CA2043147A1 - Low-foaming detergents for machines - Google Patents
Low-foaming detergents for machinesInfo
- Publication number
- CA2043147A1 CA2043147A1 CA002043147A CA2043147A CA2043147A1 CA 2043147 A1 CA2043147 A1 CA 2043147A1 CA 002043147 A CA002043147 A CA 002043147A CA 2043147 A CA2043147 A CA 2043147A CA 2043147 A1 CA2043147 A1 CA 2043147A1
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- Prior art keywords
- denotes
- alkyl
- detergent according
- surfactant components
- 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.)
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT
Detergents for washing machines which detergents contain, as surfactant components, 5-30% of alkyl polyglycoside, 5-30% of alkanol ether-carboxylates, 5-30% of soap and 0-3% of other surfactants are disclosed. The alkyl polyglycloside corresponds to the formula R-O-Zn, wherein R denotes a linear or branched, saturated or unsaturated alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn denotes a polyglycosyl radical composed of n = 1 to 3 hexose or pentose units or mixtures thereof. The detergents, whose surfactant components are prepared mostly from renewable raw materials show very good washing properties together with excellent biodegradability.
Detergents for washing machines which detergents contain, as surfactant components, 5-30% of alkyl polyglycoside, 5-30% of alkanol ether-carboxylates, 5-30% of soap and 0-3% of other surfactants are disclosed. The alkyl polyglycloside corresponds to the formula R-O-Zn, wherein R denotes a linear or branched, saturated or unsaturated alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn denotes a polyglycosyl radical composed of n = 1 to 3 hexose or pentose units or mixtures thereof. The detergents, whose surfactant components are prepared mostly from renewable raw materials show very good washing properties together with excellent biodegradability.
Description
2~31~
The present invention relates to low-foaming liquids or pulverulent detergent formulations for washing machines. More particularly, the present invention relates to detergents whose surfactant components are prepared mostly from renewable raw materials.
Modern liquid detergents consist mostly of anionic surfactants, in particular alkylbenzenesulphonate, fatty alcohol oxyethylate and soap, whereas washing powders usually contain bullder substances, bleaching agents and other electrolytes as essential active compounds, ln addition to the alkylbenzenesul-phonate and fatty alcohol oxyethylate surfactants. The common feature of liquid and pulverulent detergent formulations is that the surfactants employed are those based on petrochemicals.
In view of the future possible shortages of petroleum raw materials, this petrochemlcal basi~ is a considerable disad-vantage. Another disadvantage is that the biological degradabil-lty of these surfactants does not achieve the corresponding degradability level of surfactants based on naturally occurring substances.
The object of the invention is therefore to find a combination of surfactants for low-foaming detergents, which surfactants are prepared mostly from renewable raw materials, have an outstandlng blologlcal degradabllity and achieve very good washing results.
Thls object may be achieved by a surfactant combinatlon whlch consists essentlally of alkyl polyglycosldes, ether-- 2043~7 23443~447 carboxylates and soap.
The invention therefore relates to a low-foaming, liquid or pulverulent detergent for washing machines, which is charac-terized in that the surfactant content consists of 5 to 30% of alkyl polyglycosides, 5 to 30% of alkanol ether-carboxylate, 5 to 30% of soap and 0 to 30% of other surfactants.
Surprisingly, it has been found that very good washing results are achieved with the combinations according to the invention.
The use of alkyl polyglycoside in combination with anionic surfactants is known. Thus, German Published Patent Application 593,422 mentions the effect of alkylglycoside in inten-sifying the washing effect of soaps. Later publications, such as European Published Patent Applications 0.075,99~, 0,105,556 and 0,199,765 or German Published Patent Application 3,702,286, describe the use of alkyl polyglycosides in combination with a number of known anionic surfactants in detergents. In each case the alkylbenzenesulphonate surfactant is most important component of the disclosed compositions.
The use as detergents of carboxymethylated fatty alcohol oxyethylates, which are a subgroup of ether-carboxylates is known from German Published Patent Applications 2,327,234 and 3,320,340. In contrast thereto, the use of bisalkanol alkoxylate-acetates, which are also a subgroup of ether-carboxylates, is new.
-- 2~43~7 Also the use in detergents of the ether-carboxylates in combina-tion with alkyl polyglycosides is unknown.
Other constituents, according to the state of aggrega-tion (liquid or pulverulent formulations) are small amounts of other surfactants, complexing agents, bleaching agents, optical brlghteners, greylng inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizing agents and the like.
Alkvl polYglvcosldes Alkyl polyglycosides employed according to the invention -are of the general formula I
R~O-Zn I, ln whlch R represents a linear or branched, saturated or unsatur-ated aliphatlc alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn represents a polyglycosyl radical, where n represents 1.0 to 3 hexose or pentose units, or mixtures there-of.
Alkyl polyglycosides containing fatty alkyl radicals having 10 to 16 carbon atoms and a polyglycosyl radical of n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.
The alkyl polyglycosides employed according to the invention can be prepared by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol ; ln the presence of an acld catalyst to glve butyl polyglycoside mixtures, which are transglycosidated with long-chain alcohols, in the presence of an acid catalyst, to give the desired alkyl polyglycoside mixtures. Alternatively, dextrose is reacted directly with the desired long-chain alcohol.
The structure of the products can be varied within certain limits. The alkyl radical R is determined by the choice of long-chain alcohols. For economic reasons, the surfactant alcohols which are accessible on a large industrial scale and have 10 to 18 C atoms are preferred, in particular naturally occur-ring fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives. Zieglar alcohols or Oxo alcohols can also be used.
The polyglycosyl radical Zn is determined on the one hand by the choice of carbohydrate and on the other hand by adjust-ing the average degree of polymerization n, for example in accordance with German Published Patent Application 1,943,689.
It is known that in principle polysaccharides, for example starch, maltodextrins, dextrose, galactose, mannose, xylose and the like, can be employed. The carbohydrates starch, maltodextrins and in particular dextrose which are available on a large industrial scale are preferred. Since the alkyl polyglycoside syntheses which are of economic interest do not proceed regio- and stereo-selectively, the alkyl polyglycosides are always mixtures of oligomers, which in turn are mixtures of various isomeric forms. They are present together with ~- and ~-glycosidic bonds in the pyranose and furanose form. The linkage points between two saccharide radicals also vary.
2~3~7 Alkyl polyglycosides employed according to the inven-tion can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can be isolated or enriched from alkyl polyglycosides, for example, in accordance with European Published Patent Application 0,092,355 using polar sol-vents, such as acetone.
The degree of glycosidation can be advantageously determined by means of H-NMR.
The detergents according to the invention contain 5 to 30% of alkyl polyglycoside, preferably 7 to 20%.
In contrast to almost all the other surfactants employ- -~
ed in detergents, the alkyl polyglycosides are regarded as being entirely ecologically safe. The degree of biological degradation determined by means of a water treatment plant simulation model/
DOC analysis for the alkyl polyglycosides according to the invention is thus 96 + 3%. This figure should be considered in view of the fact that a substance showing a degree of degradation of > 70% is considered as being readily degradable according to this test method (total degradation).
~ The acute oral toxicity LD50 (rat) of > 10,000 mg/kg and the aquatic toxicity LC50 (golden orfe) of about 12 mg/l and ; EC50 (Daphnia) of 30 mg/l are also more favourable by a factor of 3 to 5 than the corresponding values of currently the most important surfactants. The same applies to the skin and mucosa tolerance.
; - 5 -2 ~ 7 Fatty alcohol ether-carboxylates Fatty alcohol ether-carboxylates are compounds of either the formula II or the formula ~II
(R-_o(cH2-cH2-o)xcH2coo)mM II, in which R' is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18, carbon atoms, x is 1 to 40, preferably 3 to 30, m is 1 or 2 and M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanol-ammonium, or ([R~'-O(CH2-CH2-O)y]2cHcoo)zN III
in which R'' denotes a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18, carbon atoms, y denotes 1 to 4, preferably 3 to 30, z denotes 1 or 2 and N
denotes H, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium.
Compounds corresponding to the formula II are called carboxymethylated oxyethylates, and those corresponding to the formula III are called bisalkanol ethoxylateacetates.
The carboxymethylated oxyethylates can be prepared in accordance with German Published Patent Application 2,418,444 or European Published Patent Application 0,106,018 by reaction of oxyethylates of the formula R'-O(CH2-CH2-O)nH with chloroacetic acid or a salt of chloroacetic acid in the presence of an alkali metal hydroxide or other ba~es. However, other preparation processes, for example by means of catalytic oxidation according to European Published Patent Application 0,018,681 and 0,039,111, 2~31~7 ~3443-447 are also suitable.
Bisalkanol ethoxylate-acetates can be prepaxed, for example, in accordance with German Published Patent Application 3,902,663 from oxyethylates and dichloroacetic acid.
Corresponding alcohols for the preparation of the fatty alcohol ether-carboxylates are preferably fatty alcohols or Ziegler alcohols, and in exceptional cases also Oxo alcohols.
The carboxymethylation which follows the oxyethylation can be complete in the case of an appropriate procedure, so that the fatty alcohol ether-carboxylates are purely anionic surfactants.
Alternatively, if the carboxymethylation is not complete, the products contain certain amounts of unreacted oxyethylate. The formulae II and III therefore usually mean a mixture containing varying amounts of unreacted oxyethylates. A degree of conversion can accordingly be defined. A degree of conversion of between 70 and 100% is preferred.
The fatty alcohol ether-carboxylates are also very ecologically-safe surfactants. Biological degradation rates of above 90% have thus been determined by means of a water treatment plant simulation model/DOC analysis. The acute oral toxicity LD50 (rat) and the aquatic toxicity hC50 (golden o_fe) are about as favourable as those of the alkyl polyglucosides. The same applies to the skin and mucosa tolerance.
The detergents according to the invention contain 5 to 30% of fatty alcohol ether-carboxylates, which can also be mixtures. A content of 7 to 20% of fatty alcohol ether-' .~
;
~ 0 ~ 7 carboxylate is preferred.
Soap Fatty acid salts according to the invention and their acids correspond to the formula IV
R'l'COOP IV, in which R'l' denotes a saturated or unsaturated alkyl radical having 8 to 22 C atoms and P denotes hydrogen, an alkali metal, ammonium or alkanolammonium.
The detergents according to the inventisn contain 5 to 30%, preferably 7 to 20% of soap, which will usually be a mixture of various components.
Other surfactant constituents Up to 3% of other anionic, nonionic, zwitter-ionic and ampholytic surfactants is to be employed according to the inven-tion. These are, in particular, alkanesulphonates, olefinsulphon-ates, alkylbenzenesulphonates, ~-sulpho-fatty acid esters, fatty alcohol sulphates, fatty alcohol ether-sulphates, sulphosuccinic acid esters, alkanol oxyethylates, fatty acid alkanolamides, ammine oxides, betains, sulphobetains and the like.
Other non-surfactant constituents Non-surfactant constituents which may be mentioned are above all builders. Water-soluble buildersj such as various polyphosphates, phosphonates, carbonates, polycarboxylates, citrates, polyacetates, such as NTA and DETA, and the like or mix-tures thereof are used according to the invention. These compounds are usually employed as the alkali metal salts, preferably as the 2~431~7 sodium salts. Although it is not a complexing agent, sodium sul-phate may also be mentioned here. Water-insoluble builders, such as aluminosilicates of suitable particle size (compare European Published Patent Application 0.075,994) can also be used. The concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50~.
Bleaching agents, such as sodium perborate, if appropriate combined with bleaching activators, such as tetra-acetylethylenediamine and the like, or percarbonate, are further-more employed according to the invention; other bleaching agents are of course also possible (compare K. Engel, Tenside Surfactants 25, page 21 (1988)). The concentration of the bleaching agent is 0 to 40%, preferably 0-30%.
If appropriate, standardizing agents, such as low molecular weight 1- or 2-hydric alcohols, alkyl ethers of poly-hydric alcohols, hydrotropic agents, such as alkylbenzenesulphon-ates having 1 to 3 C atoms in the alkyl radical, alkanolamines or ureas, enzymes, such as, in particular, proteases, and enzyme stabilizers, corrosion inhibitors, such as alkali metal silicates, optical brighteners, in particular those based on stilbene and pyrazolene, foam regulators, greying inhibitors, such as, for example, carboxymethylcellulose, perfume oils, dyestuffs and other contents customary for liquid or pulverulent detergents, may also be employed according to the invention.
The total use concentration of the surfactant content in the machine detergents according to the invention is 0.3-20 g/l. 0.5-10 g/l is preferred.
2 0 ~ 7 Examples The invention is illustrated by the following examples.
The liquid detergent formulations listed in Tables 1 and 2 each contain 6% of triethanolamine, 12% of ethanol, 6% of 1,2-propylene-glycol and water to 100%, in addition to the surfactant constituents mentioned which are used according to the invention.
The foaming capacity was determined in accordance with DIN 53 902, part 1. The concentration of detergent substance was in each case 1 g/l, and the volume of foam was recorded after 5 minutes. The washing power was measured both in a Linitest*
laboratory washing machine (that is to say under moderate mechani-cal stress) and in a normal domestic machine. The model fabric used was cloth 11 x 18 cm in size of WFK test fabric with skin grease-pigment soiling: polyester ~PE), mixed fabric (MF) and cotton (C), the water used was drinking water (13 dH). The polyester was washed at 30C and the mixed fabric and cotton at 60C. The active compound concen~ration was 1 g/1 in the Linitest* laboratory washing machine and 5 g/l in the domestic washing machine, the pH was in each case about 7, the liquor ratio was about 1:60 and 1:4 respectively and the washing times in both cases were about 30 minutes.
; In the Linitest* machine, the washing operation was repeated twice, each time after rinsing. The washing values after drying of the fabric were - as is customary - measured by spectrophotometry relative to a white standard (Datacolor*, 560 nm).
;:
*Trade-mark 2~3147 ~gLid formulations:
Tables 1 and 2 show the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and of a liquid brand detergent, for which optimization of the recipe can be assumed.
~31~7 O.Z.4491 23443-447 Table 1: Liquid detergent based on carboxymethylated oxyethylate/alkyl polyglucoside/~oap _ E~mple ~o.
Surf~nt l(V) 2~V) 3 4 5 6 7 8~V) .
~oC~ AES-Na 15 - _ _ _ _ _ ~ d C~, PS-Na _ 15 _ _ _ _ _ braDd C~(EO); cm~O0 _ _ 15 - - 15 - ~r-C~(E0)sc~ 0 _ _ _ 15 - ~ 15 gent C~ 0)3 CmO.SII _ _ _ _ 15 C~i.2*~ 15 15 15 15 15 -C~.7 _ _ - - - 15 15 Soap**~ 10 10 10 10 10 10 10 _ Pe~lts .
Cl ;~rif~:atiorl point (-C)s~1 -2 2 1 3 -1 -1 _ ViKx~ity at 25-C (mPa~)-68 55 68 72 71 66 70 90 Foamingcap~ y (60-C) DINs 120 150 50 55 45 S0 40 30 ~hinq pa~
(refleGu~xe (~)) llnitest~
P~ 30-C 6 8 15 11 11 15 }5 11 Washing m~nes MF 60-C _ 31 29 58 54 - 53 55 IS4 A~S-Na - alkylbenzene sulphonate Na salt PS-Na - paraffinsulphonate Na salt (V) s comparison example - abbreviated formula for carboxymethylated C12-C,~ fatty alcohol oxyethylates contalning 4 mol of ethylene oxide/mol, degree of con~lrersion 93%
= C,2C1~-alkyl polyglucoside having a degree of glucosidation of 1.2 *~ - coconut fatty acld (neutralized with trlethanol-amine) - - not measured 2 ~ 7 O.Z.4491 23443-447 able 2~ Liquid detergent based on bisalkanoloxy-ethylateacetate/alkyl polyglucoside/coap E~pla N~.
~ nt 9 10 11 ~ 13 14 _ . . .
eis(Cl2C~(EO)~*o.s~ 15 _ _ 15 _ 7.5 Els~C~(EO)s)~o.s3 - 15 - _ _ 7.5 1~8(C~oc~(Eo)s)aco~82 _ _ 15 - - _ ais(c~a(l~))8)ac ~ 15 _ ~ .2~* 15 1515 - - _ C~ .7 - - - 15 15 15 Soap*** 10 1010 10 10 10 R~
_ Clarification point (-C)s 2 1 2 -1 0 1 Vi~K~ity at 25-C (mPa~)~ 100 90140 120 150110 P~ng capaci~y (60-C) : 20 3020 30 20 20 Wb~hing power (reflecuuLe (%)) Linite~t~
~s MP 60-C _ 5954 59 - 58 - - - -* = -abbreviated formuls for bl~ C~C~alkanol oxy-ethylate-acetate containing 6 mol of ethylene oxid~/mol, degree of conversion 84%
** 3 C~C1~-alkyl polyglucoside having a degree of glucosidation of 1.2 *** - coconut fatty acid (neutralized with triethanol-amine~
- ~ not measured 2~431~7 O.Z.4491 23443-44 The clarification point and vlscosity entirely comply with the u~ual market standard for liquid detergents. The foaming capacity of the formulation~ according to the Lnvention show~ very favourable value~ - without other regulating additives. This particularly applie~ to the washing power. The formulation~ according to the inven-tion are far more effective here than other known com-binations in which the surfactant content likewise con~ists of an anionic surfactant, alkyl polyglucoside and ~oap (Comparison Examples 1 and 2).
Powde ~ fQrmulationss Table 3 shows the comparison of the properties of pul-verulent detergent formulations according to the inYen-tion with ~ho~e of a known combination and of a brand detergent. The bulk den~ity, angle of repose and foaming capacity were determined by DIN methods. The solubility is estimated by mean~ of a plot of the electrical conduc-tivity against time, the measurement value being taken at 80% of an average final conductivity when 1 g of powder L~ dissolved ln 800 ml of drinking water ~13 dH). $he measurement values include an error of ~ 5~.
2 0 ~ 7 o.z.4491 23443-447 able 3s Powder detergent based on carboxymethylated oxyethylate/alkyl polyglucoside/soap _ E~ple No.
S~ nt lS(V) 20(V1 16 17 18 19 . .
C~ o~* - Pul- 3 - -C~(EO)~.0~ - veru- - 3 - -oy~ol~80/85(EO)~b.s - lent - - 3 3 C~ .2~ 4 ~rand 4 4 4 -C~F~.7~ - d~ - 4 C~Cu-AES-Na 3 genS - - - -Soap*~ 5 5 5 5 5 _ P~ll.'cs .
_ Eblk ~ ty g/l~ 760 460 780 820 790 800 Angle of nq~xe (ctg~) 1.5 1.5 1.4 1.5 1.4 1.4 Solubility (mln.)~14 14 16 17 14 16 F~ng cyx~ity (ml)~
(60-C) DDN a~r 30 ~ec. 120 160 150 140 100 100 300 sec. 30 20 30 30 40 20 ~q E~
(~ (%)) ~$~:~
Pe 20-C 8 9 10 11 9 12 Wad~nq ma~es NF 60-C 33 42 43 45 42 ~3 ABS-Na - alkylbenzenesulphonate Na salt (V) - comp~ri~on example * ~ compare T~ble 1 ** - 90 part- of beef tallow, 10 parts of coconut oil hydrolyzed with NaOH
20~3:L47 o.z.4491 23443-447 Apart from a considerably higher bulk density, which is typical of agqlomerated washing powder~, in compari~on with the spray-dried brand product (Example 20), the powders according to the invention are very ~imilar and better in their washing values. The greatly improved washing effects in compari~on with known formulations of Example 15 containing anionic surfactant~ are aqain also clearly to be ~een here.
.
., . - :
.
.
The present invention relates to low-foaming liquids or pulverulent detergent formulations for washing machines. More particularly, the present invention relates to detergents whose surfactant components are prepared mostly from renewable raw materials.
Modern liquid detergents consist mostly of anionic surfactants, in particular alkylbenzenesulphonate, fatty alcohol oxyethylate and soap, whereas washing powders usually contain bullder substances, bleaching agents and other electrolytes as essential active compounds, ln addition to the alkylbenzenesul-phonate and fatty alcohol oxyethylate surfactants. The common feature of liquid and pulverulent detergent formulations is that the surfactants employed are those based on petrochemicals.
In view of the future possible shortages of petroleum raw materials, this petrochemlcal basi~ is a considerable disad-vantage. Another disadvantage is that the biological degradabil-lty of these surfactants does not achieve the corresponding degradability level of surfactants based on naturally occurring substances.
The object of the invention is therefore to find a combination of surfactants for low-foaming detergents, which surfactants are prepared mostly from renewable raw materials, have an outstandlng blologlcal degradabllity and achieve very good washing results.
Thls object may be achieved by a surfactant combinatlon whlch consists essentlally of alkyl polyglycosldes, ether-- 2043~7 23443~447 carboxylates and soap.
The invention therefore relates to a low-foaming, liquid or pulverulent detergent for washing machines, which is charac-terized in that the surfactant content consists of 5 to 30% of alkyl polyglycosides, 5 to 30% of alkanol ether-carboxylate, 5 to 30% of soap and 0 to 30% of other surfactants.
Surprisingly, it has been found that very good washing results are achieved with the combinations according to the invention.
The use of alkyl polyglycoside in combination with anionic surfactants is known. Thus, German Published Patent Application 593,422 mentions the effect of alkylglycoside in inten-sifying the washing effect of soaps. Later publications, such as European Published Patent Applications 0.075,99~, 0,105,556 and 0,199,765 or German Published Patent Application 3,702,286, describe the use of alkyl polyglycosides in combination with a number of known anionic surfactants in detergents. In each case the alkylbenzenesulphonate surfactant is most important component of the disclosed compositions.
The use as detergents of carboxymethylated fatty alcohol oxyethylates, which are a subgroup of ether-carboxylates is known from German Published Patent Applications 2,327,234 and 3,320,340. In contrast thereto, the use of bisalkanol alkoxylate-acetates, which are also a subgroup of ether-carboxylates, is new.
-- 2~43~7 Also the use in detergents of the ether-carboxylates in combina-tion with alkyl polyglycosides is unknown.
Other constituents, according to the state of aggrega-tion (liquid or pulverulent formulations) are small amounts of other surfactants, complexing agents, bleaching agents, optical brlghteners, greylng inhibitors, corrosion inhibitors, foam regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes, hydrotropic substances, solubilizing agents and the like.
Alkvl polYglvcosldes Alkyl polyglycosides employed according to the invention -are of the general formula I
R~O-Zn I, ln whlch R represents a linear or branched, saturated or unsatur-ated aliphatlc alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn represents a polyglycosyl radical, where n represents 1.0 to 3 hexose or pentose units, or mixtures there-of.
Alkyl polyglycosides containing fatty alkyl radicals having 10 to 16 carbon atoms and a polyglycosyl radical of n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly preferred.
The alkyl polyglycosides employed according to the invention can be prepared by known processes based on renewable raw materials. For example, dextrose is reacted with n-butanol ; ln the presence of an acld catalyst to glve butyl polyglycoside mixtures, which are transglycosidated with long-chain alcohols, in the presence of an acid catalyst, to give the desired alkyl polyglycoside mixtures. Alternatively, dextrose is reacted directly with the desired long-chain alcohol.
The structure of the products can be varied within certain limits. The alkyl radical R is determined by the choice of long-chain alcohols. For economic reasons, the surfactant alcohols which are accessible on a large industrial scale and have 10 to 18 C atoms are preferred, in particular naturally occur-ring fatty alcohols from the hydrogenation of fatty acids or fatty acid derivatives. Zieglar alcohols or Oxo alcohols can also be used.
The polyglycosyl radical Zn is determined on the one hand by the choice of carbohydrate and on the other hand by adjust-ing the average degree of polymerization n, for example in accordance with German Published Patent Application 1,943,689.
It is known that in principle polysaccharides, for example starch, maltodextrins, dextrose, galactose, mannose, xylose and the like, can be employed. The carbohydrates starch, maltodextrins and in particular dextrose which are available on a large industrial scale are preferred. Since the alkyl polyglycoside syntheses which are of economic interest do not proceed regio- and stereo-selectively, the alkyl polyglycosides are always mixtures of oligomers, which in turn are mixtures of various isomeric forms. They are present together with ~- and ~-glycosidic bonds in the pyranose and furanose form. The linkage points between two saccharide radicals also vary.
2~3~7 Alkyl polyglycosides employed according to the inven-tion can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides. The latter can be isolated or enriched from alkyl polyglycosides, for example, in accordance with European Published Patent Application 0,092,355 using polar sol-vents, such as acetone.
The degree of glycosidation can be advantageously determined by means of H-NMR.
The detergents according to the invention contain 5 to 30% of alkyl polyglycoside, preferably 7 to 20%.
In contrast to almost all the other surfactants employ- -~
ed in detergents, the alkyl polyglycosides are regarded as being entirely ecologically safe. The degree of biological degradation determined by means of a water treatment plant simulation model/
DOC analysis for the alkyl polyglycosides according to the invention is thus 96 + 3%. This figure should be considered in view of the fact that a substance showing a degree of degradation of > 70% is considered as being readily degradable according to this test method (total degradation).
~ The acute oral toxicity LD50 (rat) of > 10,000 mg/kg and the aquatic toxicity LC50 (golden orfe) of about 12 mg/l and ; EC50 (Daphnia) of 30 mg/l are also more favourable by a factor of 3 to 5 than the corresponding values of currently the most important surfactants. The same applies to the skin and mucosa tolerance.
; - 5 -2 ~ 7 Fatty alcohol ether-carboxylates Fatty alcohol ether-carboxylates are compounds of either the formula II or the formula ~II
(R-_o(cH2-cH2-o)xcH2coo)mM II, in which R' is a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18, carbon atoms, x is 1 to 40, preferably 3 to 30, m is 1 or 2 and M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanol-ammonium, or ([R~'-O(CH2-CH2-O)y]2cHcoo)zN III
in which R'' denotes a linear or branched, saturated or unsaturated alkyl radical having 8 to 22, preferably 10 to 18, carbon atoms, y denotes 1 to 4, preferably 3 to 30, z denotes 1 or 2 and N
denotes H, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium.
Compounds corresponding to the formula II are called carboxymethylated oxyethylates, and those corresponding to the formula III are called bisalkanol ethoxylateacetates.
The carboxymethylated oxyethylates can be prepared in accordance with German Published Patent Application 2,418,444 or European Published Patent Application 0,106,018 by reaction of oxyethylates of the formula R'-O(CH2-CH2-O)nH with chloroacetic acid or a salt of chloroacetic acid in the presence of an alkali metal hydroxide or other ba~es. However, other preparation processes, for example by means of catalytic oxidation according to European Published Patent Application 0,018,681 and 0,039,111, 2~31~7 ~3443-447 are also suitable.
Bisalkanol ethoxylate-acetates can be prepaxed, for example, in accordance with German Published Patent Application 3,902,663 from oxyethylates and dichloroacetic acid.
Corresponding alcohols for the preparation of the fatty alcohol ether-carboxylates are preferably fatty alcohols or Ziegler alcohols, and in exceptional cases also Oxo alcohols.
The carboxymethylation which follows the oxyethylation can be complete in the case of an appropriate procedure, so that the fatty alcohol ether-carboxylates are purely anionic surfactants.
Alternatively, if the carboxymethylation is not complete, the products contain certain amounts of unreacted oxyethylate. The formulae II and III therefore usually mean a mixture containing varying amounts of unreacted oxyethylates. A degree of conversion can accordingly be defined. A degree of conversion of between 70 and 100% is preferred.
The fatty alcohol ether-carboxylates are also very ecologically-safe surfactants. Biological degradation rates of above 90% have thus been determined by means of a water treatment plant simulation model/DOC analysis. The acute oral toxicity LD50 (rat) and the aquatic toxicity hC50 (golden o_fe) are about as favourable as those of the alkyl polyglucosides. The same applies to the skin and mucosa tolerance.
The detergents according to the invention contain 5 to 30% of fatty alcohol ether-carboxylates, which can also be mixtures. A content of 7 to 20% of fatty alcohol ether-' .~
;
~ 0 ~ 7 carboxylate is preferred.
Soap Fatty acid salts according to the invention and their acids correspond to the formula IV
R'l'COOP IV, in which R'l' denotes a saturated or unsaturated alkyl radical having 8 to 22 C atoms and P denotes hydrogen, an alkali metal, ammonium or alkanolammonium.
The detergents according to the inventisn contain 5 to 30%, preferably 7 to 20% of soap, which will usually be a mixture of various components.
Other surfactant constituents Up to 3% of other anionic, nonionic, zwitter-ionic and ampholytic surfactants is to be employed according to the inven-tion. These are, in particular, alkanesulphonates, olefinsulphon-ates, alkylbenzenesulphonates, ~-sulpho-fatty acid esters, fatty alcohol sulphates, fatty alcohol ether-sulphates, sulphosuccinic acid esters, alkanol oxyethylates, fatty acid alkanolamides, ammine oxides, betains, sulphobetains and the like.
Other non-surfactant constituents Non-surfactant constituents which may be mentioned are above all builders. Water-soluble buildersj such as various polyphosphates, phosphonates, carbonates, polycarboxylates, citrates, polyacetates, such as NTA and DETA, and the like or mix-tures thereof are used according to the invention. These compounds are usually employed as the alkali metal salts, preferably as the 2~431~7 sodium salts. Although it is not a complexing agent, sodium sul-phate may also be mentioned here. Water-insoluble builders, such as aluminosilicates of suitable particle size (compare European Published Patent Application 0.075,994) can also be used. The concentration of the builders in the detergent is 0 to 70%, preferably 0 to 50~.
Bleaching agents, such as sodium perborate, if appropriate combined with bleaching activators, such as tetra-acetylethylenediamine and the like, or percarbonate, are further-more employed according to the invention; other bleaching agents are of course also possible (compare K. Engel, Tenside Surfactants 25, page 21 (1988)). The concentration of the bleaching agent is 0 to 40%, preferably 0-30%.
If appropriate, standardizing agents, such as low molecular weight 1- or 2-hydric alcohols, alkyl ethers of poly-hydric alcohols, hydrotropic agents, such as alkylbenzenesulphon-ates having 1 to 3 C atoms in the alkyl radical, alkanolamines or ureas, enzymes, such as, in particular, proteases, and enzyme stabilizers, corrosion inhibitors, such as alkali metal silicates, optical brighteners, in particular those based on stilbene and pyrazolene, foam regulators, greying inhibitors, such as, for example, carboxymethylcellulose, perfume oils, dyestuffs and other contents customary for liquid or pulverulent detergents, may also be employed according to the invention.
The total use concentration of the surfactant content in the machine detergents according to the invention is 0.3-20 g/l. 0.5-10 g/l is preferred.
2 0 ~ 7 Examples The invention is illustrated by the following examples.
The liquid detergent formulations listed in Tables 1 and 2 each contain 6% of triethanolamine, 12% of ethanol, 6% of 1,2-propylene-glycol and water to 100%, in addition to the surfactant constituents mentioned which are used according to the invention.
The foaming capacity was determined in accordance with DIN 53 902, part 1. The concentration of detergent substance was in each case 1 g/l, and the volume of foam was recorded after 5 minutes. The washing power was measured both in a Linitest*
laboratory washing machine (that is to say under moderate mechani-cal stress) and in a normal domestic machine. The model fabric used was cloth 11 x 18 cm in size of WFK test fabric with skin grease-pigment soiling: polyester ~PE), mixed fabric (MF) and cotton (C), the water used was drinking water (13 dH). The polyester was washed at 30C and the mixed fabric and cotton at 60C. The active compound concen~ration was 1 g/1 in the Linitest* laboratory washing machine and 5 g/l in the domestic washing machine, the pH was in each case about 7, the liquor ratio was about 1:60 and 1:4 respectively and the washing times in both cases were about 30 minutes.
; In the Linitest* machine, the washing operation was repeated twice, each time after rinsing. The washing values after drying of the fabric were - as is customary - measured by spectrophotometry relative to a white standard (Datacolor*, 560 nm).
;:
*Trade-mark 2~3147 ~gLid formulations:
Tables 1 and 2 show the comparison of the properties of the detergents according to the invention as a liquid formulation with those of other known combinations and of a liquid brand detergent, for which optimization of the recipe can be assumed.
~31~7 O.Z.4491 23443-447 Table 1: Liquid detergent based on carboxymethylated oxyethylate/alkyl polyglucoside/~oap _ E~mple ~o.
Surf~nt l(V) 2~V) 3 4 5 6 7 8~V) .
~oC~ AES-Na 15 - _ _ _ _ _ ~ d C~, PS-Na _ 15 _ _ _ _ _ braDd C~(EO); cm~O0 _ _ 15 - - 15 - ~r-C~(E0)sc~ 0 _ _ _ 15 - ~ 15 gent C~ 0)3 CmO.SII _ _ _ _ 15 C~i.2*~ 15 15 15 15 15 -C~.7 _ _ - - - 15 15 Soap**~ 10 10 10 10 10 10 10 _ Pe~lts .
Cl ;~rif~:atiorl point (-C)s~1 -2 2 1 3 -1 -1 _ ViKx~ity at 25-C (mPa~)-68 55 68 72 71 66 70 90 Foamingcap~ y (60-C) DINs 120 150 50 55 45 S0 40 30 ~hinq pa~
(refleGu~xe (~)) llnitest~
P~ 30-C 6 8 15 11 11 15 }5 11 Washing m~nes MF 60-C _ 31 29 58 54 - 53 55 IS4 A~S-Na - alkylbenzene sulphonate Na salt PS-Na - paraffinsulphonate Na salt (V) s comparison example - abbreviated formula for carboxymethylated C12-C,~ fatty alcohol oxyethylates contalning 4 mol of ethylene oxide/mol, degree of con~lrersion 93%
= C,2C1~-alkyl polyglucoside having a degree of glucosidation of 1.2 *~ - coconut fatty acld (neutralized with trlethanol-amine) - - not measured 2 ~ 7 O.Z.4491 23443-447 able 2~ Liquid detergent based on bisalkanoloxy-ethylateacetate/alkyl polyglucoside/coap E~pla N~.
~ nt 9 10 11 ~ 13 14 _ . . .
eis(Cl2C~(EO)~*o.s~ 15 _ _ 15 _ 7.5 Els~C~(EO)s)~o.s3 - 15 - _ _ 7.5 1~8(C~oc~(Eo)s)aco~82 _ _ 15 - - _ ais(c~a(l~))8)ac ~ 15 _ ~ .2~* 15 1515 - - _ C~ .7 - - - 15 15 15 Soap*** 10 1010 10 10 10 R~
_ Clarification point (-C)s 2 1 2 -1 0 1 Vi~K~ity at 25-C (mPa~)~ 100 90140 120 150110 P~ng capaci~y (60-C) : 20 3020 30 20 20 Wb~hing power (reflecuuLe (%)) Linite~t~
~s MP 60-C _ 5954 59 - 58 - - - -* = -abbreviated formuls for bl~ C~C~alkanol oxy-ethylate-acetate containing 6 mol of ethylene oxid~/mol, degree of conversion 84%
** 3 C~C1~-alkyl polyglucoside having a degree of glucosidation of 1.2 *** - coconut fatty acid (neutralized with triethanol-amine~
- ~ not measured 2~431~7 O.Z.4491 23443-44 The clarification point and vlscosity entirely comply with the u~ual market standard for liquid detergents. The foaming capacity of the formulation~ according to the Lnvention show~ very favourable value~ - without other regulating additives. This particularly applie~ to the washing power. The formulation~ according to the inven-tion are far more effective here than other known com-binations in which the surfactant content likewise con~ists of an anionic surfactant, alkyl polyglucoside and ~oap (Comparison Examples 1 and 2).
Powde ~ fQrmulationss Table 3 shows the comparison of the properties of pul-verulent detergent formulations according to the inYen-tion with ~ho~e of a known combination and of a brand detergent. The bulk den~ity, angle of repose and foaming capacity were determined by DIN methods. The solubility is estimated by mean~ of a plot of the electrical conduc-tivity against time, the measurement value being taken at 80% of an average final conductivity when 1 g of powder L~ dissolved ln 800 ml of drinking water ~13 dH). $he measurement values include an error of ~ 5~.
2 0 ~ 7 o.z.4491 23443-447 able 3s Powder detergent based on carboxymethylated oxyethylate/alkyl polyglucoside/soap _ E~ple No.
S~ nt lS(V) 20(V1 16 17 18 19 . .
C~ o~* - Pul- 3 - -C~(EO)~.0~ - veru- - 3 - -oy~ol~80/85(EO)~b.s - lent - - 3 3 C~ .2~ 4 ~rand 4 4 4 -C~F~.7~ - d~ - 4 C~Cu-AES-Na 3 genS - - - -Soap*~ 5 5 5 5 5 _ P~ll.'cs .
_ Eblk ~ ty g/l~ 760 460 780 820 790 800 Angle of nq~xe (ctg~) 1.5 1.5 1.4 1.5 1.4 1.4 Solubility (mln.)~14 14 16 17 14 16 F~ng cyx~ity (ml)~
(60-C) DDN a~r 30 ~ec. 120 160 150 140 100 100 300 sec. 30 20 30 30 40 20 ~q E~
(~ (%)) ~$~:~
Pe 20-C 8 9 10 11 9 12 Wad~nq ma~es NF 60-C 33 42 43 45 42 ~3 ABS-Na - alkylbenzenesulphonate Na salt (V) - comp~ri~on example * ~ compare T~ble 1 ** - 90 part- of beef tallow, 10 parts of coconut oil hydrolyzed with NaOH
20~3:L47 o.z.4491 23443-447 Apart from a considerably higher bulk density, which is typical of agqlomerated washing powder~, in compari~on with the spray-dried brand product (Example 20), the powders according to the invention are very ~imilar and better in their washing values. The greatly improved washing effects in compari~on with known formulations of Example 15 containing anionic surfactant~ are aqain also clearly to be ~een here.
.
., . - :
.
.
Claims (8)
1. A low-foaming, liquid or pulverulent detergent for washing machines, said detergent containing surfactant components and non-surfactant components, the surfactant components comprising:
5 to 30% of alkyl polyglycoside, 5 to 30% of alkanol ether-carboxylate, 5 to 30% of soap and 0 to 3% of other surfactants.
5 to 30% of alkyl polyglycoside, 5 to 30% of alkanol ether-carboxylate, 5 to 30% of soap and 0 to 3% of other surfactants.
2. A detergent according to claim 1, wherein the alkyl polyglycoside corresponds to the formula I
R-O-Zn I
wherein R denotes a linear or branched, saturated or unsaturated alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn denotes a polyglycosyl radical composed of n = 1 to 3 hexose or pentose units or mixtures thereof.
R-O-Zn I
wherein R denotes a linear or branched, saturated or unsaturated alkyl radical having 10 to 18 carbon atoms or mixtures thereof and Zn denotes a polyglycosyl radical composed of n = 1 to 3 hexose or pentose units or mixtures thereof.
3. A detergent according to claim 2, wherein the alkyl polyglycoside is a fatty alcohol polyglucoside where n = 1.1 to 2.
4. A detergent according to claim 1, 2 or 3, wherein the alkanol ether-carboxylate corresponds to the formula II or III
[R'-O(CH2-CH2-O)xCH2COO]mMm+ II
([R"-O(CH2-CH2-O)y]2CHCOO)zNz+ III
in which R' and R" denote saturated or unsaturated, linear or branched alkyl radicals having 8 to 22 carbon atoms, x and y denote an integer from 1 to 40, m and z denote 1 or 2 and M and N denote hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium.
[R'-O(CH2-CH2-O)xCH2COO]mMm+ II
([R"-O(CH2-CH2-O)y]2CHCOO)zNz+ III
in which R' and R" denote saturated or unsaturated, linear or branched alkyl radicals having 8 to 22 carbon atoms, x and y denote an integer from 1 to 40, m and z denote 1 or 2 and M and N denote hydrogen, an alkali metal, an alkaline earth metal, ammonium or alkanolammonium.
5. A detergent according to claim 4, wherein the alkanol ether-carboxylate is a carboxymethylated fatty alcohol oxyethylate corresponding to formula II, in which R' denotes 10 to 18 carbon atoms, x = 3 to 20, m = 1 and M denotes sodium, potassium, ammonium or alkanolammonium.
6. A detergent according to claim 1, 2, 3 or 5, wherein the soap corresponds to the formula IV
R' "COOP IV
in which R''' denotes a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P denotes hydrogen, an alkali metal, ammonium or alkanolammonium.
R' "COOP IV
in which R''' denotes a saturated or unsaturated alkyl radical having 8 to 22 carbon atoms and P denotes hydrogen, an alkali metal, ammonium or alkanolammonium.
7. A detergent according to claim 1, 2, 3 or 5, which contains builders, bleaching agents, standardizing agents, enzymes, stabilizers, greying inhibitors, corrosion inhibitors, optical brighteners, dyestuffs, perfume oils and, if required, further additives as the non-surfactant components.
8. A detergent according to claim 1, 2, 3 or 5, wherein the concentration of the surfactant components is 0.3-20 g/l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4016819A DE4016819A1 (en) | 1990-05-25 | 1990-05-25 | Low foam liq. or powder machine washing compsn. with surfactant - comprising alkyl-poly:glycoside, alkanol ether carboxylate and soap |
| DEP4016819.0 | 1990-05-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2043147A1 true CA2043147A1 (en) | 1991-11-26 |
Family
ID=6407153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002043147A Abandoned CA2043147A1 (en) | 1990-05-25 | 1991-05-23 | Low-foaming detergents for machines |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0457965B2 (en) |
| JP (1) | JPH04227998A (en) |
| AT (1) | ATE124083T1 (en) |
| CA (1) | CA2043147A1 (en) |
| DE (2) | DE4016819A1 (en) |
| DK (1) | DK0457965T3 (en) |
| ES (1) | ES2075873T3 (en) |
| NO (1) | NO178233C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4331297A1 (en) * | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Bar soaps |
| BR9708918A (en) * | 1996-05-08 | 1999-08-03 | Henkel Corp | Surfactant process to manufacture the same cleaning product and composition |
| WO1999024538A1 (en) * | 1997-11-10 | 1999-05-20 | Henkel Corporation | Alkyl polyglycoside ether carboxylates |
| US6350727B1 (en) * | 2000-01-28 | 2002-02-26 | Amway Corporation | Non-streaking no-wipe cleaning compositions with improved cleaning capability |
| JP2004035808A (en) * | 2002-07-05 | 2004-02-05 | Nissan Soap Co Ltd | Liquid detergent composition |
| JP4247086B2 (en) * | 2003-10-06 | 2009-04-02 | 花王株式会社 | Cleaning composition |
| EP3266859A1 (en) * | 2016-07-05 | 2018-01-10 | Basf Se | Composition suitable as degreasing agent for removing greasy and/or oil type deposits |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0070075B2 (en) * | 1981-07-13 | 1992-11-04 | THE PROCTER & GAMBLE COMPANY | Foaming dishwashing liquid compositions |
| US4483787A (en) * | 1983-12-28 | 1984-11-20 | The Procter & Gamble Company | Concentrated aqueous detergent compositions |
| IL81354A (en) * | 1986-01-30 | 1990-11-05 | Colgate Palmolive Co | Liquid detergent having improved softening properties |
| FR2617862B1 (en) * | 1987-07-09 | 1994-01-07 | Sandoz Sa | BUILDER FREE DETERGENT COMPOSITIONS |
-
1990
- 1990-05-25 DE DE4016819A patent/DE4016819A1/en not_active Withdrawn
- 1990-12-13 ES ES90124032T patent/ES2075873T3/en not_active Expired - Lifetime
- 1990-12-13 DE DE59009297T patent/DE59009297D1/en not_active Expired - Fee Related
- 1990-12-13 AT AT90124032T patent/ATE124083T1/en not_active IP Right Cessation
- 1990-12-13 EP EP90124032A patent/EP0457965B2/en not_active Expired - Lifetime
- 1990-12-13 DK DK90124032.5T patent/DK0457965T3/en active
-
1991
- 1991-05-23 CA CA002043147A patent/CA2043147A1/en not_active Abandoned
- 1991-05-23 NO NO911993A patent/NO178233C/en unknown
- 1991-05-24 JP JP3119854A patent/JPH04227998A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ES2075873T3 (en) | 1995-10-16 |
| NO911993D0 (en) | 1991-05-23 |
| ATE124083T1 (en) | 1995-07-15 |
| JPH04227998A (en) | 1992-08-18 |
| EP0457965A1 (en) | 1991-11-27 |
| NO178233B (en) | 1995-11-06 |
| NO911993L (en) | 1991-11-26 |
| EP0457965B1 (en) | 1995-06-21 |
| DE59009297D1 (en) | 1995-07-27 |
| DK0457965T3 (en) | 1995-11-06 |
| EP0457965B2 (en) | 2002-04-24 |
| NO178233C (en) | 1996-02-14 |
| DE4016819A1 (en) | 1991-12-19 |
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