CA2062848A1 - Fabric softeners based on quaternary poly(oxyalkylene) alkanolamine esters - Google Patents
Fabric softeners based on quaternary poly(oxyalkylene) alkanolamine estersInfo
- Publication number
- CA2062848A1 CA2062848A1 CA002062848A CA2062848A CA2062848A1 CA 2062848 A1 CA2062848 A1 CA 2062848A1 CA 002062848 A CA002062848 A CA 002062848A CA 2062848 A CA2062848 A CA 2062848A CA 2062848 A1 CA2062848 A1 CA 2062848A1
- Authority
- CA
- Canada
- Prior art keywords
- radicals
- compounds
- fabric softener
- carbon atoms
- formula
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C11D1/38—Cationic compounds
- C11D1/645—Mixtures of compounds all of which are cationic
-
- 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
Abstract
ABSTRACT OF THE DISCLOSURE
Fabric softeners in the form of aqueous solutions, emulsions or dispersions contain as quaternary ammonium compounds at least one compound of the general formula
Fabric softeners in the form of aqueous solutions, emulsions or dispersions contain as quaternary ammonium compounds at least one compound of the general formula
Description
2 ~ 8417 l FABRIC SOFTENERS BASED ON QUATERNARY
POLY(OXYALKYLENE)ALKANOLA~INE ESTERS
The present invention relates to fabric softeners in the form of aqueous solutions, emulsions or dispersions.
In the washing of textiles it is customary to employ in the last wash cycle fabric softeners in order that harshening of the fabrics by drying be avoided and the fabric hand of the treated textiles positively influenced.
The fabric softeners used are customarily cationic compounds, for example quaternary ammonium compounds which in addition to long-chain alkyl radicals may also contain ester or amide groups. It is also advantageous to use mixtures of different softening components which are added to the rinse bath in the form of aqueous dispersions.
These cationic compounds are effective softeners when used in the last rinse bath, but they do have some disadvantages in use.
One of the disadvantages of such agents is that the softening components are not dispersible in cold water;
another is that the textiles treated therewith possess unsatisfactory remoisture capability.
Remoisture capability for the purposes of the present invention is the ability of the fiber to reabsorb moisture. Inadequate remoisture capability is a disadvantage ~c, whenever text,ile fabrics are to absorb major quantities of moisture from the surface of the skin, for example in the case of hand and bath towels, underwear and bed linen.
It is an object of the present invention to overcome the abovementioned disadvantages of conventional fabric softening formulations and to make available fabric softeners which combine ready biodegradability and a soft ,, wad/SPEC/8417 . D'F8 2~
1 fabric hand with improved remoisture capability and which give a clear solution in water or exhibit significantly improved emulsifiability or dispersibility in water.
This object is achieved, surprisingly, by fabric softeners comprising ammonium compounds which contain ester groups and a liquid carrier material.
The present invention accordingly provides aqueous fabric softeners comprising A) from 5 to 35% by weight of at least one of the compounds of the general formula ~
R~ R' +2 Rj ¦ CH~ CH3¦ R3 a N-CH-CH~O-(CH~CH-~O)~-(CHCH~O)~-(CH~CH~O)c-C~-CH-N ~X x (l) Ri' CHI R~
wherein Rl, RZ, R3 and R4 are identical or different radicals of the formula R5 -(O-CH-CH2)m- wherein ~0 R
each R can independently be -H or -CH3;
R5 can be a substituted or unsubstituted acyl radical of 6-22, preferably 8-18, carbon atoms with or without a double bond, or can be H, and wherein at least one, and preferably at least two, of the Rs radicals represent such an acyl radical and at least one of the R5 radicals is H; and R6 and R', which can be identical or different, are each selected from the group consisting of H, -CH3, -C2H5 and -C2H40H;
x-x is at least one organic and/or inorganic anion;
x is 1, 2 or 3;
wad~SPEC/~417.DT~
1 a, b and c are each 0-20;
n is the sum of (a+btc) and is 1-30, preferably 1-15, and more preferably 2-8; and m is 1-5, provided that the sum of all m's is at least 4; ~ is 1 or 2; ~ equals the product ( 0 . 5 ) ~ a) ( x); and optionally B) 10-90% by weight, based on the weight of component A), of conventional ammonium compounds; and optionally lO C) 1-5% by weight of the entire composition of customary dyes, scents and further customary fabric softener auxiliaries and additives, and water to 100% by weight.
A further aspect of the present invention comprises aqueous fabric softeners which comprise 15-30~.s by weight of a compound of the general formula (1) wherein R is -CH3, two or three of the radicals Rl, R2, R3 and R4 are each Rs-O-CH2-CH2-wherein R5 is an acyl radical of 8-18 carbon atoms and the other one or two of the Rl, R2, R3 and R4 radicals are HO-CH2-CH2-; n is 1-15; R6 and R7, which can be identical or different, are each H or -CH3; and X- is a radical of a substituted or unsubstituted carboxylic acid having 1-8 carbon atoms in the main chain or the methosulfate or ethosulfate radical.
A further aspect of the present invention comprises aqueous fabric softeners comprising 15-30% by weight of a compound of the general formula (1) where R is -CH3, three of the radicals R , R2, R and R are each R -O-CH2-CH2- where R
is an acyl radical of 8-18 carbon atoms, one of the radicals R is H, n is 2-8, R and R are each H and X- is the lactate radical.
i wad~SPEC~8417.M'9 S
l Further aspects of the invention are defined by the claims.
Possible starting compounds for preparing the ammonium compounds used according to the present invention are the following amine compounds of the formula (2):
fH3 CH3 H2N-CH-CH2 - ( PO ) ~- ( EO ), ,- ( PO ) C-CH2 -CH-NHz ( 2 ) where P0 is -(0-CH2-CH)- and EO is -(0-CH2-CH2)- and where a, b and c are each 0-20 with a + b + c = n = 1-30, preferably 1-15, in particular 2-8. Preference for the purposes of the present invention is given to compounds where a + c = 1-15, in particular 2-8, and b=0.
These compounds are commercially available and are obtained by known methods by reacting polyoxyalkylene alcohols with ammonia under superatmospheric pressure.
Polyoxyalkylene alcohols are prepared by addition of an alkylene oxide, essentially propylene oxide, ethylene oxide or a mixture of the two, in a conventional manner to a compound which contains one or more active hydrogen atoms, or by polymerization of alkylene oxides.
As compounds which contain one or more active ~c hydrogen atoms it is possible to use monoalcohols such as ~ ,~
ethanol, isopropanol, butanol, lauryl alcohol, stearyl alcohol, but in particular methanol, or glycols such as ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, polyglycerol and polyvinyl alcohols.
The polyoxyalkylene alcohols have molecular weights within the range from about 100 to 10,000, preferably about 130-5,000, particularly preferably about 150-2,000.
~dJsPEC/
Z~ 8 l Further conversion into amines takes place in a conventiona~ manner by aminolysis of the free hydroxyl groups or esters thereof, in particular the sulfuric esters. In the case of higher alcohols, the OH group is exchanged for the amino group by a homogeneous or in particular heterogeneous catalysis over fixed-bed catalysts. Two methods in particular are available here. One involves dehydrating catalysts, the other hydrogenating-dehydrogenating catalysts.
Concerning temperature and pressure effects, the effect of excess ammonia and the residence times required, extensive literature is available in each case (cf. Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart 1957, volume 11/1 pp. 108 and British Patent 384,714 and US Patents 2,017,051 and 2,078,922).
Preference for the purposes of the present invention is given to the following compounds of the formula (2):
a + c = 2 - 8 (I) b = O
or a + c = 2 - 3 (II) b = 6 - 9 The compounds of the formula (2) are subsequently conventionally alkoxylated, i.e. preferably ethoxylated or propoxylated. In general this comprises reacting the amines in a pressure reactor at 120-160C, in the presence or absence of basic, in particular alkaline, catalysts, at 1-4 bar with an amount of alkylene oxide, preferably according to the present invention ethylene oxide and propylene oxide or mixtures thereof, in an amount corresponding to the desired de~ree of alkoxylation.
wad/SP~C/8417.D~8 ]- The products are compounds of the general formula (3):
R' R~
H-(O-lH-CHz) d CH3 CH3 (CH2lH-0)~-H
\ i I /
N-CH-CH2-A-CHz-CH-N (3 H-(0-CH-CHz)~ (CH2-CH-0)~-H
R9 l1O
where A is -(P0)~-(E0)~-(P0)c and where a, b, c, E0 and P0 are each as defined above and (d + e + f + g) = 4-20 and R7, R8, R9 and R10 can be independently of one another -H or -CH3.
Preferred compounds of the formula (3) are compounds where d + e + f + g = m = 4-6 (III) R7, R8, R9 and Rl = H
The subsequent esterification of the compounds (3) with carboxylic acids or derivative thereof leads to compounds of the general formula (4):
R' R3 Rl-(0-CH-CH2) a CH3 CH3 (CH2lH-o)~-R3 `N-lH-CH2-A-CH2-lH-N (4) RZ-(0-CH-CH2). (CHz-CH-o)~-R4 R9 l1O
h A d e f g R1 R2 R3, R4, R', RB, R8 and Rl are e,ach as defined above.
~ad/SPEC~8417 . DTB
~ ?~ ~
1 The fatty acids used for the esterification or transesterification are the monobasic synthetic fatty acids which are known and customary in this field, but in particular the fatty acids based on natural vegetable and animal oils of 6-22 carbon atoms, in particular 8-18 carbon atoms, for example coconut fatty acids and palm, tallow and ricinous fatty acids. They can be used not only as glycerides but also as esters with short-chain alcohols or as free acids.
Their esterification or transesterification is carried out in a conventional manner.
The alkanolamines of the formula (4) are reacted with an amount of fatty acid or fatty acid ester cor-responding to the desired degree of esterification at 160-240C in the presence or absence of a catalyst, and the wateror alcohol formed in the course of the reaction is distilled off continuously to complete the reaction, if necessary under reduced pressure.
Preferred compounds of the formula (4) are substances where one of the R1, R , R3, R radicals is -H and three of them are 1 x H
-C-R-(IV) R1 being -Cl7H3s or having been derived from the natural '- mixture of coconut fatty acids.
The quaternization or preparation of the salts of the compounds ~4) can be carried out by the methods known in this field and leads to the novel ester-amine quats or salts of the general formula (1) where R5 and R7 are each as 3 defined above.
wadJSPEC/8417.CTB
-8- 2~
1 The salts can in general be prepared by adding the acids, optionally as aqueous or alcoholic solutlons, in an amount corresponding to the desired degree of salt formation in portions and with thorough stirring to the initially charged poly~oxyalkylene)alkanolamine esters at 20-80C, with or without cooling. Quaternization is effected in a generally known manner whereby the poly(oxyalkylene)alkanolamine esters are heated to 40-80C in the presence or absence of a solvent and admixed portionwise lO with the ~uaternizing agent in an amount corresponding to the desired degree of quaternization.
The preferred anions are accordingly:
O O
Il 11 CH3-O-S-O-, CH3CH2-O-S-O-, HCOO-, CH3COO-, ll ll o o CH3-fH-COO-, OHCH2COO-, -OOf-CH-CH-COO-, OH OH OH
OH
I
-OOC-CH-CH2-COO-, -OOCCH2-C-CH2-COO-, C6H5COO-, 1H loo--OOC-(CH2)0_~0-COO-, Cl-, Br-, I-, so4--2, PO4-3-, NO3-.
It will thu be recognized that the anions useful in this invention include anions of carboxylic acids capable of forming one, two or three carboxylate (-COO~) groups.
Particular preference for the purposes of the present invention is given to the anions 3 5 wad/SPEC/8417 . M B
9 2~
o Cl-, SO~ Z, CH3-O-S-O- and/or CH3-CH-COO-O OH
it also heing possible for a plurality of anions to be present side by side and for them to be added in an amount such that the resulting pH of the total mixture of a 30%
strength mixture is between 2-6, preferably 3-5. Of course, the relative amounts of the quaternary compound and the anion(s) present must be such that they neutralize each other; that is, referring to formula(l), a equals one-half the product of ~ times the valence of the anion X.
The compounds of the general formula (1) used for the purposes of the present invention can be used alone or as mixtures, in which case - depending to some extent on the structure of the compounds of the general formula (3) - the triesters of the general formula (1) can be converted predominantly into dispersions and the diesters of the general formula (1) into solutions.
To prepare solutions it is preferable for the purposes of the present invention to use compounds of the general formula (1~ where x-x is a methosulfate or in particular a lactate radical. It has been found, sur-prisingly, that these solutions confer on textiles treated ~, therewith not only a soft fabric hand but also excellent remoisture capability even without the use of customary ammonium salts, ~uaternized ammonium compounds and other auxiliaries and additives customary in this field.
~0 Despite the omission of otherwise customary auxiliaries it is possible to prepare highly concentrated solutions which contain up to 35% by weight of pure active ingredient. The solutions are not only readily preparable wad,/SPEC/8417 . Dq'8 ~ 10-- 2~? _r ~
l using standard stirring equipment but also are free of the known problems which can arise with the storage of dispersions.
Whereas, as mentioned, the diester compounds can be prepared by simply dissolving them in cGld or, more speedily, hot water, the triester compounds are emulsified or dispersed in a conventional manner using customary equipment and the known auxiliaries and additives.
In departure from or modification of existing procedures, which customarily take the form of preheating the water up to about 10C below the clear melting range of the softeners, the compounds according to the present invention can also be incorporated at room temperature (20-25C).
Thorough stirring is employed to disperse first the dye solution in the water, then the optionally necessary antifoam emulsion and finally the individual softeners in succession or mixed. After addition of an aliquot of an electrolyte solution (if necessary), perfume oil is metered in, followed by the remaining electrolyte solution. For the purposes of the present invention it is preferable not add an electrolyte solution.
The fabric softeners according to the present invention can each contain one or more of the components of the qeneral formula ~1) and optionally in addition 10-50% by weight, preferably 10-~% by weight, based on the amount of the compounds of the general formula (1), of one or more compounds of the formula (5) which can be prepared from hydroxyalkylenediamines and Cl6~c22 fatty acid in molar ratios of from 1:2 to 1:1:
Rll-co-NH-Rl3-N ( -Rl20H ) -CORll X ( 5 ~
3~ wad/SP~:C/8417.DT8 ~ ? ~ ~
1 where Rl1 is a substituted or unsubstituted alkyl or alkylene radical of 15-21 carbon atoms and R12 and R1 3 are divalent C1-C3-alkylene radicals, and/or 5 (6) substituted imidazolines of the general formula Rl4 I
~/N-cH2 R11_c ¦ ~ X-l (6 \ N-CH2 Ho_Rl 2 where R11 and R1 2 are each as defined above and R1 4 is H or a Cl-C4-alkyl or -hydroxyalkyl radical, and/or (7~ compounds of the formula Rl4 I
Rll-C~ I . X-1 (7) \ N-CH2 /
Rl 1 -C_O_Rl 2 where each R11, R12 and R14 is independently as ~efined above, and/or (8) reaction products of C1~-C2z fatty acids with dialkylenetriamines in a molar ratio of 2:1 Rl 1- Co-NH-Rl 2 -N~R1 4 ) 2 -Rl 3 -NHCORl 1 X- 1 (8) o where R11 R12 R13 and R14 are each independentlY
as defined above, and/or uad/SPEC/8417 . Dlq~
-12- 2~8~
l (9) substituted imidazolines of the general formula Rl4 Rll-C~ I . X-l (9) \N-CH2 O
Rl 1- C_NH_Rl 2 where R1l, Rl2 and R14 are each independently as defined above, and wherein the compounds of the formùlae (5) to (9) can each be present independently of one another, as a whole or in part, in the form of their salts with organic and/or inorganic acids or in the form of their quaternary compounds, and/or (10) quaternary ammonium compounds of the general formula [NRl5Rl6Rl7Rl~ ] +X- ( 10 ) where Rl5 is a substituted or unsubstituted alkyl or alkylene radical of 16-22 carbon atoms, Rl6 and Rl' are independently of one another C1-C4-alkyl or -hydroxyalkyl radicals, Rl8 is the same as Rl5 or R1G, and X~ is an anion.
These products are commercially available for example under the registered trademark REWOQUAT of REWO
Chemische Werke GmbH, Steinau an der StraBe, or the registered trademark VARISORT of Sherex Chemicals Group, 3 Inc., Ohio, USA.
~ SPEC~8417.DTB
2~
1 The mixing ratios in which these compounds are added can be optimized by the person sXilled in the art on the lines of generally known criteria by means of a few orienting experiments.
In addition to the softening components of the general formula (1) the fabric softeners according to the present invention can include the customary auxiliaries and additives. These are in particular dyes, scents, electrolytes and high molecular weight ether compounds for viscosity 1~ regulation, small amounts of organic solvents and - provided they have no adverse effect on the remoisture capability -customary cationic andJor nonionic surfactants.
By combining the components of the general formula (1) and optionally commercially available quaternary ammonium compounds and optionally auxiliaries it is possible to prepare fabric softeners which give a clear solution in water or are readily emulsifiable or dispersible and confer not only a pleasantly soft fabric hand but also improved remoisture capability on textile materials, in particular those made of natural and regenerated cellulose and also wool and terry.
The fabric softeners according to the present invention are therefore used not only on the usual textile materials but in particular wherever large amounts of wetness and moisture are to be removed from the body surface within a short time, such as on hand or bath towels. But the fabric softeners are also successfully usable where moisture has to be absorbed directly from the skin within longer time spans, such as on underwear or bed linen.
Like the prior art fabric softeners, the fabric softeners according to the present invention are added to the last rinse cycle immediately following the actual washing wad~SPl~C/8417.D~8 1 process. The concentration used after dilution with water varies with the field of application within the range from 0.1 to 10 g of fabric softener per liter of wash water.
In the examples which follow, the analytical methods employed are those generally customary in this field, specifically:
1. Total amine number (TOT), tertiary amine number ( TERT ) The total amine number indicates the number of milligrams of potassium hydroxide which are equivalent to the total amine basicity of 1 g of the amine compound (mg of KOH/g). The tertiary amine number indicates the number of milligrams of potassium hydroxide which are equivalent to the tertiary amine basicity of 1 g of the amine compound.
The values are determined by A.O.C.S. Official Method Tf 2a - 64.
2. SaPonification number (SN) The saponification number is a measure of the free and bound acids contained in fats and technical grade fatty acids. It indicates the number of milligrams of potassium hydroxide required to saponify 1 gram of fat or technical grade fatty acid (mg of KOH/g).
The values are determined by the standard methods of the German Society for Fat Chemistry (DGF): DGF C-V3.
3. HYdroxYl number ~OHN) The hydroxyl number is used to determine the hydroxyl group content and it indicates the number of milligrams of potassium hydroxide necessary for neutralizing the acetic acid consumed by 1 gram of fat in the course of acetylation (mg of KOH/g).
The values are determined by DGF standard method C-V17a.
w~d/SPE~C~1417 . DTB
~ ~ ~?
1 4 Acid number ~AN) The acid number is the measure of the free acid content of a fat or technical grade fatty acid and indicates the milligrams of potassium hydroxide which are necessary for neutralizing 1 gram of substance.
The values are determined by DGF standard method C-V4.
5. Cationics content (cat S031 This method is used for determining the level of cationic substances. Here the cationic substances are long-chain compounds which contain quaternary ammonium groups. The content i5 reported in percent of quaternary compound calculated as S03 equivalent with a molecular weight of 80 g/mol.
It is determined by a two-phase titration as described in ISO standards 2871-1 and 2871-2 (1988 E).
PreParation of poly(oxyalkylene)ammonium alkanol esters Examples I. Preparation of hydroxylamines of formula (3) Example 1 912 g (2 mol) of an amine of formula (2) where a + c = 6.6 b = 0 were admixed in an autoclave at 145-160~C with 352 g (8 mol) of ethylene oxide in portions so that the pressure was maintained between 1-3 bar.
Complete reaction of the added amount of ethylene oxide gave 1.264 g of a light-colored liquid of general formula (3) where 30 a + c = 6.6 b = 0 d + e + f + g = m = 4 and R , R , R , R = H
Wld~SP~C~84l7.~8 z~ a l This compound had a total amine number (TOT) of 179 mg of KOH/g, a tertiary amine number (TERT) of 175 mg of KOH/g and a hydroxyl number (OHN) of 348 mg of KOH/g.
The examples listed in Table I were prepared in a similar manner to Example 1.
~5 3o . i 3 5 w~d~ SE EC ~ 8 417 . DT3 2~ .?~3 '~ Sl - --~LE I
¦ Ex. U e of Compc ~Inds of Fc rmula 2 Wh re Resulti og 7COmlDoOU ~d6 of Fo ~ula 3 ~ ~¦
¦_ a +c= b-- molEO ) mold~e f ig= ~ -~ TOT TE~ ~¦
l 2 6.6 0 2 8 _ B q 141 141 296 ~ __ 11 l 3 2. 8 O 1 4 _ S U 275 268 567 4 2.8 0 1 8 _ B H 197 197 439 2.5 9 1 4 _.~ :~ 144 142 291 1 6 6.6 O 2 _ 8 4 CH} 163162 ~¦
EO = ethylene oxide PO ~ DroDylene oxide 3o wad~SPEC~8417. D~3 -18~
1 II. Preparation of ester-amines of formula (4) Example 7 625 g (1 mol) of the amine-ethoxylate of Example 1 were admixed with 570 g (2 mol) of tallow methyl ester (Cl7H3sCOOCH3), 1.5 g of solid, pulverulent NaOH and 3 g of sodium hypophosphite and stirred under nitrogen and heated to 180C. The methanol formed in the course of the reaction was distilled off. After about 90% of the theoretical quantity of methanol had been removed, a vacuum of about 20 mbar was 1 applied to complete the transesterification. About 7 hours produced 1.135 g of a yellow liquid of general formula (4) where a + c = 6.6 b = 0 d + e + f + g = m = 4 R7 Ra R9 R10 = H
2 of (R , R, R, R ) = H
f (R1 R7 R3, R4) = -C(O)~Cl7H33 The compound had the following analysis numbers:
TOT = 98 mg KOH/g TERT = 97 mg KOH/g OHN = 93 mg KOH/g SN = 106 mg KOH/g The examples listed in Table II were prepared ir. a similar manner to Example 7.
3o wzld~SPEC~B417 . Dq~3 -- i 9 2 ~ J r ~ ~ 3 1~ -¦ T~8LE II
Exa~ple of Eatty acid Rosulting compound of formula 4 where Ex. (ester3 Table I ¦ mol C ¦ mol n x ~ ¦ n x ester 7 1 1 18a) 2 2 2 sa 9793 8 1 1 la 3 1 3 78 74 57117 ¦¦
9 2 1 18 2 2 Z 89_ 88 8882 10 5 1 18 2 2 _ 86 85 86 _ __ ._ _~
_ 12_ 1 1 18b) 2 2 2 93 9395 98 13 1 1 18a3 1 3 128 128 64 191 __ b3 Tallow methyl ester Tallow fatty acld 1~
3o wad~SPEC~8417.DF8 l III. Preparation of quaternary ammonium compounds or amine salts Example 14 To 1.149 g (1 mol) of the ester of Example 7 were added at 60C with stirring 252 g (2 mol) of dimethyl su'fate in portions so that the temperature of the reaction mixture was maintained between 60-70C. This produced 1.397 g of a yellow liquid of formula (1) where a + c + b = n a + c = 6.6 b = 0 d + e + f + g = m = 4 R' R8 R9 R10 = H
2 of (R1, R2 R3 R4) = H
2 of (R1, R2, R3, R4) = -C(O)-C H
R~ and R' = -CH3 X- = 2 x -OS-OCH3 O
The analysis numbers of these compounds are:
Cat SO3 acid : 9.6 g of SO3/100 g ~5 TOT : 2.3 mg of KOH/g The examples listed below in Table II were carried out in a similar manner to Example 14.
3o wad/SPEC/8417 . DTB
-21- 2~
TABLE III
Resultins compounds of formula A where l Example of Quaternl~ing Agent/Acid ~ ~able I~ mol mol R6 R7 ~ Cat SO I ~CT I DH
14 7 I 2 Dimethyl sulfate CH3 1 2 9.6 2.3 7 1 2 Lactlc acid H 2 10.0 5.2 16 7 1 I Dlmethyl ~ulfate ' 1 CH3 2 10.1 l 1 Lactlc Acid 1 H
1 0 17 10 1 2 Dlmethyl sulfate CH3 2 9.0 2.2 18 7 1 2 HCl H 2 10.3 4.2 ~ __ ' pH in 1:1 isopropanol~water at 20C
' at 60-70C ln that order 3o ~ad~SPEC~8417.~8 ~ 2 2 ;~ r~
l IV. Application testinq A) Preparation of fabric softener solutions or dispersions Method 1 Charge water, dye solution and optionally an aliquot of electrolyte at 15C. Gradually emulsify in the component at 23C with stirring (propeller stirrer) or emulsify in the components in succession or as a mixture under identical conditions. During the emulsifying add further aliquots of electrolyte if necessary. Then add the perfume oil with stirring and if necessary after the emulsifying process the remaining electrolyte to adjust the viscosity.
The result is a homogeneous emulsion or solution.
Method 2 Charge water, dye solution and optionally an aliquot of electrolyte at 45C. Gradually emulsify in the component at 55C with stirring (propeller stirrer) or emulsify in the components in succession or as a mixture under identical conditions. During the emulsifying add further aliquots of electrolyte if necessary.
Stir the batch until it has cooled down to about 25C. Then add the perfume oil with stirring and if necessary adjust the viscosity with the remaining electrolyte.
The result is a homogeneous emulsion or solution.
B) Verification of soft fabric hand To assess the fabric hand, the textile material, made of wool, cotton, 50:3 polyester/cotton and polyester, is treated for about 10 minutes with a liquor comprising tap water (about 9 German hardness and a temperature of 15-20C) and the novel emulsion, dispersion or solution. The concentration of the compounds according to the present wdd/spEc~s4l7.
l invention in the liquor is 0.025% by weight, based on the total acti~e ingredient. The dried textiles were checked by nine people with experience in the assessment of the softness of textiles in respect of their soft fabric hand and assessed against texti~es which had not been treated with fabric softeners. The assessments are rated according to a graduated point system, the final reported result being the arithmetic average. After drying, the textile materials treated have an excellent soft fluffy fabric hand and, compared with commercially available agents, a much improved remoisture capability.
C) Examples Example 1 - 15.0 g of a compound according to formula (1) wherein three of R1, R2, R3 and R4 were radicals in which R was C8 18 acyl and one of them was a radical in which R was -H; all R groups were -H; R5 and R
were -H; the average value of n was 5.6; and X x was lactate;
0.7 g of dye (1% solution of SANDOLANR milling blue NBL 150; from Sandoz) - to 100.0 g water of 13 German hardness Introduce water-dye solution at 45C, emulsify in the component at 55C with stirring (propeller stirrer) and then stir the batch until cold. The _, result is a homogeneous emulsion.
Viscosity (20C measured with Brookfield LVT, spindle l at 30 rpm): < 100 mPa s The examples which follow were prepared in a similar manner to Example 1.
wadJSPE:C/8417 i~'F8 l Example 2 - 30.0 g of a compound according to formula (1) wherein three of R, R, R and R were radicals in which R was C8 18 acyl and one of them was a radical in which R was -H; all R groups were -H; R and R
were -H; the average value of n was 5.6; and X
was lactate;
- 1.3 g of dye - to 100.0 g water of 13 German hardness The result is a homogeneous emulsion.
Viscosity about 10 mPa s Example 3 - 15.0 g of a compound according to formula (1) wherein two of Rl, R2, R3 and R4 were radicals in which R was C818 acyl, and two of them were radicals in which R was -H; all R groups were -H;
R and R were -CH3; the average value of n was 5.6;
and xX was methylsulfate;
- 0.7 g of dye ~ to 100.0 g water of 13 German hardness The result is a clear solution.
Viscosity < 100 mPa s Remoisture capability = 94%
Example 4 - 15.0 g of a compound according to formula (1) wherein three of R1, R2, R and R were radicals in which R5 was C8 18 acyl, and one of them was a radical in which R was -H; all R groups were -H;
R and R were -CH3; the average value of n was 5.6;
and XX was methylsulfate;
- 0.7 g of dye - to 100.0 g water of 13 German hardness wa~/SP!~C~8417 . Dlr8 2~r'?~
l The result is a homogeneous solution.
Viscosity < 100 mPa s Example 5 - 15.0 g of a compound according to formula (1) wherein two of R1, R2, R3 and R4 were radicals in which R was C818 acyl, and two were radicals in which Rs was -H; all R groups were -H; R was -CH3;
R was -H; the average value of n was 5.6; and XX
was both methylsulfate and chloride;
10 ~ 0-7 g of dye - to 100.0 g water of 13 German hardness The result is a clear solution~
Viscosity < 100 mPa s Remoisture capability > 90%
Example 6 - 3.0 g of a compound according to formula ~1) wherein two of R1, R2, R3 and R4 were radicals in which R5 was C818 acyl and two of them were radicals in which Rs was -H; all R groups were -H; R and R
were -CH3; the average value of n was 5.6; and XX
was methylsulfate;
- 12.0 g of a second compound according to formula (1) wherein two of R1, R2, R3 and R4 were radicals in which R was C818 acyl, and two were radicals in which Rs was -H; all R groups were -H; R5 and R7 were -H; the average value of n was 5.6; and X-X
was lactate;
- 0.7 g of dye - to 100.0 g water of 13 German hardness The result is a clear solution.
Viscosity < 100 mPa s Remoisture capability = 95%
wad~SP~C/8417.~3 2 ~ r ~
1 ExamPle 7 - 15.0 g of a compound according to formula (1) wherein three R1, RZ, R and R4 were radicals in which R was C81,3 acyl, and one was a radical in which R was -H; all R groups were -H; R and R
were -CH3; the average value of n was 5.6; and XX
was methylsulfate;
- 15.0 g of a compound according to formula (1) wherein three R1, R2, R3 and R4 were radicals in which R was C8 18 acyl, and one was a radical in which Rs was -H; all R groups were -H; R6 and R
were -CH3; the average value of n was 5.6; and XX
was lactate;
- 0.7 g of dye to 100.0 g water of 13 German hardness The result is a homogeneous solution.
Viscosity about 200 mPa-s Remoisture capability about 85%
3o wz~d/~;PEC~8417 .D'P8
POLY(OXYALKYLENE)ALKANOLA~INE ESTERS
The present invention relates to fabric softeners in the form of aqueous solutions, emulsions or dispersions.
In the washing of textiles it is customary to employ in the last wash cycle fabric softeners in order that harshening of the fabrics by drying be avoided and the fabric hand of the treated textiles positively influenced.
The fabric softeners used are customarily cationic compounds, for example quaternary ammonium compounds which in addition to long-chain alkyl radicals may also contain ester or amide groups. It is also advantageous to use mixtures of different softening components which are added to the rinse bath in the form of aqueous dispersions.
These cationic compounds are effective softeners when used in the last rinse bath, but they do have some disadvantages in use.
One of the disadvantages of such agents is that the softening components are not dispersible in cold water;
another is that the textiles treated therewith possess unsatisfactory remoisture capability.
Remoisture capability for the purposes of the present invention is the ability of the fiber to reabsorb moisture. Inadequate remoisture capability is a disadvantage ~c, whenever text,ile fabrics are to absorb major quantities of moisture from the surface of the skin, for example in the case of hand and bath towels, underwear and bed linen.
It is an object of the present invention to overcome the abovementioned disadvantages of conventional fabric softening formulations and to make available fabric softeners which combine ready biodegradability and a soft ,, wad/SPEC/8417 . D'F8 2~
1 fabric hand with improved remoisture capability and which give a clear solution in water or exhibit significantly improved emulsifiability or dispersibility in water.
This object is achieved, surprisingly, by fabric softeners comprising ammonium compounds which contain ester groups and a liquid carrier material.
The present invention accordingly provides aqueous fabric softeners comprising A) from 5 to 35% by weight of at least one of the compounds of the general formula ~
R~ R' +2 Rj ¦ CH~ CH3¦ R3 a N-CH-CH~O-(CH~CH-~O)~-(CHCH~O)~-(CH~CH~O)c-C~-CH-N ~X x (l) Ri' CHI R~
wherein Rl, RZ, R3 and R4 are identical or different radicals of the formula R5 -(O-CH-CH2)m- wherein ~0 R
each R can independently be -H or -CH3;
R5 can be a substituted or unsubstituted acyl radical of 6-22, preferably 8-18, carbon atoms with or without a double bond, or can be H, and wherein at least one, and preferably at least two, of the Rs radicals represent such an acyl radical and at least one of the R5 radicals is H; and R6 and R', which can be identical or different, are each selected from the group consisting of H, -CH3, -C2H5 and -C2H40H;
x-x is at least one organic and/or inorganic anion;
x is 1, 2 or 3;
wad~SPEC/~417.DT~
1 a, b and c are each 0-20;
n is the sum of (a+btc) and is 1-30, preferably 1-15, and more preferably 2-8; and m is 1-5, provided that the sum of all m's is at least 4; ~ is 1 or 2; ~ equals the product ( 0 . 5 ) ~ a) ( x); and optionally B) 10-90% by weight, based on the weight of component A), of conventional ammonium compounds; and optionally lO C) 1-5% by weight of the entire composition of customary dyes, scents and further customary fabric softener auxiliaries and additives, and water to 100% by weight.
A further aspect of the present invention comprises aqueous fabric softeners which comprise 15-30~.s by weight of a compound of the general formula (1) wherein R is -CH3, two or three of the radicals Rl, R2, R3 and R4 are each Rs-O-CH2-CH2-wherein R5 is an acyl radical of 8-18 carbon atoms and the other one or two of the Rl, R2, R3 and R4 radicals are HO-CH2-CH2-; n is 1-15; R6 and R7, which can be identical or different, are each H or -CH3; and X- is a radical of a substituted or unsubstituted carboxylic acid having 1-8 carbon atoms in the main chain or the methosulfate or ethosulfate radical.
A further aspect of the present invention comprises aqueous fabric softeners comprising 15-30% by weight of a compound of the general formula (1) where R is -CH3, three of the radicals R , R2, R and R are each R -O-CH2-CH2- where R
is an acyl radical of 8-18 carbon atoms, one of the radicals R is H, n is 2-8, R and R are each H and X- is the lactate radical.
i wad~SPEC~8417.M'9 S
l Further aspects of the invention are defined by the claims.
Possible starting compounds for preparing the ammonium compounds used according to the present invention are the following amine compounds of the formula (2):
fH3 CH3 H2N-CH-CH2 - ( PO ) ~- ( EO ), ,- ( PO ) C-CH2 -CH-NHz ( 2 ) where P0 is -(0-CH2-CH)- and EO is -(0-CH2-CH2)- and where a, b and c are each 0-20 with a + b + c = n = 1-30, preferably 1-15, in particular 2-8. Preference for the purposes of the present invention is given to compounds where a + c = 1-15, in particular 2-8, and b=0.
These compounds are commercially available and are obtained by known methods by reacting polyoxyalkylene alcohols with ammonia under superatmospheric pressure.
Polyoxyalkylene alcohols are prepared by addition of an alkylene oxide, essentially propylene oxide, ethylene oxide or a mixture of the two, in a conventional manner to a compound which contains one or more active hydrogen atoms, or by polymerization of alkylene oxides.
As compounds which contain one or more active ~c hydrogen atoms it is possible to use monoalcohols such as ~ ,~
ethanol, isopropanol, butanol, lauryl alcohol, stearyl alcohol, but in particular methanol, or glycols such as ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, polyglycerol and polyvinyl alcohols.
The polyoxyalkylene alcohols have molecular weights within the range from about 100 to 10,000, preferably about 130-5,000, particularly preferably about 150-2,000.
~dJsPEC/
Z~ 8 l Further conversion into amines takes place in a conventiona~ manner by aminolysis of the free hydroxyl groups or esters thereof, in particular the sulfuric esters. In the case of higher alcohols, the OH group is exchanged for the amino group by a homogeneous or in particular heterogeneous catalysis over fixed-bed catalysts. Two methods in particular are available here. One involves dehydrating catalysts, the other hydrogenating-dehydrogenating catalysts.
Concerning temperature and pressure effects, the effect of excess ammonia and the residence times required, extensive literature is available in each case (cf. Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart 1957, volume 11/1 pp. 108 and British Patent 384,714 and US Patents 2,017,051 and 2,078,922).
Preference for the purposes of the present invention is given to the following compounds of the formula (2):
a + c = 2 - 8 (I) b = O
or a + c = 2 - 3 (II) b = 6 - 9 The compounds of the formula (2) are subsequently conventionally alkoxylated, i.e. preferably ethoxylated or propoxylated. In general this comprises reacting the amines in a pressure reactor at 120-160C, in the presence or absence of basic, in particular alkaline, catalysts, at 1-4 bar with an amount of alkylene oxide, preferably according to the present invention ethylene oxide and propylene oxide or mixtures thereof, in an amount corresponding to the desired de~ree of alkoxylation.
wad/SP~C/8417.D~8 ]- The products are compounds of the general formula (3):
R' R~
H-(O-lH-CHz) d CH3 CH3 (CH2lH-0)~-H
\ i I /
N-CH-CH2-A-CHz-CH-N (3 H-(0-CH-CHz)~ (CH2-CH-0)~-H
R9 l1O
where A is -(P0)~-(E0)~-(P0)c and where a, b, c, E0 and P0 are each as defined above and (d + e + f + g) = 4-20 and R7, R8, R9 and R10 can be independently of one another -H or -CH3.
Preferred compounds of the formula (3) are compounds where d + e + f + g = m = 4-6 (III) R7, R8, R9 and Rl = H
The subsequent esterification of the compounds (3) with carboxylic acids or derivative thereof leads to compounds of the general formula (4):
R' R3 Rl-(0-CH-CH2) a CH3 CH3 (CH2lH-o)~-R3 `N-lH-CH2-A-CH2-lH-N (4) RZ-(0-CH-CH2). (CHz-CH-o)~-R4 R9 l1O
h A d e f g R1 R2 R3, R4, R', RB, R8 and Rl are e,ach as defined above.
~ad/SPEC~8417 . DTB
~ ?~ ~
1 The fatty acids used for the esterification or transesterification are the monobasic synthetic fatty acids which are known and customary in this field, but in particular the fatty acids based on natural vegetable and animal oils of 6-22 carbon atoms, in particular 8-18 carbon atoms, for example coconut fatty acids and palm, tallow and ricinous fatty acids. They can be used not only as glycerides but also as esters with short-chain alcohols or as free acids.
Their esterification or transesterification is carried out in a conventional manner.
The alkanolamines of the formula (4) are reacted with an amount of fatty acid or fatty acid ester cor-responding to the desired degree of esterification at 160-240C in the presence or absence of a catalyst, and the wateror alcohol formed in the course of the reaction is distilled off continuously to complete the reaction, if necessary under reduced pressure.
Preferred compounds of the formula (4) are substances where one of the R1, R , R3, R radicals is -H and three of them are 1 x H
-C-R-(IV) R1 being -Cl7H3s or having been derived from the natural '- mixture of coconut fatty acids.
The quaternization or preparation of the salts of the compounds ~4) can be carried out by the methods known in this field and leads to the novel ester-amine quats or salts of the general formula (1) where R5 and R7 are each as 3 defined above.
wadJSPEC/8417.CTB
-8- 2~
1 The salts can in general be prepared by adding the acids, optionally as aqueous or alcoholic solutlons, in an amount corresponding to the desired degree of salt formation in portions and with thorough stirring to the initially charged poly~oxyalkylene)alkanolamine esters at 20-80C, with or without cooling. Quaternization is effected in a generally known manner whereby the poly(oxyalkylene)alkanolamine esters are heated to 40-80C in the presence or absence of a solvent and admixed portionwise lO with the ~uaternizing agent in an amount corresponding to the desired degree of quaternization.
The preferred anions are accordingly:
O O
Il 11 CH3-O-S-O-, CH3CH2-O-S-O-, HCOO-, CH3COO-, ll ll o o CH3-fH-COO-, OHCH2COO-, -OOf-CH-CH-COO-, OH OH OH
OH
I
-OOC-CH-CH2-COO-, -OOCCH2-C-CH2-COO-, C6H5COO-, 1H loo--OOC-(CH2)0_~0-COO-, Cl-, Br-, I-, so4--2, PO4-3-, NO3-.
It will thu be recognized that the anions useful in this invention include anions of carboxylic acids capable of forming one, two or three carboxylate (-COO~) groups.
Particular preference for the purposes of the present invention is given to the anions 3 5 wad/SPEC/8417 . M B
9 2~
o Cl-, SO~ Z, CH3-O-S-O- and/or CH3-CH-COO-O OH
it also heing possible for a plurality of anions to be present side by side and for them to be added in an amount such that the resulting pH of the total mixture of a 30%
strength mixture is between 2-6, preferably 3-5. Of course, the relative amounts of the quaternary compound and the anion(s) present must be such that they neutralize each other; that is, referring to formula(l), a equals one-half the product of ~ times the valence of the anion X.
The compounds of the general formula (1) used for the purposes of the present invention can be used alone or as mixtures, in which case - depending to some extent on the structure of the compounds of the general formula (3) - the triesters of the general formula (1) can be converted predominantly into dispersions and the diesters of the general formula (1) into solutions.
To prepare solutions it is preferable for the purposes of the present invention to use compounds of the general formula (1~ where x-x is a methosulfate or in particular a lactate radical. It has been found, sur-prisingly, that these solutions confer on textiles treated ~, therewith not only a soft fabric hand but also excellent remoisture capability even without the use of customary ammonium salts, ~uaternized ammonium compounds and other auxiliaries and additives customary in this field.
~0 Despite the omission of otherwise customary auxiliaries it is possible to prepare highly concentrated solutions which contain up to 35% by weight of pure active ingredient. The solutions are not only readily preparable wad,/SPEC/8417 . Dq'8 ~ 10-- 2~? _r ~
l using standard stirring equipment but also are free of the known problems which can arise with the storage of dispersions.
Whereas, as mentioned, the diester compounds can be prepared by simply dissolving them in cGld or, more speedily, hot water, the triester compounds are emulsified or dispersed in a conventional manner using customary equipment and the known auxiliaries and additives.
In departure from or modification of existing procedures, which customarily take the form of preheating the water up to about 10C below the clear melting range of the softeners, the compounds according to the present invention can also be incorporated at room temperature (20-25C).
Thorough stirring is employed to disperse first the dye solution in the water, then the optionally necessary antifoam emulsion and finally the individual softeners in succession or mixed. After addition of an aliquot of an electrolyte solution (if necessary), perfume oil is metered in, followed by the remaining electrolyte solution. For the purposes of the present invention it is preferable not add an electrolyte solution.
The fabric softeners according to the present invention can each contain one or more of the components of the qeneral formula ~1) and optionally in addition 10-50% by weight, preferably 10-~% by weight, based on the amount of the compounds of the general formula (1), of one or more compounds of the formula (5) which can be prepared from hydroxyalkylenediamines and Cl6~c22 fatty acid in molar ratios of from 1:2 to 1:1:
Rll-co-NH-Rl3-N ( -Rl20H ) -CORll X ( 5 ~
3~ wad/SP~:C/8417.DT8 ~ ? ~ ~
1 where Rl1 is a substituted or unsubstituted alkyl or alkylene radical of 15-21 carbon atoms and R12 and R1 3 are divalent C1-C3-alkylene radicals, and/or 5 (6) substituted imidazolines of the general formula Rl4 I
~/N-cH2 R11_c ¦ ~ X-l (6 \ N-CH2 Ho_Rl 2 where R11 and R1 2 are each as defined above and R1 4 is H or a Cl-C4-alkyl or -hydroxyalkyl radical, and/or (7~ compounds of the formula Rl4 I
Rll-C~ I . X-1 (7) \ N-CH2 /
Rl 1 -C_O_Rl 2 where each R11, R12 and R14 is independently as ~efined above, and/or (8) reaction products of C1~-C2z fatty acids with dialkylenetriamines in a molar ratio of 2:1 Rl 1- Co-NH-Rl 2 -N~R1 4 ) 2 -Rl 3 -NHCORl 1 X- 1 (8) o where R11 R12 R13 and R14 are each independentlY
as defined above, and/or uad/SPEC/8417 . Dlq~
-12- 2~8~
l (9) substituted imidazolines of the general formula Rl4 Rll-C~ I . X-l (9) \N-CH2 O
Rl 1- C_NH_Rl 2 where R1l, Rl2 and R14 are each independently as defined above, and wherein the compounds of the formùlae (5) to (9) can each be present independently of one another, as a whole or in part, in the form of their salts with organic and/or inorganic acids or in the form of their quaternary compounds, and/or (10) quaternary ammonium compounds of the general formula [NRl5Rl6Rl7Rl~ ] +X- ( 10 ) where Rl5 is a substituted or unsubstituted alkyl or alkylene radical of 16-22 carbon atoms, Rl6 and Rl' are independently of one another C1-C4-alkyl or -hydroxyalkyl radicals, Rl8 is the same as Rl5 or R1G, and X~ is an anion.
These products are commercially available for example under the registered trademark REWOQUAT of REWO
Chemische Werke GmbH, Steinau an der StraBe, or the registered trademark VARISORT of Sherex Chemicals Group, 3 Inc., Ohio, USA.
~ SPEC~8417.DTB
2~
1 The mixing ratios in which these compounds are added can be optimized by the person sXilled in the art on the lines of generally known criteria by means of a few orienting experiments.
In addition to the softening components of the general formula (1) the fabric softeners according to the present invention can include the customary auxiliaries and additives. These are in particular dyes, scents, electrolytes and high molecular weight ether compounds for viscosity 1~ regulation, small amounts of organic solvents and - provided they have no adverse effect on the remoisture capability -customary cationic andJor nonionic surfactants.
By combining the components of the general formula (1) and optionally commercially available quaternary ammonium compounds and optionally auxiliaries it is possible to prepare fabric softeners which give a clear solution in water or are readily emulsifiable or dispersible and confer not only a pleasantly soft fabric hand but also improved remoisture capability on textile materials, in particular those made of natural and regenerated cellulose and also wool and terry.
The fabric softeners according to the present invention are therefore used not only on the usual textile materials but in particular wherever large amounts of wetness and moisture are to be removed from the body surface within a short time, such as on hand or bath towels. But the fabric softeners are also successfully usable where moisture has to be absorbed directly from the skin within longer time spans, such as on underwear or bed linen.
Like the prior art fabric softeners, the fabric softeners according to the present invention are added to the last rinse cycle immediately following the actual washing wad~SPl~C/8417.D~8 1 process. The concentration used after dilution with water varies with the field of application within the range from 0.1 to 10 g of fabric softener per liter of wash water.
In the examples which follow, the analytical methods employed are those generally customary in this field, specifically:
1. Total amine number (TOT), tertiary amine number ( TERT ) The total amine number indicates the number of milligrams of potassium hydroxide which are equivalent to the total amine basicity of 1 g of the amine compound (mg of KOH/g). The tertiary amine number indicates the number of milligrams of potassium hydroxide which are equivalent to the tertiary amine basicity of 1 g of the amine compound.
The values are determined by A.O.C.S. Official Method Tf 2a - 64.
2. SaPonification number (SN) The saponification number is a measure of the free and bound acids contained in fats and technical grade fatty acids. It indicates the number of milligrams of potassium hydroxide required to saponify 1 gram of fat or technical grade fatty acid (mg of KOH/g).
The values are determined by the standard methods of the German Society for Fat Chemistry (DGF): DGF C-V3.
3. HYdroxYl number ~OHN) The hydroxyl number is used to determine the hydroxyl group content and it indicates the number of milligrams of potassium hydroxide necessary for neutralizing the acetic acid consumed by 1 gram of fat in the course of acetylation (mg of KOH/g).
The values are determined by DGF standard method C-V17a.
w~d/SPE~C~1417 . DTB
~ ~ ~?
1 4 Acid number ~AN) The acid number is the measure of the free acid content of a fat or technical grade fatty acid and indicates the milligrams of potassium hydroxide which are necessary for neutralizing 1 gram of substance.
The values are determined by DGF standard method C-V4.
5. Cationics content (cat S031 This method is used for determining the level of cationic substances. Here the cationic substances are long-chain compounds which contain quaternary ammonium groups. The content i5 reported in percent of quaternary compound calculated as S03 equivalent with a molecular weight of 80 g/mol.
It is determined by a two-phase titration as described in ISO standards 2871-1 and 2871-2 (1988 E).
PreParation of poly(oxyalkylene)ammonium alkanol esters Examples I. Preparation of hydroxylamines of formula (3) Example 1 912 g (2 mol) of an amine of formula (2) where a + c = 6.6 b = 0 were admixed in an autoclave at 145-160~C with 352 g (8 mol) of ethylene oxide in portions so that the pressure was maintained between 1-3 bar.
Complete reaction of the added amount of ethylene oxide gave 1.264 g of a light-colored liquid of general formula (3) where 30 a + c = 6.6 b = 0 d + e + f + g = m = 4 and R , R , R , R = H
Wld~SP~C~84l7.~8 z~ a l This compound had a total amine number (TOT) of 179 mg of KOH/g, a tertiary amine number (TERT) of 175 mg of KOH/g and a hydroxyl number (OHN) of 348 mg of KOH/g.
The examples listed in Table I were prepared in a similar manner to Example 1.
~5 3o . i 3 5 w~d~ SE EC ~ 8 417 . DT3 2~ .?~3 '~ Sl - --~LE I
¦ Ex. U e of Compc ~Inds of Fc rmula 2 Wh re Resulti og 7COmlDoOU ~d6 of Fo ~ula 3 ~ ~¦
¦_ a +c= b-- molEO ) mold~e f ig= ~ -~ TOT TE~ ~¦
l 2 6.6 0 2 8 _ B q 141 141 296 ~ __ 11 l 3 2. 8 O 1 4 _ S U 275 268 567 4 2.8 0 1 8 _ B H 197 197 439 2.5 9 1 4 _.~ :~ 144 142 291 1 6 6.6 O 2 _ 8 4 CH} 163162 ~¦
EO = ethylene oxide PO ~ DroDylene oxide 3o wad~SPEC~8417. D~3 -18~
1 II. Preparation of ester-amines of formula (4) Example 7 625 g (1 mol) of the amine-ethoxylate of Example 1 were admixed with 570 g (2 mol) of tallow methyl ester (Cl7H3sCOOCH3), 1.5 g of solid, pulverulent NaOH and 3 g of sodium hypophosphite and stirred under nitrogen and heated to 180C. The methanol formed in the course of the reaction was distilled off. After about 90% of the theoretical quantity of methanol had been removed, a vacuum of about 20 mbar was 1 applied to complete the transesterification. About 7 hours produced 1.135 g of a yellow liquid of general formula (4) where a + c = 6.6 b = 0 d + e + f + g = m = 4 R7 Ra R9 R10 = H
2 of (R , R, R, R ) = H
f (R1 R7 R3, R4) = -C(O)~Cl7H33 The compound had the following analysis numbers:
TOT = 98 mg KOH/g TERT = 97 mg KOH/g OHN = 93 mg KOH/g SN = 106 mg KOH/g The examples listed in Table II were prepared ir. a similar manner to Example 7.
3o wzld~SPEC~B417 . Dq~3 -- i 9 2 ~ J r ~ ~ 3 1~ -¦ T~8LE II
Exa~ple of Eatty acid Rosulting compound of formula 4 where Ex. (ester3 Table I ¦ mol C ¦ mol n x ~ ¦ n x ester 7 1 1 18a) 2 2 2 sa 9793 8 1 1 la 3 1 3 78 74 57117 ¦¦
9 2 1 18 2 2 Z 89_ 88 8882 10 5 1 18 2 2 _ 86 85 86 _ __ ._ _~
_ 12_ 1 1 18b) 2 2 2 93 9395 98 13 1 1 18a3 1 3 128 128 64 191 __ b3 Tallow methyl ester Tallow fatty acld 1~
3o wad~SPEC~8417.DF8 l III. Preparation of quaternary ammonium compounds or amine salts Example 14 To 1.149 g (1 mol) of the ester of Example 7 were added at 60C with stirring 252 g (2 mol) of dimethyl su'fate in portions so that the temperature of the reaction mixture was maintained between 60-70C. This produced 1.397 g of a yellow liquid of formula (1) where a + c + b = n a + c = 6.6 b = 0 d + e + f + g = m = 4 R' R8 R9 R10 = H
2 of (R1, R2 R3 R4) = H
2 of (R1, R2, R3, R4) = -C(O)-C H
R~ and R' = -CH3 X- = 2 x -OS-OCH3 O
The analysis numbers of these compounds are:
Cat SO3 acid : 9.6 g of SO3/100 g ~5 TOT : 2.3 mg of KOH/g The examples listed below in Table II were carried out in a similar manner to Example 14.
3o wad/SPEC/8417 . DTB
-21- 2~
TABLE III
Resultins compounds of formula A where l Example of Quaternl~ing Agent/Acid ~ ~able I~ mol mol R6 R7 ~ Cat SO I ~CT I DH
14 7 I 2 Dimethyl sulfate CH3 1 2 9.6 2.3 7 1 2 Lactlc acid H 2 10.0 5.2 16 7 1 I Dlmethyl ~ulfate ' 1 CH3 2 10.1 l 1 Lactlc Acid 1 H
1 0 17 10 1 2 Dlmethyl sulfate CH3 2 9.0 2.2 18 7 1 2 HCl H 2 10.3 4.2 ~ __ ' pH in 1:1 isopropanol~water at 20C
' at 60-70C ln that order 3o ~ad~SPEC~8417.~8 ~ 2 2 ;~ r~
l IV. Application testinq A) Preparation of fabric softener solutions or dispersions Method 1 Charge water, dye solution and optionally an aliquot of electrolyte at 15C. Gradually emulsify in the component at 23C with stirring (propeller stirrer) or emulsify in the components in succession or as a mixture under identical conditions. During the emulsifying add further aliquots of electrolyte if necessary. Then add the perfume oil with stirring and if necessary after the emulsifying process the remaining electrolyte to adjust the viscosity.
The result is a homogeneous emulsion or solution.
Method 2 Charge water, dye solution and optionally an aliquot of electrolyte at 45C. Gradually emulsify in the component at 55C with stirring (propeller stirrer) or emulsify in the components in succession or as a mixture under identical conditions. During the emulsifying add further aliquots of electrolyte if necessary.
Stir the batch until it has cooled down to about 25C. Then add the perfume oil with stirring and if necessary adjust the viscosity with the remaining electrolyte.
The result is a homogeneous emulsion or solution.
B) Verification of soft fabric hand To assess the fabric hand, the textile material, made of wool, cotton, 50:3 polyester/cotton and polyester, is treated for about 10 minutes with a liquor comprising tap water (about 9 German hardness and a temperature of 15-20C) and the novel emulsion, dispersion or solution. The concentration of the compounds according to the present wdd/spEc~s4l7.
l invention in the liquor is 0.025% by weight, based on the total acti~e ingredient. The dried textiles were checked by nine people with experience in the assessment of the softness of textiles in respect of their soft fabric hand and assessed against texti~es which had not been treated with fabric softeners. The assessments are rated according to a graduated point system, the final reported result being the arithmetic average. After drying, the textile materials treated have an excellent soft fluffy fabric hand and, compared with commercially available agents, a much improved remoisture capability.
C) Examples Example 1 - 15.0 g of a compound according to formula (1) wherein three of R1, R2, R3 and R4 were radicals in which R was C8 18 acyl and one of them was a radical in which R was -H; all R groups were -H; R5 and R
were -H; the average value of n was 5.6; and X x was lactate;
0.7 g of dye (1% solution of SANDOLANR milling blue NBL 150; from Sandoz) - to 100.0 g water of 13 German hardness Introduce water-dye solution at 45C, emulsify in the component at 55C with stirring (propeller stirrer) and then stir the batch until cold. The _, result is a homogeneous emulsion.
Viscosity (20C measured with Brookfield LVT, spindle l at 30 rpm): < 100 mPa s The examples which follow were prepared in a similar manner to Example 1.
wadJSPE:C/8417 i~'F8 l Example 2 - 30.0 g of a compound according to formula (1) wherein three of R, R, R and R were radicals in which R was C8 18 acyl and one of them was a radical in which R was -H; all R groups were -H; R and R
were -H; the average value of n was 5.6; and X
was lactate;
- 1.3 g of dye - to 100.0 g water of 13 German hardness The result is a homogeneous emulsion.
Viscosity about 10 mPa s Example 3 - 15.0 g of a compound according to formula (1) wherein two of Rl, R2, R3 and R4 were radicals in which R was C818 acyl, and two of them were radicals in which R was -H; all R groups were -H;
R and R were -CH3; the average value of n was 5.6;
and xX was methylsulfate;
- 0.7 g of dye ~ to 100.0 g water of 13 German hardness The result is a clear solution.
Viscosity < 100 mPa s Remoisture capability = 94%
Example 4 - 15.0 g of a compound according to formula (1) wherein three of R1, R2, R and R were radicals in which R5 was C8 18 acyl, and one of them was a radical in which R was -H; all R groups were -H;
R and R were -CH3; the average value of n was 5.6;
and XX was methylsulfate;
- 0.7 g of dye - to 100.0 g water of 13 German hardness wa~/SP!~C~8417 . Dlr8 2~r'?~
l The result is a homogeneous solution.
Viscosity < 100 mPa s Example 5 - 15.0 g of a compound according to formula (1) wherein two of R1, R2, R3 and R4 were radicals in which R was C818 acyl, and two were radicals in which Rs was -H; all R groups were -H; R was -CH3;
R was -H; the average value of n was 5.6; and XX
was both methylsulfate and chloride;
10 ~ 0-7 g of dye - to 100.0 g water of 13 German hardness The result is a clear solution~
Viscosity < 100 mPa s Remoisture capability > 90%
Example 6 - 3.0 g of a compound according to formula ~1) wherein two of R1, R2, R3 and R4 were radicals in which R5 was C818 acyl and two of them were radicals in which Rs was -H; all R groups were -H; R and R
were -CH3; the average value of n was 5.6; and XX
was methylsulfate;
- 12.0 g of a second compound according to formula (1) wherein two of R1, R2, R3 and R4 were radicals in which R was C818 acyl, and two were radicals in which Rs was -H; all R groups were -H; R5 and R7 were -H; the average value of n was 5.6; and X-X
was lactate;
- 0.7 g of dye - to 100.0 g water of 13 German hardness The result is a clear solution.
Viscosity < 100 mPa s Remoisture capability = 95%
wad~SP~C/8417.~3 2 ~ r ~
1 ExamPle 7 - 15.0 g of a compound according to formula (1) wherein three R1, RZ, R and R4 were radicals in which R was C81,3 acyl, and one was a radical in which R was -H; all R groups were -H; R and R
were -CH3; the average value of n was 5.6; and XX
was methylsulfate;
- 15.0 g of a compound according to formula (1) wherein three R1, R2, R3 and R4 were radicals in which R was C8 18 acyl, and one was a radical in which Rs was -H; all R groups were -H; R6 and R
were -CH3; the average value of n was 5.6; and XX
was lactate;
- 0.7 g of dye to 100.0 g water of 13 German hardness The result is a homogeneous solution.
Viscosity about 200 mPa-s Remoisture capability about 85%
3o wz~d/~;PEC~8417 .D'P8
Claims (11)
1. An aqueous fabric softener comprising A) 5-35% by weight of at least one of the compounds of the general formula (1) wherein R1, R2, R3 and R4 are identical or different radicals;
R5 -(O-CH(R)-CH2)m- wherein each R5 can be a substituted or unsubstituted acyl radical of 6-22 carbon atoms with or without a double bond, or can be H, and wherein at least one R5 must be an acyl radical and at least one R5 must be -H;
each of the radicals R can be identical or different, and are each H or -CH3;
R6 and R7, which can be identical or different, can each be H, -CH3,-C2H5 or -C2H4OH;
x-x is at least one organic and/or inorganic anion;
x is 1, 2 or 3;
a, b, and c are each 0-20;
n is the sum of (a+b+c) and is 1-30;
each m is independently 1-5, and the sum of all values is at least 4; B is 1 or 2; and a equals the product (0.5)(.beta.)(x); and optionally B) 10-90% by weight, based on A), ammonium compounds customary in fabric softeners and optionally wad/SPEC/8417 . DTB
C) 1-5% by weight of customary dyes, scents and further customary fabric softener auxiliaries and additives and D) water to 100% by weight.
R5 -(O-CH(R)-CH2)m- wherein each R5 can be a substituted or unsubstituted acyl radical of 6-22 carbon atoms with or without a double bond, or can be H, and wherein at least one R5 must be an acyl radical and at least one R5 must be -H;
each of the radicals R can be identical or different, and are each H or -CH3;
R6 and R7, which can be identical or different, can each be H, -CH3,-C2H5 or -C2H4OH;
x-x is at least one organic and/or inorganic anion;
x is 1, 2 or 3;
a, b, and c are each 0-20;
n is the sum of (a+b+c) and is 1-30;
each m is independently 1-5, and the sum of all values is at least 4; B is 1 or 2; and a equals the product (0.5)(.beta.)(x); and optionally B) 10-90% by weight, based on A), ammonium compounds customary in fabric softeners and optionally wad/SPEC/8417 . DTB
C) 1-5% by weight of customary dyes, scents and further customary fabric softener auxiliaries and additives and D) water to 100% by weight.
2. An aqueous fabric softener as claimed in claim 1, comprising as component A) 15-30% by weight of at least one compound of formula (1) wherein R is -CH3, two or three of the radicals R1, R2, R3 and R4 are each R -O-CH2-CH2- where R is an acyl radical containing 8-18 carbon atoms and one or two of R, R, R and R are HO-CH2-CH2-; n is 1-15; R
and R7, which can be identical or different, are each H or -CH3; and xx is a radical of a substituted or unsubstituted carboxylic acid having 1-8 carbon atoms in the main chain or the methylsulfate or ethylsulfate radical.
and R7, which can be identical or different, are each H or -CH3; and xx is a radical of a substituted or unsubstituted carboxylic acid having 1-8 carbon atoms in the main chain or the methylsulfate or ethylsulfate radical.
3. An aqueous fabric softener as claimed in claim l, comprising as component A) 15-30% by weiqht of at least one compound of formula (1) wherein R is -CH3, three of the radicals R1, R2, R and R are each R -O-CH2-CH2-- where Rs is an acyl radical containing 8-18 carbon atoms, one of the radicals Rs is HO-CH2CH2-; n is 2-8; R5 and R
are each H and X- is the lactate .adica'.
are each H and X- is the lactate .adica'.
4. An aqueous fabric softener as claimed in Claim 1, comprising as component A) 15-30% by weight of at least one compound of formula (1) wherein two or three of the radicals R1, R2, R3 and R4 are each Rs -O-CH(CH3)-CH2- where R
is an acyl radical containing 8-18 carbon atoms and one or two of R , R , R and R are HO-CH(CH3)-CH2-; n is 1-15; R and R , which can be identical or different, are each -H
or -CH3; and xx is selected from the group consisting of anions of substituted or unsubstituted carboxylic acids containing 1-8 carbon atoms in the principal chain, methylsulfate, and ethylsulfate.
is an acyl radical containing 8-18 carbon atoms and one or two of R , R , R and R are HO-CH(CH3)-CH2-; n is 1-15; R and R , which can be identical or different, are each -H
or -CH3; and xx is selected from the group consisting of anions of substituted or unsubstituted carboxylic acids containing 1-8 carbon atoms in the principal chain, methylsulfate, and ethylsulfate.
5. An aqueous fabric softener as claimed in Claim 1, comprising as component A) 15-30% by weight of at least one compound of formula (1) wherein three of the radicals R1, R2, R3 and R
are each R5-o-CH(CH3)-CH2- where Rs is an acyl radical containing 8-18 carbon atoms; one of R1, R2, R3 and R4 is HO-CH(CH3)-CH2; n is 2-8;
R5 and R7 are -H; and X-x is lactate.
are each R5-o-CH(CH3)-CH2- where Rs is an acyl radical containing 8-18 carbon atoms; one of R1, R2, R3 and R4 is HO-CH(CH3)-CH2; n is 2-8;
R5 and R7 are -H; and X-x is lactate.
6. An aqueous fabric softener as claimed in Claim 1, wherein b equals zero.
7. An aqueous fabric softener as claimed in Claim 2, wherein b equals zero.
8. An aqueous fabric softener as claimed in Claim 3, wherein b equals zero.
9. An aqueous fabric softener as claimed in Claim 4, wherein b equals zero.
10. An aqueous fabr,c softener as clalmed in Claim 5, wherein b equals zero.
11. An aqueous fabric softener as claimed in claim 1, comprising as component B) 10-50% by weight, based on A), of at least one compound selected from the group consisting of compounds of the general formula (5):
Wad/SPEC/8417.DTB
R11-CO-NH-R13-N(-R12OH)-COR11 where R11 is a substituted or unsubstituted alkyl or alkylene radical of 15-21 carbon atoms and R12 and R13 are divalent C1-C3-alkylene radicals;
substituted imidazolines of the general formula (6) ( 6) where R11 and R12 are each as defined above and R14 is H or a C1-C4-alkyl or -hydroxyalkyl radical, and X is a monovalent anion as defined hereinabove;
compounds of the formula (7) ( 7 ) where R11, R12, R14 and X are each as defined above;
reaction products of C16-C22 fatty acids with dialkylenetriamines in a molar ratio of 2:1 R11-CO-NH-R12-N(R14)2-Rl3 NHCOR11 X- 2 (8) Wad/SPEC/8417 . DTB
where R11 R12 R12, R14 and X are each as defined above;
substituted imidazolines of the general formula (9) ( 9 ) where R11, R12 R14 and X are each as defined above; salts of compounds of the formulae (5) to (9) with organic and/or inorganic acids or in the form of their quaternary compounds; and quaternary ammonium compounds of the general formula (10) [NR15R16R17R18]+X- ( 10 ) where R15 is a substituted or unsubstituted alkyl or alkylene radical of 15-22 carbon atoms, R16 and Rl7 are independently of one another C1-C4-alkyl or -hydroxyalkyl radicals, R18 is the same as R15 or R16 and X- is an anion.
Wad/SPEC/8417 . DTB
Wad/SPEC/8417.DTB
R11-CO-NH-R13-N(-R12OH)-COR11 where R11 is a substituted or unsubstituted alkyl or alkylene radical of 15-21 carbon atoms and R12 and R13 are divalent C1-C3-alkylene radicals;
substituted imidazolines of the general formula (6) ( 6) where R11 and R12 are each as defined above and R14 is H or a C1-C4-alkyl or -hydroxyalkyl radical, and X is a monovalent anion as defined hereinabove;
compounds of the formula (7) ( 7 ) where R11, R12, R14 and X are each as defined above;
reaction products of C16-C22 fatty acids with dialkylenetriamines in a molar ratio of 2:1 R11-CO-NH-R12-N(R14)2-Rl3 NHCOR11 X- 2 (8) Wad/SPEC/8417 . DTB
where R11 R12 R12, R14 and X are each as defined above;
substituted imidazolines of the general formula (9) ( 9 ) where R11, R12 R14 and X are each as defined above; salts of compounds of the formulae (5) to (9) with organic and/or inorganic acids or in the form of their quaternary compounds; and quaternary ammonium compounds of the general formula (10) [NR15R16R17R18]+X- ( 10 ) where R15 is a substituted or unsubstituted alkyl or alkylene radical of 15-22 carbon atoms, R16 and Rl7 are independently of one another C1-C4-alkyl or -hydroxyalkyl radicals, R18 is the same as R15 or R16 and X- is an anion.
Wad/SPEC/8417 . DTB
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4108025A DE4108025A1 (en) | 1991-03-13 | 1991-03-13 | SOFT SOFTEN DETERGENT BASED ON QUATERNAEREN POLY (OXYALKYLEN) ALKANOLAMINE ESTERS |
| DEP4108025.4 | 1991-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2062848A1 true CA2062848A1 (en) | 1992-09-14 |
Family
ID=6427124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002062848A Abandoned CA2062848A1 (en) | 1991-03-13 | 1992-03-12 | Fabric softeners based on quaternary poly(oxyalkylene) alkanolamine esters |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5254270A (en) |
| EP (1) | EP0503155B1 (en) |
| CA (1) | CA2062848A1 (en) |
| DE (2) | DE4108025A1 (en) |
| ES (1) | ES2089104T3 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0637625A1 (en) * | 1993-08-02 | 1995-02-08 | The Procter & Gamble Company | Super concentrate emulsions with fabric actives |
| US5750491A (en) * | 1993-08-02 | 1998-05-12 | The Procter & Gamble Company | Super concentrate emulsions with fabric actives |
| DE4405702A1 (en) * | 1994-02-23 | 1995-08-24 | Witco Surfactants Gmbh | Highly concentrated aqueous fabric softener with improved storage stability |
| AU5912700A (en) * | 1999-07-06 | 2001-01-22 | Procter & Gamble Company, The | Clear or translucent aqueous polyquaternary ammonium fabric softener compositions containing low solvent |
| US6884767B1 (en) | 1999-07-06 | 2005-04-26 | The Procter & Gamble Company | Clear or translucent aqueous polyquaternary ammonium fabric softener compositions containing low solvent |
| US7371718B2 (en) * | 2005-04-22 | 2008-05-13 | The Dial Corporation | Liquid fabric softener |
| WO2009027925A2 (en) * | 2007-08-31 | 2009-03-05 | The Procter & Gamble Company | Compositions and visual perception changing methods |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB384714A (en) * | 1930-08-27 | 1932-12-15 | Du Pont | Improvements in or relating to the catalytic production of amines from alcohols and a |
| US2017051A (en) * | 1931-02-06 | 1935-10-15 | Du Pont | Synthesis of amines |
| US2078922A (en) * | 1934-06-28 | 1937-05-04 | Du Pont | Synthesis of higher amines |
| DE3889387D1 (en) * | 1987-06-16 | 1994-06-09 | Cotelle Sa | Concentrated plasticizers. |
| DE3720331A1 (en) * | 1987-06-19 | 1988-12-29 | Huels Chemische Werke Ag | CONCENTRATED SOFT SOFTENER |
| MY103439A (en) * | 1987-10-29 | 1993-06-30 | Kao Corp | Detergent composition |
| DE68919236T2 (en) * | 1988-01-28 | 1995-04-06 | Unilever Nv | Textile treatment preparation and its manufacture. |
| EP0345842A3 (en) * | 1988-05-27 | 1990-04-11 | The Procter & Gamble Company | Fabric softening compositions containing mixtures of substituted imidazoline esters and quartenized ester-ammonium salts |
| US4946627A (en) * | 1989-07-19 | 1990-08-07 | National Starch And Chemical Investment Holding Corporation | Hydrophobically modified polycarboxylate polymers utilized as detergent builders |
| DE3926740C2 (en) * | 1989-08-12 | 1997-05-15 | Witco Surfactants Gmbh | Aqueous fabric softener and its use |
| DE4018750A1 (en) * | 1990-06-12 | 1991-12-19 | Rewo Chemische Werke Gmbh | POLY (OXYALKYLENE) AMINOAL CANOLESTERS, THEIR AMMONIUM COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN EMULSIFIERS, CLEANING AGENTS, DISINFECTANTS AND PRESERVATIVES |
-
1991
- 1991-03-13 DE DE4108025A patent/DE4108025A1/en not_active Withdrawn
- 1991-12-20 EP EP91121957A patent/EP0503155B1/en not_active Expired - Lifetime
- 1991-12-20 ES ES91121957T patent/ES2089104T3/en not_active Expired - Lifetime
- 1991-12-20 DE DE59107766T patent/DE59107766D1/en not_active Expired - Lifetime
-
1992
- 1992-03-12 CA CA002062848A patent/CA2062848A1/en not_active Abandoned
- 1992-03-13 US US07/850,578 patent/US5254270A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4108025A1 (en) | 1992-09-17 |
| US5254270A (en) | 1993-10-19 |
| EP0503155B1 (en) | 1996-05-01 |
| ES2089104T3 (en) | 1996-10-01 |
| EP0503155A1 (en) | 1992-09-16 |
| DE59107766D1 (en) | 1996-06-05 |
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