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CN1062757A - Detergents containing alkyl sulfates and polyhydroxy fatty acid amide surfactants - Google Patents

Detergents containing alkyl sulfates and polyhydroxy fatty acid amide surfactants Download PDF

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Publication number
CN1062757A
CN1062757A CN91110486A CN91110486A CN1062757A CN 1062757 A CN1062757 A CN 1062757A CN 91110486 A CN91110486 A CN 91110486A CN 91110486 A CN91110486 A CN 91110486A CN 1062757 A CN1062757 A CN 1062757A
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alkyl
composition
detergent composition
fatty acid
mixture
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CN1031721C (en
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B·P·默奇
S·W·莫拉尔
M·H·-K·毛
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/16—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
    • 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
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)

Abstract

Disclose and contained alkyl-sulphate and have general formula
Figure 91110486.0_AB_0
The cleaning composition of polyhydroxy fatty acid amide, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl is the polyhydroxy alkyl (straight hydrocarbyl chain wherein has the hydroxyl that at least 3 direct chains therewith link to each other) with straight hydrocarbyl chain with Z, or their alkoxy derivative, and this detergent composition combines with suds suppressor.On the other hand, alkyl-sulphate and polyhydroxy fatty acid amide use to improve performance together with selected ratio.On the one hand, provide a kind of polyhydroxy fatty acid amide and C of containing again 14Or the liquid washing agent of higher alkyl sulfates more.Another aspect provides the washing particle of alkyl-sulphate and polyhydroxy fatty acid amide.Again more on the one hand, the cosurfactant of specific type joins in the said composition to improve performance.

Description

The washing composition that contains alkyl-sulphate and polyhydroxy fatty acid amide surfactants
The present invention relates to contain the laundry detergent composition of alkyl-sulphate, the present invention relates to contain the laundry detergent composition of alkyl-sulphate and specific polyhydroxy fatty acid amide surfactants mixture more specifically.
The good comprehensive ability of cleaning that cloth-washing detergent flush away from various fabrics is present in multiple dirt the washing and oil mark usually is one of most important index of estimating by this class washing composition.Clean ability owing under hot water or cold water's wash conditions, all have very effective comprehensive laundry, linear alkylbenzene sulfonate (" LAS ") and alkyl-sulphate (" AS ") surfactant mixtures are used for granular detergent composition.The LAS tensio-active agent often is used because of the superior clean ability that it has wash away grease and oil stain.The combination of LAS and AS is desirable, because this has combined to the superior clean ability (the clean ability that LAS is good to broad variety oil stain tool separately) of grease and oil stain LAS with the good removal performance of AS tensio-active agent to the particulate dirt.Although the AS tensio-active agent more easily obtains from reproducible resource, a kind ofly have similarly but still wish to have, the detergent composition of improved washing (-)off properties, therein LAS or partly or entirely by easily from natural, reproducible, the tensio-active agent that nonoil raw material makes replaces.
It is desirable that specific AS tensio-active agent is attached in the heavy duty liquid detergent effectively, so that from its good comprehensive scourability, particularly benefit in its washing (-)off properties to the particulate dirt.Though the lower alkyl chains alkyl sulfate surfactant more easily is incorporated in the light dirt type liquid detergent, C 14It is difficult that the sulfate surfactant of bigger alkyl is attached in the liquid washing agent in the art those of ordinary skill.People more are willing to these long-chain tensio-active agents are used to do washing and the cleaning purposes of yarn fabric usually.
In addition, granulated detergent wishes to strengthen alkyl sulfate surfactant, and particularly those have C 14Solubility and the solubleness of the alkyl sulfate surfactant of longer alkyl chain in the aqueous solution.
The invention provides detergent composition, they contain alkyl-sulphate, and can contain the LAS(that has reduced concentration or not contain LAS), and have the good comprehensive ability (comprise washing oil greasy/oil stain) of cleaning.To the invention provides can be the granulous detergent composition, also provides liquid, comprises C 14The detergent composition of the sulfate surfactant of longer alkyl.In granular detergent composition, comprise this class polyhydroxy fatty acid amide and can increase solvability and the solubleness of alkyl sulfate surfactant in the aqueous solution.
The present invention also comprises the washing granule that granular alkyl-sulphate and polyhydroxy fatty acid amide are provided, and contains these two kinds of tensio-active agents and the third mixture of ingredients that can further strengthen solubleness in the aqueous solution in this washing granule.The superiority of these washing granules is them for polyhydroxy fatty acid amide is added to the method that the property improved is provided in the granulated detergent prescription with the form that is not clamminess, and no longer by means of using a considerable amount of inert components that produce idle cost.Usually this polyhydroxy fatty acid amide has and is clamminess or heavy-gravity character, and this is undesirable in granular recipe.These washing granules are in the aqueous solution in addition, particularly demonstrate the solvability of having improved in automatic washing machine.
Multiple multi-hydroxy fatty amide is disclosed in the prior art; as the N-acyl group; the N-methyl glucose amide is by J.W.Goodby; M.A.Marcus; E.Chin and P.L.Finn are disclosed in " The Thermotropic Liquid-Crystalline properties of Some Straight Chain Carbohydrate Amphiphiles; " (Liquid Crystals; 1988; Volume 3; No.11; PP1569-1581) in, and by A.Muller-Fahrnow, V.Zabel; M.Steifa; and R.Hilgenfeld be disclosed in " Molecular and Crystal Structure of a Nonionic Detergent:Nonanoyl-N-methylglucami de " (J.Chem.Soc.Chem.Commun., 1986, PP1573-1574.) in.The purposes of N-alkyl polyhydroxy acidamide surfactant is owing to be used in the biological chemistry, as is used to dissolve microbial film, quite paid close attention in recent years.As seen in magazine article " N-D-Gluco-N-methylalkanamide Compounds; a New Class of Non-Ionic Detergents For Membrane Biochemistry; " (Biochem.J.(1982), Vol.207, pp363-366, by J.E.K.Hildreth.).
In detergent composition, use the N-alkyl glucose amide also to disclose.Transfer the possession of ﹠amp in Thomas Hedley; Co., Ltd. United States Patent (USP) U.S.2,965,576(1960.12.20 authorize E.R.Wilson) and English Patent 809,060(1959.2.18 open) relate to the detergent composition that contains anion surfactant and specific acidamide surfactant, said composition can contain the N-methyl glucose amide that adds as low-temp foaming promotor.These compounds comprise a N-acyl group that the long linear lipid acid of 10-14 carbon atom is arranged.These compounds also can contain subsidiary material, as alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.The general annexing ingredient of giving the said composition desired properties such as fluorescence dye, SYNTHETIC OPTICAL WHITNER, the spices etc. of also showing are also contained in the said composition.
US.2,703,798(1955.3.8. authorizes A.M.Schwartz) relate to the aqueous detergent compositions of the condensation reaction products of the aliphatic ester that contains N-alkylated glucamine and a kind of lipid acid.The product of this reaction it is said can solution washing agent composition form use, and need not further purification.As at US.2,717,894(1955.9.13 authorizes A.M.Schwartz) in the sulfuric ester of disclosed preparation acidylate glycosamine also be known.
The PCT International Application No. WO 83/04412(1983.12.22 of J.Hildreth is open) relate to the amphoteric substance that contains the poly-hydroxy aliphatic group, this compound it is said and can be used for multiple purpose, this comprises as the tensio-active agent in makeup, medicine, shampoo, washing lotion and the spongaion, as the emulsifying agent and the dispersion agent of medicine, and for making film, whole cell or other tissue sample solubilising and preparation liposome be used for biological chemistry.Compound in these publications is that general formula is CON(R) CH of R ' 2R " and R " CON(R) compound of R ', the R in the formula is a hydrogen or an organic group, R ' is the aliphatic hydrocarbon group of at least 3 carbon atoms, and R " is the aldose residue.
European patent EP 0285768(1988.10.12 is open, people such as H.Kelkenberg) relate to N-polyhydroxy alkyl fatty amide is made thickening material in the aqueous detergent system purposes.Included is that general formula is R 1C(O) R N(X) 2Acid amides, R in the formula 1Be C 1-C 17(preferred C 7-C 17) alkyl, R 2Be hydrogen, C 1-C 18(preferred C 1-C 6) alkyl or alkylene oxide, and X is the multi-hydroxy alkyl that 4-7 carbon atom arranged, and as the N-methyl, the coconut fatty acid glucamide.The thickening properties of this class acid amides is that Jiang Qite is used in the liquid surfactant system and embodies, this system contains alkane sulfonate, although containing water meter promoting agent system, this can contain other anion surfactant, as alkylaryl sulfonate, ethylenic sulfonate, sulfo-succinic acid half ester salt and fatty alcohol ether sulfonate, and nonionogenic tenside, as fatty alcohol polyglycol ether, alkyl phenol polyethylene glycol ethers, fatty acid polyglycol ester, poly(propylene oxide)-polyethylene oxide mixed polymer etc.The prescription of alkane sulfonate/N-methyl coconut fatty acid glucamide/nonionogenic tenside shampoo demonstrates out.Except the thickening attribute, think that also this N-polyhydroxy alkyl fatty amide has advantages of good skin tolerance attribute.
U.S. Pat .2,982,737(1961.5.2. authorizes people such as Boettner) relate to and contain urea, sodium lauryl sulphate anion surfactant, and be selected from the N-methyl.The detergent bar of the N-alkyl glucose amide nonionogenic tenside of N-sorb base laurylamide and N-methyl N-sorb base myristic amide.
Other glucamide tensio-active agent also has been disclosed, as is disclosed in DT2, and 226,872(1973.12.20 is open, people such as H.W.Eckert) in.It relates to and contains one or more tensio-active agents and builder salt (being selected from polymeric phosphate, sequestrant and washing soda) and because of having added general formula R 1C(O) N(R 2) CH 2(CHOH) nCH 2N-acyl group polyhydroxy alkyl-amine of OH and be able to improved cleaning composition, R in the formula 1Be C 1-C 3Alkyl, R 2Be C 10-C 22Alkyl and n is 3 or 4.This N-acyl group polyhydroxy alkyl-amine is added into as the dirt suspension agent.
US.3,654,166(1972.4.4. authorizes people such as H.W.Eckert) relate to contain at least a be selected from negatively charged ion, zwitter-ion and the nonionogenic tenside thing group tensio-active agent and as fabric softener, general formula is R 1N(Z) R C(O) 2A kind of N-acyl group, the detergent composition of N-alkyl multi-hydroxy alkyl compound, R in the formula 1Be C 10-C 22Alkyl, R 2Be C 7-C 21Alkyl, R 1And R 2Total total 23-39 carbon atom, Z is a polyhydroxy alkyl, it can be-CH 2(CHOH) mCH 2OH(wherein m is 3 or 4).
US.4,021,539(1977.5.3 authorizes H.M
Figure 911104860_IMG7
People such as ller) relate to the make-up composition of the processing skin that contains N-polyhydroxy alkyl-amine, they comprise general formula R 1N(R) CH(CHOH) mR 2Compound, R in the formula 1Be H, low alkyl group, hydroxy lower alkyl or aminoalkyl and heterocycle aminoalkyl, R and R 1Identical, but the two can not all be H, and R 2Be CH 2OH or COOH.
French Patent 1,360,018(1963.4.26 transfers the possession of and gives Commercial Solvents Corporation) relate to a kind of owing to added general formula R C(O) N(R 1) acid amides of G and stable anti-polymeric formaldehyde solution, R is the carboxylic functionality that is at least 7 carbon atoms in the formula, R 1Be hydrogen or than low alkyl group, G is the sugar alcohol residue with at least 5 carbon atoms.
German Patent 1,261,861(1968.2.29, A.Heins) relating to the general formula that is used as wetting agent and dispersion agent effectively is N(R) (R 1) (R 2) the glycosamine derivative, R is the sugared lingering section of glycosamine in the formula, R 1Be C 10-C 20Alkyl, R 2Be C 1-C 5Acyl group.
GB745,036(1956.2.15 transfers the possession of and to give Atlas Powder Company) relate to heterocycleamide and carboxylicesters (they are considered to as chemical intermediate, emulsifying agent, wetting agent and dispersion agent, washing composition, fabric softener etc. is effective) thereof.This compounds is by general formula N(R) (R 1) C(O) R 2Express, R is the residual portion of anhydrous hexanepentol or its carboxylicesters in the formula, R 1Be the monovalence alkyl, and-C(O) R 2It is the acyl group that the carboxylic acid of 2-25 carbon atom is arranged.
US.3,312,627(1967.4.4, authorize D.T.Hooker) and solid toilet soap bar is disclosed, they are substantially free of anionic detergent and alkaline auxiliary washing material, and they contain the lithium soap of certain lipid acid, a kind of some propylene oxide-1 that is selected from, the nonionogenic tenside of the inferior quadrol-ethylene oxide condensate of 2-, propylene oxide-propylene glycol-ethylene oxide condensate and polymeric 1,2 ethylene glycol, and also contain the nonionic foaming component, and can comprise that also general formula is RC(O) NR 1(R 2) polyhydroxy amides, RC(O in the formula) contain about 14 carbon atoms of the 10-that has an appointment, R 1And R 2Each is H or C 1-C 6Alkyl, described alkyl have the carbon atom that adds up to 2-about 7, and that substituted hydroxy adds up to 2-is about 6, substantially similarly openly are found in US.3, and 312,626(authorizes D.T.Hooker also in 1967.4.4).
On the one hand, the invention provides in automatic washing machine the low foam laundry detergent composition of cleaning fabric effectively, described composition contains:
(a) at least about 1%(weight) general formula
Figure 911104860_IMG8
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-C 31Alkyl, and Z is the polyhydroxy alkyl (straight hydrocarbyl chain wherein has at least 3 hydroxyls that directly link to each other with this chain) with straight hydrocarbyl chain, or its oxyalkylated derivative.
(b) at least about 1%(weight) alkyl sulfate surfactant;
(c) suds suppressor of foam inhibition amount preferably is selected from by monocarboxylic acid lipid acid and salt, silicone suds suppressor, monostearate two-basic metal alkylphosphonic and phosphoric acid ester, the suds suppressor in the thing group that hydro carbons suds suppressor and composition thereof is constituted.The polyhydroxy fatty acid amide wherein and the weight ratio of alkyl sulfate surfactant are about 1: 10 to about 10: 1, preferably about 1: 6 to about 6: 1, and more preferably about 1: about 3: 1 of 4-, most preferably about 1: 4 to about 1: 1.
On the other hand, the invention provides the detergent composition that contains alkyl sulfate surfactant and polyhydroxy fatty acid amide, the weight ratio of polyhydroxy fatty acid amides such as alkyl-sulphate wherein is about 1.25: 1 to 6: 1, preferably be about 1.25: 1-4: 1, preferredly be about 1.25: 1.0, the general formula of polyhydroxy fatty acid amide wherein is
R in the formula 1Be methyl, R 2Be C 9-C 17Alkyl or alkenyl, and Z is by reducing sugar deutero-glycosyl or its oxyalkylated derivative.
On the one hand, the invention provides a kind of liquid detergent composition again, it contains:
(a) at least about 1%(weight) general formula be The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-C 31Alkyl, and Z is polyhydroxy alkyl (straight hydrocarbyl chain wherein has at least 3 hydroxyls that directly link to each other with this chain) or its a kind of oxyalkylated derivative with straight hydrocarbyl chain;
(b) at least about 1%(weight) C 14Or higher alkyl sulfate surfactant;
(c) a kind of liquid vehicle;
The weight ratio of polyhydroxy fatty acid amide in the wherein said composition and higher alkyl sulfate surfactant is about 1: 10-10: 1, preferably be about 1: 6-6: and 1, be more preferably 1: 4-3: 1 and be most preferably 1: 4-1: 1.
Again on the other hand, the invention provides the washing particle that can be used for granular detergent composition effectively, described washing particle contains following (a) and intimate mixture (b):
(a) the about 90%(of about 5%-preferred 50%) general formula of (weight) is:
Figure 911104860_IMG11
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl and Z are the polyhydroxy alkyls (wherein straight hydrocarbyl chain has at least 3 hydroxyls that directly link to each other with this chain) with straight hydrocarbyl chain, or its oxyalkylated derivative, reach
(b) about 10%(preferred 50%) to about 95%(weight) alkyl sulfate surfactant;
Wherein (b): (a) be about 20: 1-1: 1.
On the one hand, the invention provides in automatic washing machine the low foam laundry detergent composition of cleaning fabric effectively, described composition contains:
(a) at least about 1%(weight) general formula
Figure 911104860_IMG12
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl and Z are polyhydroxy alkyl with straight hydrocarbyl chain (straight hydrocarbyl chains wherein have at least 3 with its hydroxyl that directly links to each other), or its oxyalkylated derivative;
(b) at least about 1%(weight) alkyl sulfate surfactant;
(c) suds suppressor of foam inhibition amount preferably is selected from by monocarboxylic acid lipid acid and salt, silicone suds suppressor, monostearate two-alkali metal alkyl sulfate and alkyl suds suppressor, and the suds suppressor in the group formed of their mixture; Wherein the weight ratio of polyhydroxy fatty acid amide and alkyl sulfate surfactant is about 1: 10-10: 1, preferred about 1: 6-6: 1, be more preferably 1: 4-3: and 1, be most preferably 1: 4-1: 1.
Alkyl sulfate surfactant
This paper composition contains the weight at least about 1%(), preferred about 3% to about 50%, the alkyl sulfate surfactant of better about 5%-about 30%.
Alkyl sulfate surfactant is being known in the art.Alkyl sulfate surfactant herein is water-soluble salt or general formula R OSO 3The acid of M, R is C in the formula 10Or higher alkyl, be preferably C 10-C 24Alkyl is preferably alkyl or has C 10-C 20The hydroxyalkyl of alkyl composition, more preferably C 14-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 trimethyl ammonium positively charged ion and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, with by alkylamine, as ethamine, diethylamine, triethylamine deutero-quaternary ammonium cation, and their mixture and analogue.Usually, C 14Higher alkyl is recommended be used to the to do washing cleaning composition of purposes.Generally, for laundry applications (especially for automatic washing machine), C 12-C 16(C particularly 14- 16) alkyl chain is applicable to lower cleaning temperature (as being lower than about 50 ℃), and C 16-18Alkyl chain then is applicable to higher cleaning temperature (as being higher than about 50 ℃).
Polyhydroxy fatty acid amide surfactants
This paper composition contains at least about 1%, generally contains about 3% to about 50%, preferably contains the following polyhydroxy fatty acid amide surfactants of about 3%-about 30%.
Polyhydroxy fatty acid amide surfactants component of the present invention contains structural formula
Compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, preferred C 1-C 4Alkyl, more preferably C 1Or C 2Alkyl, preferably C 1Alkyl (being methyl); R 2Be C 5-C 31Alkyl, preferred straight chain C 7-C 19Alkyl or alkenyl, more preferably C 9-C 17Alkyl or alkenyl, most preferably straight chain C 11-C 17Alkyl or alkenyl or their mixture; Z is the polyhydroxy alkyl (wherein straight hydrocarbyl chain has at least 3 hydroxyls direct and this chain joins) with straight hydrocarbyl chain, or oxyalkylated derivative (being preferably ethoxylation or propoxylation).Preferred Z be in the reductive amination reaction by the reducing sugar deutero-, more preferably Z is a glycosyl.The reducing sugar that is suitable for comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle, and top listed one sugar all can use.These maize treacle can produce the sugar component mixture that is suitable for Z.It should be understood that this never attempts to get rid of other available raw material.Z preferably is selected from by-CH 2-(CHOH) n-CH 2OH,
-CH（CH 2OH）-（CHOH） n-1-CH 2OH，
-CH 2-(CHOH) 2(CHOR ') (CHOH)-CH 2In the group that OH forms, wherein n is the integer (comprising 3 and 5) of 3-5, R ' be H or ring or the monose of aliphatic series and their oxyalkylated derivative.Glycosyl (wherein n is 4) most preferably, particularly-CH 2-(CHOH) 4-CH 2OH.
In logical formula I, R 1For example can be N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.
R 2-CO-N＜can for example be coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitamide, tallow acid amides etc.
Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.
In the method for preparing polyhydroxy fatty acid amide in the art is known.Usually they can by in the reductive amination reaction with alkylamine with reducing sugar reaction to form the corresponding N-alkyl polyhydroxy amine, in condensation/amidation reaction steps, this N-alkyl polyhydroxy amine is made to form this N-alkyl, N-polyhydroxy fatty acid amide product with fatty aliphatic ester or triglyceride level reaction then.It is open to prepare the composition process that contains polyhydroxy fatty acid amide, as is disclosed in british patent specification GB809, and 060(1959.2.18 is open, Thomas Hedley ﹠amp; Co., Ltd.), U.S. Pat .2,965,576(1960.12.20, authorize E.R.Wilson) and U.S. Pat 2,703,798(1955.3.8 authorize Anthony M.Schwartz) and United States Patent (USP) 1,985,424(1934.12.25 authorizes Piggott), every part of patent is all incorporated herein through quoting as proof.
At a kind of preparation N-alkyl or N-hydroxyalkyl, (wherein this glycosyl component is by the glucose deutero-in the method for N-deoxidation glycosyl fatty amide, and this N-alkyl or N-hydroxyalkyl functionality are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, the N-hydroxyethyl, or N-hydroxypropyl), this product is by being made with the fatty ester reaction by N-alkyl or N-hydroxyalkyl-glycosamine when having catalyzer, this fatty ester is selected from fatty methyl esters, fat ethyl ester and fat triglyceride, this catalyzer is selected from by the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, sodium-potassium tartrate, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium silicoaluminate, alkali formula potassium aluminosilicate and their the thing group that mixture constituted.The amount of catalyzer (is radix with N-alkyl or N-hydroxyalkyl-glycosamine mole number) is preferably about 0.5 mole of % to about 50 moles of %, the about 10 moles of % of more preferably about 2.0 moles of %-.This reaction preferably under about 138 ℃-Yue 170 ℃, about 90 minutes of generally about 20-.When triglyceride level is used as the fatty ester source in reaction mixture, this reaction is also preferred with the about 10%(weight of about 1-) consisting of phase-transferring agent of (in total reaction mixture weight percentage) carries out, and this transfer agent is selected from the pure polyethoxylated of saturated fat, alkylpolyglycosides, the sugared acidamide surfactant of straight chain and their mixture.
This technology is advisable with following steps:
(a) fatty ester is given heat to about 138 ℃-Yue 170 ℃;
(b) join N-alkyl or N-hydroxyalkyl glycosamine in the heated fatty ester and be mixed to and form the required degree of two-phase liquid/liquid mixture;
(c) catalyzer is sneaked in this reaction mixture; And
(d) in the reaction times of regulation, stir.
If fatty ester is when being triglyceride level, in reactant weight, the straight chain N-alkyl/N-hydroxyalkyl that forms, N-straight chain glucosyl fatty amide product that adds about 2%-about 20% made consisting of phase-transferring agent to the reaction mixture and also suited.This has just activated this reaction, has improved speed of reaction whereby.Provided the detailed experiments program in the experiment below.
Poly-hydroxy " lipid acid " the acid amides material that the present invention adopts is returned the detergent formulation Designers provides lot of advantages, and promptly these materials all are or mainly are to make with natural, reproducible, nonoil raw material, and they are degradable.They are hypotoxicity to hydrobiont.
It should be understood that its preparation technology generally also produces a considerable amount of nonvolatile by products except that the polyhydroxy fatty acid amide of logical formula I, as esteramides and ring polyhydroxy fatty acid amide.The quantity of these by products becomes with specific reactant and processing condition.Preferably, provide the polyhydroxy fatty acid amide that is attached in this paper composition, promptly be added to the composition that contains polyhydroxy fatty acid amide in this washing composition and contain, preferably less than about 4% polyhydroxy fatty acid amide less than about 10% with a kind of like this form.The advantage of above-mentioned selection process is the quite few by product of their outputs (comprising this class cyclic amide by product).
Suds suppressor
As discussed above, the compound that reduction or inhibition foam form can be attached in the composition of the present invention.Mixing of this class material (hereinafter referred to as " suds suppressor ") is desirable, because polyhydroxy fatty acid amide surfactants herein can increase the froth stability of this detergent composition.When detergent composition contains quite highly when combining the foam type tensio-active agent with polyhydroxy fatty acid amide surfactants, the effect of suds suppressor is a particularly important.For desiring to be used for the composition of automatic washing machine, special hope suppresses the foamy effect.The typical feature of these machines has dress clothing and washing water, has transverse axis and around the cylinder of this rotation.This agitation type can cause a large amount of foamy to produce, and causes reducing washing (-)off properties thereupon.Under the very high condition of hot wash and surfactant concentration, using suds suppressor is particularly important.
A variety of materials can be used as the composition that suds suppressor is used for this paper.Suds suppressor be for those of ordinary skill in the art known.For example this is summarized in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, and Volume 7, Pages 430-447(John Wiley ﹠amp; Sons, Inc., 1979) in.Making us interested especially is, a kind of monocarboxylic acid lipid acid and the soluble salt thereof of containing in this class suds suppressor.These materials are disclosed in US2, and 954,347(1960.9.27 authorizes Wayne St.John) in, this patent is combined in herein through quoting as proof.Be used as the monocarboxylic acid lipid acid of suds suppressor and the hydrocarbyl chain that salt generally has about 24 carbon atoms of 10-(preferred 12-18 carbon atom) thereof.The salt that is suitable for comprises an alkali metal salt, as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.These materials are preferred suds suppressors of detergent composition.
Detergent composition also can contain the nonsurfactant suds suppressor.For example, this comprises: the high-molecular weight hydrocarbon, and as paraffin and halogenated paraffin, fatty acid ester (as fatty acid triglycercide), the fatty acid ester of monovalent alcohol, C 18-C 40Aliphatic ketone (as stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-.As three-to six-alkyl pyramine or two-to four-alkyl diamine chlorotriazine (obtaining), propylene oxide by cyanuryl chloride and 2 or 3 moles the primary amine that contains 1-20 carbon atom or the reaction of secondary amine, and a stearyl phosphoric acid salt, as a Stearyl alcohol phosphoric acid ester (as-stearyl two-basic metal (as K, Na, Li) phosphoric acid ester) and list-stearyl two-basic metal (as sodium, potassium, lithium) phosphoric acid salt.Hydro carbons can liquidly use as paraffin and halogenated paraffin.Under room temperature and normal atmosphere, this liquid hydrocarbon is liquid, and has-40 ℃ to 5 ℃ pour point, the minimum boiling points in the scope to be not less than about 110 ℃ (under normal atmosphere) approximately.Use waxy hydrocarbon, it is known that preferred fusing point is lower than about 100 ℃ of waxy hydrocarbons.This hydrocarbon becomes a preferred class of the suds suppressor in the detergent composition.The hydrocarbon suds suppressor has been disclosed in US.4, and 265,779(1981.5.5. authorizes people such as Gandolfo), this patent is incorporated herein through quoting as proof.Like this, this class hydrocarbon comprises aliphatic series that 12-70 carbon atom arranged approximately, alicyclic, aromatics and heterocyclic is saturated or unsaturated hydrocarbons.Used term " paraffin " when this class suds suppressor is discussed comprises the mixture of true paraffin and cyclic hydrocarbon.
Other preferred nonsurfactant suds suppressor comprises silicone suds suppressor.This classification comprises the combination (this organopolysiloxane is melted the back chemisorption on silica therein) that adopts organopolysiloxane oil (as the dispersion or the milk sap of polydimethylsiloxane, organopolysiloxane oil or resin) and organopolysiloxane and silica granule.Silicone suds suppressor is known in the art, as be disclosed in US.4,265,779(1981.5.5. authorizes people such as Gandolfo) and european patent application No.89307851.9(be disclosed in 1990.2.7.Starch, M.S.) these two parts of patents are incorporated into this paper through quoting as proof.
Other silicone suds suppressor is disclosed in US.3, and in 455,839, this patent has related to by adding the composition and the method that are used to make aqueous solution froth breaking that a spot of polydimethylsiloxane fluid makes therein.
The mixture of the silica of siloxanes and silanization also discloses, as is disclosed in German patent application DOS, in 2,124,526.Siloxanes defoaming agents and Foam Control in granulated detergent are disclosed in US.3, and 933,672(authorizes people such as Bartolotta) and US.4,652,392(1987.3.24 authorizes people such as Baginski) in.
Exemplary silicone suds suppressor used herein is a kind of Foam Control of foam inhibition amount, it basically by:
(ⅰ) viscosity is about the polydimethylsiloxane fluid of 20cs.-1500cs. in the time of 25 ℃;
(ⅱ) (ⅰ) about 50 parts of (weight) silicone resins of about 5-of every percentage (weight), this resin is by (CH 3) 3SiO 1/2Unit and SiO 2The unit constitutes, and (CH 3) 3SiO 1/2Unit and SiO 2Unitary ratio is about 0.6: 1-1.2: 1; And
(ⅲ) the about 20 parts of solid silicones of the about 1-of every percentage (ⅰ) are formed.
For any detergent composition that is intended for use in the automatic washing machine, the foam of its formation should not reach the degree of overflowing this washing machine.In use, suds suppressor preferably exists with " foam inhibition amount ".So-called " foam inhibition amount " is meant and can selects fully by the formulator of said composition the amount of this Foam Control of control foam forms the low foam detergent that can be used in the automatic washing machine.This foam control amount changes with selected detergent surfactant.As, with high blistered tensio-active agent with compare with low blistered tensio-active agent, then need more comparatively speaking Foam Control to obtain required foam control effect.Usually the suds suppressor of capacity should be combined in the low-sudsing detergent composition, so that the wash(ing)cycle of automatic washing machine (promptly under the condition of required wash temperature and concentration, the agitation of washing composition in the aqueous solution) foam that is produced in is no more than the vacant volumetrical of washing machine container tube about 75%, it is about 50% that preferably foam is no more than this vacant volumetrical, and wherein this vacant volume is cubic capacity and water by the container cartridge difference that adds the shared volume of clothing and definite.
When monocarboxylic acid and salt thereof were used as suds suppressor, its consumption generally mostly was most about 5%(weight of cleaning composition).Be more preferably the aliphatics unary carboxylation's suds suppressor that uses about 0.5%-3%.Although can adopt higher consumption, general maximum about 2.0%(weight with detergent composition) silicone suds suppressor.In fact this upper limit is very natural, because this mainly considers the validity of the low consumption that keeps least cost and can control foaming effectively.The silicone suds suppressor that uses about 0.01%-about 1% is for well, and is more preferably about 0.25%-about 0.5%.The value of these weight percentage used herein comprises any and organopolysiloxane bonded silica and any auxiliary material.One stearyl phosphoric acid ester is generally used with the amount of about 0.1%-about 2% of said composition weight.
Although can use the more hydrocarbon suds suppressor of a large amount, its general consumption is about 0.01%-about 5.0%.
This detergent composition also can contain auxiliary surface active agent composition, and they can comprise the anionic and non-ionic tensio-active agent except that above-mentioned alkyl-sulphate and polyhydroxy fatty acid amide and the tensio-active agent of other type.
If there is an auxiliary tensio-active agent of this class, the general about 1%(weight of detergent composition at least for this reason of its content then), be preferably the about 30%(weight of about 3%-).
When the cosurfactant with some type was used for the composition of this paper, they can further bring significantly improved cleaning performance.These cosurfactants comprise ethoxyquin alkyl-sulphate, alkylethoxylate and alkyl sulfonic ester (particularly methylmesylate), with and composition thereof.The weight ratio of polyhydroxy fatty acid amide and these cosurfactants is with about 5: about 1: 5 of 1-is for well, about 1: 4-about 4: 1 better.
Other the required cosurfactant that is included in the present composition comprises alkane sulfonate, alkylbenzene sulfonate, alkylpolyglycosides (particularly alkyl polyglucoside) and alkyl phenolic alkoxy thing, and this is not construed as limiting the present invention.
The available cosurfactant is discussed in more detail below.
Auxiliary anion surfactant
Sulfonate alkyl ester tensio-active agent herein comprises C 8-C 2-0The linear ester of carboxylic acid (being lipid acid), they are (52(1957), pp323-329) to use gaseous state SO according to " The Journal of the American oil Chemists Society " 3Sulfonated.The raw material that is suitable for comprises the natural fat material that is produced by fat, plam oil and coconut wet goods.
The preferred sulfonate alkyl ester tensio-active agent of purposes of being specially adapted to do washing comprises that structural formula is:
Figure 911104860_IMG14
Sulfonate alkyl ester tensio-active agent, R in the formula 3Be C 8-C 20Alkyl, preferably alkyl or their combination, R 4Be C 1-C 6Alkyl, preferred alkyl or their combination; M is a positively charged ion a kind of and sulfonate alkyl ester formation water-soluble salt.The salt-forming cation that is suitable for comprise metal (as sodium, potassium and lithium), and replace or unsubstituted ammonium cation (as methyl-, dimethyl-,-trimethylammonium and quaternary ammonium cation, as tetramethyl--ammonium and lupetidine, and the positively charged ion that produces by alkanolamine (as monoethanolamine, diethanolamine and trolamine).Preferred R 3Be C 10-C 16Alkyl, R 4Be methyl, ethyl or sec.-propyl.Preferred especially sulfonate methyl esters (R wherein 3Be C 14-C 16Alkyl).
The sulfate surfactant of the alkyl alkoxide in the literary composition is that general formula is RO(A) mSO 3The water-soluble salt of M or acid, R is unsubstituted C in the formula 10-C 24Alkyl or have C 10-C 24The hydroxyalkyl group of alkyl component is preferably 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, and generally between 0.5-6, more preferably from about between 0.5-3, and M is H or positively charged ion (as metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replace ammonium cation).The propenoxylated vitriol of the vitriol of alkyl ethoxylated and alkyl is among this paper considers.Replace the ammonium sun from specific example comprise methyl-, dimethyl-, trimethylammonium-ammonium and quaternary ammonium cation, for example tetramethyl--ammonium, lupetidine positively charged ion, and, reach their mixture by the positively charged ion that alkanolamine (as monoethanolamine, diethanolamine and trolamine) is produced.The example of tensio-active agent is C 12-C 18Vitriol, the C of alkyl polyethoxylated (1.0) 12-C 18Vitriol, the C of alkyl polyethoxylated (2.25) 12-C 18The vitriol of alkyl polyethoxylated (3.0), and C 12-C 18The vitriol of alkyl polyethoxylated (4.0), M wherein should be selected from sodium and potassium.
Other the anion surfactant that can be used for washing purpose also can be included in the composition of this paper.These can comprise soap salt (as comprise sodium, potassium, ammonium and substituted ammonium salt, as single, two-and triethanolamine salt), alkylbenzene sulfonate (C particularly 9-C 20Linear alkylbenzene sulfonate), C 8-C 22Uncle or secondary sulfonated alkane, C 8-C 24Sulfonated alkene; the sulfonation polycarboxylic acid that the pyrolysis product of alkaline earth metal citrate makes through sulfonation reaction is (as british patent specification No.1; 082; 179 is disclosed); alkyl glycerol sulfonate; the acyl glycerol sulfonate; fatty oil base glycerol vitriol; alkylphenol oxyethane ether sulfate; alkane sulfonate; alkylphosphonic; isethionate (as acyl isethinate); N-acyl taurine salt (taurates), the fatty amide of N-methyltaurine; alkyl succinyl-amine salt and thio succinate; the monoesters of sulfo-succsinic acid (particularly saturated and unsaturated C 12-C 18Monoesters), the diester of thio succinate (particularly saturated and unsaturated C 6-C 14Diester), the vitriol of N-acyl sarcosinate, alkyl polysaccharide, as vitriol (nonionic non-sulfuric acid salt compound will be described in the back), the primary alkyl sulphates of side chain, the alkyl polyethoxye carboxylate salt of alkyl polyglucoside, as general formula R O(CH 2CH 2O) kCH 2COO -M +Those compounds (R is C in the formula 8-C 22Alkyl, k are the integers of 0-10, M is the positively charged ion that forms soluble salt), and with isethionic acid esterification and the lipid acid that neutralized with sodium hydroxide.Resinous acid and hydrogenated resin acid also are suitable for, as rosin, hydrogenant rosin, be present in or by Yatall MA deutero-resinous acid and hydrogenant resinous acid.Other example is disclosed among " Surface Active Agents and Detergents " (Vol. I and II by Schwartz, perry and Berch).Various these class tensio-active agents also are summarized in US.3, and 929,678(1975.12.30 authorizes people such as Laughlin, 58 row-29 hurdles, 23 hurdles, 23 row) in, this patent is incorporated herein through quoting as proof.
Auxiliary nonionic detergent tensio-active agent
The nonionic detergent tensio-active agent that is suitable for briefly is disclosed in US.3, and 929,678(1975.12.30 authorizes people such as Laughlin) in the 14th row-Di 16 hurdles the 6th, the 13rd hurdle capable, this patent is incorporated herein through quoting as proof.Illustrative, nonrestrictive one group of useful nonionogenic tenside is set out in down:
1. the condenses of the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide.The condenses of usually preferred polyethylene oxide.These compounds comprise having or the straight or branched configuration, contain the alkylphenol of alkyl group of 6-12 carbon atom and the condenses of alkylene oxide.In an embodiment preferred, oxyethane exists with the amount of the oxyethane of every mole of about 5-25 mole of alkylphenol.This commercially available class ionic surfactant pack is drawn together: Igepal TMCO-630(GAF Coporation sells) and Triton TMX-45, X-114, X-100 and X-102(are the Rohm ﹠amp; Haas Company sells).These compounds can be thought the alcoxylates of alkylphenol, as the ethoxylate of alkylphenol.
2. the condensation product of the oxyethane of fatty alcohol and about 1-25 mole.The alkyl chain of this fatty alcohol can be straight or branched, uncle's or secondary, and contain usually 8-22 carbon atom arranged approximately.Particularly preferably be that to have the alcohol and the every mol of alcohol that contain about 20 carbon atom alkyls of about 10-be the condensation product of the oxyethane of 2-18 mole.The example of this commercially available class nonionogenic tenside comprises: Tergitol TM15-S-9(C 11-C 15The condensation product of linear secondary and 9 moles of ethylene oxide), Tergtol TM24-L-6NMW(C 12-C 14The condensation product of the oxyethane of primary alconol and 6 moles of narrow molecular weight distributions), these two kinds of products are sold by Union Carbide Coporation; Neodol TM45-9(C 14-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol TM23-6.5(C 12-C 13The condensation product of straight chain alcohol and 6.5 moles of ethylene oxide), Neodol TM45-7(C 14-C 15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol TM45-4(C 14-C 15The condensation product of straight chain alcohol and 4 moles of ethylene oxide) (these products are sold by Shell Chemical Company), and Kyro TMEOB(C 13-C 15The condensation product of alcohol and 9 moles of ethylene oxide), this product is by The Procter ﹠amp; Gamble Company sells.These tensio-active agents can be thought alkylethoxylate.
3. the hydrophobic group that forms of the condensation by propylene oxide and propylene glycol and the condenses of oxyethane.The best molecular weight of the hydrophobic part of these compounds is about 1800 for about 1500-, and presents water-insoluble.Polyoxyethylene partly is added on this hydrophobic part, be intended to increase as a whole water-soluble of this molecule, on the fluid characteristics of this product can be maintained at so a bit at most, be about 50% of this condensation product gross weight at this polyoxyethylene content, this condenses is equivalent to the condensation product with maximum about 40 moles of ethylene oxide condensations.The example of this compounds comprises the Pluronic that some is commercially available TMTensio-active agent.
Oxyethane with derive from the condensation product of the reaction product of propylene oxide and 1.The hydrophobic part of these products is made of the reaction product of 1 and excessive propylene oxide, and molecular weight is about 2500-about 3000 usually.This hydrophobic group and ethylene oxide condensation to this condensation product contains 40%-80%(weight approximately) polyoxyethylene, and molecular weight is about the degree of 5000-11000.The example of this class nonionogenic tenside comprises the Tetronic that some is commercially available TMCompound (BASF sale).
5. semi-polar nonionic surfactants is the special category in the nonionogenic tenside, and it comprises that the moieties that contains a 10-18 carbon atom approximately and two are selected from the water-soluble amine oxides of being made of the part in the group alkyl that contains 1-3 carbon atom approximately and hydroxyalkyl; Contain moieties and two water soluble oxidized phosphines that are selected from the part in the group that constitutes by alkyl that contains 1-3 carbon atom approximately and hydroxyalkyl of a 10-18 carbon atom approximately, and moieties and a water-soluble sulfoxide that is selected from the part that partly constitutes by alkyl that contains 1-3 carbon atom approximately and hydroxyalkyl of containing about 18 carbon atoms of about 10-.
Semi-polarity nonionic detergent tensio-active agent comprises general formula
Figure 911104860_IMG15
Amine oxide surfactant, R in the formula 3Be alkyl, the hydroxyalkyl that contains 8-22 carbon atom approximately, or alkyl phenyl and composition thereof; R 4Be alkylidene group or hydroxyl alkylidene group or its mixture that contains 2-3 carbon atom approximately.X is 0-about 3; And each R 5Be alkyl or the hydroxyalkyl that contains about 3 carbon atoms of the 1-that has an appointment, or contain the polyethylene oxide group of about 3 ethylene oxide groups of about 1-.R 5Can be connected with each other between the group (as by oxygen or nitrogen-atoms) form ring structure.
Particularly, these amine oxide surfactants comprise C 10-C 18Alkyl dimethyl amine oxide and C 8-C 12Alkoxyl oxygen alkyl ethyl dihydroxy ethyl amine oxide.
6. be disclosed in US.4,565,647(1986.1.21. authorize Llenado) in alkyl polysaccharide, it have the hydrophobic grouping that contains 6-30 carbon atom (about 16 carbon atoms of preferably about 10-) approximately and polysaccharide (as, many glycosides), contain about 10 of about 1.3-, be preferably about 3 of about 1.3-, most preferably be the hydrophilic radical of about 2.7 sugar units of about 1.3-.Any reducing sugar that contains 5 or 6 carbon atoms, all available as glucose, semi-lactosi, and the galactosyl part is desirable for the glucosyl group part.(this hydrophobic group can randomly be connected in 2-, 3-, 4-equipotential, so and the glucose or the semi-lactosi of generation are different from glucoside or galactoside).Key between this sugar is as can be between a position and 2-, 3-, 4-and/or 6-position on the aforesaid sugar unit of the sugar unit that other adds.
At random, but do not wish an available polyalkylene oxide that connects this hydrophobic part and polysaccharide part.Preferred alkylene oxide is an oxyethane.That typical hydrophobic group comprises is saturated or that insatiable hunger is closed, the alkyl that contains about 18 of about 8-(about 16 of preferably about 10-) carbon atom of side chain or non-side chain.Preferably, this alkyl is the straight chain saturated alkyl.This alkyl can contain at most 3 hydroxyls and/or this polyalkyleneimine chain can contain mostly be most about 10, preferably less than 5 alkylene oxide part.The alkyl polysaccharide that is suitable for be octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, two-, three-, four-, five-and six glucosides, galactoside, glucose, fructoside, fructose and/or semi-lactosi.The mixture that is suitable for comprise coconut alkyl, two-, three-, four-and pentasaccharides glycosides and fat alkyl four-, five-and six glucosides.
Preferred APG general formula is:
R in the formula 2Be selected from the group that is made of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyl alkane phenyl or their mixture, alkyl wherein contains about 18 carbon atoms of about 10-(about 14 of preferably about 12-); N be 2 or 3(be preferably 2); T is about 10 for about 0-, is preferably 0; X is about 3 for the preferably about 1.3-of the about 10(of about 1.3-, more preferably about 1.3-about 2.7).Preferred glycosyl derives from glucose.For preparing these compounds, at first form alcohol or alkyl polyethoxye alcohol, react and formation glucoside (being connected on the 1-position) with glucose or source of glucose then.The glycosyl units that other adds can be connected between 2-, 3-, 4-and/or the 6-position of its 1-position and aforementioned glycosyl units, is preferably mainly in the 2-position.
7. general formula is
Fatty acid amide surfactants, R in the formula 6Be to contain 7-21(approximately to be preferably about 9-about 17) alkyl of individual carbon atom; And each R 7All be selected from by H, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl and-(C 2H 4O) xH(wherein x changes to about 3 by about 1) in the group formed.
Preferred acid amides is C 8-C 20Glutamine, single ethanol amide, diglycollic amide and isopropanol amide.
Cats product
Also can comprise the cationic detersive tensio-active agent in the detergent composition of the present invention and be used as cosurfactant.Cats product comprises ammonium surfactant, and as alkyl dimethyl ammonium halogenide, and general formula is (R 2(OR 3) y) (R 4(OR 3) y) 2R 5N +X -Those tensio-active agents, R in the formula 2Be alkyl or the alkane benzyl that in alkyl chain, has about 18 carbon atoms of about 8-; Each R 3All be selected from by-CH 2CH 2-,-CH 2CH(CH 3)-,-CH 2CH(CH 2OH)-,-CH 2CH 2CH 2-or group that its mixture constituted in, each R 4All be selected from by C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, by connecting two R 4Group and the benzyl rings structure that forms ,-CH 2CHOH-CHOHCOR 6CHOHCH 2OH(is R wherein 6Be that molecular weight is approximately less than 1000 any hexose or hexose polymkeric substance) and the group formed of hydrogen (when y is not 0) in, R 5With R 4Identical, or alkyl chain (R wherein 2Add R 5The total number of carbon atoms be not more than about 18), each y is the number from 0-about 10, and the summation of y value is 0-about 15; And X is any compatible negatively charged ion.
Other cats product that can be used for this paper also is disclosed in US.4, and 228,044(1980.10.14. authorizes Cambre) in, this patent is incorporated herein through quoting as proof.
Other cosurfactant
Amphoterics can be combined in the detergent composition of the present invention.Broadly these tensio-active agents are described to the aliphatic derivatives of the second month in a season or tertiary amine or the aliphatic derivatives of the heterocycle second month in a season or tertiary amine, aliphatic group wherein can be straight chain or side chain.A kind of containing in this aliphatic series substituting group at least about 8 carbon atoms (typically being about 18 carbon atoms of about 8-), and at least a substituting group contains the anionic water-soluble group, as carboxyl, sulfonate, vitriol.The example of amphoterics is referring to US.3, and 929,678(1975.12.30. authorizes people such as Laughlin) in the 19th hurdle 18-35 capable (this patent is incorporated into herein through quoting as proof).
Zwitterionics also can be attached in the detergent composition of the present invention.Broadly these tensio-active agents can be used as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or quaternary amine, season phosphine or the derivative of uncle's sulfonium compound describe.The example of this zwitterionics sees US.3, and 929,678(1975.12.30. authorizes people such as Laughlin) in 38 row-22 hurdles, 19 hurdles, 48 row (this patent is incorporated herein through quoting as proof).
Two affine zwitterionicss use with one or more negatively charged ion and/or nonionogenic tenside bonded form usually.
On the other hand, the invention provides a kind of have be to improve the strict alkyl-sulphate of selecting of washing (-)off properties and the detergent composition of polyhydroxy fatty acid amide ratio.In fact, this notion of the present invention provides a kind of detergent composition, and it contains:
(a) at least about 1%(weight) general formula be:
Figure 911104860_IMG17
Polyhydroxy fatty acid amide, R wherein 1Be methyl, R 2Be C 9-C 17Alkyl or alkenyl, preferred C 11-C 17Alkyl or alkenyl, Z are by reducing sugar deutero-glycosyl or its oxyalkylated derivative;
(b) at least about 1%(weight) alkyl sulfate surfactant; Wherein (b): weight ratio (a) is about 1.25: about 1: 6 of 1-.
Preferred above-mentioned ratio is about 1.25: about 1: 4 of 1-, more preferably about 1.25: the about 1.0-1.25 of 1.0-.
Amazingly be, these compositions can obtain good comprehensive scourability under various wash conditions, particularly to the cleaning of greasy dirt/oil stain, especially from the viewpoint of its quite high polyhydroxy fatty acid amide and alkyl-sulphate weight ratio, this makes us surprised especially.
On the one hand, the invention provides a kind of liquid detergent composition again, it contains:
(a) at least about 1%(weight) general formula be
Figure 911104860_IMG18
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl and Z are polyhydroxy alkyl with straight hydrocarbyl chain (and at least 3 hydroxyls chain directly link to each other) therewith, or its oxyalkylated derivative;
(b) at least about 1%(weight) C 14Or higher alkyl-sulphate surfactivity agent;
(c) a kind of liquid vehicle;
Polyhydroxy fatty acid amide and C in the wherein said composition 14Or more the weight ratio of high-grade alkyl sulfate surfactant is about 1: 10-10: 1, preferably be about 1: 6-6: 1, more preferably about 1: about 3: 1 of 3-.
From traditionally, with C 14It is very difficult that higher alkyl sulfate surfactant is attached in the liquid detergent composition always.This is because the crystallization property of these tensio-active agent height at least in part.Very unfortunate, because in laundry detergent, wish to have very much C 14Higher alkyl sulfate surfactant is even also be like this for the washing composition that is intended to the low 50 ° of uses of wash temperature; This washing composition also contains C usually 12Alkyl sulfate surfactant.Yet since employing polyhydroxy fatty acid amide surfactants herein, C 14Higher alkyl sulfate surfactant just can be attached to liquid detergent formula at an easy rate and suffer.
Described composition preferably contains the polyhydroxy fatty acid amide surfactants of 3%-30% and the described alkyl sulfate surfactant of about 3%-about 30% approximately.Liquid composition of the present invention similarly also can randomly contain alkyl chain less than C 14Alkyl sulfate surfactant.
Again on the one hand, the invention provides that to be used for granulated detergent be effectively to wash particle, it contains following (a) and intimate mixture (b):
(a) the general formula about 50%(weight of about 5%-) is
Figure 911104860_IMG19
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-C 31Alkyl, and Z be polyhydroxy alkyl that straight hydrocarbyl chain is arranged (wherein at least 3 hydroxyls directly and this chain join), or its oxyalkylated derivative; And
(b) the alkyl sulfate surfactant about 95%(weight of about 50%-);
Wherein (a): ratio (b) is about 20: 1-1: 1.For C 12-C 14The alkyl sulfate surfactant mixture, the weight ratio of alkyl-sulphate and polyhydroxy fatty acid amide preferably is about 20: 1-4: 1; For C 14-C 16Alkyl sulfate surfactant then is about 20: 1-3: 1; To C 16-C 18Alkyl sulfate surfactant then is about 20: about 1: 1 of 1-.
This washing particle can contain co-solubilizer with the solubleness of this particle of further raising in the aqueous solution.The optional free anion sulfoacid salt surfactant of solubilizing agent that is suitable for, the tensio-active agent (degree of ethoxylation is at least 0.5) of ethoxylation, ring polyhydroxy fatty acid amide, APG, polyethylene glycol polymer reaches the thing group that poly-(vinylformic acid) polymkeric substance and their mixture are formed.Preferred solubilizing agent comprises alkylethoxylate, alkyl ethoxylate sulfate, alkyl ester sulfonate, ring polyhydroxy fatty acid amide, APG or polyoxyethylene glycol or poly-(vinylformic acid) polymkeric substance or their mixture.Other can improve the solubility of alkyl-sulphate polyhydroxy fatty acid amide particle or the material of solubleness also can use.
In the weight of washing particle, the content of co-solubilizer can change between 0%-preferably is not more than 30%.
" intimate mixture " of so-called this alkyl-sulphate and polyhydroxy fatty acid amide and optional co-solubilizer refers to before forming the washing particle or in its formation each component thorough mixing (although particle need not accurately mixing).The technology of being made particle by the intimate mixture of scrubbed component is known in the art, for example comprises using high energy and High shear device.Demonstrated in an embodiment and formed the method for detergent granules.The size of particle can become according to prescription teacher's requirement.Usually, for granular composition, other particle size is similar comparatively speaking in the size of washing particle of the present invention and the composition.General particle is of a size of about 100～about 1000 microns of diameter.
This washing particle also can contain other component that is used for satisfying washing, processing, aesthetics or other purpose.
This washing particle can use individually, also can be included in the granular detergent compositions that contains additional scrubbed component.Generally, this class detergent composition contains about 5%(weight at least) the washing particle.
Washing assistant
Detergent composition of the present invention can contain inorganic or organic washing auxiliary detergent to help hardness of minerals control.
The content of washing assistant can change in wide range, and this depends on the end-use and the desired physical aspect that has thereof of composition.Liquid formulations generally contains at least about 1%, and the more typical 5%-50% that is about preferably is about 5%-30%(weight) detergent builders.Granular prescription generally contains at least about 1%, the more typical 10%-80% of being about, and is preferably the about 50%(weight of about 15%-) detergent builders.Yet and do not mean that and get rid of to use lower or more high-load washing assistant.
Inorganic detergent builders comprises, but be not limited to the poly-phosphate of basic metal, ammonium and alkanol ammonium (as tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.The borate washing assistant and when washing composition is stored or the washing assistant (be referred to as later on " borate washing assistant) that under wash conditions, can produce the material of borate form also can use.Preferably, the non-boric acid washing composition that is used for the present composition is intended to be used under the wash conditions less than about 50 ℃ (particularly less than about 40 ℃).
The example of silicate-like builder is alkali metal silicate sodium, particularly SiO 2: Na 2O is than 1.6: 1-3.2: the alkalimetal silicate in 1 scope, and layered silicate, as U.S. Pat .4,664,839(1987.5.12. authorizes H.P.Rieck) described in layered silicate, this patent is incorporated into this paper through quoting as proof.Yet other silicate also is useful.Can be used as the distinct agent of granular preparation as Magnesium Silicate q-agent, as the stablizer of oxygen bleaching and the component of foam control system.
The example of carbonate builders is moral figure patent application No.2,321,001(1973.11.15. open, this application is incorporated into this paper through quoting as proof) in disclosed alkaline-earth metal and alkaline carbonate, this comprise yellow soda ash and concentrated crystal soda and with the mixture of superfine lime carbonate.
The silico-aluminate washing assistant is particularly useful in the present invention.Silico-aluminate is most important in the heavy duty type granular detergent composition of present most commercial, and also is the builder component that Special Significance is arranged in liquid detergent formula.The silico-aluminate washing assistant comprises the silico-aluminate with following empirical formula:
M is potassium, sodium, ammonium or replaces ammonium in the formula, Z be about 0.5～about 2, and y is 1.It is 50 milligramequivalent CaCO that the magnesium ion exchange capacity of this material is at least the anhydrous silico-aluminate of every gram 3Hardness.The structural formula of preferred silico-aluminate is:
Z and y are at least 6 integer in the formula, and the mol ratio of z and y is in 1.0～0.5 scopes, and X is the integer of about 15-264.
Effectively the silico-aluminate ion exchange material can be buied on market.These silico-aluminates structurally can be crystalline or amorphous, and can be naturally occurring silico-aluminate or synthetic the generation.The method for preparing the silico-aluminate ion exchange material is disclosed in US.3, and 985,669(1976.10.12. authorizes people such as Krummel) in, that this patent is incorporated herein through quoting as proof.Preferably can be used for synthetic crystalline form silico-aluminate ion exchange material of the present invention can zeolite A, zeolite P(B) and the trade mark of X zeolite obtain.In a particularly preferred embodiment, the chemical formula of crystalline form silico-aluminate ion exchange material is:
X is about 20-30 in the formula, and especially about 27.This material is known as zeolite A.The particle size of preferred silico-aluminate is about 0.1～10 μ m(diameter).
The specific example of poly-phosphate is orthophosphoric acid salt, Sodium polymetaphosphate (polymerization degree scope is about 6-21 therein) and the phytate of pyrophosphate salt, sodium and the potassium of alkali metal tripolyphosphates, sodium, potassium and ammonium.
The example of phosphonate washing assistant is an ethane 1-hydroxyl-1, the water-soluble salt of 1-diphosphonate, especially sodium salt and sylvite; The water-soluble salt of methylenediphosphonate (MDP), as, its trisodium and tripotassium salt, and the water-soluble salt of the methylenediphosphonate (MDP) that replaces are as ethylidene, isopropylidene, benzyl methylene radical and the halogenated methylene phosphonate of trisodium and tripotassium.The phosphonate washing assistant of the above-mentioned type is disclosed in US.3, and 159,581 and 3,213,030(1964.12.1 and 1965.10.19. authorizes Diehl), US.3,422,021(1969.1.14. authorize Roy) and US.3,400,148 and 3,422,137(1968.9.3. and 1969.1.14. authorizes Quimby) in, above-mentioned patent is incorporated into this paper through quoting as proof.
The organic detergent washing assistant that is applicable to purpose of the present invention includes, but not limited to multiple polycarboxylic acid salt compound.Used " polycarboxylate " means and has many carboxylate groups, the compound of preferable at least three carboxylate salts in the literary composition.
The polycarboxylate washing assistant usually can acid form add in the said composition, but the form of the salt that also can neutralize adds.When using with salt form, with an alkali metal salt, as sodium, potassium and lithium salts, especially sodium salt or ammonium salt and substituted ammonium salt (as alkanolamine) are better.
The active substance that comprises plurality of classes in the polycarboxylate washing assistant.An important kind of polycarboxylate washing assistant comprises that ether gathers hydroxy acid salt.Some are open as the ether polycarboxylate of detergent builders.Useful ether polycarboxylate's example comprises that oxygen di-succinate (as is disclosed in the US.3 that authorizes Berg, 128,287, (1964.4.7. mandate) and authorize people's such as Lamberti US.3,635,830(1972.1.18. authorizes)) in, this two patent is incorporated into this paper through quoting as proof.
The ether polycarboxylate who is used as the particular type of washing assistant in the present invention also comprises the material that general formula is following:
A is H or OH in the formula; B be H or-O-CH(COOX)-CH 2(COOX); X is H or salt-forming cation.Such as, all be H as if A in the above-mentioned general formula and B, then this compound is oxygen di-succsinic acid and water-soluble salt thereof.If A is that OH and B are H, then this compound is tartrate-succsinic acid (TMS) and water-soluble salt thereof.If A is H and B is-O-CH(COOX)-and CH 2(COOX), then this compound is tartrate disuccinic acid (TDS) and water-soluble salt thereof.The mixture of these washing assistants particularly is applicable to the present invention.(wherein the weight ratio of TMS and TDS is about 97: 3-20: 80) particularly preferably to be TMS and TDS mixture.These washing assistants are disclosed in the US.4 that 1987.5.5 authorizes people such as Bush, in 663,071.
The ether polycarboxylate who is suitable for also comprises ring compound, especially aliphatic ring compound, as be disclosed in US.3,923,679; 3,835,163; 4,158,635; Those compounds in 4,120,874 and 4,102,903, that these patents are incorporated herein through quoting as proof.
Other useful detergent builders comprises the ether hydroxy-polycarboxylate with following structural formula representative:
HO-〔C（R）（COOM）-C（R）（COOM）-O〕 n-H
M is a hydrogen or by its positively charged ion that can produce water-soluble salt in the formula, is preferably the ammonium cation of basic metal, ammonium or replacement, and n is about the preferable 2-10 of being about of 2-15(; The mean value that is more preferably n is about 2-4), and each R can be identical or different, and be selected from hydrogen, C 1-C 4Alkyl or C 1-C 4Substituted alkyl (R with hydrogen for well).
The poly-carboxylic salt of other ether also comprise maleic anhydride, with ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4, the multipolymer of 6-trisulfonic acid and carboxymethyl oxydisuccinic acid.
Organic polycarboxylate washing assistant also comprises the poly-acetate of various basic metal, ammonium and replacement ammonium.The example of poly-acetate washing assistant is sodium, potassium, lithium, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA).
What also comprised is such as mellitic acid, succsinic acid, polymaleic acid, benzene 1,3, the polycarboxylate of 5-tricarboxylic acid, benzene pentacarbonic acid and carboxymethyl oxydisuccinic acid and soluble salt thereof and so on.
The Citrate trianion washing assistant be the polycarboxylate washing assistant that is used for heavy duty liquid detergent prescription particularly important as citric acid and soluble salt thereof, but they also can be used for granular composition.The salt that is suitable for comprises metal-salt and ammonium salt and the substituted ammonium salt such as sodium, lithium, sylvite.
Other carboxylate salt washing assistant comprises and is disclosed in US.3,723,322, and the carboxylation carbohydrate in (1973.3.28. authorizes Diehl), this patent is combined in herein through quoting as proof.
What be applicable to detergent composition of the present invention also has 3,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound (be disclosed in US, 4,566,984 in (1986.1.28 authorizes Bush, and this patent is combined in herein through quoting as proof)).Useful succsinic acid washing assistant comprises C 5-C 20Alkyl succinic acid and salt thereof.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type of.Typical alkyl succinic acid is that general formula is R-CH(COOH) CH 2(COOH) succsinic acid, i.e. the derivative of succsinic acid, wherein R is an alkyl, as C 10-C 20Alkyl or alkenyl are (with C 12-C 16For well) or wherein R can be replaced by hydroxyl, sulfo group, sulfoxylic acid root or sulfone substituting group, all these materials have been set forth in the above-mentioned patent.
The succinate washing assistant preferably uses with the form of its water-soluble salt, and these salt comprise the salt of sodium, potassium, ammonium and alkanol ammonium.
The object lesson of succinate washing assistant comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferable), 2-15 carbene base succinates etc.Dodecyl succinate salt is preferable washing assistant in this group, and is set forth in the disclosed european patent application 86200690.5/0,200,263 of 1986.11.5..
The example of useful washing assistant also comprises the sodium salt and the sylvite of carboxymethyl oxygen propylmalonic acid, carboxymethyl oxydisuccinic acid, cis-hexanaphthene hexacarboxylic acid, cis-pentamethylene tetracarboxylic acid, water-soluble polypropylene acid (these molecular weight also can be used as dispersion agent effectively greater than 2000 polyacrylate approximately), and the multipolymer of maleic anhydride and vinyl methyl ether or ethene.
Other polycarboxylate that is suitable for is to be disclosed in US, and 4,144,226(1979.3.13. authorizes people such as Crutchfield) in the polyacetal carboxylation, this patent is combined in herein through quoting as proof.Can prepare these polyacetal carboxylations by under polymerizing condition, glyoxylic esters and polymerization starter being got together.Subsequently the polyacetal carboxylation of gained is connected to chemically stable end group and stops depolymerization rapidly in basic solution, change into corresponding salt again and be added in the tensio-active agent so that this polymeric acetal carboxylate is salt-stabilized.
At U.S. Pat .3,308,067(1967.3.7. authorizes Diehl) in the polycarboxylate washing assistant is also disclosed, this patent is incorporated herein through quoting as proof.These materials comprise the homopolymerization of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and so on aliphatic carboxylic acid and the water-soluble salt of multipolymer.
Also can use other organic washing-assisting detergent as known in the art.As the monocarboxylic acid and the soluble salt thereof that can use long chain hydrocarbon groups.These may comprise the material that is called " soap ".The general C that adopts 10-C 20Chain length.These alkyl can be saturated or unsaturated.
Enzyme
The detergency enzyme can be included in the detergent formulation for various purposes, these purposes as comprise remove protein for base, carbohydrate for base or triglyceride level for the dirt of base with prevent that color from polluting mutually.The enzyme of desiring to be added into comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and their mixture.They can be the enzymes from any appropriate source, such as from vegetables, animal, bacterium, fungi and yeast.Yet several factors are depended in the selection of enzyme, as pH-activity and/or optimal stability value, thermostability with depend on activated detergent, washing auxiliary detergent and other stability.In this respect, bacterium or fungal enzyme are preferred, are preferred as bacterial amylase and proteolytic enzyme and fungal cellulase.
Suitable examples of proteases is a subtilisin, and it derives from the special bacterial strain of B.Subtilis and B.lichenifoms.Another kind of suitable proteolytic enzyme derives from the Bacillus bacterial strain, and it has maximum activity in the scope of whole pH8-12, and it is with trade mark Esperase by Novo IndustriesA/S
Figure 911104860_IMG20
Sell.1,243, No. 784 british patent specification of Novo have been narrated the preparation method of this kind of enzyme and similar enzyme.The commercially available proteolytic enzyme that is suitable for removing protein-based dirt comprises Novo Industries A/S(Denmark) with trade mark ALCALASE TMAnd SAVINASE TMSell with International Bio-Synthetic.Inc.(Holland) with trade mark MAXATASE TMThe enzyme of selling.
The kind of interesting proteolytic enzyme, the enzyme that especially is applicable to liquid detergent composition are to be referred to as protease A and proteolytic enzyme B in this article.Protease A and preparation method thereof is set forth in the disclosed european patent application 130,756 of 1985.1.9., and is that this patent application is incorporated herein through quoting as proof.Proteolytic enzyme B is different from protease A, and its difference is in 217 of aminoacid sequence at it leucine that has substituted tyrosine.Proteolytic enzyme B is set forth in 1987.4.28, and in the european patent application 87303761.8 of application, this application is incorporated herein through quoting as proof.The preparation method of proteolytic enzyme B also is disclosed in people's such as the disclosed Bott of 1985.1.9. the european patent application 130,756, and this application is combined in herein through quoting as proof.
Amylase comprises, as the α-Dian Fenmei that obtains from special B.licheniforms bacterial strain, it is at the british patent specification No.1 that is incorporated into this paper, 296, more detailed description is arranged in 839(Novo).Amylolytic proteolytic enzyme comprises, as RAPIDASE TM(Internatinal Bio-Sythetics, Inc) and TERMAMYL TM(Novo Industries).
The cellulase that can be used among the present invention comprises bacterium and fungal cellulase.Preferably the optimal ph of these cellulases is between 5 and 9.5.Suitable cellulase is disclosed in that 1984.3.6. authorizes, and is incorporated into the US.4 of this paper through quoting as proof, in 435,307 people such as () Barbesgoard, this patent disclosure make fungal cellulase from Humicolainsolens.Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.
The example of the plain enzyme of this fibrid is bacterial strain (the Humicola grisea var with Humicola insolens, thermoidea), the cellulase of particularly using Humicola Strain DSM1800 to produce, with the Mierocrystalline cellulose that produces with Bacilus N or belong to the mycetogenetic cellulase 212 of genns Aeromonas, and the cellulase that extracts from the liver pancreas of aquatic mollusk (Dolabella Auricula Solan der).
The lipase that is applicable to washing composition comprises those by the unicellular Pseudomonas group of vacation microorganism, as is disclosed in English Patent 1,372, and false unicellular this patent of Stutzeri ATCC19.154(in 034 is incorporated herein through quoting as proof) enzyme produced.Suitable lipase comprises that those and lipase antibody show positive immunology cross reaction, by the lipase of Pseudomonas fluorescens IAM1057 microorganisms.This lipase and purification process thereof are set forth in 1978.2.24, Japanese Patent Application Publication 53-20487 in.This lipase can obtain from the Amano Pharmaceutical Co.Ltd. of the Nagoya of Japan, and trade mark is Lipas P " Amano ", hereinafter is referred to as " Amano-p ".Adopt Ouchterlony(Acta.Med.Scan., 133, Pages76-79(1950)) standard and known positive immunology diffusion process program, these enzymes of the present invention should demonstrate positive immunology cross reaction with Amano-P antibody.These lipase and its method to the immunology cross reaction of Amano-P also are issued to people's such as Thom U.S. Pat .4 at 1987.11.17., 707,291, in narrate, this patent is incorporated herein through quoting as proof.The exemplary of these enzymes is that Ameno-P lipase, lipase ex Pseudomonas fragi FERM P1339(can trade name Amano-B obtain), lipase ex Psuedomonas nitroreducens var.lipolyticum FERM P1338 is with (trade(brand)name Amano-CES obtains), lipase ex Chromobacter viscosum, as can be more than the Chromobacter Viscosum Var.lipolyticum NRRLB3673(from Toyo Jozo Co., Tagata, Japan buys); And derive from U.S Biochemical Corp., (U.S.) and Disoynth Co., the Chromobacter Viscosum lipase of (Holland), and lipase ex Pseudomonas gladioli.
Peroxidase and oxygen source are used in combination as percarbonate, perborate, persulphate, hydrogen peroxide etc.They are used for " solution bleaching ", prevent promptly in the washing process that other matrix that the dyestuff taken off from matrix or pigment are transferred to the washings gets on.Peroxidase is being known in the art, and for example this comprises horseradish peroxidase, lignoenzyme and the haloperoxidase such as chloro-and bromo-peroxidase.As, it is open that the detergent composition that contains peroxidase has been disclosed in the PCT International Application No. WO 89/099813(o.Kirk.1989.10.19 that transfers Novo Industries A/S) in, this application has been quoted as proof and has been incorporated into this paper.
Various enzyme materials and the method that they are attached in the synthetic detergent particle also are disclosed in the US that 1971.1.5. authorizes people such as Mc Carty, in 3,553,139 (this patent is incorporated into this paper through quoting as proof).At people's such as Place US4,101,457(1978.7.18. authorizes) and the US of Hughes, 4,507,219(1985.3.26. mandate) in plurality of enzymes is also disclosed.Through quoting as proof this two patent is incorporated into this paper.Can be used for the enzyme material of liquid detergent formula and they are attached to the US.4 that method in this class prescription is disclosed in people such as Hora, 261,868(1981.4.14. authorizes), this patent is incorporated herein through quoting as proof.
Usually the add-on of enzyme is for every gram composition provides maximum about 5mg, is more generally the organized enzyme of the about 3mg of about 0.05mg-.
For granulated detergent, the most handy is that the inert additive makes the formation of dust reduce to minimum level with the enzyme coating or with its granulation to enzyme, and improves storage stability.The technology of finishing these purposes is well known in the art.In liquid formulations, preferably adopt the enzyme stabilising system.The enzyme stabilization technique of aqueous liquid detergent compositions also is known in the art.As, the enzyme stabilization technique comprises that use derives from a kind of aqueous solution, as the free calcium ions of lime acetate, calcium formiate and calcium propionate.Calcium ion can with short chain carboxy acid's salt, preferably formate is used in combination.As, referring to the people's such as Letton that quoted US, 4,318,818(1982.3.9. authorizes).The somebody proposes to use the polyvalent alcohol as glycerol and sorbyl alcohol and so on.Mixture and the boric acid or the alkali metal borate of alkoxyl alcohol, the sweet ether of dialkyl group, polyvalent alcohol and multifunctional aliphatic amide (as alkanolamine, such as diethanolamine, trolamine, diisopropanolamine (DIPA) etc.).The enzyme stabilization technology also discloses and is illustrated in US.4 separately, 261,868(1981.4.14. authorize people such as Horn) and US.3,600,319(1971.8.17 authorize people such as Gedge) (this two patent is incorporated into this paper through quoting as proof) and the open No.0199405(application number No 86200586.5 of the disclosed european patent application of 1986.10.29, the Venegas application) in.Non-boric acid and borate stablizer are preferred.US.4,261,868; 3,600,319 and 3,519,570 have also described the enzyme stabilising system.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent
The detergent composition of this paper can contain SYNTHETIC OPTICAL WHITNER or contain bleaching composition and one or more bleach-activating agents of SYNTHETIC OPTICAL WHITNER.When containing bleaching compounds, it is about 20% that its amount is generally about 1%-of detergent composition, is more typically about 1%-about 10%.Usually, at the on-liquid prescription, as in granulated detergent, SYNTHETIC OPTICAL WHITNER is an optional components.If when containing bleach-activating agent, it is about 60% that its content is generally about 0.1%-of bleaching composition, is more typically about 0.5%-about 40%.
SYNTHETIC OPTICAL WHITNER used herein is to can be used for that fabric cleans, hard surface cleaning, or any SYNTHETIC OPTICAL WHITNER in the known detergent composition that maybe will become known cleaning use.These materials comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.To about below 50 ℃, especially about wash conditions below 40 ℃.Said composition is with boracic hydrochlorate not or be not contained in washing composition and store or can form on the spot boratory material (being that borate forms material) for well under wash conditions.Therefore under these conditions, preferably use non-borate, non-borate to form the thing SYNTHETIC OPTICAL WHITNER.Preferably, the washing composition that uses under this class temperature is gone up not boracic hydrochlorate and borate formation thing substantially.The borate that " be substantially free of borate and borate form thing " used herein means the material of the contained boracic hydrochlorate of this composition and any kind forms thing and all is not more than approximately 2%, better is to be not more than 1%, is more preferably 0%.
A spendable class SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The example that this class SYNTHETIC OPTICAL WHITNER is suitable comprises monoperphthalic acid magnesium hexahydrate, partially the magnesium salts of chlorine peroxybenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecandioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in US.4,483,781(1989.11.20. authorize Hartman), U.S. Patent application 740,446(Burns equals 1985.6.3. application), european patent application 0,133, people such as 354(Banks, 1985.2.20. open) and US.4,412,934(1983.11.1. authorizes people such as Chung) in, above-mentioned document is incorporated herein through quoting as proof.Highly preferred SYNTHETIC OPTICAL WHITNER also comprises US.4, and 634,551(1987.1.6. authorizes people such as Burns) described in 6-amino in the ninth of the ten Heavenly Stems-6-oxo cross oxy hexanoic acid, the document is incorporated herein through quoting as proof.
The another kind of SYNTHETIC OPTICAL WHITNER of available comprises the halogen SYNTHETIC OPTICAL WHITNER.The example of hypochlorite bleach agent comprises as the potassium of TCCA (Trichloroisocyanuric acid), dichloroisocyanuric acid, sodium salt and N-chlorine and N-bromine alkane sulfonamide.This class material is usually with the 0.5-10%(weight of final product), be preferably 1-5%(weight) amount add.
Also can use the peroxygen bleach that did not comprise boron compound.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.
Peroxygen bleach preferably combines with bleach-activating agent, and this activator causes that (being in the washing process) produces the peroxy acid corresponding to this bleach-activating agent on the spot in aqueous solution.
The general formula that mixes the preferable bleach-activating agent in the present composition is:
Figure 911104860_IMG21
Wherein R is for containing the alkyl of 1-18 carbon atom approximately, and wherein the longest straight alkyl chain extends from carbonyl carbon, and comprises carbonyl carbon, and it contains about 6-10 carbon atom; L is-leavings group that the pKa of its conjugate acid is in the scope of 4-13.US.4,915,854(1990.4.10 authorizes people such as Mao) and US.4,412,934(has been incorporated into this paper) these bleach-activating agents have been described.Through quoting as proof US4,915,854 are incorporated into this paper.
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is well known in the art and can uses at this.A significant especially class non-oxygen bleaching agent comprises photosensitive bleaching agent, as the phthalocyanine of sulfonated zinc and/or aluminium.These materials can be deposited on the Substrate during washing.In case when aerobic existed with illumination, when clothing being hung over the outside with solar drying, sulfonation zinc phthalocyanine phthalocyanine just was activated and bleaches matrix thereupon.Preferable zinc phthalocyanine and photosensitive bleaching method are set forth in US.4, and 033,718(1977.7.5. authorizes people such as Holcombe, this patent is incorporated herein through quoting as proof).Generally, detergent composition contains 0.025%-1.25%(weight approximately) sulfonation zinc phthalocyanine phthalocyanine.
Polymeric dirt release agent
In the present invention's practice, can adopt the known polymerization dirt of any those skilled in the art release agent.The feature of polymerization dirt release agent is the surface hydrophilic that tool hydrophilic and hydrophobic two segments, hydrophilic segments make hydrophobic fibre (as polyester and nylon), and hydrophobic part is deposited on the hydrophobic fiber in the whole process of finishing washing and rinsing, and adhere to herein, thereby hydrophilic segment is played the set effect.This just can make adopt the dirt release agent handle after and easy-clear more in the stain washing step afterwards that produces.
Though in any composition of this paper, especially be used for doing washing or other needs to deoil from the hydrophobic surface degrease that to adopt polymerization dirt release agent be useful for the composition of purposes at those, can strengthen the performance of many employings than the polymerization dirt release agent of general types but in the detergent composition that also contains anion surfactant, there is polyhydroxy fatty acid amide.Anion surfactant has disturbed some dirt release agent deposition and has adhered to the ability of hydrophobic surface, and these polymerization dirt release agents have and interactional nonionic hydrophilic segment of anion surfactant or hydrophobic segment.
The composition of the present invention that can obtain to improve polymerization dirt release agent performance by the use polyhydroxy fatty acid amide is such material, they contain anionic surfactant system, polyhydroxy fatty acid amide (PEA) with interactional dirt release agent of anion surfactant and reinforcement dirt release agent aequum, wherein, dirt release agent in (I) detergent composition and the anion surfactant between anionic surfactant system interact can be by comparison (A) and (B) dirt release agent (SRA) is deposited on the hydrophobic fibre (as polyester) in the aqueous solution under two kinds of situations amount show, (A) be simultaneous test, wherein, when not having other detergent ingredients, measure the SRA deposition that aqueous wash medium is washed the agent composition, and (B) be " SRA/ anion surfactant " testing experiment, wherein with the same weight ratio of SRA in the detergent composition and anion surfactant, to be used for similar and anionic surfactant system equivalent of detergent composition and in the aqueous solution, combine with SRA, thus by (B) relatively (A) deposition that is reduced shown the interaction of anion surfactant; And the dirt release agent deposition of the SRA/ anion surfactant/PFA in (II) SRA/ anion surfactant by compare test test (B) and the testing experiment (C) just can determine whether to contain in the composition of detergent polyhydroxy fatty acid amide (polyhydroxy fatty acid amide of the similar and equivalent of this composition of detergent combines with dirt release agent and anionic surfactant system corresponding to described SRA/ anion surfactant testing experiment in (C)) of dirt release agent reinforcement aequum, the improvement of the dirt release agent in relative with testing experiment (B) the whereby testing experiment (C) deposition shown the polyhydroxy fatty acid amide that exists dirt release agent amount of reinforcement. For purposes of the present invention, the test of this paper should be carried out under the concentration of anion surfactant in the aqueous solution is higher than the condition of its micelle-forming concentration (CMC) in the aqueous solution of testing experiment (A), better is to carry out being approximately higher than under the concentration of 100ppm.The concentration of this polymerization stain remover should be 15ppm at least.Should adopt the polyester textile cloth specimen to do the source of hydrophobic fibre.In dividing other testing experiment, 35 ℃ of of of aqueous of be immersed in solution identical cloth specimen and stirred, 12 minutes, take out then and analyze.By technology as known in the art, carry out the deposition that radiochemical analysis just can be determined polymerization dirt release agent subsequently by before processing, the dirt release agent being made radio-labeled.
Radiochemical method discussed above as an alternative, by technology as known in the art, by the ultraviolet ray in the determination test solution (UV) absorb just can another kind of method determine above the deposition of dirt release agent in each testing experiment (promptly testing A, B and C).After taking out hydrophobic fiber material, the reduction that UV absorbs in the testing liquid is just corresponding to the sedimentary increase of SRA.As known to persons of ordinary skill in the art, for the interfering substance that the undue UV of the generation that contains certain kind and content absorbs, as high-load, the testing liquid with tensio-active agent (as alkylbenzene sulfonate) of aryl should not adopt UV to analyze.
Like this, the polyhydroxy fatty acid amide of so-called " the dirt release agent is strengthened aequum " means the aforesaid amount that will improve this class tensio-active agent of the deposition of dirt release agent on hydrophobic fiber; Or refer in another follow-up cleaning operation, can make in this paper detergent composition washed cleaning fat/oiliness that fabric obtained to strengthen can aequum.
Strengthen the amount of the amount of the required polyhydroxy fatty acid amide of deposition, the difference of selected concrete dirt release agent and selected concrete polyhydroxy fatty acid amide and becoming with selected anion surfactant, anion surfactant.Usually composition contains 0.01%-10%(weight approximately), typically be about 0.1%-5%(weight) polymerization dirt release agent and the about 50%(weight of about 1%-), more be typically the about 30%(weight of about 4%-) anion surfactant.This based composition generally should contain at least about 1%(weight), preferable at least about 3%(weight) polyhydroxy fatty acid amide, but do not mean and must so limit.
When having anion surfactant to exist, the polymerization dirt release agent of having strengthened performance with polyhydroxy fatty acid amide comprises that those have (a) component or (b) component or (a) and (b) component bonded dirt release agent.(a) be one or more nonionic hydrophilic components, it basic composition is (ⅰ) polymerization degree and is at least 2 polyoxyethylene segment, or (ⅱ) polymerization degree is propylene oxide or the polyoxypropylene segment of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless it is bonded to adjacent part by the ether chain in each end, or (ⅲ) contain the oxyalkylene units of ethylene oxide and the mixture of about 1-30 propylene oxide unit, wherein said mixture contains the ethylene oxide unit of capacity so that the wetting ability of hydrophilic component is deposited on the wetting ability on its surperficial normal polyester synthon surface even as big as raising dirt release agent, described hydrophilic segment preferably contains at least about 25% ethylene oxide unit, be more preferably at least about 50% ethylene oxide unit, this is especially true for the component that contains about 20-30 propylene oxide unit; Or (b) be one or more hydrophobic materials components, it contains (ⅰ) C 3Oxyalkylene terephthalate segment wherein also contains the ethylene oxide terephthalate as if described hydrophobic materials component, then ethylene oxide terephthalate: C 3The ratio of oxyalkylene terephthalate unit is about 2: 1 or is lower, (ⅱ) C 4-C 6Alkylidene group or C 4-C 6Oxyalkylene segment, or its mixture, (ⅲ) polymerization degree is at least poly-(vinyl ester) segment of 2, better is poly-(vinylacetate), or (ⅳ) C 1-C 4Alkyl oxide or C 4Hydroxyalkyl ether substituting group, or its mixture, wherein said substituting group is with C 1-C 4Alkyl oxide or C 4The form of mixtures of hydroxyalkyl ether derivatived cellulose or this derivative exists, and the plain derivative of this fibrid is amphipathic, thereby it has the C of capacity 1-C 4Alkyl oxide and/or C 4The hydroxyalkyl ether unit deposition is on the polyethylene terephthalate surface of routine, and in a single day adheres to the polyethylene terephthalate surface of this routine when it, and the hydroxyl that just keeps capacity is to improve the wetting ability of fiber surface.
Generally, (a) polymerization degree of the polyoxyethylene segment of (ⅰ) is about 200 for about 2-, and (though also can adopt the higher polymerization degree), the better polymerization degree is about 3-150, better is about 6-100.Suitable C 4-C 6Oxyalkylene hydrophobic materials segment includes, but not limited to polymerization dirt release agent end-blocking, as MO 3S(CH 2) nOCH 2CH 2O-, wherein M is a sodium, n be 4-6 an integer (as, be disclosed in US.4,721,580(1988.1.26. authorizes Gosselink, this patent is incorporated into this paper through quoting as proof) in).
Useful in the present invention polymerization dirt release agent comprises derivatived cellulose, as the hydroxy ethers cellulose polymer compound, and the copolymerization block of ethylene terephthalate or propylene terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate etc.
Playing the derivatived cellulose of dirt release agent function can buy on market, and comprises cellulosic hydroxy ethers, as Methocel R(DOW).
The Mierocrystalline cellulose dirt release agent that is used for this paper also comprises and being selected from by C 1-C 4Alkyl and C 4Material in the thing group that hydroxy alkyl cellulose (as methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose) is formed.The various derivatived celluloses that can be used as the dirt release polymers are disclosed in US.4, and 000,093(1976.12.28. authorizes people such as Nicol, this patent is incorporated into this paper through quoting as proof) in.
The dirt release agent that is feature with poly-(vinyl ester) hydrophobic materials segment comprises the polyvinylesters of receiving on the polyalkylene oxide main chain (as the polyethylene oxide main chain), as C 1-C 6Vinyl ester, the preferably graft copolymer of poly-(vinylacetate).This class material is known in the art, and it is open to be disclosed in european patent application 0.219048(1987.4.22., people such as Kud) in.Suitable this commercially available class dirt release agent comprises Sokalan TMThe type material is as can be available from BASF(West Germany) Sokalan TMHP-22.
One class dirt release agent preferably is the multipolymer with random block of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.More specifically say, these polymkeric substance are made up of the repeating unit of ethylene terephthalate and PEO terephthalate, the mol ratio of ethylene terephthalate unit and PEO terephthalate unit is about 25: 75-35: 65, and described PEO terephthalate unit contains the polyethylene oxide that molecular weight is about 300-2000.The molecular weight of this polymerization dirt release agent is in the scope of 25000-55000.See US.3,959,230(1976.5.25. authorizes Hays, this patent is incorporated into this paper through quoting as proof).Also referring to US.3,893,929, (1975,7.8. authorizes Basadur, and this document is combined in herein through quoting as proof), it discloses similar multipolymer.
Another kind of preferable polymerization dirt release agent is the polyester with the unitary repeating unit of ethylene terephthalate, it contains 10-15%(weight) ethylene terephthalate unit and 20-80%(weight) polyoxyethylene terephthalate unit (being derived from the polyoxyethylene glycol that molecular-weight average is 300-5000), the mol ratio of ethylene terephthalate unit and polyoxyethylene terephthalate unit is between 2: 1 and 6: 1 in this polymerizable compound, and the example of this base polymer comprises commercially available Zelcon R5126, (from Dupont) and Milease RT(is from ICI).These polymkeric substance and preparation method thereof all are disclosed in US.4, and 702,857(1987.10.27. authorizes Gosselink, this patent is incorporated herein through quoting as proof) in.
The sulfonated products that another preferred polymerization dirt release agent is a basic linear ester oligopolymer, this oligopolymer is made up of the oligomer ester main chain of terephthaloyl and oxyalkylene oxygen repeating unit and the end that covalency is received on this main chain, described dirt release agent is derived from ethoxyquin vinyl carbinol, terephthalic acid dimethyl ester and 1,2 propylene glycol, wherein after the sulfonation, the about 1-4 of the sulfonate group that the end had of each oligopolymer sum average out to.Detailed description to this class dirt release agent is seen US.4,968,451(1990.11.6. authorizes J.Scheibl and E.P.Gosselink) and U.S. Patent application No 07/474, the 709(1990.1.29. application, this part is incorporated in the literary composition through quoting as proof.）
Other suitable polymerization dirt release agent comprises US.4,711,730(1987.12.8. day is authorized people such as Gosselink) ethyl capping or methyl blocking 1, the polyester of 2 propylidene terephthalates-polyoxyethylene terephthalate, US.4,721,580(1988.1.26 authorize Gosselink) in negatively charged ion end-blocking oligomer ester class (wherein this negatively charged ion end-blocking contains the sulfo-polyethoxye that is derived from polyoxyethylene glycol (PEG)), US.4,702,857(1987.10.27. authorize Gosselink) in the block polyester oligomeric compound, it is X-(OCH that this compound has general formula 2CH 2) nThe polyethoxye end-blocking, wherein n is that 12-is about 43, X is C 1-C 4Alkyl or be preferably methyl.Above-mentioned patent all is incorporated into this paper through quoting as proof.
Other polymerization dirt release agent comprises US.4, and 877,896(1989.10.31. authorizes people such as Maldonado) the dirt release agent, the document discloses negatively charged ion, the end capped terephthalate of sulphur aroyl especially, the document is incorporated into this paper through quoting as proof.This terephthalate contains the oxygen-1 of asymmetric replacement, and 2-alkylidene group oxygen unit is included in US.4, and the dirt release polymers in 877,896 is for having (ⅰ) C in the hydrophobic components scope of polyoxyethylene hydrophilic component or above-mentioned (b) 3The material of oxyalkylene terephthalate (propylidene terephthalate) repeating unit.This with one of these two criterions or its two be the polymerization dirt release agent of feature when having anion surfactant to exist, have benefited from being included in polyhydroxy fatty acid amide herein especially.
If use the dirt release agent, they account for the about 10.0%(weight of about 0.01-of this paper detergent composition weight usually), it is about 5% typically to be about 0.1-, the preferable 0.2-3.0% that is about.
Sequestrant
The detergent composition of this paper also can randomly contain one or more, as the iron and the manganese sequestrant of washing assistant additive.The optional free amino group carboxylate salt of this class sequestrant, phosphoro-amidate be multifunctional-thing group that the aromatic chelating agent that replaces and composition thereof constitutes, and they are definition hereinafter all.Be not intended to bound by theory, the favourable part that it is believed that these materials is that partly it forms solvable inner complex and remove abnormal ability of iron and mn ion from washings.
The aminocarboxylate that is used as preferred sequestrant in composition of the present invention can have one or more, preferably at least 2 following substructure units
M is hydrogen, basic metal, ammonium or replaces ammonium (as thanomin) in the formula, and X is about 1-3, is preferably 1.Be preferably, these aminocarboxylates do not contain more than the alkyl of 6 carbon atoms or alkenyl.The salt that practical amine carboxylate salt comprises an alkali metal salt of ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine nitrilotriacetic, nitrilotriacetic acid(NTA), ethylenediamine tetrapropionic acid(EDTP), triethylenetetraaminehexaacetic acid, diethylene triaminepentaacetic acid(DTPA) and ethanol Diglycocol and ammonium and replacement ammonium with and composition thereof.
When allowing in the detergent composition when being at least very low total phosphorus content, amino phosphonates do also is suitable for use as the sequestrant in the present composition.Have one or more, better be the compound of at least two following substructure units
Figure 911104860_IMG23
(M is hydrogen, basic metal, ammonium or replaces ammonium in the formula, and X is about 1-3, is preferably 1) is effectively, and they comprise ethylenediamine tetraacetic (methylene phosphonic acid salt), nitrilo three (methylene phosphonic acid salt) and diethylenetriamine five (methylene phosphonic acid salt).Preferably, these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.Alkylidene group can be total by substructure.
The aromatic chelating agent of multi-functional-replacement also can be used in the composition of this paper.These materials can comprise the compound that general formula is following:
Figure 911104860_IMG24
At least one R is-SO in the formula 3H or-COOH, or its soluble salt and composition thereof.US.3,812,044(1974.5.21. authorizes people such as Connor, this patent is incorporated into this paper through quoting as proof) multi-functional-aromatic chelating agent and sequestering agent of replacing disclosed.The preferable acd compound of this class is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.But this class material of alkaline detergent composition alkali metal containing, ammonium or replacement ammonium (as monoethanolamine or trolamine) salt form.
If use this class sequestrant, its amount generally is about the 0.1-10% of this paper detergent composition weight.Being more preferably sequestrant is about 0.1-3.0% of this composition weight.
Remove dirt/anti redeposition agent
Composition of the present invention also can randomly contain the water-soluble ethoxylated amine with dirt and antiredeposition performance.The granular detergent composition that contains these compounds generally contains 0.01%-10.0%(weight approximately) water-soluble ethoxylated amine; General content is about 0.01%-5% in the liquid detergent composition.This compounds is preferable over the thing group of following material:
(1) chemical formula is (X-L-)-N-(R 2) 2The ethoxyquin monoamine,
(2) the following ethoxyquin diamines of chemical formula:
Figure 911104860_IMG25
(3) the following ethoxyquin polyamines of chemical formula:
Figure 911104860_IMG26
(4) the following ethoxylated amine polymkeric substance of general formula:
Figure 911104860_IMG27
(5) mixture of above-mentioned substance, wherein A 1For:
Figure 911104860_IMG28
R is H or C 1-C 4Alkyl or hydroxyalkyl; R 1Be C 1-C 12Alkylidene group, the hydroxyl alkylidene group, alkylene group, arylidene or alkarylene, or for the C of 2-20 oxyalkylene units is arranged approximately 2-C 3Oxyalkylene part, condition are not form the O-N key; Whenever-R 2Be C 1-C 4Or hydroxyalkyl ,-L-X part, or two R 2Formation-(CH together 2) r,-A 2-(CH 2) s-, A wherein 2For-O-or-CH 2-, r is 1 or 2, S is 1 or 2, and r+s is 3 or 4; X is-non-ionic group anionic group or its mixture; R 3C for replacement with the position of substitution 3-C 12Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R 4Be C 1-C 12Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkarylene, or C for having about 20 oxyalkylene units of 2- 2-C 3Oxyalkylene part, condition are that no O-O or O-N key form; L is for containing the polyoxyalkylene part
-((R 5O) m(CH 2CH 2O) n)-hydrophilic chain, R wherein 5Be C 3-C 4Alkylidene group or inferior hydroxyalkyl, and the number of m and n should make this-(CH 2CH 2O) n-part contains the weight at least about 50%() described polyoxyethylene part; For described monoamine, m is that 0-is about 4, and n is at least about 12; For described diamines, m is that 0-is about 3, and works as R 1Be C 2-C 3When alkylidene group, inferior hydroxyl or alkylene group, then n is at least approximately 6, and works as R 1Not C 2-C 3When alkylidene group, inferior hydroxyalkyl or alkylene group, n is at least about 3; For described polyamines and amine polymer, m is that 0-is about 10, and n is at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is that q is that 1 o'clock t is 1; W is 1 or 0; X+y+z is at least 2; Y+z is at least 2.Best dirt frees-and anti redeposition agent is the tetren of ethoxylation.US.4,597,898(1986.7.1. authorizes Vandermeer, this patent is incorporated into this paper through quoting as proof) exemplary ethoxylated amine has been done further description.Preferable dirt/the anti redeposition agent that goes of another group is to be disclosed in european patent application 111, and 965(Oh and Gosselink, 1984.6.27. is open, and is that it is incorporated herein through quoting as proof) in cation compound.Other available goes dirt/anti redeposition agent to comprise and is disclosed in european patent application 111, and 984(Gosselink, 1984.6.27. is open) in ethoxylated amine polymer; Be disclosed in european patent application 112,592(Gosselink, 1984.7.4. is open) in amphoteric ion polymer; And be disclosed in US.4,548,744(1985.10.22. authorizes Connor) in amine oxide, above-mentioned application and patent are combined in herein through quoting as proof.
Well known in the art other goes dirt/anti redeposition agent also to can be used for the composition of this paper.Another kind of preferred anti-deposition agent comprises carboxymethyl cellulose (CMC) material, and they are known in the art.
The polymeric dispersion agent
The composition that polymeric dispersant is used for this paper is useful.These materials help the control to calcium and magnesium hardness.
Suitable polymeric dispersant comprises polycarboxylate and poly-1,2 ethylene glycol (though other material as known in the art is also available).
The consumption that polymeric dispersant is general is about the 0.5-5% of this cleaning composition weight, and more frequent is about 1.0-about 2.0%.
The polycarboxylate material of dispersion agent component that can be used as polymeric polycarboxylate herein is for containing 60%(weight at least) the segmental polymkeric substance or the multipolymer of following general formula:
Figure 911104860_IMG29
Wherein x, y and z respectively are selected from the group that is made of hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol; Salt-forming cation and n is about 30-400.Preferably x is hydrogen or hydroxyl, and y is hydrogen or carboxyl, and z is that hydrogen and M are hydrogen, basic metal, ammonia or replace ammonium.
Can be by making suitable unsaturation monomer, the unsaturated monomer polymerization or the copolymerization that are preferably its acid prepare this class polymeric polycarboxylate material.The unsaturated monomer acid that can be aggregated and form suitable polymeric polycarboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.The existence of carboxy-containing acid group's monomer segment (as vinyl methyl ether, vinylbenzene, ethene etc.) in this paper polymeric polycarboxylate do not suit, and condition is the no more than about 40%(weight of these segment content).
Shi Yi polymeric polycarboxylate can be derived by vinylformic acid especially.This class is useful in the present invention, is that the polymkeric substance of base is the water-soluble salt of polymeric acrylic acid with vinylformic acid.The preferable 2000-10000 that is about of the average molecular weight range of this class acid polymkeric substance, the better 4000-7000 that is about, the best is about 4000-5000.The water-soluble salt of this class acrylate copolymer can comprise, as an alkali metal salt, ammonium and substituted ammonium salt.Such soluble polymer is a known substance.This class polyacrylate use in detergent composition is as being disclosed in US.3, and 308,067(1967.3.7. authorizes Diehl, this patent is incorporated into this paper through quoting as proof).
Also available multipolymer based on vinylformic acid/toxilic acid is as the preferred ingredient of dispersion agent/anti redeposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The preferable 2000-100000 that is about of the average molecular weight range of this class acid multipolymer.The better 5000-75000 that is about, the best is about 7000-65000.Vinylformic acid and the common scope of toxilic acid segmental ratio are about 30 in this analog copolymer: 1-1: 1, goodly be about 10: 1-2: 1.The water-soluble salt of this class vinylformic acid/maleic acid comprises as an alkali metal salt, ammonium and substituted ammonium salt.This class solubility vinylformic acid/maleic acid is open at european patent application No 66915(1982.12.15., and this article is incorporated into this paper through quoting as proof) in quilt described and be known substance.
The another kind of polymeric material that can be comprised is polyoxyethylene glycol (PEG).PEG has the performance of dispersion agent, and plays dirt/anti redeposition agent.For these purposes, its molecular weight ranges generally is about 500-100000, and the preferable 1000-50000 that is about is more preferred from about 1500-10000.
Brightening agent
In detergent composition of the present invention, can mix any fluorescence brightening agent as known in the art or other brightening agent or whitening agent.
Depend on series of factors for being used in the detergent composition selection, account for the ratio of washing container size as the type of washing composition, the character that is present in other component in the detergent composition, washing water temperature, stirring degree and substrate brightening agent.
The type of material to be cleaned is also depended in the selection of brightening agent, as cotton products, and synthetic products etc.Because most of laundry detergent will be used to clean various fabrics, so detergent composition should contain the effective brightening agent mixture of various fabrics.Certainly, necessary is that each component of this brightening agent mixture should be compatible.
Can be effectively used to commercially available fluorescence brightening agent of the present invention and can be divided into several groups, this includes, but is not limited to Stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, 5, derivative and other reagent of 5-dibenzothiophene dioxide, pyrroles, 5 and 6 yuan of ring heterocyclic substrates.The example of this class brightening agent is disclosed in " The Production and Application of Fluorecent Brightening Agents " (M.Zahradnik Published by John Wiley ﹠amp; Sons, New York(1982)) in, this Wen Jing quotes as proof and is incorporated into this paper.
Can be used for stilbene derivative of the present invention effectively and include (but are not necessarily limited to) two (triazinyl) amino stilbene derivatives; Two acylamino derivatives of Stilbene; The triazole derivative of Stilbene; Stilbene De oxadiazole derivative; The styryl derivative of Stilbene De oxazole derivative and Stilbene.
To the derivative of two (triazinyl) the amino Stilbene of useful some of the present invention can be by 4,4 '-diamines-Stilbene-2,2 '-the disulfonic acid preparation.
To the useful coumarin derivatives of the present invention include (but are not necessarily limited to) in the 3-position, 7-position and the derivative that replaces in 3-position and 7-position.
The effective carboxylic acid derivative of the present invention is included (but are not necessarily limited to) fumaric acid derivatives; Benzoic acid derivative; To phenylene-two-acrylic acid derivative; Naphthalene dicarboxylic acid derivant; The heterocyclic acids derivative; And cinnamic acid derivative.
The cinnamic acid derivative useful to the present invention also can be subdivided into several groups, includes (but are not necessarily limited to) cinnamic acid derivative, vinylbenzene azole, vinylbenzene cumarone, Ben Yi Xi oxadiazole, vinylbenzene triazole and the many benzene of vinylbenzene (being disclosed in 77 pages of Zahradnik reference).
The vinylbenzene azole can be further divided into vinylbenzene benzoxazole, vinylbenzene imidazoles and vinylbenzene thiazole (being disclosed in 78 pages of Zahradnik reference).Be appreciated that these three kinds of disaggregated classifications that provide may need not to reflect with the vinylbenzene azoles segment into the detailed catalogue of grouping.
To the useful another kind of fluorescence brightening agent of the present invention for being disclosed in " The Kirk-othmer Encyclopedia of Chemical Technology " (Volum 3.pages 737-750(John Wiley ﹠amp; Sons Inc., 1962) dibenzothiophene-5 in, the derivative of 5-dioxide (being incorporated into this paper through quoting as proof), and comprise 3,7-diamino dibenzothiophene-2,8-disulfonic acid 5,5 dioxide.
The another kind of fluorescence brightening agent useful to the present invention comprises the pyrroles, and it is a five-ring heterocyclic substrate derivative.They further can be categorized into single pyrroles and two pyrroles.Single pyrroles and two pyrroles' example is disclosed in the KirK-Othmer reference.
To the useful class brightening agent again of the present invention is six-ring heterocyclic substrate derivative (being disclosed in the KirK-Othmer reference).The example of this compounds comprises the brightening agent that is derived from pyrazine and is derived from the brightening agent of 4-amino naphthalenes methylene amide.
Except that the brightening agent of having discussed, miscellaneous reagent also can be used as brightening agent effectively.The example that this class mixes reagent is disclosed in the Zahradnik reference 93-95 page or leaf, and it comprises 1-hydroxyl-3,6,8-pyrene trisulfonic acid; 2,4-dimethoxy-1,3,5-triazines-6-base-pyrene; 4,5-two-phenylimidazole ketone trisulfonic acid; And pyrazoline-quinoline.
Object lesson to other useful fluorescence brightening agent of the present invention is US.4, and 790,856(1988.12.13 authorizes Wixon, this Wen Jing quotes as proof and is incorporated into this paper) in those materials of determining.These brightening agent comprise the Phorwhite from Verna TMThe brightening agent of series.Other brightening agent that is disclosed in the document comprises: Tinopal UNPA, Tinopal CBS and the Tinopal 5BM that can be buied by Ciba-Geigy; The Arctic White CC and the Artic White CWD that can buy by gondola Hilton-Davis; 2-(4-styryl-phenyl)-2H-naphthols (1,2-d) triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-Stilbene; 4,4 '-two (styryl) two phenyl, and the y-aminocoumarin.The object lesson of these brightening agent comprises 4-methyl-7-diethyl-aminocoumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho--(1,2-d 〕 oxazole; And 2-(stilbene-4-yl)-2H-naphtho--(1,2-d) triazole.
Other fluorescence brightening agent useful to the present invention comprises US.3, and 646,015(1972.2.29. authorizes Hamilton, this patent is incorporated into this paper through quoting as proof) described in those brightening agent.
Other composition
All can be included in the composition of this paper the useful various other components of washing composition combination, this comprises other active ingredient, carrier, hydrotropic agent, processing material, dyestuff or pigment, is used for the solvent of liquid formulations etc.
Liquid detergent composition can moisturely be made the solvent of carrier with other.Low-molecular-weight primary alconol or secondary alcohol suit, and this class alcohol is methyl alcohol, ethanol, propyl alcohol and Virahol in this way.Monohydroxy-alcohol is preferably for the solubilization tensio-active agent, but also available polyvalent alcohol contains the polyvalent alcohol (as propylene glycol, ethylene glycol, glycerol and 1,2-propylene glycol) of about 6 carbon atoms of 2-and about 6 hydroxyls of 2-as those.
The batching of detergent composition of the present invention preferably makes at its pH that is used to wash working life chien shih washing water about between 6.5-11, and is preferable about between 7.5-10.5.The pH of liquid formulations is preferable about between 7.5-9.5, and is better between 7.5-9.0.The technology that pH is controlled at the scope of recommend using comprises to be used buffer reagent, alkali, acid etc. and is the known technology of those of ordinary skills.
The present invention is by individually or with the form that also contains alkyl sulfate surfactant washing particle polyhydroxy fatty acid amide surfactant is attached in the washing composition that contains alkyl sulfate surfactant of granulous and liquid and forms a kind of method of improving such washing composition performance.
The present invention also further provides the basic thing of a kind of cleaning (as fiber, fabric, crust, skin etc.) method, this method contacts described basic thing at least with detergent composition at least about the polyhydroxy fatty acid amide that contains 1% tensio-active agent and 1%, wherein a) said composition also comprises ⅰ) a kind of suds suppressor of foam inhibition amount, or ⅱ) preferably be about 3%-30% at least about 1%() be selected from by alkylethoxylate, alkyl ethoxylate sulfate, auxiliary surface in the thing group that alkyl ester sulfonate or their mixture are formed surface-active agent alive, wherein the weight ratio of alkyl sulfate surfactant and polyhydroxy fatty acid amide is about 1: 10-10: 1, or preferably in aforesaid preferred weight ratio scope, or b) composition wherein contains alkyl sulfate surfactant and polyhydroxy fatty acid amide (R wherein 1Be methyl, R 2Be C 9-C 7Alkyl or alkenyl, Z are that reducing sugar (is preferably glucosides, glucoside more preferably) institute's deutero-, and the weight ratio of alkyl-sulphate and polyhydroxy fatty acid amide is about 1.25: 1-1: 6, preferably be about 1.25: 1-1: 4, more preferably 1.25: 1.0-1.0: 1.25.For strengthening washing, preferably to stir.The method that stirring can be provided that is suitable for comprises hand rubbing or is more preferably by brush or other cleaning apparatus, automatic washing machine, automatic dishwasher etc.
Experiment
Here understand for example that preparation is used for the method for N-methyl of the present invention, 1-deoxy-glucose base laurylamide tensio-active agent.The equipment that is applicable to this paper although skilled chemist can change the shape and structure of equipment comprises one 3 liters four neck flasks, this flask is equipped with a motor and drives the blade agitators of fortune and the thermometer that length is enough to contact reaction medium, other of flask two necks are equipped with the side arm in a nitrogen swabbing pig and a wide aperture, and (note: under the situation that very rapidly produces methyl alcohol, wide aperture side arm is very important.), this bypass is connected in one and collects condenser and vacuum outlet efficiently, and the latter is connected to that nitrogen is extracted out mouthful and vacuumometer and then be connected in a vent fan and a cold-trap.To have be used for 500 watts the heating mantles of thermostat (" Variac ") of variable-voltage transformer of reacting by heating place one rapidly lifting the laboratory with on the elevator so that further control reaction temperature.
With N-methylglucosamine (195g, 1.0 moles, Aldrich.M4700-O) and Laurate methyl (Procter ﹠amp; Gamble CE1270,220.9g, 1.0 moles) put into flask.Under the nitrogen cleaning, heat this solid/liquid mixture while stirring to form melts (about 25 minutes).Adding catalyzer when melt temperature reaches 145 ℃ (anhydrous sodium carbonate powder 10.5g, 0.1 mole, J.T.Baker).Close nitrogen cleaning and regulate vent fan and the nitrogen bleed to reach the big pressure of 5 inch Hg(5/31) vacuum tightness.On this point, by regulating Variac and/or rising or reducing heating mantles temperature of reaction is remained on 150 ℃.
In 7 minutes, can see first methyl alcohol bubble at the meniscus place of reaction mixture.Violent reaction then takes place.Methyl alcohol is distilled till its speed reduces.Vacuum tightness is transferred to about 10/31 normal atmosphere of about 10 inch Hg().The increase of vacuum tightness is roughly carried out as follows: 10 inch Hg in the time of 3 minutes, 20 inch Hg in the time of 7 minutes, 25 inch Hg in the time of 10 minutes.From producing the 11st minute that methyl alcohol begins, stop and the heating and the stirring of bubbling and being associated.With product cooling and curing.
Following embodiment is intended to exemplary illustration composition of the present invention, but does not mean that restriction or delimit scope of the present invention separately, and described scope will be determined according to appended claim.
Embodiment 1-6
These embodiment show the preferred compositions that contains alkyl-sulphate and polyhydroxy fatty acid amide, and said composition is suitable for the concentration (is base with washing water weight) with about 6000-8000ppm to be used for washing when being approximately higher than 40 ℃.
Basal granule 123
C 14-15Alkyl-sulphate 4.6 4.6
C 16-18Alkyl-sulphate 2.4 2.4 2.4
Straight chain C 12Alkylbenzene sulfonate 7.6
C 16-18Alkylethoxylate
(11 moles) 1.1 1.1 1.1
Zeolite 22.0 24.0 21.3
Acrylate/maleate copolymer
（60000MW）??4.3??5.6??4.3
Water and miscellaneous 9.4 9.2 10.1
Blending and spraying
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 7.0
N-methyl N-1-deoxy-glucose base
Oleylamide 7.0 4.0
Trisodium Citrate 8.0 8.0
Yellow soda ash 17.5 17.3 17.5
Water glass (SiO 2/ Na 2O
＝1.6）??3.5??3.0??3.5
Spices 0.4 0.4 0.4
Siloxane fluid 0.5 0.5 0.5
Other (filling salt, enzyme, SYNTHETIC OPTICAL WHITNER
Dirt release polymers etc.) 19.3 26.8 19.4
100.0??100.0??100.0
The composition of embodiment 1-3 is base with the about 6000ppM(of concentration with washing water weight preferably), under about 30 ℃ of-95 ℃ of temperature, use.These compositions be by the basal granule component is done form slurry then spraying drying to the moisture content that contains 9% approximately make.With the powdery or the blending of granular component of keeping dry, spray last liquid ingredient addition material then.
Basal granule 456
Straight chain C 12Alkylbenzene sulfonate 5.9
N-methyl N-1-deoxy-glucose base
Fat fatty amide 7.1
C 14-15Alkyl-sulphate 5.9 5.9
C 16-18Alkyl-sulphate 2.5 2.5 2.5
Zeolite 20.5 14.0 20.5
Polyacrylic ester (4500MW) 3.9 3.9 3.9
Trisodium Citrate 6.0
Yellow soda ash 12.7 16.0 12.7
Water and other 8.1 8.2 8.7
Blending and spraying
N-methyl N-1-deoxy-glucose base
Laurylamide 7.1
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 6.6
Other (SYNTHETIC OPTICAL WHITNER, filling salt,
Builder salt, enzyme, etc.) 39.3 36.9 38.7
100.00??100.0??100.0
It is base with washing water that embodiment 4-6 shows with the about 8000ppm(of concentration), the heavy duty type granular detergent composition of the standard density of between about 30 ℃-Yue 95 ℃, using.These compositions are by the slurry of basal granule component is spray-dried to the moisture content that contains 10-13% approximately, add additional dry powder component (as SYNTHETIC OPTICAL WHITNER, promoting agent and other auxiliary materials) and spray liquid then, as spices, nonionogenic tenside or suds suppressor fluid make.
Embodiment 7-20
These embodiment have shown the heavy duty type granular detergent composition that contains polyhydroxy fatty acid amide, alkyl-sulphate and suds suppressor.
Basal granule 789 10
C 14-15Alkyl-sulphate 18.7 10.1 11.3
C 14-15Alkyl ethoxy
(2.25) vitriol 5.6
C 12-18Alkyl-sulphate 16.9
Straight chain C 12Alkylbenzene sulfonate 10.1
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 3.8 2.4 5.6 5.6
Zeolite A 30.1 18.8 18.8 30.1
Trisodium Citrate 11.3 11.3
Yellow soda ash 16.9 16.9 16.9 16.9
Water glass 3.1 2.5 2.5 2.5
Sodium sulfate 15.0 15.0 15.1 15.1
Fat lipid acid 1.1 1.1 1.1
Other are 3.1 3.2 2.7 4.4 years old
Blending and spraying
Other are 2.5 3.5 3.5 2.5 years old
The suds suppressor thin slice *0.5 0.5 1.0
Surplus water 5.0 5.0 5.0 5.0
100.0??100.0??100.0??100.0
*The suds suppressor thin slice contains 5% the silica/silicone oil dispersion of having an appointment, and this dispersion is encapsulated in the thin slice that mainly contains polyoxyethylene glycol (" PEG " 8000MW) (greater than 80%) and a small amount of water soluble ingredient arbitrarily.
Embodiment 7-10 exemplary illustration is base with about 1400ppm(with washing water weight preferably) the prescription that is lower than 50 ℃ of uses.The foregoing description be by with the pulp of basic granules component be slip and spraying drying make its residue water content be about 4-8%; remaining dried component is admixed with spray-dried granules in the rotation mixing drum with particle or powder type, and liquid ingredient (nonionogenic tenside and spices) spray is made thereon.
Basal granule 11 12
Straight chain C 12Alkylbenzene sulfonate 7.6
C 14-15Alkyl-sulphate 3.3
Fat lipid acid 3.0
Zeolite A 13.4 19.8
Polyacrylic ester (4500MW) 3.5 4.5
Polyoxyethylene glycol (8000MW) 2.0 2.0
Water glass (SiO 2/ Na 2O=1.6) 2.0 2.0
Yellow soda ash 15.0 15.0
Sodium sulfate 12.0 6.0
Other are 1.5 1.0 years old
Blending and spraying
The washing granule 14.3 of embodiment 29
The washing granule 30.0 of embodiment 30
Zeolite A 5.0 5.0
Trisodium Citrate 5.0
The suds suppressor thin slice *0.5 0.5
Other are 7.1 5.0 years old
Surplus water 7.8 6.2
100.0??100.0
*The suds suppressor thin slice contains 5% the silica/silicone oil dispersion of having an appointment, and they are encapsulated in about 85%PEG(8000WM) and the thin slice of about 10% fat lipid acid in.
Embodiment 11 and 12 is base with about 1000ppm(with washing water weight preferably) be lower than about 50 ℃ of uses down.They are that a basic grain component makes slip and spraying drying to its water content is about 7-10% by inciting somebody to action, and admix then or spray other remaining ingredients to make.
Basal granule 13 14 15
C 14-15Alkyl-sulphate 4.3 6.0
C 16-18Lipid acid 2.2 2.2
Zeolite A 7.0 7.0 7.0
Polyacrylic ester (4500MW) 3.3 3.3 3.3
Polyoxyethylene glycol (8000WM) 1.3 1.3 1.3
Yellow soda ash 10.7 10.7 10.7
Sodium sulfate 5.0 5.0 5.0
Water glass (SiO 2/ Na 2O=2) 5.0 5.0 5.0
Other are 7.1 7.1 7.1 years old
Blending and spraying
Zeolite A 5.0 5.0 5.0
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 6.4 6.4
The washing granule 21.3 of embodiment 28
C 12-18Alkyl-sulphate 13.1 13.1
C 12-18Alkyl ethoxy
(2) vitriol 6.0
The suds suppressor thin slice *1.0 0.5
Optional blending component 17.2 17.2 16.5
C 12-13Alkylethoxylate
(6.5 moles) 2.0 2.0 2.0
Spices 0.5 0.5 0.5
Water and other 8.2 9.4 8.4
Amount to 100.0 100.0 100.0
*The suds suppressor thin slice contains has an appointment 5%, is encapsulated in mainly to contain PEG(8000WM) silica/silicone oil dispersion in the thin slice of the water soluble ingredient of (greater than 80%) and minor optional.
The composition of embodiment 13-15 is represented the granular prescription of condensation, and they are by being about 5% to water content and sneaking into additional powdery again and do component and make the pulp of basal granule component being spray-dried again.Make the mixture of gained take off dirt by spraying liquid ingredient.This product is intended to the concentration with about 1000ppm, uses being less than about under 30 ℃ the wash temperature.
Basal granule 16 17
C 14-15Alkyl-sulphate 4.6
C 16-18Alkyl-sulphate 2.4 2.4
Straight chain C 12Alkylbenzene sulfonate 7.6
C 16-18Alkylethoxylate
(11 moles) 1.1 1.1
Fat lipid acid 1.1 1.1
Zeolite 21.3 22.0
Acrylate/maleate copolymer
（60000MW）??4.3??5.6
Water and other 10.1 9.2
Blending and spraying
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 7.0
N-methyl N-1-deoxy-glucose base
Fat fatty amide 4.0
Trisodium Citrate 8.0
Yellow soda ash 17.5 17.3
Water glass (1.6 ratios) 3.5 3.0
Spices 0.4 0.4
Siloxane fluid 0.5 0.5
Other (SYNTHETIC OPTICAL WHITNER, filling salt, enzyme,
Builder salt etc.) 18.3 25.7
100.0??100.0
Embodiment 16 and 17 composition are base with the about 6000ppm(of concentration with washing water weight preferably in about 30 ℃ of-95 ℃ of temperature ranges) use.These compositions can be by making pulp of basal granule component and spraying drying to water content for about 9%.Remaining dried powder or particulate component add and mix in the rotation mixing drum, spray last liquid ingredient addition material then.
Basal granule 18 19 20
Straight chain C 12Alkylbenzene sulfonate 5.9
N-methyl N-1-deoxy-glucose base
Fat fatty amide 7.1
C 14-15Alkyl-sulphate 5.9 5.9
C 16-18Alkyl-sulphate 2.5 2.5 2.5
Zeolite 20.5 14.0 20.5
Fat lipid acid 1.1 1.1
Polyacrylic ester (4500MW) 3.9 3.9 3.9
Citrate trianion 6.0
Yellow soda ash 12.7 15.6 12.7
Water and other 8.1 8.2 8.7
Blending and spraying
N-methyl N-1-deoxy-glucose base
Laurylamide 7.1
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 7.1
Spices 0.4 0.4 0.4
Siloxane fluid 1.0 0.5 0.5
Other (SYNTHETIC OPTICAL WHITNER, filling salts
Builder salt, enzyme, etc.) 36.8 34.8 37.8
100.0??100.0??100.0
It is base with washing water weight that embodiment 18～20 shows with the about 8000ppm(of concentration) standard density used between about 30 ℃～95 ℃ of the wash temperature heavily uses as a servant granular detergent composition.The slip of said composition by spraying drying basal granule component adds additional dried powder component to the water content of about 10-13%, and for example SYNTHETIC OPTICAL WHITNER, promoting agent and other assistant agents spray liquid such as spices, nonionic or suds suppressor liquid then and make.
Embodiment 21-27
Below these embodiment representative contain the heavy duty detergent liquid composition of alkyl-sulphate and polyhydroxy fatty acid amide.
Component 21 22 23 24
C 12-14Alkyl-sulphate 12.9 12.9 9.0 11.5
N-methyl N-1-deoxy-glucose
Base coconut monoethanolamide 8.4 8.4
N-methyl N-1-deoxy-glucose
Base oil acid amides 8.4 6.5
Oleic acid 1.8 1.8 3.5 2.0
Citric acid 4.1 4.1 10.0 9.0
Dodecenyl succinic succsinic acid 11.1 11.1 4.0 5.0
Silicone oil 0.2 0.2 0.2 0.2
Other (as solvent, enzyme, increase gorgeous
Agent, stablizer, buffer reagent) 16.1 16.1 16.6 17.7
Water 45.5 45.5 48.3 48.1
100.0??100.0??100.0??100.0
Embodiment 21-24 is base with about 12000ppm(with washing water weight preferably) under 30-95 ℃ of temperature, use.
Component 25 26 27
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 4.2 3.1 3.1
N-methyl N-1-deoxy-glucose base
Oleylamide
C 14-15Alkyl ethoxy
(2.25) vitriol 8.4 6.1
C 14-15Alkyl-sulphate 4.2 3.1
C 12-18Alkyl ethoxy
(2.5) vitriol 6.2
C 12-14Alkyl-sulphate 3.1
C 12-14Alkylethoxylate 3.4 0.0 0.0
Dodecyl trimethyl ammonium chloride 0.5 0.0 0.0
Dodecenyl succinic succinate 5.0
Citrate trianion 3.4 0.0 15.0
TMS/TDS（80/20） ＊3.4 0.0 0.0
C 12-14Lipid acid 3.0 0.0 0.0
Oxygen di-succinate 20.0
The tetren 1.5 0.0 0.0 of ethoxylation
Polyacrylic ester (4500MW) 1.5 1.5
(enzyme, brightening agent, dirt are freed for other
Agent, stablizer, etc.) 15.3 14.9 14.9
Water 52.7 51.2 51.2
100.0??100.0??100.0
*TMS/TDS is tartrate monobasic succinate/tartrate binary succinate.
Embodiment 25-27 is base with about 2000ppm(with washing water weight preferably) be lower than 50 ℃ of uses in wash temperature.
Embodiment 21-27 is by with non-aqueous solvent, aqueous surfactant slurry or solution, the tetren of fused lipid acid, polycarboxylate washing assistant and the aqueous solution of other salt, moisture ethoxylation, buffer reagent, oxyhydroxide and surplus water in conjunction with and make.Or use aqueous citric acid solution, or with sodium hydroxide solution pH is transferred to and to be about 8.5.After adjusting the pH value, add last component such as dirt release agent, enzyme, colorant and spices, and with this mixture stir to single phase for this reason.
Embodiment 28-30
Following embodiment has illustrated and has been applicable to the washing granule that contains alkyl-sulphate and polyhydroxy fatty acid amide that directly joins in the heavy duty detergent granular detergent composition.
Component 28 29 30
C 12-18Alkyl-sulphate 75.0
C 14-15Alkyl-sulphate 65.0 83.0
N-methyl N-1-deoxy-glucose base
Coconut monoethanolamide 18.7 21.7 12.0
Other are 1.3 8.3 years old
Surplus water and other 5.0 5.0 5.0
100.0??100.0??100.0
Embodiment 26-28 makes by the polyhydroxy fatty acid amide of fusing between 70 ℃-100 ℃ is mixed in the alkyl-sulphate slip.Then this product is dried to water content less than 5%, last broken and make its size be about the 0.1-1mm diameter and make.
Embodiment 31
A kind of alternative method for preparing polyhydroxy fatty acid amide used herein is as follows.Employing contains the 84.87g fatty acid methyl ester (from Procter ﹠amp; Gamble methyl esters (E1270), 75g N-methyl D-glycosamine (source: Aldrich Chemical Company M4700-O), the 1.04g sodium methylate (source: Aldrich Chemical Company16,499-2) and the reaction mixture of 68.51g methyl alcohol.This reactor comprises reflux, condenser and the stirring rod that drying tube is housed.In this technological process, along with the stirring N-methylglucosamine under argon atmospher combines with methyl alcohol, and with good stirring begin the heating (stirring rod, backflow).After 15-20 minute, when this solution reaches temperature desired, add ester and sodium methoxide catalyst.Periodic sampling should note making the complete clear thorough need of solution 63.5 minutes with the process of monitoring reaction.In fact, just judge reaction in this near having finished.This reaction mixture was kept 4 hours under refluxing.After removing methyl alcohol, obtain the 156.16g crude product.After vacuum-drying and purifying, obtain adding up to the purified product of 106.96g.Yet the percentage ratio productive rate does not calculate as radix, because periodic sampling makes that total productive rate percentage ratio is meaningless in entire reaction course.This reaction can 80% and 90% reactant density carry out and the few product of output by product with maximum 6 hours time.
That following is not intended the present invention, and is intended to further specify an additional aspect (this technology is that the prescription teacher that can be made multiple detergent composition with polyhydroxy fatty acid amide considers) of this technology.
Clearly, because the cause of the amido linkage of polyhydroxy fatty acid amide, they bear certain instability under strong acid or highly basic condition.Though some decomposition can be born, better do not allow these materials be in pH for a long time and be higher than 11, be more preferably and be not more than 10 also under low 3 the condition.The pH(liquid of final product) be generally 7.0-9.0.
In the process of preparation polyhydroxy fatty acid amide, in usually needing and the basic catalyst that is used to form amido linkage of small part.Though any acid all can be used for this purpose, the detergent formulation teacher will recognize, use that a kind of to provide anionic acid useful in addition and that plan as the finished product detergent composition be thing simply easily.As, citric acid can be used for this in and purpose, and the citrate ion that is produced (about 1%) can with about 40% polyhydroxy fatty acid amide slip coexistence, be pumped into the preparatory phase of the back of whole washing composition manufacturing process then.Sour form such as oxidation disuccinic acid, nitrilotriacetic acid(NTA), ethylene diaminetetraacetic acid, tartrate/succsinic acid and the analogue of material all can use similarly.
By the coconut alkyl fatty acid (mainly is C 12-C 14) the deutero-polyhydroxy fatty acid amide (mainly is C than their Tallow, beef alkyl 16-C 18) counterpart easier to be molten.Therefore, C 12-C 14Material more easily is formulated in the liquid composition, and easier to be molten in the cold water washing lotion.Yet C 16-C 18Material also is very useful, particularly in temperature-use to the environment of-Re washing water particularly useful.Really, C 16-C 18Material is a kind of than its C 12-C 14The better detergent surfactant of counterpart.Therefore, the prescription teacher can be desirably between the convenience of preparation and the performance and reaches balance when selecting to be used for the concrete polyhydroxy fatty acid amide of given prescription.
It is apparent that also the solvability of polyhydroxy fatty acid amide can be improved by the point that has unsaturated and/or chain component at fatty acid part.Therefore, easier to be more molten as the polyhydroxy fatty acid amide that obtains by oleic acid and Unimac 5680 than its n-alkyl counterpart.
Equally, the polyhydroxy fatty acid amide by preparations such as disaccharides, trisaccharides is bigger than its solubility by monose deutero-counterpart.When the obtaining liq composition, this higher solubility is helpful especially.And then, poly-hydroxy group wherein be by maltose deutero-polyhydroxy fatty acid amide when itself and conventional alkylsulfonate (" LAS ") when tensio-active agent is used in combination, it shows extraordinary function as washing composition.Though do not attempt to be limited by theoretical, be clear that LAS and polysaccharide, can cause big and decline beyond thought interfacial tension as the combination of maltose institute deutero-polyhydroxy fatty acid amide, thereby improve clean ability.(preparation by maltose deutero-polyhydroxy fatty acid amide will be set forth in down.）
Not only can produce polyhydroxy fatty acid amide by pure sugar, also can be by hydrolyzed starch, as W-Gum, potato starch or other be any, and to contain the prescription teacher desirable single, two-wait the starch that plant easily produced of sugar and make.Consider that from economic point of view this point is very important.Therefore " high glucose maize treacle ", " high malt sugar " maize treacle etc. can use very convenient and economically.Go xyloidly, the cellulose pulp of hydrolysis also can become the raw material sources of polyhydroxy fatty acid amide.
As suggested in preceding,, more more solvable than its glucose counterpart as deutero-polyhydroxy fatty acid amides such as maltose, lactose by high sugar.And then be clear that more soluble polyhydroxy fatty acid amide is helping its not too soluble counterpart dissolving in varying degrees.Therefore, the prescription teacher for example can select to use the raw material that contains high glucose maize treacle, and contains the syrup of a small amount of maltose (as 1% or more).Usually, resulting thus polyhydroxy fatty acid amide shows better solubility in very wide temperature and concentration range internal ratio " pure " glucose deutero-polyhydroxy fatty acid amide.Therefore, except with the mixture of sugar economically than superior with pure sugared reagent, the polyhydroxy fatty acid amide that is prepared by mixing sugar is with regard to its performance and/or be easy to also all provide substantial advantage with regard to the preparation aspect.Yet in some example, observe, when lipid acid Fructus Hordei Germinatus amide content greater than 25% the time, can lose performances that some remove degreasing (washing dishes), and the foaming loss means the percentage ratio that Fructus Hordei Germinatus acid amides deutero-polyhydroxy fatty acid amide is compared with glucose deutero-polyhydroxy fatty acid amide in mixture greater than the described per-cent of 33%().This may be the slight change of depending on the chain length of fatty acid part.Yet select for use the prescription teacher of this class mixture to be very easy to find: select monose (as glucose) and two, or the ratio of high sugar (as maltose) is about 4: the polyhydroxy fatty acid amide mixture that 1-is about 99: 1 is useful.
Preparing not the polyhydroxy fatty acid amide of Cheng Huan by aliphatic ester and N-alkyl polyalcohols is preferably under about 30 ℃-90 ℃ (being preferably about 50 ℃-80 ℃) temperature and carries out in alcoholic solvent.As now clear and definite, to liquid detergent formula Shi Eryan, 1, carrying out this technology in the 2-propylene glycol solvent is easily, because reaction product is used for need not this alcoholic solvent is removed fully from reaction product before the final detergent formulation.Equally, for example solid (being generally granular) detergent composition prescription teacher can find containing ethoxylated alcohol (as ethoxylation (EO3-8) C 12-C 14Alcohol, the NEODOL23 EO6.5(Shell that for example buys)) in the solvent, be convenient to carry out very much this technology at 30 ℃-90 ℃.When using this class ethoxylate, they are advisable with the alcohol that does not contain a large amount of not ethoxylations, are more preferably the alcohol (" T " regulation) that does not contain a large amount of single ethoxylations.
Do not constitute a part of the present invention though prepare the method for polyhydroxy fatty acid amide itself, the prescription teacher can notice the method for the synthesis of polyhydroxy fatty amide of as described below other.
Generally, the reactions steps that preparation does not in commercial quantity preferably become to encircle polyhydroxy fatty acid amide will comprise: step 1-prepares mixture deutero-N-alkyl polyhydroxy amine by desirable sugar or sugar by the adducts that forms N-alkylamide and sugar, is having under the condition of catalyzer and H-H reaction then; Preferably aforesaid polyhydroxy amine is reacted to form amido linkage with aliphatic ester by step 2-subsequently.Although multiple prior art disclosed method all can be used to prepare the various N-alkyl polyhydroxy amines that are used for reactions steps 2, following method is easily, and is used economic syrup to make raw material.Should be understood that the producer should select color very shallow when using this class syrup to make raw material and will obtain best effect, the syrup of preferably colourless (" water, white " look).
Prepare the N-alkyl polyhydroxy amine with the syrup that plant produced
I. form adducts-below be a standard procedure, wherein about 420 grams, about 55% the nail (unit of length) color that adds are lower than 1 glucose solution (maize treacle, about 231 gram glucose, about 1.28 moles) with about aqueous methylamine solution of 119, about 50% (59.5 gram methylamines, 1.92 moles) reaction.This methylamine (MMA) solution is to use N 2Cleaning is protection also, and is cooled to about 10 ℃ or following.This maize treacle N 2Cleaning and protection are about under 10 ℃～20 ℃ in temperature.Specified temperature of reaction condition shown in pressing slowly is added to maize treacle in the MMA solution, adds the nail (unit of length) color in each fixed time (branch) (about) mensuration.
Table 1
Time (branch): 10 30 60 120 180 240
Temperature of reaction ℃ adds nail (unit of length) color (approximation)
0??1??1??1??1??1??1
20??1??1??1??1??1??1
30??1??1??2??2??4??5
50??4??6??10??-??-??-
From above data as can be seen, when temperature is higher than about 30 ℃ and during at about 50 ℃, this adducts add many that the nail (unit of length) color will differ from, and the nail (unit of length) color that adds of adducts is lower than time of 7 and only had an appointment 30 minutes.For reaction and/or the hold-time of longer time, this temperature of reaction should be lower than 20 ℃.The glycosamine that color is good adds your color of sodium and should be lower than 7, is preferably lower than 4.
When adopting the temperature of lower formation adducts, to sugared ratio, shortened adducts and reached the time of equilibrium concentration substantially with higher amine.When the amine of indication is 1.5: 1 mol ratios to the sugar ratio, when temperature of reaction is about 30 ℃, reached the balance offer 2 hours; When being 1.2: 1 mol ratios, under the similarity condition, this time is at least about wanting 3 hours.For color good, to select amine and cooperating of sugared ratio, temperature of reaction and reaction times, in order to reaching conversion in a basic balance, as be higher than about 90%, preferably to be higher than about 95%, better even will to be higher than 99%(be benchmark with sugar), and make the adducts color be less than about 7, preferably be less than about 4, better be less than about 1.
Be lower than 20 ℃ temperature of reaction with shown in the different maize treacle that add the nail (unit of length) color adopt aforesaid methods, then the color of MMA adducts (reached at least about 2 hours in a basic balance after) be listed in the following table:
Table 2
Add nail (unit of length) color (approximately)
Maize treacle 111 1+ 00 0+
Adducts 3 4/5 7/8 7/8 121
As can be seen from the above, definitely can be accepted in order to make adducts, the glycogen material must be bordering on colourless; When the adding the nail (unit of length) color and be about 1 of sugar, then adducts is that can to accept be unacceptable sometimes sometimes.When adding the nail (unit of length) color greater than 1 the time, the adducts that is produced is unacceptable.This sugared primitive color is good more, and then the color relation of adducts is good more.
II. hydrogenation reaction-according to following program to above-mentioned add the nail (unit of length) color be 1 or littler adducts carry out hydrogenation.
Adducts and the about 23.1 gram United Catalyst G49B Ni catalyzer of about 539 grams in water are added in 1 liter of autoclave, with 200 pounds/inch 2H 2Purge twice at 20 ℃.With H 2Pressure is elevated to about 1400 pounds/inch 2, temperature is elevated to about 50 ℃.Pressure is elevated to about 1600 pounds/inch then 2, temperature is maintained at about 50～55 ℃ and was about 3 hours.Reactant has 95% to be hydrogenated in this.Temperature is raised to 85 ℃ then, is about 30 minutes, then, drains reaction mixture, filters out catalyzer.Evaporation remove anhydrate and MMA after, product is about 95%N-methylglucosamine of white powder.
Repeat said process with about 23.1 gram Raney Ni catalyzer with following change.This catalyzer will wash the reactor that is placed with catalyzer for three times, with 200 pounds/inch 2The H of pressure 2Purge twice, with 1600 pounds/inch 2H 2To reactor pressurization 2 hours, at 1 hour air pressure is bled off, again reactor is pressurized to 1600 pounds/inch 2Then at 200 pounds/inch 2Under pressure and 20 ℃, adducts is pumped in the reactor, with 200 pounds/inch 2H 2Purge, or the like as above.
The product of Chan Shenging all is to be higher than about 95% N-methylglucosamine in each case; The nickel that contains the about 10ppm that is less than this glycosamine, and solution colour is less than adding nail (unit of length) 2.
Be exposed to about 140 ℃ in this thick N-methylglucosamine short period of time, color is stablized constant.
There importantly have to be good, and the color that low sugar content (be lower than about 5%, be preferably lower than about 1%) the becomes reconciled adducts of (less than about 7, preferably adding nail (unit of length) less than about 4, preferably less than about 1) is arranged.
In another reaction, the preparation adducts is earlier the aqueous methylamine solution N of about 159 grams about 50% 2Under about 10-20 ℃, purge and protect.The maize treacle of about 330 grams about 70% (being close to water-white) is used N at about 50 ℃ 2The degassing slowly is added to this syrup in the methylamine solution when being lower than 20 ℃ then.This solution was mixed 30 minutes, and 95% affixture of having an appointment generates, and it is very light yellow solution.
Adducts and the about 9 United Catalyst G49B Ni catalyzer that restrain of about 190 grams in water are added in 200 milliliters of autoclaves, under about 20 ℃, use H again 2Purge three times.Then with H 2Air pressure is raised to about 200 pounds/inch 2, temperature is raised to about 50 ℃.Again H 2Voltage rise to 250 pound/inch 2, temperature keep about 50～55 ℃ long 3 hours.Then 95% hydrogenation is arranged in this product be raised to about 85 ℃, be about 30 minutes, remove anhydrate and evaporate after, product is about 95% N-methylglucosamine, a kind of white powder.
A bit it is important to work as H in addition 2Air pressure is lower than about 1000 pounds/inch 2The time, connecing between adducts and the catalyzer melted reach minimum, so that the content of nickel is minimum value in this glycosamine.In this reaction in the N-methylglucosamine content of nickel be about 100ppm, with the before reacting phase than lacking 10ppm.
Carry out following and H 2The influence that temperature of reaction is directly compared in reaction.
Prepare adducts and carry out hydrogenation with 200 milliliters of hot high pressure reactors under differing temps according to being similar to the exemplary program that provides previously.
The adducts that preparation is used to make glycosamine is by glucose (maize treacle) solution (the 231 gram glucose with about 420 grams about 55%, 1.28 (this solution is to use from the 99DE maize treacle of CarGill to make mole), this solution colour is less than and adds nail (unit of length) 1) and about 119 grams, methylamine of 50% (59.5 gram MMA, 1.92 moles) (deriving from Air Products) blending form together.
This response procedures is as follows:
1. about 119 grams, 50% methylamine solution is put into a N 2In the reactor that purged, use N 2The protection and be cooled to about below 10 ℃,
2. use N at 10-20 ℃ 2This corn syrup solution of 55% is outgased and/or purges, removing the oxygen in the solution,
3. at leisure this corn syrup solution is added in the methylamine solution, and maintain the temperature at about below 20 ℃,
4. in case all corn syrup solutions all add, stir about 1-2 hour.
After making, adducts is used for hydrogenation at once.Perhaps store at low temperatures to prevent further decomposition.
Glycosamine adducts hydrogenation is as follows:
1. the G49B Ni of about 134 gram adductss (color is less than and adds nail (unit of length) 1) and about 5.8 grams is added in 200 milliliters of autoclaves,
At about 20-30 ℃ with about 200 pounds/inch 2H 2Purge reaction mixture twice,
3. use H 2Be pressurized to about 400 pounds/inch 2, temperature is raised to about 50 ℃,
4. pressure is raised to about 500 pounds/inch 2Reacted about 3 hours, and maintained the temperature at about 50～55 ℃.Sampling 1.
5. temperature is raised to about 85 ℃ (about 30 minutes).
6. decantation and remove by filter the Ni catalyzer.Sampling 2.
The isothermal reaction situation:
1. about 134 gram adductss and about 5.8 gram G49B Ni are added in 200 milliliters of autoclaves,
At low temperature with about 200 pounds/inch 2H 2Purge twice,
3. use H 2Be pressurized to about 400 pounds/inch 2, be warmed up to about 50 ℃,
4. improve pressure to about 500 pounds/inch 2, reacted about 3.5 hours, maintain the temperature at set-point.
5. decantation and elimination Ni catalyzer, sample 3 is under about 50～55 ℃ of conditions, and sample 4 is at about 75 ℃, and sample 5 is to obtain about 85 ℃ (85 ℃ reaction times is about 45 minutes).
Test all produces the N-methylglucosamine (about 94%) of similar purity; And when just react each time test to add the nail (unit of length) color all similar, but have only the product of that secondary heat treated generation that good colour stability is just arranged; Back color making the grade is just reacted in 85 ℃ test just.
Embodiment 32
Be the method for preparing fat (hardened) fatty amide of the N-methyl Fructus Hordei Germinatus osamine that uses in the detergent composition of the present invention below.
Step 1-reactant: maltose-hydrate (Aldrich, lot 01318KW); Methylamine (40%(weight) is in water) (Aldrich, lot 03325TM); Raney Ni, and 50% slurry (UAD52-73D, Aldrich, lot12921LW).
Reactant is added in the glass bushing pipe (250 gram maltose, 428 gram methylamine solutions, 100 gram catalyst pulps-50 gram Raney Ni) and it is put into 3 liters shakes in the autoclave, autoclave is with (3 * 500 pounds/inch of nitrogen 2) and (2 * 500 pounds/inch of hydrogen 2) purged, and at room temperature H 2Under shake, through a weekend, temperature range is 28 ℃ to 50 ℃.Crude product mixture is carried out twice of vacuum filtration (2x) by a glass microfiber filters that has silica gel plug, filtrate is condensed into viscous substance.By with this substance dissolves in methyl alcohol, then with rotary evaporator remove methanol again azeotropic remove last trace water.Under high vacuum, carry out last drying.This crude product is dissolved in the methyl alcohol of backflow, filters, be cooled to recrystallize, filter and filter cake drying under 35 ℃ of vacuum.This is the #1 fraction.Filtrate is concentrated up to there being throw out to begin to form, and then in refrigerator overnight, solid filtering and dry under vacuum, this is the #2 fraction.Again filtrate is concentrated into half of volume and then crystallization; Form considerably less precipitation.Add small amount of methanol, solution is placed in the refrigerator spends a weekend.Under vacuum, filter and dry this solid matter.This blended solid contains N-methyl Fructus Hordei Germinatus osamine, and it is used for entire synthesis process step 2.
Step 2-reactant: N-methyl Fructus Hordei Germinatus osamine is (from step 1); Hardened tallow methyl esters; Sodium methylate (25%, in methyl alcohol); Anhydrous methanol (solvent); Amine: the mol ratio of ester is 1: 1; The catalyzer initial content is 10 moles of %(w/r Fructus Hordei Germinatus osamines), be elevated to 20 moles of %, solvent 50%(weight).
In an air-tight bottle, 20.36 gram tallow methyl esters are heated to its fusing point (water-bath), pouring one then into has in churned mechanically 250 milliliters of three mouthfuls of round-bottomed flasks.Flask is heated to about 70 ℃, solidifies to prevent ester.Respectively 25.0 gram N-methyl Fructus Hordei Germinatus osamines and 45.36 are restrained methanol mixed together, again the slurry that produces is added in the tallow ester with abundant stirring.The methanol solution that adds the sodium methylate of 1.51 grams 25%.It is transparent that 4 hours afterreaction mixtures also do not have, owing to add other 10 moles of % catalyzer (total amount reaches 20 moles of %), reaction continues to spend the night (about 68 ℃), and the back mixture is transparent during this period of time.Then reaction flask is reequiped so that distillation.Temperature is elevated to 110 ℃.Under atmospheric pressure continue distillation 60 minutes.Begin molecular distillation then, to continuing 14 minutes, product at this moment is thickness very.Under 110 ℃ (outside temperatures), product stayed in the reaction flask and kept 60 minutes.Product scraped off in the flask grind, be placed in the ether and spend a weekend.Remove ether with rotatory evaporator, product is stored in the baking oven spends the night, then grinding powder.From product, remove any remaining N-methyl Fructus Hordei Germinatus osamine with silica gel.Silica gel slurry in 100% methyl alcohol is placed in the funnel, several times with 100% methanol wash.The spissated sample of this product (20 gram products are in 100 milliliter of 100% methyl alcohol) is put on the silica gel, uses vacuum and several methyl alcohol washing lotion wash-outs several times.The elutriant of collecting is evaporated to drying (rotatory evaporator).Any remaining tallow ester spends the night by developing in ethyl acetate, then filters and removes, and filter cake spends the night through vacuum-drying.Product is exactly a tallow alkyl N-methyl maltose acid amides.
In the another kind of alternating pattern, the step 1 of above-mentioned reaction process can be carried out with commercially available maize treacle, and this maize treacle comprises glucose or glucose and is generally 5% or the mixture of higher maltose.Any detergent composition that polyhydroxy fatty acid amide that produces and mixture can be used for this paper.
In another kind of pattern, the step 2 of above-mentioned reaction process can be 1, carries out among 2-propylene glycol or the NEODOL.Decide in its sole discretion with the prescription teacher, before this reaction product is used to prepare detergent composition and nonessential propylene glycol or the NEODOL that removes wherein.And according to prescription teacher's wish, can be with in the citric acid and the methylate catalyzer, and form the Trisodium Citrate that can stay in the polyhydroxy fatty acid amide.
The wish that depends on the teacher that fills a prescription, this paper composition can contain various suds suppressors more or less.Generally, washing dish needs high bubble, so without suds suppressor; Laundering of textile fabrics need be controlled to some extent to foam in the dress washing machine of top, and laundering of textile fabrics need have the control of certain degree to foam in pre-installed washing machine.Multiple suds suppressor is known in the prior art and can selects for use in the present invention routinely.Really, be that any concrete cleaning composition selects suds suppressor or mix suds suppressor, not only will be according to the consumption of used polyhydroxy fatty acid amide, and will decide according to other tensio-active agents that have in the prescription.Yet apparent, for using with polyhydroxy fatty acid amide, all kinds of is that the Foam Control of base is than all other type suds suppressors more effective (being that consumption can hang down) with the siloxanes.Be specially adapted to of the present invention be can X2-3419 and Q2-3302 be the silicone suds suppressor that trade mark (Dow Corning) is buied.
To contain the dirt release agent is that useful fabric washing agent prescription teacher has kind known materials is available widely, as from (U.S. Pat, 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580; With 4,877,896) choose.Be applicable to that other dirt herein frees the oligomeric esterification products of nonionic that material comprises a kind of reaction mixture, this reaction mixture contains a kind of C 1-C 4Alkoxyl group is that the unitary source of the polyethoxye of end group is (as CH 3(OCH 2CH 2) 16OH), the unitary source of a kind of terephthaloyl (as dimethyl terephthalate), a kind of many unitary sources of (oxygen ethene) oxygen (as polyethylene glycol 1500), the unitary source of a kind of oxygen isopropylidene oxygen are (as 1, the 2-propylene glycol) and the unitary source of a kind of oxygen ethylidene oxygen (as 1, the 2-ethylidene glycol), oxygen ethylidene oxygen unit especially wherein; The unitary mol ratio of oxygen isopropylidene oxygen is at least about 0.5: 1.This class nonionic soil release agent has following general formula:
Figure 911104860_IMG30
R wherein 1Be rudimentary (as C 1-C 4) alkyl, especially methyl; X and y respectively are the integers of an about 6-about 100; M is the integer of about 0.75-about 30; N is an integer of about 0.25～about 20; R 2Be to make oxygen ethylidene oxygen: the mol ratio of oxygen isopropylidene oxygen is at least about 0.5: 1 H and CH 3Mixture.
Another kind is applicable to that the preferred dirt release agent of this paper is U.S. Pat .4, and the general anionic dirt release agent described in 877,896 does not contain HOROH type monomer substantially but condition is such dirt release agent, and wherein R is propylene or higher alkyl.Therefore, U.S. Pat .4 for example, the dirt release agent in 877,896 can comprise that by dimethyl terephthalate, 1,2 ethylene glycol, 1 2-propylene glycol and 3-sodium are for the product of sulfosalicylic acid reaction.Simultaneously these auxiliary dirt release agents can comprise: for example by dimethyl terephthalate, 1,2 ethylene glycol, 5-sodium for sulfoisophthalic acid ester and 3-sodium product for the sulfosalicylic acid reaction.These reagent preferably are used in the granular laundry detergent.
Also certainly, it is useful containing non-perborate bleach to the prescription teacher, especially true in the heavy duty type granular laundry detergent.Multiple peroxygen bleach is commercially available, and can be used for this paper, and is economical but the percarbonate among them is then convenient.Therefore, the composition of this paper can contain the solid percarbonate bleach, uses with its sodium-salt form usually, and its add-on is 3%～20% of a said composition weight, is preferably 5%～18%, and is preferably 8%～15%.
SPC-D is that chemical formula is corresponding to 2Na 2CO 33H 2O 2Adducts, and for a kind of crystalline form solid commercially available.The heavy metal chelant of low amount is contained in most commercially available material, as EDTA, 1-hydroxy ethylene 1, and two phosphonic acids (HEDP) of 1-or amino phosphonates do, these are all sneaked in process of production.In the use of this paper, percarbonate is blended in the detergent composition with can not adding protection in addition, but preferred version of the present invention then adopts the stable form (FMC) of this material.Though can use multiple coating layer, most economical is water glass, as solution, and SiO wherein 2: Na 2The O ratio is 1.6: 1 to 2.8: 1, is preferably 2.0: 1, and the 2%-10%(that dry back silicate solid content is percarbonate weight is generally 3%～5%).Magnesium Silicate q-agent also can use, and one of sequestrant mentioned above also can be included in the coating.
The particle size range of crystalline form percarbonate is 350 μ m-450 μ m, and average particle size particle size is about 400 μ m.After the coating, this crystalline size scope is 400-600 μ m.
Though can control the heavy metal that is present in the yellow soda ash that is used for producing percarbonate by add sequestrant in this reaction mixture, percarbonate also needs protection with the influence of the heavy metal that exists as impurity in other component of avoiding product.Find that also the total content of iron, copper and mn ion should not surpass 25ppm in the product, and preferablely should be lower than 20ppm to avoid unacceptable deleterious effect to percarbonate stability.
A kind of modern times, condensation detergent for washing clothes particle is as follows.
Embodiment 33
Component %(weight)
C 14-15Alkyl alcohol sulfonic acid 13
C 14-15The many oxyethyl groups of alkyl (2.25) sulfonic acid 5.60
C 12-13The many ethoxylates (6.5) 1.45 of alkyl
C 12-14Lipid acid N-methyl glucose amide 2.50
Sodium silicoaluminate (as hydrated zeolite A) 25.2
The silicate-like builder of laminated crystalline 123.3
Citric acid 10.0
Yellow soda ash is to obtain washing lotion pH=9.90
Sodium polyacrylate (m.w.2000～4500) 3.2
Five acetic acid diethylenetriamine 0.45
Savinase 20.70
6-pelargonamide-6-oxygen base-mistake oxy hexanoic acid 7.40
Sodium peroxoborate-hydrate 2.10
Nonanoyl oxygen Phenylsulfonic acid 5.00
Brightening agent 0.10
1The layered silicate washing assistant is being known in the art.Preferred lamina sodium silicate.For example referring to US.4,664,859(1987 May 12 invested H.P.Rieck) in the lamina sodium silicate washing assistant, this patent is incorporated into this paper through quoting as proof.The layered silicate washing assistant that is suitable for can be buied with the SKS-6 trade(brand)name from Hoechst company.
2. from Novo Nordisk A/S, Copenhagen buys.
The particle of very preferred aforementioned type is that those contain the 0.0001%～about 2%(weight of having an appointment) organized enzyme and at least about 1%(weight) described polyhydroxy fatty acid amide, and most preferably wherein anion surfactant is not the particle of alkyl benzene sulfonate surfactant.
Embodiment 34
Following embodiment has shown the perborate bleaching-Jia of the present invention-bleach activator detergent composition that makes by the listed component of blending in mixing drum.
In the present embodiment, zeolite A refers to that it is 1-10 that the crystalline zeolite A(of hydration contains have an appointment 20% water and average particle size particle size, is preferably 3～5 microns); LAS refers to C 123Linear alkylbenzene sulphonic acid; AS refers to C 14-C 15Sodium alkyl sulfate; Nonionic refers to use with the ethylene oxide condensation of 6.5 moles of every mol of alcohol and with ethoxylation and a pure stripped coconut alcohol ethoxylation, and it also is abbreviated as CnAE 6.5T.; And DTPA refers to diethylenetriamine five sodium-acetates.
Account in the final composition
Umber (weight) account for particle %
Basal granule 151.97 100.00
AS??9.44??18.16
LAS??2.92??5.62
Moisture content 4.47 8.60
Water glass (1.6 ratios) 1.35 2.60
Sodium sulfate 6.47 12.45
Sodium polyacrylate (4500MW) 2.61 5.02
PEG8000??1.18??2.27
Nonionic thing 0.46 0.89
Yellow soda ash 13.29 25.57
Brightening agent 0.20 0.38
Sodium silicoaluminate 9.11 17.53
DTPA??0.27??0.52
Spices 0.20 0.38
The NAPAA particle 26.09 100.00
NAPAA??2.86??46.96
LAS??0.30??4.93
Vitriol and other miscellaneous 2.93 48.11
The NOBS particle 33.88 100.00
NOBS??3.15??81.19
LAS??0.12??3.09
PEG8000??0.19??4.90
Other are 0.42 10.82 years old
Zeolite granular 412.00 100.00
Sodium silicoaluminate 7.39 61.58
PEG8000??1.50??12.47
Nonionic thing 1.16 9.70
Moisture content 1.66 13.83
Other are 0.29 2.42 years old
Blending
SKS-6 lamina sodium silicate 15.84
Proteolytic enzyme (0.078
The mg/g activity) 0.52
Sodium peroxoborate-hydrate 1.33
Citric acid 6.79
C 12-C 14The N-methyl
Glucamide 1.58
Final composition total amount 100.00
1. this basal granule is that the water liquid with listed component mixes the mixture spraying drying and makes.
2. the moistening cake piece of the NAPAA that newly the makes sample of acquisition, it typically is made of oxygen (AVO) (NAPAA corresponding to about 36%) and remaining (about 4%) unreacting material that about 60% water, about 2% peroxy acid obtain.This moistening cake piece is NAAA(hexanodioic acid-nonyl acid amides), the crude reaction product of sulfuric acid and hydrogen peroxide, it is the chilling by adding entry subsequently, its after-filtration again, with distilled water wash, phosphate buffered saline buffer washing and final suction strainer to obtain moistening cake piece.Moistening cake piece some is at room temperature air-dry typically to be contained 50%AVO(corresponding to about 90%NAPAA) and the dry-eye disease of about 10% reacted.When drying, the pH of sample is 4.5.
The preparation of NAPAA particulate is the moistening cake piece of NAPAA (containing 10% unreacted reactant approximately), the about 11.1 parts of C that mix about 51.7 parts drying in the CUISINART mixing tank 12.3Linear alkylbenzene sulphonic acid (LAS) slip (45% activity), about 43.3 parts sodium sulfate and about 30 parts of water.After the drying, particle is not determined size by all particles of No.65 purpose to give particle (containing about 47%NAPAA) by No.14Tyler mesh sieve and reservation.Determine that by the Malvern grain size analysis mean sizes of superamide particle (attached collection thing) is about 5～40 microns, the meta particle size is about the 10-20 micron.
3. according to U.S. Pat, 4,997,596(1991 March 5 authorized people such as Bowling) in method prepare NOBS(acyloxy in ninth of the ten Heavenly Stems phenylsulfate) particle, this patent is incorporated into this paper through quoting as proof.
4. by mixed zeolite A in Eirich RO8 high energy mixers and PEG8000 and CnAE6.5T prepare contain below the zeolite granular of composition.
Part (weight)
After the dry preceding drying
Zeolite A(comprises combination water) 70.00 76.99
PEG8000??10.80??12.49
CnAE6.5T ＊8.40 9.72
Free water content 10.80 0.80
PEG8000 is the temperature that contains the aqueous solution form of 50% water and be in about 55 (12.8 ℃).CnAE6.5T is for liquid state and be maintained at about 90 °F (32.2 ℃).By through the pumping of 12 unitary static mixers and with these two kinds of liquid combinations.The viscosity of about 75 (23.9 ℃) of the temperature out of consequent tackiness agent material and about 5000cps..By the PEG8000 of static mixer and the ratio of CnAE6.5T is 72: 28.
With batch-wise pattern operation Eirich R08 high energy mixers.At first, the powdery zeolite A of 34.1Kg is put into the dish of mixing tank, at first with counterclockwise, this dish of the rotational speed of 75 rev/mins (rpm) starts mixing tank with 1800rpm its rotating paddle that turns clockwise then.Then the tackiness agent material is directly pumped into from static mixer in the Eirich R08 high energy mixers that contains zeolite A.Tackiness agent material feeding speed is about 2 minutes.This mixing tank continued to mix 1 minute again, and the total mixing time of this batch of material is 3 minutes.Then this batch of material is emitted and collected in the fiber tube.
Repeat this batch process step until the wet product of collecting about 225Kg.The product that obtains thus is dry in the fluidized-bed of 240-270 (116～132 ℃) then.Drying step has been removed most free-water and has been changed above-mentioned composition.Is 1.31 * 10 by the total energy that mixing tank is defeated by product at this batch in cycle 12Erg/Kg(speed is about 2.18 * 10 9Erg/KgS).
The average particle size particle size that the free-pouring agglomerate that obtains thus has is about 450～500 microns.
Embodiment 35
A kind of being applicable to suitable high density is used for common preceding charging automatic washing machine (particularly in Europe) and is applicable to that the granular laundry cleaning composition of large-temperature range is as follows:
Component %(weight)
SOKALAN CP5(100% activity is as sodium salt) 13.52
DEQUEST 2066(100% is as acid) 20.45
TINOPAL DMS 30.28
MgSO 40.49
Zeolite A(is anhydrous) 17.92
The CMC(100% activity) 40.47
Na 2CO 39.44
Citric acid 3.5
Layered silicate SKS-6 12.9
Fat alkyl-sulphate (100% activity: sodium salt) 2.82
C 14-C 15Alkyl-sulphate (100% activity: sodium salt) 3.5
C 12-C 15Alkyl EO(3) vitriol 1.76
C 16-C 18N-methyl glucose amide 4.1
DOBANOL C 12-C 15EO（3） 3.54
LIPOLASE（100，000 LU/g） 50.42
SAVINASE（4.0KNPU） 61.65
Spices 0.53
X2-3419 70.22
Starch 1.08
Stearyl alcohol 0.35
SPC-D (coating) 22.3
Tetra-acetylated ethylene diamine (TAED) 5.9
Zinc phthalocyanine 0.02
Water (from zeolite) surplus
1SOKALAN is can be by the sodium polyacrylate/sodium maleate of Hoechst acquisition.
2The trade mark of the Monsanto of five (phosphonomethyl) diethylenetriamine.
3The white dyes that obtains from Ciba Geigy.
4The trade(brand)name FINNFIX that obtains from Metasaliton.
5The enzyme of the LIPOLASE steatolysis that obtains from Novo.
6The SAVINASE proteolytic enzyme that obtains from Novo.
7X2-3419 is the silicone suds suppressor that is obtained by Dow Corning.
It is as follows to prepare this particulate operation, comprises various tower dryings, agglomeration, does interpolation etc.Weight percentage wherein is based on final composition.
A. mix by tower and dry
Use standard technique that following component is mixed and tower drying.
SOKALAN??CP5??3.52%
DEQUEST??2066??0.45%
TINOPAL??DMS??0.28%
Sal epsom 0.49%
Zeolite A(is anhydrous) 7.1%
CMC??0.47%
B. surfactant agglomerates
B 1. tallow alkyl sodium sulfate and C 12-15EO(3) the following surface compositions of the agglomeration-foundation of sodium sulfate slip is with tallow alkyl sulfate 50% active slip and 70%C 12-C 15EO(3) vitriol slip and zeolite A and yellow soda ash carry out agglomeration (offering detergent formulation after the agglomerate drying).
Tallow alkyl sulfate 2.82%
C 12-15EO(3) vitriol 1.18%
Zeolite A 5.3%
Yellow soda ash 4.5%
B 2.C 14-C 15Alkyl-sulphate, C 12-15Alkyl ethoxy sulfate, DOBANOL C 12-C 15EO(3) and C 16-18Agglomerate-the C of N-methyl glucose amide 16-C 18Glucamide nonionic material be methyl ester and between the N-methylglucosamine reaction period with the DOBANOL C that exists 12-15EO(3) synthetic.C 12-15EO(3) played the fusing point depressant, it can make reaction carry out, and does not form undesirable ring glucamide.
Obtain 20% DOBANOL C 12-15EO(3) and 80% C 16The surfactant mixture of-18 N-methyl glucose amides, co-agglomerated with 10% yellow soda ash then.
Then with above-mentioned particle and C 14-C 15Sodium alkyl sulfate and C 12-15EO(3) highly active slurry (70%) of vitriol and zeolite A and extra yellow soda ash is co-agglomerated.This particle is at C 16-18Has good dispersiveness in the cold water of N-methyl glucose amide.
The complete formula of this particle (offering detergent formulation after this agglomerate drying) is:
C 16-18N-methyl glucose amide 4.1%
DOBANOL C 12-15EO（3） 0.94%
Yellow soda ash 4.94%
Zeolite A 5.3%
C 14-C 15Sodium alkyl sulfate 3.5%
C 12-15EO(3) sodium sulfate 0.59%
C. exsiccant additive
Add following component
Percarbonate 22.3%
The tetra-acetylated ethylene diamine of TAED() 5.9%
Layered silicate SKS6(is available from Hoechst) 12.90%
Citric acid 3.5%
Lipase (lipolase) 0.42%
100，000LU/g
SAVINASE4.0KNPU??1.65%
Zinc phthalocyanine (sensitization SYNTHETIC OPTICAL WHITNER) 0.02%
D. spraying
DOBANOL C 12-15EO（3） 2.60%
Spices 0.53%
E. suds suppressor
Silicone suds suppressor X2-3419(95%-97% high-molecular weight linear siloxanes available from Dow Corning: 3%～5% hydrophobic silex) co-agglomerated with zeolite (size 2～5 μ), starch and Stearyl alcohol tackiness agent.This particle has following surface compositions:
Zeolite A 0.22%
Starch 1.08%
X2-3.419??0.22%
Stearyl alcohol 0.35%
When this detergent body is used for the washing machine in Europe, as when the washing machine of AEG trade mark washs with 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of operating process, present good solubility, superior performance and good foam control with the 85g washing composition.
Embodiment 37
In arbitrary the above embodiments, available equivalent replace lipid acid glucamide tensio-active agent from the Fructus Hordei Germinatus acid amides surfactivity in plant sugar source or the mixture of glucamide/Fructus Hordei Germinatus acidamide surfactant.In this composition, adopt glycollic amide to show the low-temperature stability that helps end formulation.Further, use thetine (aka " Sultaine ") tensio-active agent that superior foam also is provided.
Under the situation of the high especially foamy composition of needs, preferably contain be less than about 5%, more preferably approximately less than 2%, most preferably is and do not contain C substantially 14Or higher fatty acid more, because these materials suppress foams.Therefore, high foam composition prescription Shi Xiwang avoids this class lipid acid of foam inhibition amount is added in the high foam composition with polyhydroxy fatty acid amide, and/or avoids forming when final composition stores C 14Higher fatty acid more.A simple method is to use C 12The ester reagent prepares the polyhydroxy fatty acid amide in the literary composition.Fortunately, use amine oxide or thetine tensio-active agent can overcome some foaming negative effects that cause by lipid acid.
Wish to add anionic optical brighteners to contain suitable high density (as 10% and Geng Gao) formulator in the liquid washing agent of negatively charged ion or polyanion substituent (as the polycarboxylate washing assistant) can find that this can be with whitening agent and water and polyhydroxy fatty acid amide pre-mixing, it is effective then premixture being joined in the final composition.
Polyglutamic acid or poly aspartic acid dispersion agent can be effectively help with zeolite to be washed washing composition and uses.AE liquid or thin slice and DC-544(Dow Corning) be the effective other example of suds suppressor herein.
Those skilled in the art are understood that in the literary composition with two and more high-grade sugar such as maltose prepare polyhydroxy fatty acid amide and will form wherein straight chain substituting group Z by the polyhydroxy fatty acid amide of poly-hydroxy ring structure " end-blocking ".This class material is used for the present invention wishes fully, and does not also break away from disclosed in this invention and spirit and scope claim.

Claims (44)

1, a kind of laundry detergent composition that is used at the automatic washing machine cleaning fabric is characterized in that said composition contains:
(a) general formula at least about 1% (weight) is
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl, and Z is polyhydroxy alkyl with straight hydrocarbyl chain (wherein straight hydrocarbyl chain has at least 3 hydroxyls that directly link to each other with this chain), or its oxyalkylated derivative;
(b) at least about the alkyl sulfate surfactant of 1% (weight); With
(c) randomly, the suds suppressor of foam inhibition amount; (b) that wherein said composition has: (a) weight ratio is about 1: 10 to about 10: 1.
2, detergent composition as claimed in claim 1, wherein said detergent composition also contain at least about 3% polyhydroxy fatty acid amide with at least about 3% alkyl-sulphate, and described weight ratio is about 6: 1 to about 1: 6.
3, detergent composition as claimed in claim 2, it also contain have an appointment 1% to about 30% be selected from negatively charged ion, nonionic and cats product, and composition thereof the cosurfactant component.
4, detergent composition as claimed in claim 1, wherein said cosurfactant comprise sulfate surfactant, alkyl benzene sulfonate surfactant, alkyl sulfonate surfactants, alkyl ethoxylates tensio-active agent, alkyl poly glucoside tensio-active agent, alkane sulfonate tensio-active agent or alkyl phenolic alkoxy thing tensio-active agent or their mixture of alkyl ethoxylated.
5, detergent composition as claimed in claim 1, wherein said suds suppressor are selected from silicone suds suppressor, hydrocarbon suds suppressor and single stearyl phosphoric acid salt suds suppressor, and composition thereof.
6, detergent composition as claimed in claim 1, it contains the unary carboxylation's lipid acid at least about 0.5%, or its salt, suds suppressor.
7, detergent composition as claimed in claim 1, wherein R 1Be methyl, R 2Be C 11-C 17Alkyl or alkenyl, Z are-CH 2(CHOH) nCH 2OH ,-CH(CH 2OH)-(CHOH) N-1-CH 2CH, or-CH 2-(CHOH) 2(CHOR ') (CHOH)-CH 2OH, wherein n is 3 to 5 integer (comprising 3 and 5), and R ' is H or ring or aliphatic monose.
8, detergent composition as claimed in claim 7, wherein Z is a reducing sugar institute deutero-.
9, composition as claimed in claim 1, wherein for polyhydroxy fatty acid amide, Z is by glucose or maltose or their mixture institute deutero-.
10, composition as claimed in claim 1, wherein Z is monose, disaccharide and randomly contains 1%(weight at least) the mixture institute deutero-of polysaccharide of disaccharide, described mixture can be by obtaining in the plant origin.
11, detergent composition as claimed in claim 1 also contains the weight at least about 1%() detergent builders.
12, detergent composition as claimed in claim 1, wherein said alkyl sulfate surfactant comprises C 14-C 18Alkyl-sulphate.
13, as the detergent composition of claim 11, wherein said alkyl sulfate surfactant comprises C 14-C 18Alkyl-sulphate.
14, a kind of detergent composition, contain:
(a) at least about 1%(weight) general formula be
Figure 911104860_IMG3
The polyhydroxy fatty acid amide compound, R in the formula 1Be methyl, or its mixture, R 2Be C 9-C 17Alkyl or alkenyl, reaching Z is by reducing sugar deutero-glycosyl, or the derivative of its alcoxylates; With
(b) at least about 1%(weight) alkyl sulfate surfactant:
Wherein (a): weight ratio (b) is about 1.25: 1 to about 1: 6.
15, as the composition of claim 14, wherein for polyhydroxy fatty acid amide, Z is by glucose or maltose or their mixture institute deutero-.
16, as the composition of claim 14, wherein Z is by monose, disaccharide and randomly, contains the weight at least about 1%() the mixture institute deutero-of the polysaccharide of disaccharide, described mixture can be obtained by plant origin.
17, as the detergent composition of claim 14, wherein said (a): ratio (b) is about 1.25: 1 to about 1: 4.
18,, also contain weight at least about 1%(as the detergent composition of claim 14) detergent builders.
19, as the detergent composition of claim 14, the sulfate surfactant, alkyl benzene sulfonate surfactant, alkyl sulfonate surfactants, the alkylethoxylate tensio-active agent that also contain alkyl ethoxylated, alkyl poly glucoside tensio-active agent, alkane sulfonate tensio-active agent and alkyl phenolic alkoxy thing tensio-active agent, or their mixture.
20, a kind of liquid detergent composition is characterized by and contains:
(a) at least about 1%(weight) general formula be
Figure 911104860_IMG4
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl, be polyhydroxy alkyl with straight hydrocarbyl chain (wherein straight hydrocarbyl chain has at least 3 hydroxyls that directly link to each other with this chain) with Z, or its oxyalkylated derivative;
(b) at least about 1%(weight) C 14Or high-grade alkyl sulfate surfactant more;
(c) a kind of liquid vehicle;
Polyhydroxy fatty acid amide in the wherein said composition and C 14Or more the weight ratio of high-grade alkyl sulfate surfactant is about 10: 1 to 1: 10.
21, as the detergent composition of claim 20, wherein said composition contains have an appointment 3% to about 30% polyhydroxy fatty acid amide and about 3% to about 30% described alkyl-sulphate.
22,, also contain 1% to about 30% the cosurfactant that comprises negatively charged ion or nonionic or their mixtures of having an appointment as the detergent composition of claim 21.
23, as the detergent composition of claim 22, wherein said cosurfactant is selected from vitriol, alkyl ethoxylates, alkylbenzene sulfonate, alkane sulfonate, alkyl ester sulfonate, alkyl phenolic alkoxy thing and the alkyl poly glucoside of alkyl ethoxylated, and their mixture.
24, as the composition of claim 21, wherein for polyhydroxy fatty acid amide, Z is by glucose and maltose or their mixture institute deutero-.
25, as the composition of claim 21, wherein Z is by monose, disaccharide and randomly contains the weight at least about 1%() the mixture institute deutero-of polysaccharide of disaccharide, described mixture can be obtained by plant origin.
26,, also contain the suds suppressor of foam inhibition amount as the detergent composition of claim 25.
27, as the detergent composition of claim 26, also contain washing assistant.
28, the washing particle that is used for granular detergent composition is characterized in that described washing particle contains (a) and intimate mixture (b):
(a) about 5% to about 90%(weight) general formula be
Figure 911104860_IMG5
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl is the polyhydroxy alkyl (wherein straight hydrocarbyl chain has at least 3 hydroxyls that directly link to each other with this chain) with straight hydrocarbyl chain with Z, or its oxyalkylated derivative;
(b) about 10% to about 95%(weight) alkyl sulfate surfactant.
29,, also contain 1% to about 30% the solubilizing agent of having an appointment as the washing particle of claim 28.
30, as the washing particle of claim 29, wherein said solubilizing agent is selected from the anion sulfoacid salt surfactant, have degree of ethoxylation is at least 0.5 alcohol ethoxylate surfactant, ring polyhydroxy fatty acid amide, APG, poly-1,2 ethylene glycol polymkeric substance and poly-(vinylformic acid) polymkeric substance and their mixture.
31, as the washing particle of claim 30, wherein said solubilizing agent comprises alkyl ethoxylates, alkyl ethoxylated sulfate, alkyl ester sulfonate, ring polyhydroxy fatty acid amide, APG or poly-1,2 ethylidene glycol or poly-(vinylformic acid) polymkeric substance or their mixture.
32, as the washing particle of claim 31, the R in the polyhydroxy fatty acid amide of wherein said component (a) 1Be methyl, R 2Be C 9-C 17Alkyl or alkenyl and Z are-CH 2(CHOH) nCH 2OH ,-CH-(CH 2OH) (CHOH) N-1-CH 2OH or-CH 2-(CHOH) 2(CHOR ') (CHOH)-CH 2OH(wherein n is 4, and R ' is H or ring or aliphatic monose) or their mixture.
33, as the composition of claim 32, wherein for polyhydroxy fatty acid amide, Z is by glucose or maltose or their mixture institute deutero-.
34, as the composition of claim 33, wherein Z is by monose, disaccharide and randomly contains the weight at least about 1%() the mixture institute deutero-of the polysaccharide of disaccharide, described mixture can be obtained by plant origin.
35, a kind of detergent composition contains the weight at least about 5%() the washing particle and the detergent builders of claim 22.
36,, also contain the suds suppressor of foam inhibition amount as the detergent composition of claim 35.
37, a kind of detergent composition is characterized in that containing:
(a) at least about 1%(weight) general formula be
Figure 911104860_IMG6
The polyhydroxy fatty acid amide compound, R in the formula 1Be H, C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-C 31Alkyl is the polyhydroxy alkyl (wherein straight hydrocarbyl chain has at least 3 hydroxyls that directly link to each other with this chain) with straight hydrocarbyl chain with Z, or its oxyalkylated derivative;
(b) at least about 1%(weight) alkyl sulfate surfactant; With
(c) cosurfactant is selected from the vitriol of alkylethoxylate, alkyl ethoxylated and alkyl alkoxylated sulfonate, or their mixture;
Wherein (b): weight ratio (a) is about 10: 1 to about 1: 10, and (a): weight ratio (c) is about 1: 10 to about 10: 1.
38, as the composition of claim 37, wherein for polyhydroxy fatty acid amide, Z is by glucose or maltose or their mixture institute deutero-.
39, as the composition of claim 37, wherein Z is by monose, disaccharide and randomly contains the weight at least about 1%() the mixture institute deutero-of the polysaccharide of disaccharide, described mixture can be obtained by plant origin.
40, as the detergent composition of claim 37, wherein said detergent composition contains at least about 3% polyhydroxy fatty acid amide, at least about 3% alkyl-sulphate and (b): (a) weight ratio is about 6: 1 to about 1: 6, and (a): (c) weight ratio is about 5: 1 to about 1: 5.
41, as the detergent composition of claim 37, it contains the suds suppressor of foam inhibition amount.
42, as the detergent composition of claim 37, R wherein 1Be methyl, R 2Be C 11-C 17Alkyl or alkenyl and Z are by reducing sugar institute deutero-.
43,, also contain weight at least about 1%(as the detergent composition of claim 37) detergent builders.
44, as the detergent composition of claim 42, wherein said ratio (b): (a) be about 4: 1 to about 1: 4, and described ratio (a): (c) be about 3: 1 to about 1: 3.
CN91110486A 1990-09-28 1991-09-27 Detergent containing sulfate and polyhydroxy fatty acid amide surfactants Expired - Fee Related CN1031721C (en)

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