.~1 N N C~J C~J ~ C~l , ~3:
C~
!:
,, .
; o . ,~ , o ~' _ o U~
ID ~ ~ O ~ ~ ~ C O r-- ~ Ul r- O aJ~ L I U- V C ~ O aJ
E --rrJ ~) O--~ ~)o ~ ~ ~ E --' j O , X o ~ W '~ ~ 0-- L~
: ~ Q ~ C~ O ~ 1 0 0 -- Q ~ C~ O O
W L O --O ~ 0 L ~ Z O W L O Z Z
L ~ > ~ O . O r~ OS_ O O .--C~ ~ ~ . -~ ~ o ~ ~--~ L-- ~ ~ ~-- ~ ~ V~ QJ r~ --~ 3 t_~ -- o .-- ~ ~ 3 0 0 ~1) ~ ~t N O LC-I10 0~ l ~ N ~ N O Cl E o o o o o o o o o o o O o o o E N c~ d- O O o .o;~
' loIS) O ~D N ~D D d 1~ 1~ C~i CO a~ 1~ CO O
., jL ~ ~ N C~l L~Lf~ 0~ N~r) C`J t~l ~1 ~;t C~l;
, i ~C
j a~ ~ i ~ r--S o o o o,o~oot~ o o o o o LO ~
N N ~J N N N N N C`~ l N '.~J ~
I;W '~ = = = j;
ii -- ici i j N
. -- E ~ E
¦ E ~ I ~_) ~
>, c -- L _ '~ ~ --O '- E
!i E = = = E = = = = o C
.j ' Il i ~ ~6447() , " o 1: E O O O O O O
il i' U~ ~ _ 0 0 0 0 d- ~) . N
i o 1 i ~_ aJ N N N N~) ~
~3 ~lJ
i;
ii li ~ ~ ~ ~ o 1: o o o o u~
.~ 0 aL, ~ 0 0 i l oo o o ~ C, ~. ZZ Z Z V~ O
>
~r~r~r ~j-- O ~
O Oo O o 3 ~ J CO O O
o ~ L~) N
I E o o o o o o . .
.
O OO ~ U~ ~
i! ~
I j C
S ~ !; O O
:~ 3 !: .
l. ~ !
I ! r~ a1 C aJ
E -- =
tl~ 3 ' 'O,_ o i i C11 ~ ,_ i~ Ec_) ~
~ ! ai '~N ~1 ,_ C a~ oI a~ N ~ C
CJ r-i E 1~ r~ r--j ~ X ~ Z r ,, ~` O S
jl . S~ S aJ ~ -~ E ~ O
S E -- ~ rsl O
~ I o ~ N
j, ~ 2 ~ L" v) g ~ ~.3 0 'r- - I
n c~ c~ m N
li ' ,i . .
~ '3 - 3 3 -~ lB447~ , , Examples 67 & 6~ - Preparation Two moles ofoC-olefin oxides of the general formula RCHCH2C ;equiv~l~nt ntight 206) were r~ac~ù w,ti, one mole of N,N-dimethyl-1,3-diaminopropane to yield a product of the formula (HOCl~cH2)2~c~2cH2cH2N(cl~3)2~ having an equivalent weight of 673. One mole of the product was reacted with one mole of oleic acid (Example 67) and one mole of the product was reacted with two moles of oleic acid (Example 68) to yield compositions ; within the scope of the present invention.
Examples 69 throu~h 74 - Preparation Two moles of propylene oxide were reacted with one mole of N,N-dimethyl-1,3-diaminopropane to yield a product of the formula [HocH(cH3)cH2]2 N(CH2)3 N(CH3)2 One mole of the product was reacted with one mole of oleic acid (Example 69) and with two moles of oleic acid (Example 70) to yield compositions within the scope of the invention.
In the same manner as above, five moles of propylene oxide were utilized to yield a mixture containing products of the ll~ formula:
H[OCH(CH3)CH2] ~
(CH2)3N(CH3)2, where x+y=5 I, H[OCH(CH3)CH2]x ' ., j One mole of the product mixture was reacted with one mole of oleic 1 acid (Example 71) and with two moles of oleic acid (Example 72) to yield compositions within the scope o~ the invention.
Again, similar to the above procedure, ten moles of pro-pylene oxide were reacted to yield a mixture containing products of the formula:
!
.j , .
~ 16447~ ;
,; HLOCH(C~l3)cH2]~\
` ~ N(C~lz)3N(CH3) where x+y=10 . ~[nCH(CH3)C~12]y : One mole of the product mixture was reacted with one mole oleic acid (Example 73) and with two moles of oleic acid (Example 74) to yield compositions within the scope of the invention.
; Examples 67-74 represent alternative embodiments to the general tertiary amines disclosed hereinbefore. In the embodiment represented by Examples 67 and 68 the tertiary amine utilized in the production of the salt and other product has the general formula ~- /N
R2 \ R3 wherein R1 is (HOCHCH2)2 NCH2CH2CH - R5 representing an aliphatic group containing from about 8 to about 22 carbon atoms . and R2 and R3 are CH3-.
In the embodiment represented by Examples 69-73 the tertiary amine utilized in the production of the salt and other products has the general formula ; N
wherein R1 has the formula H[OCH(CH3)cH2]
~
" NCH2CH2CH2 ` H[OCH(CH3)CH2]y l l ~ -35-4 ~ 7(~
wherein x and y are integers from 1 to 9 and the sum of x and y is from 2 to about 10 and R2 and R3 are Cl~3-.
i In either of the ab~P embodiments, the tertiary amine , may be reacted with any of the acids represented by the formula 5 . R4-H as defined hereinabove, in any molar ratio of amine:acid . from about 0.3:1 to about 3.3:1.
The resulting salts and products may be utilized in the same manner as the other salts and products of this invention, , such as, in making skin and hair contacting formulations, dish-washing formulations, and soap bars.
.
I~ .
. I .
. . -ll !1l -36-
Claims (34)
1. A tertiary amine salt of the formula wherein R1 is selected from the group consisting of saturated and unsaturated aliphatic groups containing from about 8 to about 22 carbon atoms, R?NHCH2CH2CH2-, R?ONHCH2CH2-, RN(CH3)CH2CH2CH2-, RN(CH2CH2O)1-5HCH2CH2CH2, R?OCH2CH2-, CH3O[CH2CH(CH3)O]1-5CH2CH2 CH2-, H[O(CH3)CHCH2]3-8, H[O(CH3)CHCH2]3-8OCH2CH2-, RCHOHCH2-, ROCH2CH2CH2-, (HO?HCH2)2NCH2CH2CH2-, and R3 is selected from the group consisting of aliphatic groups containing from one to about two carbon atoms H[O(CH3)CHCH2]?-15 and H(OCH2CH2)?-15, R2 is selected from the group consisting of saturated and unsaturated aliphatic groups containing from about 8 to about 22 carbon atoms, R?NHCH2CH2CH2-, R?ONHCH2CH2-, R(OCH2CH2CH2)ZN(CH3)CH2CH2CH2-, R(OCH2CH2CH2)ZN(CH2CH2O)1-5 HCH2CH2 CH2-, R?OCH2CH2-, CH3O[CH2CH(CH3)O]1-5CH2CH2CH2-, H[O(CH3)CHCH2]3-8, H[O(CH3)CHCH2]3-8 OCH2CH2-, RCHOHCH2-, ROCH2CH2 CH2-, aliphatic groups containing from one to about two carbon atoms and H[O(CH3)HCH2]?-15 H(OCH2CH2)?-15, and R4 is selected from the group consisting of R-?-O-, RCH=CH2SO3-, RCONHCH(CH3)CO2-, ROSO3-, RC6H5SO3-, RO[CH2CH2O]1-10 CH2CO2-, RNHCOCH=CHCO2-, isostearic acid residue, ricinoleic acid residue, hydroxystearic acid residue, phenylstearic acid residue and residues of dibasic acids containing from about 6 to about 36 carbon atoms, wherein in all instances R represents a saturated or unsaturated aliphatic group containing from about 8 to about 18 carbon atoms, x and y are integers from 1 to 9, the sum of x + y is an integer from 2 to 10, and z is 0 or 1.
2. The salt of claim 1 wherein R1 is a saturated or unsaturated aliphatic group containing from about 8 to about 22 carbon atoms, R2 and R3 are selected from the group consisting of methyl, ethyl H[O(CH3)CHCH2]?-15 and H(OCH2CH2)?-15, and R4-H is a saturated or unsaturated aliphatic carboxylic acid containing from about 8 to about 22 carbon atoms.
3. A tertiary amine salt selected from the group con-sisting of dimethyllaurylamine oleate, dimethyllaurylamine stearate, dimethylpalmitylamine oleate, diethyllaurylamine oleate, dimethylpalmitylamine stearate, polyoxyethylene(15)tallowamine oleate, N,N-dimethylcocoamine isostearate, and N,N-dimethyloctadecylamine oleate.
4. The product made by the process of reacting a terti-ary amine of the formula:
and an acid of the formula:
wherein R1, R2, R3, and R4 have the meanings defined in claim 1, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
and an acid of the formula:
wherein R1, R2, R3, and R4 have the meanings defined in claim 1, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
5. The product of claim 4 made by the process wherein R1 is a saturated or unsaturated aliphatic group containing from about 8 to about 22 carbon atoms, R2 and R3 are selected from the group consisting of methyl, ethyl, H[O(CH3)CHCH2]1-15 and H(OCH2CH2)1-15, and R4-H is a saturated or unsaturated aliphatic carboxylic acid containing from about 8 to about 22 carbon atoms.
6. The product of claim 4 made by the process wherein the tertiary amine is selected from the group consisting of di-methyllaurylamine, dimethylpalmitylamine, diethyllaurylamine, polyoxyethylene(15)tallowamine, N,N-dimethylcocoamine and N,N-dimethyloctadecylamine and the acid is selected from the group consisting of oleic acid, stearic acid, and isostearic acid.
7. The product made by the process of mixing water, a tertiary amine of the formula and an acid of the formula:
wherein R1, R2, R3, and R4 have the meanings defined in claim 1, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
wherein R1, R2, R3, and R4 have the meanings defined in claim 1, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
8. The product of claim 7 made by the process wherein R1 is a saturated or unsaturated aliphatic group containing from about 8 to about 22 carbon atoms, R2 and R3 are selected from the group consisting of methyl, ethyl, H[O(CH3)CIiCH2]?-15 and H(OCH2CH2)?-15, and R4-H is a saturated or unsaturated aliphatic carboxylic acid containing from about 8 to about 22 carbon atoms.
9. The product of claim 7 made by the process wherein the tertiary amine is selected from the group consisting of dimethyllaurylamine, dimethylpalmitylamine, diethyllaurylamine, polyoxyethylene(15)tallowamine, N,N-dimethylcocoamine and N,N-di-methyloctadecylamine and the acid is selected from the group consisting of oleic acid, stearic acid, and isostearic acid.
10. A skin or hair-contacting composition comprising from about 0.1 to about 2.0 percent, by weight, based on the total weight of the composition of a tertiary amine salt of claim 1.
11. The composition of claim 10 wherein the skin or hair-contacting composition is selected from the group consisting of aftershave lotions, pre-electric shave lotions, shaving prepa-rations, bath oils, after-bath preparations, hair preparations, sunscreen preparations, skin and hand creams, and shampoos.
12. A soap bar comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt of claim 1, 2, or 3.
13. A dishwashing detergent comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt of claim 1, 2, or 3.
14. A skin or hair-contacting composition comprising from about about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt of claim 4.
15. The composition of claim 14 wherein the skin or hair-contacting composition is selected from the group consisting of aftershave lotions, pre-electric shave lotions. shaving formu-lations, bath oils, after-bath preparations, hair preparations, sunscreen preparations, skin and hand creams, and shampoos.
16. A soap bar comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt of claim 4, 5, or 6.
17. A dishwashing detergent comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt of claim 4, 5, or 6.
18. A skin or hair-contacting composition comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition of a tertiary amine salt of claim 7.
19. The composition of claim 18 wherein the skin or hair-contacting composition is selected from the group consisting of aftershave lotions, pre-electric shave lotions, shaving formu-lations, bath oils, after-bath preparations, hair preparations, : sunscreen preparations, skin and hand creams, and shampoos.
; 20. A soap bar comprising from about 0.1 to about 2.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt of claim 7, 8, or 9.
21. A dishwashing detergent comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, or a tertiary amine salt of claim 7, 8, or 9.
22. A tertiary amine salt of the formula wherein R1 is , R5 representing an aliphatic group containing from about 8 to about 22 carbon atoms, R2 and R3 and CH3-, and R4 is as defined in claim 1.
23. A product prepared by the process of reacting a tertiary amine of the formula with an acid of the formula:
in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1, wherein R1, R2, R3, and R4 are as defined in claim 22.
in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1, wherein R1, R2, R3, and R4 are as defined in claim 22.
24. The product made by the process of reacting water, a tertiary amine as defined in claim 23, and an acid as defined in claim 23, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
25. A tertiary amine salt of the formula OR
wherein R1 is , or wherein x and y are integers from 1 to 9 and the sum of x and y is from 2 to about 10, R2 and R3 are CH3-, and R4 and R5 are as defined in claim 1.
wherein R1 is , or wherein x and y are integers from 1 to 9 and the sum of x and y is from 2 to about 10, R2 and R3 are CH3-, and R4 and R5 are as defined in claim 1.
26. A product prepared by the process of mixing a tertiary amine of the formula with an acid of the formula in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1, wherein R1, R2, R3, and R4 are as defined in claim 25.
27. The product made by the process of mixing water, a tertiary amine as defined in claim 26, and an acid as defined in claim 26, in a molar ratio of amine:acid from about 0.3:1 to about 3.3:1.
28. The product of claim 26 or 27 wherein R4 - H is a dibasic acid as defined in claim 1.
29. A skin or hair-contacting composition comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt as defined in claim 22 or 25.
30. A soap bar comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt as defined in claim 22 or 25.
31. A dishwashing composition comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a tertiary amine salt as defined in claim 22 or 25.
32. A skin or hair-contacting composition comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a product of claim 23, 24 or 26.
33. A soap bar comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a product of claim 23, 24 or 26.
34. A dishwashing composition comprising from about 0.1 to about 5.0 percent, by weight, based on the total weight of the composition, of a product of claim 23, 24 or 26.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3586679A | 1979-05-03 | 1979-05-03 | |
| US035,866 | 1979-05-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1164470A true CA1164470A (en) | 1984-03-27 |
Family
ID=21885257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000344156A Expired CA1164470A (en) | 1979-05-03 | 1980-01-22 | Tertiary amine salts of long-chain acids compositions and methods utilizing the same |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1164470A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698167A (en) * | 1983-08-11 | 1987-10-06 | The Procter & Gamble Company | Detergent with fabric softener |
-
1980
- 1980-01-22 CA CA000344156A patent/CA1164470A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698167A (en) * | 1983-08-11 | 1987-10-06 | The Procter & Gamble Company | Detergent with fabric softener |
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