CN1219959A - Low sudsing liquid detergent compositions - Google Patents
Low sudsing liquid detergent compositions Download PDFInfo
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- CN1219959A CN1219959A CN97195043A CN97195043A CN1219959A CN 1219959 A CN1219959 A CN 1219959A CN 97195043 A CN97195043 A CN 97195043A CN 97195043 A CN97195043 A CN 97195043A CN 1219959 A CN1219959 A CN 1219959A
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- detergent composition
- composition
- liquid detergent
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D1/40—Monoamines or polyamines; Salts thereof
-
- 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
- C11D1/75—Amino oxides
-
- 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
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Abstract
A liquid detergent comprising a silicone suds suppressor and a short chain length amine surfactant selected from the formulas (i)-(viii): (i) R1 - NH2; (ii) R1 - N(R2)2; (iii) R1 - N(R2)2O; (iv) R1 - (CO) - N (CH2)3 - N (R3)2; (v) R1 - (CO) - N (CH2)3 - N (R3)2O; (vi) R1 - (CO) - N (CH2)2 - N (R3)2O; (vii) R1 - (CO) - N [(CH2)2 - O]x - N (R3)2O; (viii) and mixture thereof, wherein R1 is a linear, branched, cyclic, saturated or unsaturated alkyl group having 6 to 10 carbon atoms; R2 is a hydrogen or methyl group; R3 is independently selected from a hydrogen, methyl, CH2CH2OH, polyethoxy or polypropoxy group and x is between 1 to 5.
Description
Invention field
The present invention relates to have the detergent composition of controlled lathering property.Further, the present invention relates to comprise the liquid detergent composition that presses down foam system, the described foam system that presses down comprises polysiloxane suds suppressor and specific short chain amine tensio-active agent.
Background of invention
What effectively and evenly be controlled at formed bubble amt in the washing operation is an existing known product prescription difficult problem, and this difficult problem needs further to improve.Excess foam formation can influence the integral fabric cleaning force given by current detergent composition and to the benefit of fabric, especially when in carrying out washing treatment carries out in rotary drum type washing machine.Too much foam in the washing machine is undesirable, and this is because not only it can disturb and weaken the effect of washings to fabric, and the remaining foam in the washing machine also can be brought into rinse stage.This will not only can increase the foam volume in the rinsing, and suppressing foam in the rinse cycle has its inherent difficulty; And may disturb active agent (as textile softener) in the rinse step.
Often press down foam system and solve above-mentioned these problems in the prior art by in the composition of conventional surfactants detergent mixture, mixing.Press down foam system and comprise, as polysiloxane as suds suppressor.But, press down foam system as polysiloxane one class and be difficult in liquid composition, keep disperseing, and be difficult to handle.In addition, the polysiloxane inhibitor is very expensive.
Under this background, on June 28th, 1993, the european patent application 94922023.0 of application disclosed a kind of low sudsing liquid detergent compositions, and this detergent composition comprises and the conventional anion surfactant of alpha-branched anion surfactant bonded.On October 24th, 1994, the european patent application 94307794.1 of application was described concentrated cleaning compositions, and this detergent composition comprises by 2-alkyl-alkanol deutero-branching nonionogenic tenside and has controlled lathering property.The european patent application 94307979.8 of on October 28th, 1994 application proposed a kind of be used for concentrated liquid detergent press down foam system, should press down foam system and comprise specific lipid acid and polysiloxane defoamers and controlled lathering property can be provided.
Have now found that, surprisingly, press down in the foam system to the polysiloxane of liquid detergent composition and to add specific short chain C
6-C
10The amine tensio-active agent can strengthen the bubble effect that presses down of polysiloxane suds suppressor synergistically.This discovery can make us can reduce the content of polysiloxane suds suppressor in the foaming control performance of the liquid washing agent that keeps containing polysiloxane.
Therefore, the object of the present invention is to provide a kind of suds suppressor system, this suds suppressor system has effective foaming controllability to liquid washing agent.
Another object of the present invention is to provide the homogeneous liquid detergent composition, it is stable that this detergent composition can keep, and particularly can keep stable when standing storage.
Above-mentioned purpose can be by containing the specific short chain C that combines and use with the polysiloxane suds suppressor
6-C
10The pressing down foam system and reach of amine tensio-active agent.
WO95/05440 discloses the automatic cleaning composition of granular tableware, and said composition comprises long-chain (＞12C) amine oxide and polysiloxane suds suppressor.It is few to be realized foaming than the short chain amine oxide, but clean-up performance is relatively poor.In the prior art, people know, compare with the long-chain tensio-active agent, that short chain surfactants can bubble is few (J.Coll.Int.Sci., 159, pp214-225 (1993)-Kirk-Othner ' s Enc.Chem.Techn., p359).Really, the european patent application 93870050.7 of on March 19th, 1993 application disclose following nonionogenic tenside (being the short chain alcohol alcoxylates) in cleaning especially effectively and foam low, soft to skin.
In general detergent formulations (J04011698, GB2229460), dish washing detergent (WO95/20026, WO95/07971) and Personal hygiene application (GB2160541, US5290471, DE4020500), amine oxide has been described extensively.C
10-C
18Amine oxide (J59196395, J56087000), trimethyl-glycine generally are described as suds booster (WO94/05758, WO92/06161, US4879051).WO95/20028 has explained really and has comprised degreasing and the oil removing performance that relative a large amount long chain amine oxide can significantly improve detergent composition, obtains preparation or obtains the detergent composition of low bubble, stable and homogeneous.
Summary of the invention
The present invention relates to a kind of liquid washing agent, this washing composition comprises and presses down foam system, and described system comprises polysiloxane suds suppressor and specific short chain amine tensio-active agent, and described amine tensio-active agent is selected from (ⅰ)-(ⅷ): (ⅰ) R
1-NH
2(ⅱ) R
1-N (R
2)
2(ⅲ) R
1-N (R
2)
2→ O; (ⅳ) R
1-(CO)-N (CH
2)
3-N (R
3)
2(ⅴ) R
1-(CO)-N (CH
2)
3-N (R
3)
2→ O; (ⅵ) R
1-(CO)-N (CH
2)
2-N (R
3)
2→ O; (ⅶ) R
1-(CO)-N[(CH
2)
2-O]
x-N (R
3)
2→ O; (ⅷ) and composition thereof, R wherein
1Be straight chain, side chain, ring, the saturated or unsaturated alkyl that contains 6 to 10 carbon atoms; R
2Be hydrogen or methyl; R
3Be independently selected from hydrogen, methyl, CH
2CH
2OH, polyethoxye or poly-propoxy-and x are 1 to 5.
Detailed Description Of The Invention
But liquid washing agent of the present invention comprises foam system, should press down foam system and be made up of polysiloxane suds suppressor and the short chain amine tensio-active agent that is selected from formula (ⅰ)-(ⅷ): (ⅰ) R
1-NH
2(ⅱ) R
1-N (R
2)
2(ⅲ) R
1-N (R
2)
2→ O; (ⅳ) R
1-(CO)-N (CH
2)
3-N (R
3)
2(ⅴ) R
1-(CO)-N (CH
2)
3-N (R
3)
2→ O; (ⅵ) R
1-(CO)-N (CH
2)
2-N (R
3)
2→ O; (ⅶ) R
1-(CO)-N[(CH
2)
2-O]
x-N (R
3)
2→ O; (ⅷ) and composition thereof, R wherein
1Be straight chain, side chain, ring, the saturated or unsaturated alkyl that contains 6 to 10 carbon atoms; R
2Be hydrogen or methyl; R
3Be independently selected from hydrogen, methyl, CH
2CH
2OH, polyethoxye or poly-propoxy-and x are 1 to 5.
Preferred short chain amine tensio-active agent is selected from acid amides propylamine, dimethylamine, front three ammonium salt, hydroxyethyl diformazan ammonium salt, double hydroxyethyl ammonium carbamate, dimethyl amine oxide, trimethyl-glycine, amido propyl betaine; Preferred short chain C
6-C
10The amine tensio-active agent is amine oxide and amido propyl dimethylamine; Most preferably DEHA, octylame and hexylamine.
The content of short chain amine tensio-active agent will change along with the required special characteristic of final detergent composition, be generally 0.2% to 10% of detergent composition gross weight.
For any detergent composition that is used for automatic washing machine, formed foam should not overflow washing machine.When having suds suppressor, described suds suppressor preferably exists with " control foaming amount "." control foaming amount " is meant that the amount of Foam Control of the prescription personnel selection of composition can be enough to control foam, thereby obtains the low-sudsing detergent applicable to automatic washing machine.
Preferably, the weight ratio of short chain amine tensio-active agent and polysiloxane is 0.1 to 250, more preferably 0.5 to 150, most preferably 1 to 50.
Find, short chain amine tensio-active agent of the present invention increased synergistically the polysiloxane suds suppressor to press down bubble active.According to statistics, polysiloxane of the present invention/short chain amine combinations-of surfactants has obtained that very superior to press down bubble active, should press down the bubble activity and be better than two kinds of single active summations of bubble that press down of composition.
In industrial practice, term " polysiloxane suds suppressor " has become a kind term, and it comprises a large amount of relative high molecular weight polymers that contains siloxane unit and all kinds alkyl.Usually, the polysiloxane Foam Control can be described as the siloxanes with following general structural formula:
Wherein n is 20 to 2,000, and each R is alkyl or aryl independently.The substituent example of this class is methyl, ethyl, propyl group, isobutyl-and phenyl.Preferred polydiorganosiloxane is that the viscosity when having trimethyl silyl end-blocking unit and 25 ℃ is 5 * 10
-5m
2/ s to 0.1m
2The polydimethylsiloxane of/s, promptly n is 40 to 1,500.Why preferably these are because they obtain and relative low price easily.
Be applicable to that other suitable polysiloxane of the present invention comprises functional polysiloxanes.Preferred functional polysiloxanes is negatively charged ion or cationic polysiloxane.
Other polysiloxane comprises the mixture of organopolysiloxane and silica dioxide granule, and wherein said organopolysiloxane utilizes chemical process to absorb on the silicon-dioxide or is fused on the silicon-dioxide.
The polysiloxane suds suppressor is being known in the art, comprise as United States Patent (USP) 4,265,779 and February 7 nineteen ninety disclosed Starch, those polysiloxane of describing in the european patent application 89307851.9 of M.S..
Other polysiloxane suds suppressor is disclosed in United States Patent (USP) 3,455, and in 839, this patent relates to composition and prepares the method for the froth breaking aqueous solution by mixing a small amount of polydimethylsiloxane fluid.
The mixture of polysiloxane and silanized silica is disclosed in as German patent application DOS2, in 124,526.Polysiloxane defoamers in the granular detergent composition and Foam Control are disclosed in United States Patent (USP) 3,933, in 672 and 4,652,392.
The example of employed here polysiloxane group suds suppressor is the foaming amount of suppression suds suppressor of mainly being made up of following ingredients:
(ⅰ) viscosity 25 ℃ the time is about 20cs to about 1, the polydimethylsiloxane of 500cs;
(ⅱ) for per 100 parts of weight (ⅰ), about 5 to about 50 parts silicone resin, and described silicone resin is by SiO
2Unitary (CH
3)
3SiO
1/2The unit is formed, wherein (CH
3)
3SiO
1/2Unit and SiO
2Unitary ratio is about 0.6: 1 to about 1.2: 1, and
(ⅲ) for per 100 parts of weight (I) about 1 to about 20 parts solid silicone.
In the employed here preferred polysiloxane suds suppressor, the solvent of external phase is made up of some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably) or polypropylene glycol.Preferred main polysiloxane suds suppressor is a branching/crosslinked.
In order to further specify this point, the typical liquid laundry detergent composition that contains Foam Control can at random contain about 0.001% to the described polysiloxane suds suppressor of about 2% (weight), preferably approximately 0.01% is to about 0.7%, most preferably about 0.05% to about 0.5%, this polysiloxane suds suppressor comprises the nonaqueous emulsion of (1) main defoamer, and described main defoamer is the mixture of following material: (a) organopolysiloxane, (b) silicone compounds of resinous material siloxanes or generation polyorganosiloxane resin, (c) flour filler and (d) promotion (a), (b) and (c) the mixing element reaction generates the catalyzer of silanization thing; (2) at least a nonionic silicones tensio-active agent and (3) polyoxyethylene glycol or at room temperature in the water solubleness greater than about 2% (weight) and do not contain the polyoxyethylene glycol of polypropylene glycol and the multipolymer of polypropylene glycol.In granular composition, gel, can use similar amount; Referring to United States Patent (USP) 4,978,471 and 4,983,316, United States Patent (USP) 5,288,431 and United States Patent (USP) 4,639,489,4,749,740.
The polysiloxane suds suppressor here preferably comprises polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, and its molecular-weight average is all less than about 1,000, preferred about 100 to 800.Polyoxyethylene glycol here and polyethylene/polypropylene glycol the multipolymer at room temperature solubleness in water are preferably greater than about 5% (weight) greater than about 2% (weight).
The preferred solvent here is a polyoxyethylene glycol, and its molecular-weight average is less than about 1,000, and is preferred about 100 to 800, most preferably 200 to 400; And the polyethylene/polypropylene glycol multipolymer, preferred PPG200/PE6300.The preferred weight ratio of polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer is about 1: 1 to 1: 10, most preferably 1: 3 to 1: 6.
Here employed preferred suds suppressor does not contain polypropylene glycol, does not particularly contain molecular weight and be 4,000 polypropylene glycol.They preferably do not contain the segmented copolymer of oxyethane and propylene oxide yet, as PURONICL101.
Although can use the more polysiloxane suds suppressor of a large amount, its typical amounts is no more than about 2.0% (weight) of detergent composition; This upper limit comes from practice fully, and this mainly is owing to consider the reduction price and can control foaming effectively under the situation of low levels.Can preferably use about 0.01% to about 1% polysiloxane suds suppressor, more preferably from about 0.05% to about 0.5%.Just as used herein, these weight percentage numerical value comprise and can be used for any silicon-dioxide and the spendable any interpolation material that are used in combination with organopolysiloxane.
With regard to processing, can will be that cationic polysiloxane/short chain amine tensio-active agent joins in the liquid detergent composition with premixture or with the form of mixtures with other detergent ingredients and goes when the low pH.The aucillary detergent composition
In another embodiment of the present invention, the liquid detergent composition that is provided comprises and detergent ingredients blended surfactant system of the present invention.The tensio-active agent that can be used for detergent composition of the present invention is very extensive.
Enumerated the kind of typical negatively charged ion, nonionic, both sexes and zwitter-ion type and these tensio-active agents in the United States Patent (USP) 3,664,961 of the Norris that on May 23rd, 1972 published.Anion surfactant
The suitable anion surfactant that comprises alkyl alkoxylated suifate is formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is not for replacing C
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of alkyl composition, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, particularly about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or positively charged ion, and described positively charged ion can be as metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium cation or replaces ammonium cation.Here can consider to use alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The special case that replaces ammonium cation comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, as tetramethyl--ammonium and lupetidine positively charged ion and by those quaternary ammonium cations of alkylamine (as ethamine, diethylamine, triethylamine and composition thereof) deutero-etc.The tensio-active agent example is C
12-C
18Alkyl polyethoxylated (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylated (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol (C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxylated (4.0) vitriol (C
12-C
18E (4.0) M), wherein M can be selected from sodium and potassium easily.
Spendable suitable anion surfactant comprises the sulfonic alkyl ester surfactant, comprises C
8-C
20Carboxylic acid (being lipid acid) straight chained alkyl ester, this alkyl ester can be according to " TheJournalof American Oil Chemists Society ", and 52 (1975), pp.323-329 utilizes gaseous state SO
3Carry out sulfonation.Suitable starting raw material comprises the natural fat acid substance, as by tallow, palm wet goods deutero-natural fat material.
The preferred alkyl sulfonate esters tensio-active agent that can be specially adapted to laundry applications comprises following structural sulfonic alkyl ester surfactant:
R
3-CH (SO
3M)-C (O)-OR
4R wherein
3Be C
8-C
20Alkyl, preferred alkyl or its combination, R
4Be C
1-C
6Alkyl, preferred alkyl or its combination, and M is the positively charged ion that forms water-soluble salt with alkyl sulfonate esters.Suitable salt-forming cation comprises metal (as sodium, potassium and lithium) and replacement or unsubstituting ammonium positively charged ion (as monoethanolamine, diethanolamine and trolamine).Preferably, R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Especially preferred R wherein
3Be C
10-C
16The methylmesylate of alkyl.
Other suitable anion surfactant comprises alkyl sodium sulfate ester salt, i.e. formula ROSO
3The water-soluble salt of M or acid, wherein R is preferably C
10-C
24Alkyl, preferred alkyl or have C
10-C
20The hydroxyalkyl of alkyl composition, more preferably C
12-C
18Alkyl or hydroxyalkyl, and M is H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium) or ammonium or replace ammonium (as methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, as tetramethyl--ammonium and lupetidine positively charged ion and by those quaternary ammonium cations of alkylamine (as ethamine, diethylamine, triethylamine and composition thereof) deutero-etc.Typically, C
12-C
16Alkyl chain is preferred for low wash temperature (as being lower than about 50 ℃), C
16-C
18Alkyl chain is preferred for higher wash temperature (as being higher than about 50 ℃).
Other anion surfactant that is used for the decontamination purpose also can be included in laundry detergent composition of the present invention.These can comprise soap salt (comprise as sodium, potassium, ammonium and substituted ammonium salt, as one-, two-and three-ethanolamine salt), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24Alkenyl sulphonate, the sulfonation polycarboxylic acid (as british patent specification 1,082, described in 179), the C that make by the pyrolysis products sulfonation of alkaline earth metal citrate
8-C
24Alkyl polyglycol ether sulfate (containing oxyethane) up to 10mol; Alkyl glycerol sulphonate salt, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkylphenol ethylidene oxygen ether sulfate, paraffin sulfonate, alkyl phosphate salt, isethionate (as acyl isethinate), N-acyl taurine salt, alkyl amidosuccinic acid salt and alkyl sulfo succinate, sulfosuccinic acid monoesters (particularly saturated and unsaturated C
12-C
18Monoesters) and sulfosuccinic acid diesters (particularly saturated and unsaturated C
6-C
12Diester), acyl sarcosinate, alkyl polysaccharide vitriol (as alkyl polyglucoside vitriol) (nonionic non-sulfuric acid salt compound is described below), branched primary alkyl sulphates and alkyl polyethoxye carboxylate salt are (suc as formula RO (CH
2CH
2O) k-CH
2Those carboxylate salts that COO-M+ represents, wherein R is C
8-C
22Alkyl, k are 0 to 10 integer, and M is for forming the positively charged ion of soluble salt).Resinous acid and hydrogenated resin acid also are suitable for, as rosin, staybelite, be present in the Yatall MA or by Yatall MA derive and resinous acid and hydrogenated resin acid.Further case description is at " Surface Active AgentsandDetergents " (Vol.Iand II, by Schwartz, Perryand Berch).Many these class tensio-active agents also usually are described in the people's such as Laughlin that published on December 30th, 1975 United States Patent (USP) 3,929, and 678 the 23rd hurdles the 58th walk in the 29th hurdle 23 row (being hereby incorporated by reference).
When having anion surfactant, the content of this analog anion surfactants typically is about 1% to about 40% (weight) in the laundry detergent composition then of the present invention, and preferred about 3% to about 20%.Nonionogenic tenside
The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing can be used as the nonionogenic tenside of surfactant system of the present invention, and wherein the polyoxyethylene condenses is preferred.These compounds comprise the condensation product of alkylphenol and alkylene oxide, and described alkylphenol has and contains about 6 to about 14 carbon atoms, preferred about 8 alkyl to about 14 carbon atoms, and this alkyl exists with the straight or branched form.In preferred embodiments, the amount of ethylene oxide be every mole of alkylphenol about 5 to about 25m0l ethylene oxide, preferred about 3 to about 15mol.This commercially available class ionic surfactant pack is drawn together: Igepal
TMCO-630 is sold by GAF company; Triton
TMX-45, X-114, X-100 and X-102, they are sold by Rohm ﹠ Haas company.The so-called alkylphenol alkoxylates of these tensio-active agents (as alkylphenol ethoxylate).
Primary aliphatic alcohols and secondary alcohol and about l can be used as the nonionogenic tenside of nonionic surfactant system of the present invention to the condensation product of about 25mol ethylene oxide.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be a straight or branched, can be primary alconol or secondary alcohol, generally contains to have an appointment 8 to about 22 carbon atoms.Have and contain about 8 condensation products for preferred to the alcohol of about 20 carbon atoms (more preferably containing about 10) and every mol of alcohol about 2 to about 10mol ethylene oxide to about 18 carbon atoms.This commercially available class ionic surfactant pack is drawn together Tergitol
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9mol ethylene oxide), Tergitol
TM24-L-6NMW (C
12-C
14The condensation product that secondary alcohol and 6mol ethylene oxide have narrow molecular weight distributions), the two is sold by Union Carbide Corporation (UnionCarbide Coporation); Neodol
TM45-9 (C
14-C
15The condensation product of straight chain alcohol and 9mol ethylene oxide), Neodol
TM23-6.5 (C
12-C
13The condensation product of straight chain alcohol and 6.5mol ethylene oxide), Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7mol ethylene oxide), Neodol
TM45-4 (C
14-C
15The condensation product of straight chain alcohol and 4mol ethylene oxide), they are sold by shell chemical company (Shell Chemical Company); And Kyro
TMEOB (C
13-C
15The condensation product of alcohol and 9mol ethylene oxide), this condensation product is sold by company of P﹠G (Procter ﹠ Gamble Company).
Be issued to the United States Patent (USP) 4 of Llenado on January 21st, 1986,565,647 disclosed alkyl polysaccharides also can be used as the nonionogenic tenside of surfactant system of the present invention, described alkyl polysaccharide has and contains about 6 hydrophobic grouping and polysaccharide (as polyglucoside) hydrophilic radicals to about 30 carbon atoms (preferred about 10 to about 16 carbon atoms), and described polysaccharide group contains about 1.3 to about 10, preferred about 1.3 to about 3, most preferably from about 1.3 to about 2.7 sugar units.Can use any reducing sugar that contains 5 or 6 carbon atoms, as the alternative grape base section of glucose, semi-lactosi and galactosyl part (hydrophobic grouping can at random be connected 2-, 3-, 4-position etc., obtains glucose or the semi-lactosi different with glucoside or galactoside).Key between sugar can as in addition between 2-, 3-, 4-and/or the 6-position of a position of sugar unit and last sugar unit.
Can there be the polyalkyleneimine chain that connects hydrophobic part and polysaccharide part in any and less ground that needs.Preferred alkylene oxide is an ethylene oxide.Typical hydrophobic grouping comprises alkyl group, and this alkyl can be to contain about 8 to about 18, preferred about 10 saturated or unsaturated, branching or nonbranched groups to about 16 carbon atoms.Preferably, this alkyl is the straight chain saturated alkyl.This alkyl can comprise up to about 3 hydroxyls and/or polyalkyleneimine chain, can contain up to about the individual alkylene oxide part in 10 (preferably less than 5).Suitable alkyl polysaccharide is octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, two-, three-, four-, five-and six-glucoside, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises the coconut alkyl, two-, three-, four-and five-glucoside and tallow alkyl four-, five-and six-glucoside.
Preferred alkyl polyglucoside has formula:
R
2O (C
nH
2nO)
t(glycosyl)
xR wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein alkyl contains and has an appointment 10 to about 18, and preferred about 12 to about 14 carbon atoms; N is 2 or 3, preferred 2; T is 0 to about 10, is preferably 0; And x is about 1.3 to about 10, and preferred about 1.3 to about 3, most preferably from about 1.3 to about 2.7.Glycosyl is preferably derived by glucose and is got.In order to prepare these compounds, at first form alcohol or alkyl polyethoxye alcohol, with glucose or source of glucose reaction, form glucoside (connecting) then in the 1-position.Other glycosyl units can be connected between 2-, 3-, 4-and/or the 6-position of its 1-position and last glycosyl units, preferably mainly is connected the 2-position.
Although be not preferred, ethylene oxide and the condensation product of the hydrophobic matrix that is formed by condensation propylene oxide and propylene glycol also can be used as other ionic surface active agent of nonionic surfactant system of the present invention.The hydrophobic part of these compounds will preferably have molecular weight about 1500 to about 1800, and they demonstrate and water-insoluble performance.Adding the polyoxyethylene part in these hydrophobic parts can increase the solvability of whole molecule, and the fluid characteristics of product can remain to about 50% level that polyoxyethylene content is the condensation product gross weight, this just corresponding to the ethylene oxide condensation of about 40mol.The example of this compounds can comprise the Pluronic that some are commercially available
TMTensio-active agent, this tensio-active agent is sold by BASF.
Ethylene oxide and the condensation product of the product that is obtained by propylene oxide and reacting ethylenediamine also can be used as the nonionogenic tenside of nonionic surfactant system of the present invention.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive oxidation propylene, and its molecular weight is generally about 2500 to about 3000.This hydrophobic part and ethylene oxide are condensed to following degree: it is 5,000 to about 11,000 that condensation product contains 40% polyoxyethylene and its molecular weight to about 80% weight of having an appointment.The example of this class nonionogenic tenside comprises some commercially available Tetronic
TMCompound, this compound is sold by BASF.
As the preferred nonionic surfactants of surfactant system of the present invention is polyoxyethylene condenses, primary aliphatic alcohols and the secondary alcohol of alkylphenol and about 1 condensation product to about 25mol ethylene oxide, alkyl polysaccharide and composition thereof.The C that most preferably contains 3 to 15 oxyethyl group groups
8-C
14Alkylphenol ethoxylate and the C that contains 2 to 10 oxyethyl group groups
8-C
18Alcohol ethoxylate (preferred average C
10) and composition thereof.
Highly preferred nonionogenic tenside is a polyhydroxy fatty acid amide surfactant.
Following formula polyhydroxy fatty acid amide surfactant or its ethoxylated derivative also can be used as nonionogenic tenside:
R
2-C (O)-N (R
1)-Z is R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl, and Z is polyhydroxy alkyl, it has a straight-chain alkyl, has at least 3 hydroxyls directly to be connected with it on the alkyl.Preferably, R
1Be methyl, R
2Be straight chain C
11-15Alkyl or alkenyl, as coconut alkyl or its mixture, and Z autoreduction sugar (as glucose, fructose, maltose, lactose) is derived in reductive amination process.
When in laundry detergent composition of the present invention, comprising this type of nonionic surfactant system, its role is to improve this class laundry composition in the go down performance of grease removal/oil of laundry situation widely.
Laundry detergent composition of the present invention also can contain nonionic, both sexes, zwitter-ion and semi-polarity tensio-active agent, and contains the cats product outside above-mentioned.
Preferred other cationic surfactant system comprises nonionic and amphoterics.Other positively charged ion de-sludging tensio-active agent that is applicable to laundry detergent composition of the present invention is those tensio-active agents with long chain hydrocarbon groups.The example of this cationoid tensio-active agent comprises ammonium surfactant, as the halogenated alkyl dimethylammonium, and those tensio-active agents of following formula:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N+X-is R wherein
2For alkyl or wherein contain 8 the alkyl benzyls of having an appointment in the alkyl chain, each R to about 18 carbon atoms
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-and composition thereof; Each R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by with two R
4The benzyl rings structure that group connects ,-CH
2CHOHCHOHCOR
6CHOHCH
2OH (R wherein
6For any hexose or molecular weight less than about 1000 hexose polymkeric substance), when y is not 0, R
4Be hydrogen; R
5With R
4Identical, or be alkyl chain, wherein R
2And R
5The total number of carbon atoms be no more than about 18; Each y be 0 to about 10 and the summation of y value be 0 to about 15; X is any compatible negatively charged ion.
The preferred cationic tensio-active agent that is applicable to the present composition is the water-soluble quaternary ammonium compound of following formula:
R
1R
2R
3R
4N
-X (I) is R wherein
1Be C
8-C
16Alkyl, each R
2, R
3And R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
4O)
xH (wherein x is value 2 to 5), and X is a negatively charged ion.R
2, R
3And R
4In be no more than one and be necessary for benzyl.Preferred R
1Alkyl chain is C
12-C
15, particularly alkyl is for by coconut or palm kernel fat deutero-long-chain mixture or be the synthetic or pure synthetic alkyl of deriving and obtaining of OXO by alkene.Preferred R
2, R
3And R
4Be methyl and hydroxyethyl, negatively charged ion X is selected from halogen, methylsulfate (methosulphate), acetate moiety and phosphate anion.
Here employed suitable formula (ⅰ) quaternary ammonium compound is: chlorination or bromination coconut TMA (TriMethylAmine); Chlorination or bromination coconut methyl dihydroxy second ammonium; Chlorination decyl three second ammoniums; Chlorination or bromination decyl dimethyl hydroxyl second ammonium; Chlorination or bromination C
12-
15Dimethyl hydroxyl second ammonium; Chlorination or bromination coconut dimethyl hydroxyl second ammonium; Sulfuric acid myristyl TMA (TriMethylAmine) methyl esters; Chlorination or bromination lauryl dimethyl benzyl ammonium; Chlorination or bromination lauryl dimethyl (oxygen ethene) 4 ammoniums; Cholinesterase (R wherein
1For-CH
2-O-C (O)-C
12-14Alkyl and R
2, R
3And R
4Formula (ⅰ) compound for methyl).
Here spendable other cats product also is described in the United States Patent (USP) 4,228,044 that was issued to Cambre on October 14th, 1980.
When comprising this cationoid tensio-active agent, laundry detergent composition of the present invention can typically comprise 0% to about 25% (weight), this type of cats product of preferred about 3% to about 15%.
Amphoterics is also applicable to laundry detergent composition of the present invention.These tensio-active agents can comprise the aliphatic derivatives of secondary amine or tertiary amine or the aliphatic derivatives of heterocyclic secondary or tertiary amine widely, and wherein aliphatic group can be a straight or branched.Aliphatic series one of substituting group contains at least about 8 carbon atoms, typically is about 8 to about 18 carbon atoms, and at least one contains the anionic water-soluble group, as carboxyl, sulfonate radical, sulfate radical.For examples of amphoteric surfactants, can be referring to the people's such as Laughlin that published on December 30th, 1975 United States Patent (USP) 3,929,678 the 19th hurdle 18-35 are capable.
When comprising this class amphoterics, laundry detergent composition of the present invention can typically comprise 0% to about 15% (weight), this type of amphoterics of preferred about 1% to about 10%.
Zwitterionics is also applicable to laundry detergent composition of the present invention.These tensio-active agents can comprise the derivative of secondary amine or tertiary amine widely, the derivative of the derivative of heterocyclic secondary or tertiary amine or quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.For the example of zwitterionics, can be referring to the people's such as Laughlin that published on December 30th, 1975 United States Patent (USP) 3,929,678 the 19th hurdles the 38th walk to the 22nd hurdle the 48th row.
When comprising this class zwitterionics, laundry detergent composition of the present invention can typically comprise 0% to about 15% (weight), preferred about 1% this type of tensio-active agent to about 10% (weight).
Semi-polar nonionic surfactants is the special nonionogenic tenside of a class, comprise water-soluble amine oxides, described amine oxide comprises one and contains about 10 and be selected from the alkyl that contains about l to 3 carbon atom and the part of hydroxyalkyl to the moieties of about 18 carbon atoms and two; Water soluble oxidized phosphine, described phosphine oxide comprise one and contain about 10 and be selected from the alkyl that contains about l to 3 carbon atom and the part of hydroxyalkyl to the moieties of about 18 carbon atoms and two; And water-soluble sulfoxide, described sulfoxide comprises one and contains about l0 and be selected from the alkyl that contains about l to 3 carbon atom and the part of hydroxyalkyl to the moieties of about 18 carbon atoms and one.
Semi-polarity nonionic detergent tensio-active agent comprises the following formula amine oxide surfactant:
R
3(OR
4)
xN (O) (R
5)
2R wherein
3For containing about 8 alkyl, hydroxyalkyl or alkyl phenyl or its mixture to about 22 carbon atoms; R
4For containing about 2 alkylidene group or hydroxy alkylidene or its mixtures to about 3 carbon atoms; X is 0 to about 3; Each R
5For containing about 1 to the alkyl or the hydroxyalkyl of about 3 carbon atoms or contain about 1 polyoxyethylene to about 3 ethylene oxide groups.R
5Group can be connected with each other, and forms ring structure as linking to each other by oxygen or nitrogen-atoms.
These amine oxide surfactants comprise C especially
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
When comprising this class semi-polar nonionic surfactants, laundry detergent composition of the present invention can typically comprise 0% to about 15% (weight), preferred about 1% this type of semi-polar nonionic surfactants to about 10% (weight).
The present invention further provides a kind of laundry detergent composition, the total amount of tensio-active agent accounts at least 1% (weight) of composition weight in the said composition, and preferred about 3% to about 65%, and more preferably from about 10% to about 25%.Washing assistant
The present composition can contain builder system further.Any conventional builder system is all applicable to the present invention, comprise aluminosilicate material, silicate, polycarboxylate and lipid acid and some other materials, as edetate, metal ion chelation agent (as amino polyphosphate), particularly ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Although it is not preferred considering tangible environment reason, the present invention still can use phosphate builders.
Here spendable polycarboxylate washing assistant comprises: citric acid preferably exists with its water-soluble salt form; Formula R-CH (COOH) CH
2(COOH) succinic acid derivative, wherein R is C
10-20Alkyl or alkenyl, preferred C
12-16, or wherein R can be replaced by hydroxyl, sulfo group time sulfonyl or sulfone substituting group.Specific example comprises succsinic acid lauryl, succsinic acid myristyl ester, succsinic acid palmityl ester, succsinic acid 2-dodecyl ester, succsinic acid 2-tetradecene ester.The succsinic acid washing assistant preferably uses with its water-soluble salt form, comprises sodium, potassium, ammonium and alkanol ammonium salt.
Other preferred polycarboxylate is as US4, the oxosuccinic acid salt of describing in 663,071 and the mixture of a succsinic acid tartrate and disuccinic acid tartrate.
Particularly for liquid detergent composition, spendable here suitable lipid acid washing assistant can be saturated or unsaturated C
10-18Lipid acid and corresponding salt.Preferred saturated fatty acid and salt thereof have 12 to 16 carbon atoms in its alkyl chain.Another kind of preferred liquid washing agent builder system is based on succsinic acid dodecylene ester and citric acid dodecylene ester.
The detergent builders salts contg is generally 10% to 80% of composition weight, and is preferred 20% to 70%, is generally 30% to 60% most.
Also can use other composition that is used for detergent composition, as enzyme and stablizer or its activator, outstanding dirty agent, abrasive, sterilant, tarnish inhibitor, tinting material, corrosion inhibitor and spices.Especially preferably utilize the composition of zymotechnic, this also can provide the color protection.Example comprises the cellulase of maintenance/regeneration color.Other example in the EP92870017.8 of 31 applications January in 1992 disclosed polymkeric substance and in the EP92870018.6 of application on January 31st, 1992 disclosed oxydasis scavenging agent.
In addition, also particularly suitable disclosed amine catalyst stablizer in the EP92870019.4 of on January 31st, 1992 application.
Detergent composition of the present invention also can be used as the detergent additives product.This class additive product can provide or promote the performance of conventional detergent composition.
Detergent composition of the present invention comprises the composition that can be used for cleaning substrate (as fabric, fiber, crust etc.), as laundry detergent composition, automatic or non-automatic dish washing compositions and hard surface cleaner.
The following example can be used to the illustration present composition and does not constitute limitation of the scope of the invention.
The embodiment I:
Solution washing agent composition produced according to the present invention found that said composition is effective especially to the control foaming when long-time storage maintenance is stable.
I II III IV V alkyl sodium sulfate ester 15.75 15.75 15.75 15.75 15.75 alkylethoxylates 3.0 3.0 3.0 3.0 3.0C
13-15Mixed ethoxylated/2.5 2.5 2.5 2.5 2.5 propoxylated fatty alcohol polyhydroxy fatty acid amides, 6.8 6.8 6.8 6.8 6.8 polysiloxanes, 0.1 0.1 0.1 0.1 0.1 ethylhexylamines-1.0--0.5 hexylamine 0.5-1.0--octylame 0.5--1.0 0.5 fore-running palm kernel fatty acid-10.0 10.0 10.0 2.0 Fatty Acid in Rapeseed 10.0---8.0 citric acids 1.6 1.6 1.6 1.6 1.6 protease 1.5 1.5 1.5 1.0 1.5 amylase-0.8 0.8 1.0-lipase 0.5--0.1 0.5 cellulase-0.1 0.2 0.1 0.2 calcium chloride 0.1 0.1 0.1 0.1 0.1 boric acid 2.0-2.0-1.0 micro constitutent * to 100%
* comprise ethanol, propylene glycol, monoethylamine and NaOH
The embodiment II:
Non-aqueous solution detergent composition produced according to the present invention found that said composition is effective especially to the control foaming when long-time storage maintenance is stable.
I II III IV V Phenylsulfonic acid straight chained alkyl ester 20.0 20.0 20.0 20.0 20.0C
13-15Mixed ethoxylated 18.0 18.0 18.0 18.0 18.0/ propoxylated fatty alcohol butoxy propoxyl group propyl alcohol 18.0 18.0 18.0 18.0 18.0 polysiloxanes 0.9 0.9 0.9 0.9 0.9 hexamethylene diamines 0.9 0.9 0.9 0.9 0.9 4-E24 oxygen base second-1.0--0.5 base hexylamine hexylamine 0.5-1.0--octylame 0.5--1.0 10.5 acrylic acid/maleic acid is totally 3.3 3.3 3.3 3.3 3.3 polymers citric acids 1.4 1.4 1.4 1.4 1.4Na2CO
33.4 3.4 3.4 3.4 3.41,1-hydroxyl ethane 1.8 1.8 1.8 1.8 1.8 di 2 ethylhexyl phosphonic acid TiO
20.4 the sulfophenylate micro constitutent to 100% of amino oneself 6.9 6.9 6.9 6.9 6.9 acid of 0.4 0.04 0.4 0.4 protease, 1.5 1.5 1.5 1.0 1.5 amylase-0.8 0.8 1.0-lipase 0.5--0.1 0.5 cellulases-0.1 0.2 0.1 0.2 percarbonate, 19.0 19.0 19.0 19.0 19.0N-nonanoyls-6-
Claims (8)
1. a liquid detergent composition comprises polysiloxane suds suppressor and the short chain amine tensio-active agent that is selected from formula (ⅰ)-(ⅷ): (ⅰ) R
1-NH
2(ⅱ) R
1-N (R
2)
2(ⅲ) R
1-N (R
2)
2→ O; (ⅳ) R
1-(CO)-N (CH
2)
3-N (R
3)
2(ⅴ) R
1-(CO)-N (CH
2)
3-N (R
3)
2→ O; (ⅵ) R
1-(CO)-N (CH
2)
2-N (R
3)
2→ O; (ⅶ) R
1-(CO)-N[(CH
2)
2-O]
x-N (R
3)
2→ O; (ⅷ) and composition thereof, R wherein
1Be straight chain, side chain, ring, the saturated or unsaturated alkyl that contains 6 to 10 carbon atoms; R
2Be hydrogen or methyl; R
3For independently being selected from hydrogen, methyl, CH
2CH
2OH, polyethoxye or poly-propoxy-and x are 1 to 5.
2. according to the liquid detergent composition of claim 1, the part by weight of wherein said amine tensio-active agent and polysiloxane suds suppressor is 1 to 250, more preferably 0.5 to 150, most preferably 1 to 50.
3. according to the liquid detergent composition of claim 1-2, wherein said amine tensio-active agent is selected from ethamine, octylame and hexylamine.
4. according to the detergent composition of claim 1-3, said composition further contains tensio-active agent, washing assistant, enzyme and other conventional detergent ingredients.
5. according to the liquid detergent composition of claim 1-4, said composition further contains anion surfactant, and described anion surfactant is selected from alkyl ethoxylated sulfate and/or alkyl sulfuric ester salt surfactant.
6. according to the detergent composition of claim 1-5, said composition exists with the additive form.
7. claim 1-6 liquid detergent composition is used for clean textile, tableware and crust.
8. claim 1-6 liquid detergent composition is used for pretreating fabrics, tableware and crust.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96870038A EP0798370B1 (en) | 1996-03-29 | 1996-03-29 | Low sudsing liquid detergent compositions |
| EP96870038.5 | 1996-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1219959A true CN1219959A (en) | 1999-06-16 |
Family
ID=8226132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97195043A Pending CN1219959A (en) | 1996-03-29 | 1997-03-25 | Low sudsing liquid detergent compositions |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0798370B1 (en) |
| JP (1) | JP3242668B2 (en) |
| CN (1) | CN1219959A (en) |
| AR (1) | AR006412A1 (en) |
| AT (1) | ATE278001T1 (en) |
| BR (1) | BR9708464A (en) |
| CA (1) | CA2250486C (en) |
| CZ (1) | CZ310698A3 (en) |
| DE (1) | DE69633493T2 (en) |
| DK (1) | DK0798370T3 (en) |
| ES (1) | ES2230558T3 (en) |
| TR (1) | TR199801947T2 (en) |
| WO (1) | WO1997036982A1 (en) |
| ZA (1) | ZA972725B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197670A (en) * | 2005-12-27 | 2007-08-09 | Kao Corp | Detergent composition |
| CN101663383B (en) * | 2007-04-13 | 2011-09-07 | 埃科莱布有限公司 | Floor cleaning composition with reduced foaming properties |
| JP5337371B2 (en) * | 2007-11-28 | 2013-11-06 | 花王株式会社 | Detergent composition for automatic dishwasher |
| JP5491770B2 (en) * | 2009-05-29 | 2014-05-14 | 花王株式会社 | Detergent composition for automatic dishwasher |
| JP5491773B2 (en) * | 2009-06-10 | 2014-05-14 | 花王株式会社 | Detergent composition for automatic dishwasher |
| CN106807123A (en) * | 2016-12-28 | 2017-06-09 | 广东中联邦精细化工有限公司 | A kind of foam inhibitor and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7800451A (en) * | 1977-02-03 | 1978-08-07 | Ciba Geigy | MIXTURE OF DI- OR TRITHIOPHOSPHORIC ACID DIESTERS, METHODS FOR PREPARATION AND USE THEREOF. |
| US4324674A (en) * | 1980-08-28 | 1982-04-13 | Chevron Research Company | Amine salt stabilized phosphate ester-based functional fluid |
| US4584125A (en) * | 1984-08-10 | 1986-04-22 | Sws Silicones Corporation | Antifoam compositions |
| US4855070A (en) * | 1986-12-30 | 1989-08-08 | Union Carbide Corporation | Energy transmitting fluid |
| WO1995020028A1 (en) * | 1994-01-25 | 1995-07-27 | The Procter & Gamble Company | Low to moderate sudsing detergent compositions containing long chain amine oxide |
| CA2144781C (en) * | 1994-03-30 | 1999-10-05 | Thomas J. Wierenga | Detergent compositions comprising a synergistic antifoaming combination |
-
1996
- 1996-03-29 AT AT96870038T patent/ATE278001T1/en not_active IP Right Cessation
- 1996-03-29 DE DE69633493T patent/DE69633493T2/en not_active Expired - Lifetime
- 1996-03-29 EP EP96870038A patent/EP0798370B1/en not_active Expired - Lifetime
- 1996-03-29 ES ES96870038T patent/ES2230558T3/en not_active Expired - Lifetime
- 1996-03-29 DK DK96870038T patent/DK0798370T3/en active
-
1997
- 1997-03-25 CA CA002250486A patent/CA2250486C/en not_active Expired - Lifetime
- 1997-03-25 JP JP53536897A patent/JP3242668B2/en not_active Expired - Fee Related
- 1997-03-25 BR BR9708464A patent/BR9708464A/en not_active Application Discontinuation
- 1997-03-25 WO PCT/US1997/004795 patent/WO1997036982A1/en not_active Application Discontinuation
- 1997-03-25 CN CN97195043A patent/CN1219959A/en active Pending
- 1997-03-25 TR TR1998/01947T patent/TR199801947T2/en unknown
- 1997-03-25 CZ CZ983106A patent/CZ310698A3/en unknown
- 1997-03-26 AR ARP970101228A patent/AR006412A1/en unknown
- 1997-03-27 ZA ZA9702725A patent/ZA972725B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0798370A1 (en) | 1997-10-01 |
| EP0798370B1 (en) | 2004-09-29 |
| ES2230558T3 (en) | 2005-05-01 |
| BR9708464A (en) | 1999-04-13 |
| TR199801947T2 (en) | 1998-12-21 |
| CA2250486A1 (en) | 1997-10-09 |
| DE69633493D1 (en) | 2004-11-04 |
| WO1997036982A1 (en) | 1997-10-09 |
| AR006412A1 (en) | 1999-08-25 |
| DE69633493T2 (en) | 2006-02-16 |
| CA2250486C (en) | 2003-12-16 |
| ATE278001T1 (en) | 2004-10-15 |
| DK0798370T3 (en) | 2005-01-03 |
| CZ310698A3 (en) | 1999-02-17 |
| JP3242668B2 (en) | 2001-12-25 |
| ZA972725B (en) | 1997-10-23 |
| JP2000509078A (en) | 2000-07-18 |
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