CN1228111A - Low sudsing liquid detergent compositions comprising silicone suds suppressor and fatty acid ester - Google Patents
Low sudsing liquid detergent compositions comprising silicone suds suppressor and fatty acid ester Download PDFInfo
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- CN1228111A CN1228111A CN 97197319 CN97197319A CN1228111A CN 1228111 A CN1228111 A CN 1228111A CN 97197319 CN97197319 CN 97197319 CN 97197319 A CN97197319 A CN 97197319A CN 1228111 A CN1228111 A CN 1228111A
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- alkyl
- fatty acid
- suds suppressor
- acid ester
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-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- 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
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- 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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
A liquid detergent comprising a silicone suds suppressor and a fatty acid ester of formula (1), wherein R1 is an alkyl chain branched, linear, unsaturated or cyclic with 1 to 20 carbon atoms and R2 is a linear, branched or unsaturated alkyl chain with 7 to 25 carbon atoms.
Description
FIELD OF THE INVENTION
The present invention relates to have the detergent composition of controlled foaming effect.More particularly, the invention relates to and contain the liquid detergent compositions that presses down foam system, but siloxanes contains in described foam system and special fatty acid ester presses down foam system.
The background of invention
In the washing clothes operating process, evenly control gas release effectively, aspect the product preparation be a well-known for a long time improved problem of needs.Too much foaming can influence the cleaning of the whole textiles that usually reaches with modern detergent formulation and to the effect of fabric, particularly wash in barrel washing machine.Too many foaming is undesirable in washing machine, because not only can disturb-reduce-washings is to the washing effect of textiles, and remain in foam in the washing machine and can transfer in the rinse cycle and go, consequently increased the foam volume in the rinse cycle on the one hand, brought the inherent difficulty that presses down bubble, also disturbed the effect of rinse stage promoting agent on the other hand, for example the effect of textile softener.
In technology, it is that compatibility solves in the surfactant detergent component of mixture of routine that this problem is often placed on by pressing down foam in the past.Press down foam system and comprise, suds suppressor for example is as siloxanes.But press down foam system as the siloxanes, in fluid composition, be difficult to keep dispersion state, bring difficulty to washing process, in addition, the type siloxane suds suppressor is expensive too.
In the data of those narrating process, the european patent application No.94922023.0 that on June 28th, 1993 submitted to discloses low sudsing liquid detergent compositions, comprises the conventional anion surfactant that combines with band α-branched anionic surfactants.The european patent application No.94307794.1 that on October 24th, 1994 submitted to has described the concentrated cleaning compositions that is comprising the side chain nonionic surface active agent, its side chain nonionic surface active agent is by 2-alkyl-alkanol deutero-, has the controlled foaming effect.The european patent application No.94307979.8 that on October 28th, 1994 submitted to proposes, and includes the suds suppressor system of the special mixture of lipid acid and silicone antifoam agent, and the effect of control foam can be provided for spissated liquid detergent.
Now people are surprised to find, and special fatty acid ester is joined in the silicone suds suppressor in the liquid detergent composition go, and for the bubble effect that presses down of silicone suds suppressor synergy are arranged, and have improved the bubble effect that presses down of siloxanes.This discovery makes us can reduce the content of silicone suds suppressor in the liquid detergent, and the effect of retentive control foamy is constant.
Therefore, target of the present invention is to provide the suds suppressor system that can effectively control foaming for liquid detergent.
Another target of the present invention provides uniform liquid detergent compositions, and it can keep stable.Especially after the long storage, still can keep stable.
Use contains the suds suppressor system that combines with special fatty acid ester silicone suds suppressor, has reached above-mentioned target.
Both contain fatty acid ester, contained the composition of siloxanes again.At dishwashing detergent, high foaming shampoo (J07048234), and (J06048921-J03172397) uses already in the personal clean-out system.Fatty acid ester also is used as the organic coating material (EP493 345-EP517 298) that contains the siloxanes granule.
WO94/24253 discloses the composition of the low rinse aid of lathering property, it contains sorbitan aliphatic ester and siloxanes, CA1081081 has described the composition of a liquid household cleaners, comprising a foam that presses down that contains fatty acid ester and fatty acid soaps is.
The general introduction of invention
The present invention relates to comprise the liquid washing agent of suds suppressor system, described system contains silicone suds suppressor and has the fatty acid ester of following general formula.
R wherein
1Be side chain, straight chain, the unsaturated or cycloalkyl that contains 1 to 20 C atom, R
2It is the alkyl chain that contains 7 to 25 C atoms.The detailed description of invention
Liquid washing agent of the present invention comprises that a foam that presses down that contains the fatty acid ester of silicone suds suppressor and following general formula is,
R in the formula
1Be side chain, straight chain, the unsaturated or cycloalkyl that contains 1 to 20 C atom, R
2Be linearity, side chain or the unsaturated alkyl chain that contains 7 to 25 C atoms.
Preferred fatty acid ester is by 2 to 16 fatty acid esters that carbon atom alcohol is derived and obtained.
The example of suitable alcohol is that the following name of an article of discussing face to face is sold: Isofol , Isalchem , Lial , Dobano and Natural .
The example of fatty acid part is the palm-kernel of Semen Brassicae campestris, oleic acid, fore-running topping in the ester, stearic acid, hydrogenant lipid acid.
The fatty acid ester contents level depends on the feature of the expectation that last washing composition is formed.General content is between the 0.2%-10% of detergent composition gross weight.
Preparation is applied to any detergent composition in the automatic washing machine, and its gas release should not overflow washing machine, if use suds suppressor, it preferably exists by " pressing down the bubble amount ".So-called " pressing down bubble amount " is meant, the prescription teacher of composition can select to be enough to the consumption of the suds suppressor of control foam, obtains a kind of low foam laundry washing composition, is used for automatic washing machine.
Fatty acid ester is to the weight ratio of siloxanes, and preferably 0.1 to 1000, more preferably 0.5 to 150, most preferably 1 to 50.
Have been found that according to fatty acid ester of the present invention pressing down of silicone suds suppressor being steeped activity has collaborative enhancement.According to the present invention, siloxanes/fatty acid ester combines, and sees on the statistics, obtains the reasonable bubble effect that presses down, and its effect is better than the effect that these two kinds of suds suppressors use separately.
In industrial practice, " silicone suds suppressor " become is a general term, and it comprises contains siloxane unit and various types of alkyl, relatively high-molecular weight polymer.In general, silicone foam control agent, can describe by general structural formula with following siloxanes:
N is 20 to 2,000 in the formula, and each R can represent alkyl or aryl independently.Those substituent examples are methyl, ethyl, propyl group, isobutyl-and phenyl.Preferred polydiorganosiloxane is a polydimethylsiloxane, and it has the end-blocked unit of three silyls, and in the time of 25 ℃, its viscosity number scope is 5 * 10
-5m
2/ s is to 0.1m
2/ s, the n value is in 40 to 1500 scopes.Why these be preferred, be they be easy to obtain and price lower.
Other is applicable to silicone oil of the present invention, is functional siloxane oil.Preferred functional siloxane oil is negatively charged ion and cationic silica alkane oil.
Other siloxanes comprises the combination of organopolysiloxane with silica dioxide granule, here, the organopolysiloxane chemical absorption to or melt in silicon-dioxide.
Silicone suds suppressor is well known in the art, for example, United States Patent (USP) 4,265,779 and February 7 nineteen ninety Starch, the European Patent Application No. No.89307851.9 of M.S. just announced.
Other silicone suds suppressor is disclosed in United States Patent (USP) 3,455,839, and this is about adding composition that makes aqueous solution froth breaking and the method that a small amount of polydimethylsiloxane liquid is made.
The mixture of the silicon-dioxide of siloxanes and silanization was introduced, for example at German patent application DOS2, in 124,526.United States Patent (USP) 3,933,672 and United States Patent (USP) 4,652,392 silicone antifoam agent and the Foam Control in the granular detergent composition disclosed.
Be used for of the present invention, be to suppress foam suds suppressor aequum, that form by following ingredients basically based on an example of the suds suppressor of siloxanes:
(ⅰ) polydimethylsiloxane liquid, it is about 1 to be 25 ℃ of its viscosity that 20cs arrives, 500cs;
(ⅱ) DC resin accounts for about 5 parts to about 50 parts in per 100 parts of weight (ⅰ), and this resin is by (CH
3)
3SiO
1/2Unit and SiO
2The unit is formed, (CH
3)
3SiO
1/2Unit and SiO
2Unitary ratio was from about 0.6: 1 to about 1.2: 1.
(ⅲ) in (ⅰ) of per 100 parts of weight, solid silicone accounts for about 1 part to about 20 parts.
,, be here by some polyoxyethylene glycol as the solvent of external phase as in the preferred silicone suds suppressor, or the polyethylene glycol-propylene glycol copolymers, or its mixture (preferably), or polypropylene glycol constitutes.Preferred main silicone suds suppressor is a side chain/crosslinked.
For further illustrating this point, the laundry of typical may command foaming washes the agent composition by liquid, randomly include above-mentioned silicone suds suppressor, its content (weight percent) from about 0.001 to 2 about, preferably from about 0.01 to 0.7 about, and most preferably from about 0.05 to 0.5 about, this silicone suds suppressor comprises the non-aqueous emulsion of (1) main defoamer, it is mixture (a) organopolysiloxane of following material, (b) silicone compounds of resinous material siloxanes or generation silicone resin, (c) filler of Fen Suiing (d) promotes (a), (b) and (c) the mixing element reaction produces the catalyzer of silicon alcoholate (Silanolate); (2) at least one nonionic siloxane tensio-active agent, (3) polyoxyethylene glycol, perhaps the polyethylene glycol-propylene glycol copolymers does not wherein contain polypropylene glycol, and the molten Jie's degree under the room temperature in water is greater than 2% (weight).Similar amount can be used for granule and forms, and gel etc.Also see also 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 and 4,749,740.
Here, silicone suds suppressor preferably comprises polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, and their molecular-weight average is all less than 1,000, preferably between 100 and 800.At room temperature, polyoxyethylene glycol here and polyethylene/polypropylene glycol multipolymer in water molten Jie's degree greater than about 2% (weight), preferably greater than about 5% (weight).
Here preferred solvent is polyoxyethylene glycol (its molecular-weight average is less than 1,000, preferably between 100 to 800, and most preferably between 200 to 400) and polyethylene/polypropylene glycol multipolymer (preferably PPG200/PEG300).Polyoxyethylene glycol is to the weight ratio of polyethylene glycol-propylene glycol copolymers, and preferably about 1: 1 to 1: 10, most preferably 1: 3 to 1: 6.
Here used preferred silicone suds suppressor does not comprise polypropylene glycol, especially the polypropylene glycol of 4,000 molecular weight.Preferred these silicone suds suppressors do not comprise oxyethane and propylene oxide block copolymer yet, as PURONICL101.
The consumption of silicone suds suppressor generally is up to about 2.0% (weight) of detergent composition, and but, higher amount also may be employed.Here the practical significance of the upper limit is to consider can effectively control the effect of foaming and keep lower price when consumption is low.The consumption of silicone suds suppressor (weight percent), preferably from about 0.01% to 1% about, more preferably from about 0.05% to 0.5%.Here these weight percentage of usefulness comprise the silicon-dioxide all with the organopolysiloxane bonded, and the additive of all uses.
According to complete processing, compound is given in siloxanes/fatty acid ester (under low pH, becoming positively charged ion) conduct, or mixes with other Synergist S-421 95 of washing composition, joins in the liquid detergent composition.The auxiliary material of washing composition
In another embodiment of the invention, liquid detergent composition includes tensio-active agent of the present invention, and it mixes mutually with the component of washing composition.In detergent composition of the present invention, can adopt the tensio-active agent of broad range.
On May 23rd, 1972 was presented to the United States Patent (USP) 3,664,961 of Norris and has listed the tensio-active agent of anionic, non-ionic type, amphoteric and amphoteric ion type and the kind of these tensio-active agents.Aniorfic surfactant
Suitable anion surfactant comprises alkyl alkoxylated sulfuric acid ester surfactant, is meant that here general formula is RO (A) mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl, or have C
10-C
24The hydroxyalkyl group of moieties, preferably C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, m＞0, general about 0.5 to 6 about between, more preferably between about 0.5 to about 3; M is H or positively charged ion, for example a kind of metallic cation (Na for example
+, K
+, Li
+, Ca
+, Mg
+Deng), NH
4 +, or substituted ammonium cation.The alkyl-sulphate of ethoxylation, and propenoxylated alkyl-sulphate also are considered here.Substituted ammonium cation specific examples comprises methyl, dimethyl, trimethylammonium-ammonium cation and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine salt cation, and by alkylamine deutero-positively charged ion, for example from deutero-ammonium cations such as ethamine, diethylamine, triethylamines and composition thereof.Exemplary surfactants is C
12-C
18Alkyl gathers ethoxyquin (1.0) sulfuric ester (C
12-C
18E (1.0) M), C
12-C
18Alkyl gathers ethoxyquin (2.25) sulfuric ester (C
12-C
18E (2.25) M), C
12-C
18Alkyl gathers ethoxyquin (3.0) sulfuric ester (C
12-C
18And C E (3.0) M),
12-C
18Alkyl gathers ethoxyquin (4.0) sulfuric ester (C
12-C
18E (4.0) M), M is Na normally
+Or K
+
Suitable anion surfactant is the alkylsulphonic acid ester surfactant, comprises C
8-C
20Carboxylic acid (being lipid acid) linear ester according to the method that " american petroleum chemist association magazine " [(" TheJournal of the American Oil Chemists Society "), 52 (1975), pp.323-329.] introduces, is used SO
3The gas sulfonation.Suitable initial substance comprises as from tallow, plam oil deutero-natural fat material.
Preferred alkyl sulfonate surfactants, particularly the laundry is used, and includes the alkyl sulfonate surfactants of following general structure:
R
3-CH(SO
3M)-C(O)-OR
4
R wherein
3Be C
8-C
20Alkyl, preferably alkyl, or their binding substances; R
4Be C
1-C
6Alkyl, preferably alkyl, or their binding substances; M is a positively charged ion, and it and alkyl sulfonic ester form water-soluble salt.The salifiable positively charged ion of suitable shape comprises metal such as Na
+, K
+And Li
+, and that replace and unsubstituted ammonium cation, as monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Particularly preferably be the sulfonic acid methyl ester, wherein R
3Be C
10-C
16Alkyl.
Other suitable anion surfactant comprises the alkylsurfuric acid ester surfactant, is that general formula is ROSO
3The water-soluble salt of M or acid, R C preferably in the formula
10-C
24Alkyl, preferred alkyl or hydroxyalkyl have C
10-C
20Alkyl composition, more preferably C
12-C
18Alkyl or hydroxyalkyl; M is H or positively charged ion, for example alkali metal cation (Na for example
+, K
+, Li
+) or ammonium, perhaps the ammonium of Qu Daiing (for example methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, and by deutero-quaternary ammonium cations such as alkylamine such as ethamine, diethylamine, triethylamines and composition thereof).General, C
12-C
16Alkyl chain is more suitable in lower wash temperature (for example being lower than about 50 ℃), and C
16-C
18Alkyl chain is more suitable in higher wash temperature (for example, being higher than about 50 ℃).
Other also can be included in the detergent composition of laundry usefulness of the present invention as the anion surfactant of washing composition purpose.These can comprise soap salt (comprising for example sodium salt, sylvite, ammonium salt and the ammonium salt that replaces, as monoethanolamine, the soap salt of diethanolamine and trolamine), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24Alkene sulfonate, the many carboxylic acids of sulfonation, these many carboxylic acids are according to English Patent explanation No.1, and 082,179 method of introducing makes the sulfonation of alkaline earth metal citrate pyrolysis product C
8-C
24Alkyl polyglycol ether sulfate (containing oxyethane) up to 10 moles; Alkyl glycerol sulfonate; fatty acyl group glycerol sulfonate; fatty oil base glycerol vitriol; alkane phenolic group oxyethane ether sulfate, paraffinic hydrocarbons sulphonate, alkylphosphonic; isethionate such as acyl isethinate; the N-acyl taurine salt, alkylamino succinate and sulfosuccinate, sulfosuccinic acid monoesters (especially saturated and undersaturated C
12-C
18Monoesters) and sulfosuccinic acid diesters (especially saturated and undersaturated C
6-C
12Diester), acyl sarcosinate, alkyl polysaccharide vitriol such as alkyl poly glucoside vitriol (non-ionic type that describes below, the compound of non-sulfuric acidization), the primary alkyl sulphates of collateralization and alkyl polyethoxye carboxylate salt are RO (CH as general formula
2CH
2O)
K-CH
2COO-M
+Carboxylate salt, R is C in the formula
8-C
22Alkyl, K is 0 to 10 integer, M is the positively charged ion that generates soluble salt.Resinous acid and hydrogenated resin acid also are suitable, as rosin, staybelite, are present in and starch the resinous acid and the hydrogenated resin acid of deriving and in the pine slurry or by pine." tensio-active agent and washing composition " book (Vol. I and II, author Schwartz, Perry and Berch) has been introduced more example.Be presented to the United States Patent (USP) 3,929,678 of Laughlin etc. on December 30th, 1975, to 29 hurdles, 23 row, also disclose various these class washing composition (being incorporated herein by reference) at 23 hurdles, 58 row.
Comprise that in the present invention the detergent composition of washing usefulness usually contains and has an appointment 1% to 40%, preferably this analog anion surfactants (weight percent) of 3% to 20%.Nonionics
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are suitable for the nonionic surface active agent as surfactant system of the present invention, and polyethylene oxide condensation compound is preferred.This compounds comprises the condensed products of these alkylphenols and alkylene oxide, and wherein alkyl comprises about 6 to 14 carbon atoms, and preferably about 8 to 14 carbon atoms become the straight or branched configuration with alkylene oxide.In preferred embodiments, with respect to every mole of alkylphenol, the amount of oxyethane is about 5 to 25 moles, and what be more preferably is about 3 to 15 moles.This type nonionic surface active agent, available on the market, comprise the lgepal that GAF company sells
TMCO-630, the Triton that Rohm and Haas company sell
TMX-45, X-114, X-100 and X-102.These tensio-active agents are generally considered to be the alkoxy compound (for example ethoxy compound of alkylphenol) of alkylphenol.
The primary and secondary Fatty Alcohol(C12-C14 and C12-C18) is suitable as the nonionic surface active agent of nonionic surface active agent system of the present invention with the condensation product of about 1 to 25 mole oxyethane.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be side chain or straight chain, uncle's or the second month in a season, generally contain 8 to 22 carbon atoms of having an appointment.The condensation product that preferably contains the Fatty Alcohol(C12-C14 and C12-C18) of 8 to 20 the carbon atom alkyl groups of having an appointment more preferably contains the condensation product of Fatty Alcohol(C12-C14 and C12-C18) of the alkyl group of 10 to 18 carbon atoms of having an appointment, and carries out condensation with about 2 to 10 moles of ethylene oxide with 1 mol of alcohol.Can access the example of this type nonionogenic tenside on the market, comprise Tergitol
TM15-S-9 (C
11-C
15Straight chain alcohol is with the condensation product of 9 moles of ethylene oxide), Tergitol
TM24-L-6NMW (C
12-C
14Secondary alcohol is with 6 moles of ethylene oxide condensation products, and molecular weight distribution is in narrow scope), they all are to be sold by Union Carbide company; Neodol
TM45-9 (C
14-C
15Straight chain alcohol is with 9 moles of ethylene oxide condensation products), Neodol
TM23-6.5 (C
12-C
13Straight chain alcohol is with 6.5 moles of ethylene oxide condensation products), Neodol
TM45-7 (C
14-C
15Straight chain alcohol is with 7 moles of ethylene oxide condensess), Neodol
TM45-4 (C
14-C
15Straight chain alcohol is with 4 moles of ethylene oxide condensess), all sell the Kyro that also has Procter and Gamble company to sell by Shell chemical company
TMEOB (C
13-C
15Alcohol and 9 moles of ethylene oxide condensess).
On January 21st, 1986 laid-open U.S. Patents 4,565,647, Llenado, introduce the nonionic surface active agent that alkyl polysaccharide also is used as surfactant system of the present invention, it has the hydrophobic grouping that comprises about 6 to 30 carbon atoms, preferably comprises about 10 to 16 carbon atoms, has also introduced polysaccharide also as nonionic surface active agent, for example poly-glycoside, comprise about 1.3 to 10, preferably about 1.3 to 3, the hydrophilic radical of most preferably about 1.3 to 2.7 sugar units.Any one reducing sugar that contains 5 or 6 carbon atoms can be employed, for example this part of glucose, semi-lactosi and galactosyl can replace glucosyl group part (hydrophobic group randomly is connected on 2-, 3-, positions such as 4-, glucose or semi-lactosi just are on the relative position of glucoside or galactoside like this).Enough and the 2-of prime sugar unit in additional sugar unit of bond energy between sugar, 3-, 4-and (or) between the 6-position.
Randomly, but very do not wish have a polyalkylene oxide chain to connect hydrophobic part and polysaccharide part.Preferred epoxy alkane is an oxyethane.General hydrophobic grouping comprises alkyl, and is saturated or unsaturated, side chain or non-side chain, contain 8 to 18 carbon atoms approximately, preferably contain 10 to 16 carbon atoms approximately.Preferred alkyl is the straight chain saturated alkyl.Alkyl can comprise at the most 3 hydroxyls and/or the polyalkylene oxide chain can comprise 10 at the most, preferably is less than 5 epoxy alkane parts.The alkyl polysaccharide that is fit to is n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, two, three, four, five and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises the coconut alkyl, two, three, four and five glucosides and Tallow, beef alkyl four, five and six glucosides.
Preferred alkyl poly glucoside has following general formula:
R
2O (CnH
2nO)
t(glucosyl)
x
R in the formula
2Be selected from following groups: alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture; The abovementioned alkyl group comprises 10 to 18 carbon atoms approximately, preferably comprises 12 to 14 carbon atoms approximately; N is 2 or 3, preferably 2; T is about 0 to 10, preferably 0; X is 1.3 to 10 approximately, preferably is 1.3 to 3 approximately, and most preferred is 1.3 to 2.7 approximately.Glucosyl preferably derives from glucose.In order to prepare these compounds, the poly-ethoxy alcohol of alcohol or alkyl at first forms, and with glucose or the glucogenic material reaction of energy, forms glucoside (receiving on the 1-position) then.Additional glucosyl unit can be by their 1-position and the unitary 2-of prime glucosyl, and 3-links to each other between 4-and/or the 6-position, preferably, mainly is connected on the 2-position.
The hydrophobic group that propylene oxide generates with the propylene glycol condensation, the product that generates with ethylene oxide condensation more also is suitable as the additional nonionic surface active agent of nonionic surface active agent of the present invention system, but is not preferred.The hydrophobic part of these compounds, preferred molecular weight is about 1500 to 1800, and presents water-fast character.Add the polyoxyethylene part to this hydrophobic part, tend to increase the water-soluble of whole molecule, and when polyoxyethylene content reached 50% this point of condensation product gross weight, this was equivalent to about 40 moles of ethylene oxide condensations at the most, and product still keeps liquid characteristic.The example of this type compound comprises the Pluronic that is sold by BASF
TMTensio-active agent.
Propylene oxide again with the product of ethylene oxide condensation gained, also is suitable as the nonionogenic tenside of nonionic surface active agent of the present invention system with the product of reacting ethylenediamine.The hydrophobic part of these products is made up of the superfluous together epoxy propane reaction product of quadrol, and its molecular weight is generally by about 2500 to 3000.This hydrophobic part reaches such degree with ethylene oxide condensation, and its condensed products comprises about polyoxyethylene of 40% to 80% (weight percent), and molecular weight approximately from 5000 to 11,000.This type examples of nonionic surfactants comprises some Tetronic that BASF sells on market
TM
Preferred is the condenses of alkyl alcohol with polyethylene oxide as the nonionic surface active agent in the surfactant system of the present invention, and the primary and secondary Fatty Alcohol(C12-C14 and C12-C18) is with the condenses of about 1 to 25 moles of ethylene oxide, alkyl polysaccharide, and their mixture.C most preferably
8-C
14Alkylphenol ethoxylate, they have 3 to 15 ethoxy groups; C
8-C
18Alcohol ethoxylate (average out to C preferably
10), they have 2 to 10 ethoxy groups, also have their mixture.
Highly preferred nonionic surface active agent is a polyhydroxy fatty acid amide surfactant.
Polyhydroxy fatty acid amide surfactant also is suitable nonionic surface active agent, and general formula is as follows:
R
2-C(O)-N(R
1)-Z
R in the formula
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixture; R
2Be C
5-31Alkyl; Z is a polyhydroxy alkyl, and it has a straight-chain alkyl and has at least 3 hydroxyls directly to link on this chain, or its alkoxy derivative.Preferably, R
1Be methyl, R
2It is straight chain C
11-15Alkyl or alkenyl, as coconut palm alkyl or its mixture, Z is the derivative of reducing sugar in reductive amination process, reducing sugar such as glucose, fructose, maltose, lactose etc.
Nonionic surface active agent of the present invention system when in the detergent composition that is included in laundry usefulness, is to be used to improve this washing composition under the laundry situation of broad range, the character greasy, decontamination point of deoiling.
Laundry detergent composition of the present invention except by the agency of, also may comprise non-ionic, amphoteric, zwitterionic and semi-polarity tensio-active agent, and cats product.
Preferred other cationic surfactant system, comprise non-ionic type with the amphoteric tensio-active agent.Other cationic detergent tensio-active agent that is suitable in laundry detergent composition of the present invention has a long chain hydrocarbon groups.The example of this cationoid tensio-active agent comprises ammonium surfactant, as the halogenide of alkyl-dimethyl ammonium with have the tensio-active agent of following general formula:
[R
2(OR
3)
y][R
4(OR
3)
y]
2R
5N+X-
R in the formula
2Be alkyl or alkyl benzyl group, 8 to 18 carbon atoms are arranged on its alkyl chain approximately; Each R
3All be to be selected from following groups :-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-or their mixture; Each R
4All be to be selected from following groups: C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by two R
4The connection of group and the benzyl ring structure that forms ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH, the R here
6Be any one hexose, or molecular weight is less than about 1000 hexose polymkeric substance, and when y does not wait zero, R
4Also may be hydrogen; R
5With R
4Identical, perhaps R
5Be alkyl chain, at this moment a R
2With R
5Contained the total number of carbon atoms is no more than about 18; Each y value is about from 0 to 10, two y value sums about from 0 to 15, and x is any compatible negatively charged ion.
The preferred cationic surfactants that is used for component of the present invention is the soluble quaternary ammonium compound, has following general formula:
R
1R
2R
3R
4N
+X
-(ⅰ)
R in the formula
1Be C
8-C
16Alkyl; R
2, R
3And R
4Each be respectively C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
40)
xH, the x value is from 2 to 5 here; X is a negatively charged ion.R
2, R
3Or R
4In can only to have one at most be benzyl.R
1Alkyl chain length is C preferably
12-C
15, especially alkyl group is the various mixture of chain lengths from coconut or palm hull fat, or obtains by alkene is synthetic, perhaps obtains by OXO alcohol is synthetic.R
2R
3And R
4Preferred group is a methyl, hydroxyethyl, and negatively charged ion X may be selected from halogenide, Methylsulfate, acetate and phosphate ion.
The example of the suitable ammonium compound of the general formula of Cai Yonging (ⅰ) expression here has:
Chlorination (or bromination) coco group TMA (TriMethylAmine);
Chlorination (or bromination) coco group methyl dihydroxy ethyl ammonium;
Chlorination second ammonium in the last of the ten Heavenly stems three;
Chlorination (or bromination) dimethyl in last of the ten Heavenly stems hydroxyl second ammonium;
Chlorination (or bromination) C
12-15Dimethyl hydroxyl second ammonium;
Chlorination (or bromination) coco group dimethyl hydroxyl second ammonium;
Semen Myristicae TMA (TriMethylAmine) methyl sulfate salt;
Chlorination (or bromination) lauryl dimethylamino benzylidene ammonium;
Chlorination (or bromination) lauryl dimethyl four oxyethylene group ammoniums;
Cholinesterase class (compound of general formula (ⅰ), wherein R
1Be-CH
2-O-C (O)-C
12-14Alkyl, R
2R
3R
4All be methyl).
United States Patent (USP) 4,228,044 Cambre of issue on October 14th, 1980 has introduced other cats product that adopts here.
Be included in the amount (weight percent) of this cationoid tensio-active agent in the laundry detergent composition of the present invention here, generally about from 0 to 25%, preferably be 3% to 15% approximately.
Amphoterics also is suitable as laundry detergent composition of the present invention.These tensio-active agents can briefly be described as the aliphatic derivatives of secondary amine or tertiary amine, or are described as heterocyclic secondary or tertiary amine aliphatic derivatives, and wherein fatty group can be a straight or branched.One of aliphatics substituting group comprises about 8 carbon atoms at least, general about 8 to 18 carbon atoms, and have at least one to include water lyotropy anionic group, and for example, carboxyl, sulfonate, vitriol.The U.S. Patent No. 3,929,678 of in December, 1975 issue such as Laughlin on the 30th, the 19th hurdle wherein, 18-35 is capable, and the example of amphoterics is arranged.
If comprise amphoterics, the amount (weight percent) that laundry detergent composition of the present invention generally comprises amphoterics is about from 0% to 15%, preferably approximately from 1% to 10%.
Zwitterionics also is suitable for laundry detergent composition.These tensio-active agents can briefly be described as secondary and tertiary amines derived thing, heterocycle secondary and tertiary amines derived thing, the perhaps derivative of quaternary ammonium salt ， quaternary alkylphosphonium salt and uncle's sulfonium compound.The U.S. Patent No. 3,929,678 of issue on December 30th, 1975 to 22 hurdles, 48 row, has been listed the example of zwitterionics from the 19th hurdle 38 row.
If comprise zwitterionics, the amount of this zwitterionics (weight percent) generally is about from 0% to 15% in the laundry detergent composition of the present invention, preferably approximately from 1% to 10%.
The Semi-polarity nonionic surface active agent is a special category of nonionic surface active agent, it comprises water miscible amine oxide, this amine oxide includes by about 10 to 18 moieties that carbon atom is formed and two other part, and these two portions are selected from by about 1 to 3 alkyl that carbon atom is formed and hydroxyalkyl group; Water miscible phosphine oxide, this phosphine oxide comprise one by about 10 to 18 moieties that carbon atom is formed and two other part, and these two parts are selected from by about 1 to 3 alkyl that carbon atom is formed and hydroxyalkyl group; Water-soluble sulfoxide, this sulfoxide comprise one and are selected from part by about 1 to 3 alkyl that carbon atom is formed and hydroxyalkyl by about 10 to 18 moieties that carbon atom is formed and another.
Semi-polarity non-ionic detergent tensio-active agent comprises amine oxide surfactant, and general formula is
R
3(OR
4)
xN(O)(R
5)
2
R in the formula
3Be alkyl, hydroxyalkyl, alkylphenyl group and their mixture, they contain 8 to 22 carbon atoms approximately; R
4Be alkylidene group or the hydroxy alkylidene that comprises 2 to 3 carbon atoms approximately, perhaps their mixture; X is about 0 to 3; Each R
5Be alkyl or the hydroxyalkyl that comprises about 1 to 3 carbon atom, or comprise the polyethylene oxide of about 1 to 3 ethylene oxide group.R
5Group can be connected to each other, and for example, by oxygen or nitrogen-atoms, forms ring texture.
These amine oxide surfactants include oxidation C especially
10-C
18Alkyl dimethylamine and oxidation C
8-C
12The alkoxyethyl diethanolamine.
In the laundry detergent composition of the present invention, the amount (weight percent) of the Semi-polarity nonionic surface active agent that comprises usually from about 0% to 15%, preferably is about 1% to 10%.
The present invention further provides a kind of laundry detergent composition, the tensio-active agent total amount (weight percent) that wherein comprises is at least 1%, preferably is about 3% to 65%, more preferably is 10% to 25%.Builder
May also include the builder system according to composition of the present invention, the builder system of any routine here all is suitable for, and comprises aluminosilicate material, silicate, polycarboxylate and lipid acid; Also have some materials such as ethylenediamine tetraacetate, metal ion chelation agent such as aminopolyphosphonic acid salt, particularly ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP) also are suitable for.Phosphate builder also is applicable to this, but owing to consider the environmental protection factor, not too welcome.
Suitable polycarboxylate builder comprises that citric acid, its water-soluble salt are preferred, and general formula is R-CH (COOH) CH
2(COOH) succinic acid derivative, R is C in the formula
10-C
20Alkyl or alkenyl, C preferably
12-C
16Perhaps R is replaced by following groups; Hydroxyl, sulfo group, inferior sulfo group or sulfuryl.Concrete example comprises the succsinic acid lauryl, succsinic acid myristin, succsinic acid palm ester, succsinic acid 2-dodecylene ester, succsinic acid 2-tetradecene ester.The succinate that exists with the water-soluble salt form is preferred, and this comprises its sodium salt, sylvite, ammonium salt and alkanol ammonium salts.
The polycarboxylate that other is suitable, as United States Patent (USP) 4,663,071 introduce oxo disuccinic acid ester, the mixture of mono laurate tartrate and two lauric acid tartrates arranged.
Be specifically designed to liquid washing agent, the suitable fatty acids builder is saturated or unsaturated C
10-18Lipid acid, and corresponding soap.Preferred saturated fatty acid is to contain 12 to 16 carbon atoms on the alkyl chain.Other the builder that is used for liquid detergent composition is by succsinic acid dodecylene ester and citric acid preparation.
The amount (weight percent) of the detergent builder salt that comprises in the detergent composition generally is 10% to 80%, preferably 20% to 70%, most preferably 30% to 60%.
Be used for other composition of detergent composition, have: enzyme, stablizer or activator, soil-suspending agent, abradant, sterilant, fade inhibitor, tinting material, corrosion-resistant agent and spices.Particularly preferably be the desmoenzyme technology, this technology helps protecting the color that is washed clothing.Cellulase for example, it can keep the color and luster of clothing, and crease-resistant effect is arranged.Other example is the patent EP 92870017.8 disclosed polymkeric substance of submitting on January 31st, 1992, and the patent EP 92870018.6 disclosed oxydasis scavenging agents of submitting on January 31st, 1992.
The patent 92870019.4 disclosed amido catalysis stablizers that on January 31st, 1992 submitted to also are specially suitable.
Detergent composition of the present invention also can be as the additive of washing composition, in order to the effect of replenishing or promoting conventional washing composition.
Detergent composition of the present invention comprises the composition that is used for the clear base thing, as clean textile, fiber and crust or the like, for example contains laundry detergent composition, automatic and non-automatic laundry detergent composition and hard surface cleaner composition.
Following Example only is giving an example of the present composition, rather than limits the scope of the invention.Example 1:
According to the present invention, prepared aqueous liquid detergent composition, it can control foaming effectively.
I II III IV V 1 alkyl-sulphate 15.75 15.75 15.75 15.75 15.752 alkyl ethoxy compounds 3.0 3.0 3.0 3.0 3.03 contain C
13-15Ethoxylation and palm kernel fatty acid-10.0 10.0 10.0 2.07 vegetable seed aliphatic acid 10.0---8.08 Isofol-vegetable seed greases 200 0-9 Isalchem-vegetable seed greases 02 0--10 dodecanol-stearates 00 2-011 citric acids 1.6 1.6 1.6 1.6 1.612 protease 1.5 1.5 1.5 1.0 1.513 amylase-0.8 0.8 1.0-14 fat (fat) enzyme 0.5--0.1 0.515 cellulase-0.1 0.2 0.1 0.216 calcium chloride 0.1 0.1 0.1 0.1 0.117 boric acid 2.0-2.0-1.018 auxiliary materials of 2.5 2.5 2.5 2.5 2.5 propenoxylated fatty alcohol mixture 4 polyhydroxy fatty acid amides 6.8 6.8 6.8 6.8 6.85 siloxanes 0.1 0.1 0.1 0.1 0.16 fore-running toppings (comprise ethanol, water, until 100% propane diols, mono aminoethane and NaOH)
Claims (7)
1. liquid detergent, it comprises silicone suds suppressor and has the fatty acid ester of following general formula
R wherein
1Be side chain, straight chain, unsaturated or cyclic alkyl, contain 1 to 20 carbon atom; R
2Be straight chain, side chain or unsaturated alkyl chain, contain 7 to 25 carbon atoms.
2. the liquid detergent compositions of claim 1, wherein fatty acid ester is 0.1 to 1000 to the weight ratio of silicone suds suppressor, more preferably 0.5 to 200, most preferably 1 to 50.
3. the liquid detergent compositions of claim 1-2, wherein fatty acid ester is the pure deutero-by 2 to 16 carbon atoms.
4. the detergent composition of claim 1-3, also comprises surfactant, builder, enzyme and other conventional detergent ingredients.
5. the detergent composition of claim 1-4 also includes anion surfactant, and it is selected from alkyl ethoxylated sulfate and/or alkyl sulfate surfactant.
6. the detergent composition of claim 1-5 adds and form.
7. the detergent composition of claim 1-6 is used for laundering of textile fabrics, tableware and crust.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96870082A EP0816480A1 (en) | 1996-06-26 | 1996-06-26 | Low sudsing liquid detergent compositions |
| EP96870082.3 | 1996-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1228111A true CN1228111A (en) | 1999-09-08 |
Family
ID=8226151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97197319 Pending CN1228111A (en) | 1996-06-26 | 1997-06-23 | Low sudsing liquid detergent compositions comprising silicone suds suppressor and fatty acid ester |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0816480A1 (en) |
| JP (1) | JPH11513066A (en) |
| CN (1) | CN1228111A (en) |
| AR (1) | AR007473A1 (en) |
| BR (1) | BR9712784A (en) |
| CA (1) | CA2258703A1 (en) |
| WO (1) | WO1997049788A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296770C (en) * | 2002-10-30 | 2007-01-24 | 株式会社Adeka | Foam eliminating dispersing agent for developer solution of photosensitive resists |
| CN109983108A (en) * | 2016-11-24 | 2019-07-05 | 荷兰联合利华有限公司 | Liquid detergent composition |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002230378A1 (en) * | 2000-11-29 | 2002-06-11 | The Procter And Gamble Company | Hand dishwashing composition containing a suds suppresser and a method of use therefor |
| GB2388610A (en) * | 2002-05-17 | 2003-11-19 | Procter & Gamble | Detergent composition containing silicone and fatty acid |
| EP1595940A1 (en) * | 2004-05-12 | 2005-11-16 | Malaysian Palm Oil Board | High performance cleaning agent |
| JP5243522B2 (en) * | 2007-04-13 | 2013-07-24 | イーコラブ インコーポレイティド | Floor cleaning composition with reduced foaming properties |
| FR2940151B1 (en) | 2008-12-23 | 2010-12-17 | Solystic | MACHINE FOR SORTING LARGE FORMAT POSTAL OBJECTS AND LETTERS |
| SG10201408435UA (en) | 2009-12-17 | 2015-01-29 | Stepan Co | Foaming light duty liquid detergent compositions, methods of making and uses thereof |
| MY165143A (en) * | 2011-10-03 | 2018-02-28 | Lion Corp | Detergent and liquid detergent for textile products |
| JP6071717B2 (en) * | 2012-04-11 | 2017-02-01 | ライオン株式会社 | Liquid detergent for textile products |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2115082C3 (en) * | 1971-03-29 | 1980-05-14 | Henkel Kgaa, 4000 Duesseldorf | Antifoam agents for dishwashers |
| LU71583A1 (en) * | 1975-01-02 | 1976-11-11 | Procter & Gamble Europ | |
| JPS5266887A (en) * | 1975-11-29 | 1977-06-02 | Shin Etsu Chem Co Ltd | Defoaming agent composition |
| GB2040982B (en) * | 1977-06-23 | 1982-08-25 | Procter & Gamble | Detergent composition with a suds-regulaing system |
| FR2570602B1 (en) * | 1984-09-21 | 1986-11-28 | Cird | PHARMACEUTICAL VEHICLE FOR ACTIVE SUBSTANCES IN THE FORM OF ANHYDROUS GEL |
| DE69104972T2 (en) * | 1991-01-16 | 1995-05-18 | Procter & Gamble | Foam control agent in granular form. |
| US5380455A (en) * | 1992-06-01 | 1995-01-10 | Kao Corporation | Detergent composition |
| EP0709451A1 (en) * | 1994-10-28 | 1996-05-01 | The Procter & Gamble Company | Stable liquid detergent compositions |
-
1996
- 1996-06-26 EP EP96870082A patent/EP0816480A1/en not_active Withdrawn
-
1997
- 1997-06-23 CA CA 2258703 patent/CA2258703A1/en not_active Abandoned
- 1997-06-23 JP JP10503479A patent/JPH11513066A/en active Pending
- 1997-06-23 CN CN 97197319 patent/CN1228111A/en active Pending
- 1997-06-23 WO PCT/US1997/010974 patent/WO1997049788A1/en active Application Filing
- 1997-06-23 BR BR9712784-1A patent/BR9712784A/en unknown
- 1997-06-25 AR ARP970102782A patent/AR007473A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296770C (en) * | 2002-10-30 | 2007-01-24 | 株式会社Adeka | Foam eliminating dispersing agent for developer solution of photosensitive resists |
| CN109983108A (en) * | 2016-11-24 | 2019-07-05 | 荷兰联合利华有限公司 | Liquid detergent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| AR007473A1 (en) | 1999-10-27 |
| EP0816480A1 (en) | 1998-01-07 |
| WO1997049788A1 (en) | 1997-12-31 |
| BR9712784A (en) | 1999-12-07 |
| CA2258703A1 (en) | 1997-12-31 |
| JPH11513066A (en) | 1999-11-09 |
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