CN1281502A - Non-aqueous liquid detergent compositions comprising mid-chain branched surfactants - Google Patents

Non-aqueous liquid detergent compositions comprising mid-chain branched surfactants Download PDF

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Publication number
CN1281502A
CN1281502A CN 98812146 CN98812146A CN1281502A CN 1281502 A CN1281502 A CN 1281502A CN 98812146 CN98812146 CN 98812146 CN 98812146 A CN98812146 A CN 98812146A CN 1281502 A CN1281502 A CN 1281502A
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integer
chain
composition
surfactant
branched
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P·K·文森
T·A·克里佩
R·拉贝奎
R·E·斯蒂德哈姆
D·S·康诺尔
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/835—Mixtures of non-ionic with cationic 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
    • C11D1/38—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

Abstract

The present invetntion discloses a non-aqueous, particulate-containing liquid laundry detergent compositions, which are in the form of a suspension of particulate material, essentially including mid-chain branched surfactants and preferably including a peroxygen bleaching agent and an organic detergent builder, dispersed in a liquid phase preferably structured with additional surfactants. Such compositions provide especially desirable cleaning and bleaching of fabrics laundered therewith.

Description

The non-aqueous liquid detergent compositions that contains the medium chain branched chain surfactant
Invention field
The present invention relates to the liquid laundry detergent product, it is being non-water in nature, it is the stable dispersions form of particulate matter, and it comprises that medium chain branched chain surfactant and it preferably also comprise other material, for example SYNTHETIC OPTICAL WHITNER and/or conventional detergent composition auxiliary agent.
Background of invention
Detergent product is considered to be more convenient for using than dry powder or granulated detergent product usually, and therefore, liquid washing agent is found and obviously helps the human consumer.This detergent product is easy to measure, be dissolved in fast washing water, can be applied to zone dirty on the clothes that is washed and non-dusting easily as concentrated solution or dispersion liquid.Usually they also account for less storage space than granular product.In addition, liquid washing agent can add the formula materials that can not stand drying operation and can not degenerate, and drying operation is generally used for preparing particulate or granulated detergent product.
Although liquid washing agent has many advantages that are better than granular detergent products, obviously also have some shortcomings.Especially, detergent composition component compatible in particulate product can interact in liquid or react to each other, especially in liquid, aqueous environment.Therefore, these components, for example enzyme, tensio-active agent, spices, whitening agent, solvent and especially SYNTHETIC OPTICAL WHITNER and bleach activator especially are difficult to add in the detergent product with acceptable chemical stability.
A kind of trial of the chemical compatibility of raising detergent composition component in detergent product is preparation non-water (or anhydrous) liquid detergent composition.In these non-fishery products, the component of some common solid detergent composition has the undissolved tendency of maintenance in liquid product at least, therefore compares their less each other reactions with its situation about being dissolved in the fluid matrix.Contain active substance, for example the non-aqueous liquid detergent compositions of peroxygen bleach is disclosed in the US4615280 of the Hepworth etc. of promulgation on October 17th, 1986 for example; The US4929 380 of the Schultz of promulgation on May 29 nineteen ninety etc.; The US5008031 of the Schultz of promulgation on April 16th, 1991 etc.; June in 1981 disclosed Elder on the 10th etc. EP-A-030096; June in 1992 disclosed Hall on the 11st etc. WO 92/09678 and October in 1993 disclosed Sanderson on the 13rd etc. EP-A-565017.
Although can improve the chemical compatibility of component in non-aqueous liquid detergent compositions, the physical stability of said composition can become a problem.This is owing to be separated in this product suspension as dispersive undissolved solid particulate matter and descend and be deposited on the container bottom that detergent product is housed.As the result of this class problem, also be difficult in the non-aqueous liquid detergent product, add the enough suitable types and the surfactant materials of quantity.Therefore, must select surfactant materials, thereby make them be suitable for providing acceptable fabric washing performance, but use this material must not can to cause the unacceptable degree that is separated of composition to composition.Can add phase stabilizer in this product, for example thickening material or viscosity control agent are to improve its physical stability.Yet these materials can increase the cost and the volume of product, and the laundry/scourability of this detergent composition is not had help.
Can also select to be used for the surfactant system of this liquid laundry detergent product, in fact it can influence the liquid phase structure of product, thereby promote to be dispersed in the suspension of particulate constituent in this structurizing liquid phase.Example with product of structured surfactant system is the US 5389284 of the van der Hoeven of February 14 nineteen ninety-five promulgation etc., and it adopts based on the alcohol alkoxylate nonionogenic tenside of relative high density and the structured surfactant system of negatively charged ion defloculating agent.In adopting the product of structured surfactant system, structurized liquid phase must be enough viscosity, with the sedimentation of the particulate constituent avoiding suspending be separated, thereby but can not too stickingly influence the pourability and the dispersiveness of Betengent product unfriendly.
As mentioned above, obviously people need to find always and provide the liquid of on-aqueous liquid product form to contain particulate detergent compositions, it has high-caliber chemical substance, the stability of SYNTHETIC OPTICAL WHITNER and enzyme for example, thus commercial acceptable phase stability, pourability and detergent composition laundry, cleaning or bleachability are arranged.Therefore, the purpose of this invention is to provide the method that the non-water of preparation contains the particle liquid Betengent product, it has chemistry and physical stability and outstanding pourability and the fabric laundry/bleaching characteristic that especially needs.
As mentioned above, people also constantly need preparation on-aqueous liquid product, and it provides accepting and desirable balance between scourability and the product stability.Therefore the purpose of this invention is to provide non-aqueous liquid detergent compositions, it is especially stable and effective in the hard water environment.
Have been found that medium chain branched chain surfactant of the present invention provides the low-temperature stability of the improvement of the finished product, less bottom product and the product of improvement and the mixing rate of water in bottle.
Have been found that the surfactant system that contains as some selection of the medium chain branched chain surfactant of giving a definition and other auxiliary agent provides the non-aqueous liquid detergent compositions of realizing above-mentioned purpose.The key element of the combination of components of these selections is described below.
Background technology
The US3480556 of the Witt of on November 25th, 1969 promulgation etc., July in 1991 disclosed Lever on the 31st EP439316 and November nineteen ninety-five disclosed Lever on the 25th EP684300 the alkyl-sulphate of β side chain has been described.EP439316 has described some detergent for washing clothes that contains the special commercial C14/15 chain primary alkyl sulfate that is called LIAL145 vitriol.It is considered to contain 61% side chain on the 2-position, its 30% relates to the collateralization of the hydrocarbon chain with 4 or above carbon atom.US3480556 has described the mixture of β side chain (the 2-position side chain) primary alcohol sulfate, of 10-90 part linear primary alkyl-sulphate and 90-10 part following formula:
Figure 9881214600071
Wherein the total number of carbon atoms is 12-20, and R1 is the straight chained alkyl that contains 9-17 carbon atom, and R2 is the straight chained alkyl (being 67%2-methyl and 33%2-ethyl branch for example) that contains 1-9 carbon atom.
As mentioned above, R.G.Laughlin is in " the water behavior of tensio-active agent ", AcademicPress, and N.Y. (1994) has described when side chain is shifted to the center of hydrophobic alkyl by 2-alkyl position for the 347th page, and the Krafft temperature descends.Also referring to " detergent alcohol-pure structure and molecular weight are to the influence of surfactant properties " such as Finger, J.Amer.Oil Chemists ' Society rolls up 44,525 pages (1967) and " technology bulletin ", Shell Chemical Co., SC:364-80.
November in 1989, the EP342917 of disclosed Unilever on the 23rd described the detergent for washing clothes that contains surfactant system, and wherein main anion surfactant is to contain so-called " wide region " alkyl chain length alkyl-sulphate of (the experiment demonstration comprises blended coconut and Tallow, beef chain length tensio-active agent).
US4102823 and GB1399966 have described other laundry composition that contains conventional alkyl-sulphate.
July in 1975, the GB1299966 of disclosed Matheson on the 2nd etc. disclosed a kind of detergent composition, and wherein surfactant system is made up of the mixture of Tallow, beef sodium alkyl sulfate and nonionogenic tenside.
Methyl substituted vitriol comprises known " iso stearyl " vitriol, and they normally contain the mixture of the isosulf hydrochlorate of 18 carbon atoms altogether.For example December nineteen ninety disclosed Henkel on the 12nd EP401462 pure and mild their sulfation of the pure and mild ethoxylation iso stearyl of some iso stearyl has been described preparing corresponding alkyl-sulphate, iso stearyl sodium sulfate for example.Also referring to K.R.Wormuth and S.Zushma, Langmuir rolls up 7 (1991), 2038-2053 page or leaf (to many branched-chain alkyl vitriol, the especially technical study of " side chain Guerbet " type); R.Varadaraj etc., J.Phys.Chem., volume 95 (1991), 1671-1676 (it has described various " straight chain Guerbet " and " side chain Guerbet "-comprise surface tension of the sorted table surface-active agent of alkyl-sulphate); Varadaraj etc., J.Colloid and Interface Sci., volume 140 (1990), 31-34 page or leaf (the foam data that relate to the tensio-active agent of the C12 that comprises 3 and 4 methyl branches respectively and C13 alkyl-sulphate); With Vara daraj etc., Langmuir, volume 6 (1990), 1376-1378 page or leaf (it has described the micropolar of the aqueous micellar solution of the tensio-active agent that comprises branched-chain alkyl vitriol).
" straight chain Guerbet " alcohol is obtained by Henkel, for example EUTANOL G-16.
Describe in the US5245072 of Mobil Corp. by the primary alkyl sulphates that the alcohol of the Oxo prepared in reaction by propylene or n-butene oligopolymer obtains.Also referring to the US5026933 and 4870038 (by at high temperature preparing the method for straight chain hydrocarbon basically) of: the US5284989 of Mobil Oil Corp. (preparing the method for straight chain hydrocarbon basically) and Mobil Oil Corp. with siliceous acid ZSM-23 zeolite oligomerisation light alkene by the siliceous acid zeolite oligomerisation of interstitial hole light alkene at high temperature with restriction.
Also referring to " tensio-active agent science series ", Marcel Dekker, N.Y. (each volume comprises that name is called the volume of " anion surfactant " and " biological degradation of tensio-active agent ", the latter is write by R.D.Swisher, the 2nd edition, publishing in 1987, is the 18th volume, especially 20-24 page or leaf " hydrophobic grouping and their source "; The 28-29 page or leaf, " alcohol "; 34-35 page or leaf " primary alkyl sulphates " and 35-36 page or leaf " secondary alkyl sulfate ") with relevant document that is generally used for preparing " senior " or " washing composition " alcohol of alkyl-sulphate, comprise: CEH market intelligence " detergent alcohol ", R.F.Modler etc., Chemical Economics Handbook, 1993,609.5000-609.5002; Kirk Othmer ' s chemistry is economical complete works of, and the 4th edition, Wiley, N.Y.1991 " higher fatty alcohol ", volume 1, the 865-913 page or leaf, reference is content wherein.
Summary of the invention
The invention provides non-aqueous liquid detergent compositions, it contains solid, and the stable suspension of undissolved particulate matter basically, described particulate matter comprise the medium chain branched chain surfactant that is dispersed in the whole non-water liquid phase that contains tensio-active agent.
Specifically, the present invention includes non-water, liquid, the heavy-dirty liquid-detergent composition, it is a solid, the stable suspension form of undissolved particulate matter basically, described particulate matter are dispersed in entire structureization, contain in the liquid phase of tensio-active agent.Detergent composition contains by the about 55%-98.9% of composition weight meter structurized, contains the liquid phase of tensio-active agent, and it forms by mixing following component:
ⅰ) by one or more non-water organic thinners of the about 1%-80% of described liquid phase weight; With
ⅱ) by the surfactant system of the about 20%-99% of described liquid phase weight, it contains the tensio-active agent that is selected from negatively charged ion, nonionic, cats product and their mixture.Surfactant system does not preferably have unreacted alcohol basically.
The surfactant system of liquid detergent composition of the present invention contains by weight at least about 10%, preferably at least about 20%, more preferably at least about 30%, most preferably at least about 50% branched chain surfactant mixture, described branched chain surfactant mixture contains medium chain side chain and straight chain surfactant compounds, be less than 25% by the described straight chain compound of branched chain surfactant mixture weight, preferably be less than about 15%, more preferably less than about 10%, most preferably be less than approximately 5%, described medium chain branched compound has following formula:
A b-(EO/PO/BO) mOH is wherein:
A bBe total carbon number C9-C18 in group, the hydrophobic medium chain branched-chain alkyl of the about C15 of preferably about C10-, it contains be connected in (EO/PO/BO) of (1) 8-17 carbon atom mThe long linear carbochain of OH part; (2) one or more C of stretching out of thus long linear carbochain 1-C 3Moieties; (3) at least one branched-chain alkyl partly is directly connected in the carbon of long linear carbochain, and this carbon is by being connected in (EO/PO/BO) mPosition 3 carbon of the carbon #1 counting of OH part are to position ω-2 carbon, and promptly end carbon deducts on the interior position of 2 carbon ranges; (4) A of surfactant composition in above-mentioned formula bPart has the average the total number of carbon atoms greater than 12-about 14.5.
EO/PO/BO is the alkoxyl group part that is selected from oxyethyl group, propoxy-, butoxy and their mixture, and m is at least about 1-about 30.A in branched chain surfactant mixture as defined above bThe average total number of part carbon atom should be about 14.5 greater than about 12-, and it is about 14 to be preferably greater than about 12-, most preferably in the scope greater than about 12-about 13.5." always " number that is used for the carbon atom of this paper is meant that promptly the average carbon atom number in the molecular skeleton adds at all short chains, i.e. the number of the carbon atom in the side chain at long-chain.
The detergent composition of this paper definition also contains the particulate matter that is of a size of about 0.1-1500 micron by the about 0.01%-50% of composition weight meter, it is not dissolved in the described liquid phase basically, and it is selected from peroxygen bleach, bleach activator, color spot decorations, organic detergent auxiliary agent, inorganic alkaline source and their mixture are arranged.
The detailed description of invention
Non-aqueous liquid detergent compositions of the present invention comprises and contains tensio-active agent, the structurized liquid phase of preferred surfactant, and it contains the mixture of branched chain surfactant, and it contains straight chain and medium chain branched chain surfactant.The surfactant mixture of detergent composition of the present invention main and optionally the form method for making of component and other selective substances and composition and purposes in following detailed description: (all concentration and ratio are by weight, except as otherwise noted.)
Specifically, the present invention includes non-water, liquid, the heavy-dirty liquid-detergent composition, it is a solid, the stable suspension form of undissolved particulate matter basically, described particulate matter are dispersed in entire structureization, contain in the liquid phase of tensio-active agent.Detergent composition contains by the about 55%-98.9% of composition weight meter structurized, contains the liquid phase of tensio-active agent, and it forms by mixing following component:
ⅰ) by one or more non-water organic thinners of the about 1%-80% of described liquid phase weight; With
ⅱ) by the surfactant system of the about 20%-99% of described liquid phase weight, it contains the tensio-active agent that is selected from negatively charged ion, nonionic, cats product and their mixture.
As discussing in the following detailed description, surfactant system does not preferably have unreacted alcohol basically.Specifically, the surfactant system that contains straight chain and branched chain surfactant composition should contain and be less than 3% by weight, preferably is less than 1% by weight, most preferably is less than 0.5% unreacted alcohol by weight.
The surfactant system of liquid detergent composition of the present invention contains by weight at least about 10%, preferably at least about 20%, more preferably at least about 30%, most preferably at least about 50% branched chain surfactant mixture, described branched chain surfactant mixture contains medium chain side chain and straight chain surfactant compounds, be less than about 25% by the described straight chain compound of branched chain surfactant mixture weight, preferably be less than about 15%, more preferably less than about 10%, most preferably be less than approximately 5%, described medium chain branched compound has following formula:
A b-(EO/PO/BO) mOH is wherein:
A bBe total carbon number C9-C18 in group, the hydrophobic medium chain branched-chain alkyl of the about C15 of preferably about C10-, it contains be connected in (EO/PO/BO) of (1) 8-17 carbon atom mThe long linear carbochain of OH part; (2) one or more C of stretching out of thus long linear carbochain 1-C 3Moieties; (3) at least one branched-chain alkyl partly is directly connected in the carbon of long linear carbochain, and this carbon potential is in by being connected in (EO/PO/BO) mPosition 3 carbon of the carbon #1 counting of OH part are to position ω-2 carbon, and end carbon deducts on the interior position of 2 carbon ranges; (4) A of surfactant composition in above-mentioned formula bPart has the average the total number of carbon atoms greater than 12-about 14.5.
EO/PO/BO is the alkoxyl group part that is selected from oxyethyl group, propoxy-, butoxy and their mixture, and m is at least about 1-about 30.The average total number of Ab part carbon atom should be about 14.5 greater than about 12-in branched chain surfactant mixture as defined above, and it is about 14 to be preferably greater than about 12-, most preferably in the scope greater than about 12-about 13.5." always " number that is used for the carbon atom of this paper is meant that promptly the carbonatoms in the molecular skeleton adds at all short chains, i.e. the number of the carbon atom in the side chain at long-chain.
The A of medium chain branched chain surfactant component of the present invention bPart is the branched-chain alkyl part of following formula preferably: Wherein comprising R, R 1And R 2The sum of carbon atom is 10-17 in the branched-chain alkyl part of side chain.R, R 1And R 2Be selected from hydrogen and C respectively 1-C 3Alkyl, preferable methyl, its condition are R, R 1And R 2Be not hydrogen simultaneously.In addition, when z=0, R or R at least 1Not hydrogen.In addition, the integer of w=0-10; The integer of x=0-10; The integer of y=0-10; The integer of z=0-10; And w+x+y+z=3-10.
In another preferred embodiment of claim of the present invention, the A of medium chain branched chain surfactant component bPart is the branched-chain alkyl part that is selected from following formula:
Figure 9881214600112
Wherein a, b, d and e are integers, and a+b is 6-13, and d+e is 4-11; With
When a+b=6, a is the integer of 2-5, and b is the integer of 1-4;
When a+b=7, a is the integer of 2-6, and b is the integer of 1-5;
When a+b=8, a is the integer of 2-7, and b is the integer of 1-6;
When a+b=9, a is the integer of 2-8, and b is the integer of 1-7;
When a+b=10, a is the integer of 2-9, and b is the integer of 1-8;
When a+b=11, a is the integer of 2-10, and b is the integer of 1-9;
When a+b=12, a is the integer of 2-11, and b is the integer of 1-10;
When a+b=13, a is the integer of 2-12, and b is the integer of 1-11;
When d+e=4, d is the integer of 2-3, and e is the integer of 1-2;
When d+e=5, d is the integer of 2-4, and e is the integer of 1-3;
When d+e=6, d is the integer of 2-5, and e is the integer of 1-4;
When d+e=7, d is the integer of 2-6, and e is the integer of 1-5;
When d+e=8, d is the integer of 2-7, and e is the integer of 1-6;
When d+e=9, d is the integer of 2-8, and e is the integer of 1-7;
When d+e=10, d is the integer of 2-9, and e is the integer of 1-8;
When d+e=11, d is the integer of 2-10, and e is the integer of 1-9.Medium chain branched primary alkyl moiety polyoxyalkylene surfactants
Branched chain surfactant composition of the present invention can contain the medium chain branched primary alkyl moiety polyoxyalkylene surfactants of one or more following formulas:
Figure 9881214600121
Surfactant mixture of the present invention contains and comprises the linear primary polyoxyalkylene chain backbone molecule of (promptly the longest straight chain carbochain comprises the alkoxylate carbon atom).These alkyl chain skeletons contain 10-18 carbon atom; In addition, molecule comprises and contains at least about 1, but is no more than the branched primary alkyl moiety part of 3 carbon atoms.In addition, surfactant mixture partly has carbon atom average total number greater than 12-about 14.5 for branched primary alkyl moiety.Therefore, mixture of the present invention contains at least a polyoxyalkylene compounds, it contains the long linear carbochain that is no less than 9 carbon atoms or surpasses 17 carbon atoms, the carbon atom average total number of branched primary alkyl moiety chain is greater than 12-about 14.5, it is about 14 to be preferably greater than about 12-, most preferably greater than about 12-about 13.5.
For example, must to contain 1,2 or 3 chain unit (be R, R to the C14 total carbon atom number uncle polyoxyalkylene surfactants that contains 11 carbon atoms in skeleton 1And/or R 2), thereby the total number of carbon atoms is 14 in the molecule.In this example, need can a propyl group props up chain unit to the total carbon number of C14 or three methyl branch unit satisfy by for example containing.
R, R 1And R 2Be selected from hydrogen and C respectively 1-C 3Alkyl (preferred hydrogen or C 1-C 2Alkyl, more preferably hydrogen or methyl, most preferable), its condition is R, R 1And R 2Not all be hydrogen.In addition, when z=0, R or R at least 1Not hydrogen.
Although for the present invention, the surface active agent composition of above-mentioned molecular formula does not comprise wherein unit R, R 1And R 2All are molecules (being the non-side chain uncle of straight chain polyoxyalkylene) of hydrogen, but should understand the straight chain that composition of the present invention can also contain some amount, non-side chain uncle polyoxyalkylene.In addition, the non-side chain uncle of this straight chain polyoxyalkylene surfactants can be owing to be used to prepare the result's existence with method of required medium chain side chain uncle polyoxyalkylene of the present invention, or in order to prepare detergent composition, the non-side chain uncle of the straight chain of some amount polyoxyalkylene may be mixed in the finished product prescription.
In addition, will be appreciated that equally not oxyalkylated medium chain branched-chain alcoho can contain the composition that contains polyoxyalkylene of the present invention of some amount.This material can be to exist or these alcohol may be to add detergent composition of the present invention with medium chain side chain polyoxyalkylene surfactants of the present invention owing to the incomplete oxyalkylated result of alcohol who is used for preparing polyoxyalkylene surfactants.Yet as mentioned above, surfactant system does not preferably have unreacted alcohol basically.Specifically, the surfactant system that contains straight chain and branched chain surfactant composition should contain and be less than 3% by weight, preferably is less than 1% by weight, most preferably is less than 0.5% unreacted alcohol by weight.
In addition for above-mentioned molecular formula, the integer of w=0-10, the integer of x=0-10, the integer of y=0-10, the integer of z=0-10; Integer with w+x+y+z=2-11.
EO/PO/BO is the alkoxyl group part, is preferably selected from oxyethyl group, propoxy-and mixing oxyethyl group/propoxy-/butoxy radicals, more preferably oxyethyl group, and wherein m is at least about 1, and preferably about 3-is about 30, and more preferably from about 5-is about 20, and most preferably from about 5-about 15.(EO/PO/BO) mPart can be that the distribution of average alkoxylate (for example ethoxylation and/or propoxylation and/or the butoxyization) degree corresponding to m or it can be unitary alkoxylate (for example ethoxylation and/or propoxylation and/or the butoxyization) specific chains separately corresponding to the definite number of m.
Preferred surfactants mixture of the present invention contains by weight at least about 10%, more preferably at least about 20%, also preferably at least about 30%, most preferably at least about the medium chain branched primary alkyl moiety polyoxyalkylene mixture of one or more following formulas of 50%:
Figure 9881214600131
Sum comprising the carbon atom of side chain is 10-16, and the average total number of carbon atom is greater than 12-about 14 in the branched primary alkyl moiety part.R 1And R 2Be selected from hydrogen or C respectively 1-C 3Alkyl, x=0-10, y=0-10, z=0-10 and x+y+z=4-10, its condition is R 1And R 2Not hydrogen simultaneously.EP/PO is the alkoxyl group part that is selected from oxyethyl group, propoxy-and mixing oxyethyl group/propoxy-group, more preferably oxyethyl group.Wherein m is at least about 1, and preferably about 3-is about 30, and more preferably from about 5-is about 20, and most preferably from about 5-about 15.More preferably composition contains at least 5% mixture, it contain one or more wherein z be at least 1 medium chain side chain uncle polyoxyalkylene.
Surfactant mixtures preferably contains at least 5%, preferably at least about 20% R 1And R 2Be respectively the medium chain branched primary alkyl moiety polyoxyalkylene of hydrogen or methyl, its condition is R 1And R 2Be not hydrogen simultaneously, in addition, x+y=5,6 or 7 and z be at least 1.
The preferred detergent composition that for example is used for laundering of textile fabrics of the present invention contains the mixture of the medium chain branched primary alkyl moiety polyoxyalkylene surfactants of the 0.001%-that has an appointment about 99%, and described mixture contains by weight at least about one or more medium chain branched-chain alkyl polyoxyalkylenes of 5% following formula and their mixture: Wherein a, b, d and e are integers, a+b=6-13, d+e=4-11.In addition,
When a+b=6, a is the integer of 2-5, and b is the integer of 1-4;
When a+b=7, a is the integer of 2-6, and b is the integer of 1-5;
When a+b=8, a is the integer of 2-7, and b is the integer of 1-6;
When a+b=9, a is the integer of 2-8, and b is the integer of 1-7;
When a+b=10, a is the integer of 2-9, and b is the integer of 1-8;
When a+b=11, a is the integer of 2-10, and b is the integer of 1-9;
When a+b=12, a is the integer of 2-11, and b is the integer of 1-10;
When a+b=13, a is the integer of 2-12, and b is the integer of 1-11;
When d+e=4, d is the integer of 2-3, and e is the integer of 1-2;
When d+e=5, d is the integer of 2-4, and e is the integer of 1-3;
When d+e=6, d is the integer of 2-5, and e is the integer of 1-4;
When d+e=7, d is the integer of 2-6, and e is the integer of 1-5;
When d+e=8, d is the integer of 2-7, and e is the integer of 1-6;
When d+e=9, d is the integer of 2-8, and e is the integer of 1-7;
When d+e=10, d is the integer of 2-9, and e is the integer of 1-8;
When d+e=11, d is the integer of 2-10, and e is the integer of 1-9.
In addition, the average total number with carbon atom in the branched primary alkyl moiety part of following formula is about 14.5 greater than 12-, and EP/PO is the alkoxyl group part that is selected from oxyethyl group, propoxy-and mixing oxyethyl group/propoxy-group.Wherein m is at least about 1, and preferably about 3-is about 30, and more preferably from about 5-is about 20, and most preferably from about 5-about 15.
In addition, surfactant composition of the present invention can contain the mixture of the branched primary alkyl moiety polyoxyalkylene of following formula:
Figure 9881214600151
Sum comprising the carbon atom of the per molecule of side chain is 10-17, and the average total number of carbon atom is greater than 12-about 14.5 in having the branched primary alkyl moiety part of following formula.R, R 1And R 2Be selected from hydrogen and C respectively 1-C 3Alkyl, its condition are R, R 1And R 2Be not hydrogen simultaneously.W=0-10, x=0-10, y=0-10, z=0-10, and w+x+y+z=3-10.EO/PO is the alkoxyl group part that is preferably selected from oxyethyl group, propoxy-and mixing oxyethyl group/propoxy-group, and wherein m is at least about 1, and preferably about 3-is about 30, and more preferably from about 5-is about 20, and most preferably from about 5-about 15.But work as R 2Be C 1-C 3During alkyl, the ratio of the tensio-active agent of z=1 or above tensio-active agent and z=0 is at least about 1: 1, preferably at least about 1.5: 1, more preferably at least about 3: 1, most preferably at least about 4: 1.Also the preferred surfactants composition is worked as R 2Be C 1-C 3During alkyl, contain and be less than approximately 50%, preferably be less than 40%,, most preferably be less than the about 20% branched primary alkyl moiety polyoxyalkylene of the following formula of z=0 wherein more preferably less than about 25%.
Preferred monomethyl branched primary alkyl moiety ethoxylate is selected from: 3-methyl dodecanol ethoxylate, 4-methyl dodecanol ethoxylate, 5-methyl dodecanol ethoxylate, 6-methyl dodecanol ethoxylate, 7-methyl dodecanol ethoxylate, 8-methyl dodecanol ethoxylate, 9-methyl dodecanol ethoxylate, 10-methyl dodecanol ethoxylate, 3-methyl tridecyl alcohol ethoxylate, 4-methyl tridecyl alcohol ethoxylate, 5-methyl tridecyl alcohol ethoxylate, 6-methyl tridecyl alcohol ethoxylate, 7-methyl tridecyl alcohol ethoxylate, 8-methyl tridecyl alcohol ethoxylate, 9-methyl tridecyl alcohol ethoxylate, 10-methyl tridecyl alcohol ethoxylate, the mixture of 11-methyl tridecyl alcohol ethoxylate and they is wherein with the average degree of ethoxylation ethoxylated compound of about 5-about 15.
Preferred dimethyl branched primary alkyl moiety ethoxylate is selected from: 2,3-dimethyl hendecanol ethoxylate, 2,4-dimethyl hendecanol ethoxylate, 2,5-dimethyl hendecanol ethoxylate, 2,6-dimethyl hendecanol ethoxylate, 2,7-dimethyl hendecanol ethoxylate, 2,8-dimethyl hendecanol ethoxylate, 2,9-dimethyl hendecanol ethoxylate, 2,3-dimethyl dodecanol ethoxylate, 2,4-dimethyl dodecanol ethoxylate, 2,5-dimethyl dodecanol ethoxylate, 2,6-dimethyl dodecanol ethoxylate, 2,7-dimethyl dodecanol ethoxylate, 2,8-dimethyl dodecanol ethoxylate, 2,9-dimethyl dodecanol ethoxylate, 2, the mixture of 10-dimethyl dodecanol ethoxylate and they is wherein with the average degree of ethoxylation ethoxylated compound of about 1-about 15.
The preparation of medium chain branched chain surfactant
The general method of following reaction scheme explanation preparation medium chain branched-chain primary alcohol, described alcohol is used for alkoxylate to prepare medium chain branched primary alkyl moiety tensio-active agent of the present invention.
Alkyl halide is converted into Grignard reagent, Grignard reagent and halogenated ketone reaction.After conventional acidic hydrolysis, ethanoylization and heating remove acetate, produce intermediate alkene (not shown in scheme), it is with any conventional hydrogenation catalyst, for example Pd/C hydrogenation.
This approach is favourable than other, at the early stage introducing side chain of reaction sequence, is the 5-methyl branch in reaction formula wherein.
Described in scheme, produce pure product by the forming of alkyl halide that the first time, step of hydrogenation produced, its available standards technology alkoxylate is to obtain final branched primary alkyl moiety tensio-active agent.Exist adaptability to stretch an additional carbon atom with outside at (chain) that obtain by independent formation process.This stretching, extension can be for example by finishing with reacting ethylene oxide.Referring to " Grignard reaction of nonmetallic substance ", M.S.Kharasch and O.Reinmuth, Prentice-Hall, N.Y., 1954; J.Org.Chem., J.Cason and W.R.Winans, volume 15 (1950), 139-147 page or leaf; J.Org.Chem., J.Cason etc., volume 13 (1948), 239-248 page or leaf, J.Org.Chem., J.Cason etc., volume 14 (1949), 147-154 page or leaf and J.Org.Chem., J.Cason etc., volume 15 (1950), the 135-138 page or leaf is all classified this paper reference as.
In the variation of aforesaid method, can use other halogenated ketone or Grignard reagent.PBr by preparation or the alcohol that obtains of ethoxylation 3Halogenation can be used for finishing chain-unfolding repeatedly.
Preferred medium chain branched primary alkyl moiety polyoxyethylene of the present invention can easily prepare as follows:
Figure 9881214600171
Common bromhydrin and triphenylphosphine reaction form the Wittig adducts with the sodium hydride reaction subsequently suitably in dimethyl sulfoxide (DMSO)/tetrahydrofuran (THF).The alcoholate of unsaturated methyl branch in Wittig adducts and the reaction of α methyl ketone form.Hydrogenation alkoxylate and/or sulfation subsequently obtains required medium chain branched primary alkyl moiety tensio-active agent.Though the Wittig method can not stretch hydrocarbon chain as the Ge Liya method, Wittig provides higher yield usually.Referring to Agricultural andBiological Chemistry, M.Horiike etc., 42 volume (1978) 1963-1965 pages or leaves are classified this paper reference as.
Any other kind synthetic method of the present invention can be used for preparing the branched primary alkyl moiety tensio-active agent.Except synthetic in the presence of the conventional homologue or preparation, medium chain branched primary alkyl moiety tensio-active agent can for example be to produce any material that forms in the commercial run of 2-alkyl branches by carbonylation process.
In some preferred embodiment of surfactant mixture of the present invention, especially the material that obtains by the fossil fuel sources of business method, described surfactant mixture contains at least a medium chain branched primary alkyl moiety tensio-active agent, preferably at least 2 kinds, more preferably at least 5 kinds, most preferably at least 8 kinds.Especially suitable be used to prepare some surfactant mixture of the present invention be " oxo " reaction, wherein before alkoxylate, branched-chain alkene carries out isoversion and carbonylation.The preferred method that obtains this mixture adopts mineral fuel as starting raw material.Preferable methods adopts the Oxo reaction of the alkene (α or internal olefin) with limited amount side chain.Suitable alkene can be by the dimerization of straight chain alpha or internal olefin, low molecule normal olefine the skeleton of alkene of oligomerisation, detergent range of control reset, dehydrogenation/skeleton of the paraffinic hydrocarbons of detergent range resets or the Fischer-Tropsch prepared in reaction.These reactions are controlled to usually:
1) in required detergent range, obtain the alkene (allowing simultaneously increases carbon atom in subsequently Oxo reaction) of vast scale,
2) produce limited amount side chain, preferred medium chain,
3) produce C 1-C 3Side chain, more preferably ethyl, most preferable,
4) limit or avoid promptly avoiding forming quaternary carbon atom together with the dialkyl group side chain.
Suitable alkene can the Oxo reaction obtain primary alconol by corresponding aldehyde directly or indirectly.When using internal olefin, use the Oxo catalyzer usually, it mainly forms alhpa olefin by earlier pre-isomerization internal olefin.Can carry out separately and catalysis (being non-Oxo) internal olefin is the isomerization of alhpa olefin, this is optionally.On the other hand, directly obtain alhpa olefin (for example adopting the high pressure Fischer-Tropsch alkene of detergent range) if alkene forms step itself, it is possible then to use non-isomerization Oxo catalyzer to be not only, and is preferred.
Use tridecylene, above-mentioned method obtains preferred 5-methyl-tridecyl alcohol, therefore obtains tensio-active agent with high yield, be better than not too preferred 2,4-dimethyl dodecyl material.This mixture is desirable within the scope of the invention, and wherein each product contains 14 carbon atoms altogether, contains the linear alkyl chain of at least 12 carbon atoms.
The average total carbon atom number of branched primary alkyl moiety tensio-active agent of the present invention can be by the hydroxyl value of precursor fatty alcohol mixture or by calculating by the hydroxyl value that extracts the alcohol that reclaims after the hydrolysis of alcohol sulfate mixture according to usual method, described method is for example at " Bailey ' s Industrial Oiland Fat Preducts ", volume 2, the 4th edition, Daniel Swern edits, the 440-441 page or leaf.
The liquid phase that contains tensio-active agent
The non-water liquid phase that contains tensio-active agent of the present invention accounts for about 49%-99.95% by detergent composition weight usually.This liquid phase is more preferably surfactant structureization, accounts for about 52%-98.9% of composition by weight.This non-water liquid phase most preferably accounts for about 55%-70% of composition by weight.This liquid phase that contains tensio-active agent have an appointment usually 0.6-1.4g/cc, the more preferably from about density of 0.9-1.3g/cc.The liquid phase of detergent composition of the present invention is preferably formed by one or more non-water organic thinners, has wherein mixed the surfactant structure agent, and it preferably contains the powder of the anion surfactant of specific type.
(A) non-water organic thinner
The main ingredient of the liquid phase of detergent composition of the present invention contains one or more non-water organic thinners.It can be surface-active being used for non-water organic thinner of the present invention, promptly is surfactant liquids, or non-water, nonsurfactant liquid, is called non-aqueous solvent herein.Be used for nonsurfactant, on-aqueous liquid part that term of the present invention " solvent " refers to composition.And the main and/or optional ingredient in some present composition in fact can be dissolved in the liquid phase that contains " solvent ", and the particulate matter that other component will contain as being dispersed in the liquid phase of " solvent " exists.Therefore term " solvent " and not meaning that requires vehicle substance can dissolve all to add wherein all detergent composition components.
The on-aqueous liquid thinner composition will contain about 50%-100%, more preferably from about 50%-80%, the most preferably from about structurized liquid phase that contains tensio-active agent of 55%-75%.The liquid phase of composition of the present invention, promptly the on-aqueous liquid thinner composition preferably contains on-aqueous liquid tensio-active agent and nonsurfactant non-aqueous solvent simultaneously.
ⅰ) non-water surface promoting agent liquid
The adequate types of non-water surface promoting agent liquid that can be used for forming the liquid phase of the present composition comprises alcohol alcoxylates, oxyethane (EO)-propylene oxide (PO) segmented copolymer, polyhydroxy fatty acid amide, alkyl polysaccharide etc.This liquid surfactant normally has the material that HLB is 10-16.Surfactant liquids most preferably is the alcohol alkoxylate nonionogenic tenside.
Alcohol alkoxylate is the material corresponding to following general formula:
R 1(C mH 2mO) nOH is R wherein 1Be C 8-C 16Alkyl, m are that 2-4 and n are about 2-12.Preferred R 1Be alkyl, it can be a primary and secondary, contains 9-15 the carbon atom of having an appointment, more preferably from about 10-14 carbon atom.The preferred alkoxylated Fatty Alcohol(C12-C14 and C12-C18) is the ethoxylation material, and its per molecule contains 2-12 the ethylene oxide moiety of having an appointment, and more preferably per molecule contains the 3-10 ethylene oxide moiety of having an appointment.
The alkoxy fatty alcohols component that is used for liquid phase has the hydrophile-lipophile balance value (HLB) of about 3-17 usually, and the more preferably about 6-15 of the HLB of this material most preferably is about 8-15.
Be used for or comprise the material alcohol preparation and that contain 7 moles of ethylene oxide of having an appointment by 12-15 carbon atom as the example of the fatty alcohol alkoxy compound of the non-water liquid phase of composition of the present invention.This material is sold with trade(brand)name Neodol 25-7 and Neodol 23-6.5 by shell chemical company commercial.Other useful Neodol comprises Neodol 1-5, and alkyl chain has the ethoxylized fatty alcohol of average 11 carbon atoms and about 5 moles of ethylene oxide; Neodol 23-9 contains the ethoxylation uncle C of 9 moles of ethylene oxide of having an appointment 12-C 13Pure and mild Neodol 91-10 contains the ethoxylation C of 10 moles of ethylene oxide of having an appointment 9-C 11Primary alconol.Such alcohol ethoxylate is also sold with trade(brand)name Dobanol by shell chemical company.Dobanol 91-5 is the ethoxylation C with average 5 moles of ethylene oxide 9-C 11Fatty Alcohol(C12-C14 and C12-C18), Dobanol 25-7 are the oxyethyl group C that every mole of Fatty Alcohol(C12-C14 and C12-C18) contains average 7 moles of ethylene oxide 12-C 15Fatty Alcohol(C12-C14 and C12-C18).
Other example of suitable ethoxylated alcohol comprises Tergitol 15-S-7 and Tergitol15-S-9, and they all are the linear secondary ethoxylates by Union Carbide Corp's commercial distribution.The former is C 11-C 15The mixed ethoxylated product of linear secondary and 7 moles of ethylene oxide, the latter is similar product, but reacts with 9 moles of ethylene oxide.
Other type that is used for the alcohol ethoxylate of the present composition is the high molecular nonionogenic tenside, Neodol 45-11 for example, it is the similar oxirane condensation product of high fatty alcohol, contains the high fatty alcohol of 14-15 carbon atom, and every mole oxyethane number is about 11.This product is also sold by shell chemical company commerce.
If the alcohol alkoxylate nonionogenic tenside is as the non-water liquid phase of part of detergent composition of the present invention, about 1%-60% content that it will account for composition structurizing liquid phase exists, and the alcohol alkoxylate component more preferably accounts for about 5%-40% of structurizing liquid phase.Alcohol alkoxylate most preferably accounts for about 5%-35% of detergent composition structurizing liquid phase.In liquid phase, use alcohol alkoxylate to be equivalent in total composition the alcohol alkoxylates substrate concentration for by the about 1%-60% of composition weight meter, more preferably from about 2%-40%, most preferably from about 5%-25% with this concentration.
The non-water surface promoting agent liquid that can be used for another type of the present invention is oxyethane (EO)-propylene oxide (PO) block polymer, and such material is known nonionogenic tenside, and it is sold with trade(brand)name Pluronic.These materials form by the end that ethylene oxide block is added the polypropylene glycol chain, the surfactivity of the block polymer that obtains with adjusting.Such EO-PO block polymer nonionogenic tenside is at Davidson and Milwidsky; Synthetic detergent, the 7th edition; Describe in Langman Scientific and Technical (1987) 34-36 pages or leaves and 189-191 page or leaf and US2674619 and 2677700.All these publications are classified this paper reference as.The nonionogenic tenside of these Pluronic types is considered to have the effect of effective suspension agent of the particulate matter in the liquid phase that is dispersed in detergent composition of the present invention.
Another the possible type that is used for the non-water surface promoting agent liquid of the present composition comprises polyhydroxy fatty acid amide surfactant.If exist, polyhydroxy fatty acid amide surfactant preferably exists with the concentration of about 0.1-8%.The material of this class nonionogenic tenside is the material with following formula:
Figure 9881214600201
Wherein R is C 9-17Alkyl or alkenyl, p are 1-6, and Z is the glycosyl (glyeitly) that is obtained by reducing sugar or its alkoxy derivative.This material comprises C 12-C 18The N-methyl glucose amide.Example is N-methyl N-1-deoxy-glucose base coconut monoethanolamide and N-methyl N-1-deoxy-glucose base oil acid amides.The method for preparing polyhydroxy fatty acid amide is known, can find in the US2703798 of the US2965576 of for example Wilson and Schwartz, and they classify this paper reference as.The preparation method of material itself and they also describes in detail in the US5174937 of the Honsa of promulgation on December 26th, 1992, and this patent is also classified this paper reference as.
The quantity of total liquid surfactant will be by type and the quantity and the required composition character decision of other composition component in the structurized non-water liquid phase of preferred surfactant of the present invention.The liquids in general tensio-active agent can account for about 35%-70% of the non-water liquid phase of the present composition, and liquid surfactant more preferably accounts for about 50%-65% of non-water structure liquid phase.This is equivalent in total composition the on-aqueous liquid surfactant concentration for by the about 15%-70% of composition weight meter, more preferably from about 20%-50% by weight.
ⅱ) nonsurfactant non-aqueous organic solvent
The liquid phase of detergent composition of the present invention also can contain one or more nonsurfactants, non-water organic substance.The preferably low polarity person of this class nonsurfactant, on-aqueous liquid.Be used for the present invention, " low polarity " liquid is meant one of preferred type of the particulate matter that is used for the present composition, i.e. the dissolving trend junior of peroxygen bleach, Sodium peroxoborate or SPC-D.Therefore, should not use the solvent of relative polarity, for example ethanol.The low polar solvent that is used for the suitable type of non-aqueous liquid detergent compositions of the present invention comprises non-adjacent C 4-C 8Aklylene glycol, alkylene glycol mono lower alkyl ether, low molecular poly, lower molecular weight methyl esters and acid amides or the like.
The non-water low polar solvent that is used for the preferred type of the present composition comprises non-ortho position C 4-C 8Side chain or straight-chain alkyl-sub-glycol.Such material comprises hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexylene glycol, 1,3 butylene glycol and 1,4-butyleneglycol.Hexylene glycol is most preferred.
That the non-water low polar solvent that is used for another preferred type of the present invention contains is single-, two-, three-or four-C 2-C 3Alkylene glycol mono C 2-C 6Alkyl oxide.The specific examples of this compound comprises Diethylene Glycol single-butyl ether, TEG single-butyl ether, dihydroxypropane single-ethyl ether and dipropylene glycol single-butyl ether.Diethylene Glycol single-butyl ether, dipropylene glycol single-butyl ether and butoxy-propoxy--propyl alcohol (BPP) are especially preferred.This compounds is sold with trade(brand)name Dowanol, Carbitol and Cellosolve commercial.
The low polar organic solvent of non-water that is used for another preferred type of the present invention is low molecular poly (PEG), and this material has the molecular weight at least about 150, and molecular weight is most preferred for the PEG of about 200-600.
The nonpolar non-aqueous solvent of another preferred type comprises the lower molecular weight methyl esters.This material has general formula: R 1-C (O)-OCH 3, R wherein 1Be 1-about 18.The example of suitable lower molecular weight methyl esters comprises methyl acetate, methyl propionate, methyl caprylate and methyl laurate.
Certainly, the low polarity nonsurfactant organic solvent of employed non-water should with other composition component that is used for liquid detergent composition of the present invention, for example SYNTHETIC OPTICAL WHITNER and/or activator are compatible and be nonreactive activity.This solvent composition uses in the amount by the about 1%-70% of liquid phase weight usually.The low polarity nonsurfactant solvent of non-water more preferably accounts for about 10%-60% by structurizing liquid phase weight, most preferably by the about 20%-50% of composition structurizing liquid phase weight.In liquid phase, use nonsurfactant solvent to be equivalent in total composition the nonsurfactant solvent strength for by the about 1%-50% of composition weight meter, more preferably about by weight 5%-40%, most preferably about by weight 10%-30% with this concentration.
ⅲ) tensio-active agent and nonsurfactant solvent mixes
Adopt at the same time in the system of non-water surface promoting agent liquid and non-water nonsurfactant-solvent, tensio-active agent and nonsurfactant liquid, for example alcohol alkoxylate and the low polar solvent ratio in structurized, as to contain tensio-active agent liquid phase can be used for changing the rheological of the detergent composition of final formation.The weight ratio of surfactant liquids and nonsurfactant organic solvent is generally about 50: 1-1: 50, and this ratio more preferably about 3: 1-1: 3, most preferably from about 2: 1-1: 2.
(B) surfactant structure agent
The non-water liquid phase of detergent composition of the present invention usually, but is not essential by mixing the preparation of above-mentioned non-water organic liquid diluent and tensio-active agent, and the option table surface-active agent adds structure with the non-water liquid phase of giving detergent composition of the present invention.Structured surfactant can be negatively charged ion, nonionic, positively charged ion and/or amphoteric type.
The preferred construction tensio-active agent is the anion surfactant material, for example alkyl-sulphate, the polyalkoxylated vitriol of alkyl and linear alkylbenzene sulfonate.The another kind of common type that optionally adds in the detergent composition of the present invention as the anion surfactant of structural agent comprises the carboxylic acid type anion surfactant.The carboxylic acid type anion surfactant comprises C 10-C 18Alkyl alkoxy carboxylate salt (especially EO1-5 ethoxy carboxylate) and C 10-C 18Sarcosinate, especially oleoyl sarcosinate.The anion surfactant material that can be used as other common type of structural agent comprises other sulfonic acid salinization anion surfactant material, for example C 8-C 18Alkane sulfonate and C 8-C 18Alkene sulfonate.The structurizing anion surfactant will account for about 1%-30% of composition weight usually.
As mentioned above, the preferred type of structurizing anion surfactant comprises uncle or secondary alkyl sulfate anion surfactant, and this tensio-active agent is by the senior C of sulfation 8-C 20The Fatty Alcohol(C12-C14 and C12-C18) preparation.
Conventional primary alkyl sulphates tensio-active agent has following general formula:
ROSO 3 -M +R straight chain C normally wherein 8-C 20Alkyl, it can be a straight or branched, M is a water-soluble cationic.R is C preferably 10-C 14Alkyl, M are basic metal.R most preferably is about C 12, M is a sodium.
Conventional secondary alkyl sulfate also can be used as the structurizing anion surfactant of the liquid phase of the present composition.Conventional secondary alkyl sulfate surfactant is those materials with sulfate groups of the irregular distribution of alkyl " skeleton " along molecule.These materials can be used following structrual description:
CH 3(CH 2) n(CHOSO 3 -M +) (CH 2) mCH 3Wherein m and n are 2 or greater than 2 integer, and it is about 9 to 15 that the m+n summation is generally, and M is a water-soluble cationic.
If use, alkyl-sulphate will account for about 1%-30% of composition weight usually, more preferably account for about 5%-25% of composition weight.The non-aqueous liquid detergent compositions that contains alkyl-sulphate, peroxygen bleach and bleach activator is described in detail in the WO 96/10073 of disclosed Kong-Chan on the 4th etc. April in 1996, and this application is classified this paper reference as.
The anion surfactant material that optionally adds in the non-water washing composition of the present invention as the another kind of preferred type of structural agent comprises the polyalkoxylated vitriol of alkyl.The polyalkoxylated vitriol of alkyl also can be described as alkoxylated alkyl sulphate or sulfated alkyl ether.This material is the material corresponding to following formula:
R 2-O-(C mH 2mO) n-SO 3M is R wherein 2Be C 10-C 22Alkyl, m are 2-4, and n is about 1-15, and M is a salt-forming cation.Preferred R 2Be C 12-C 18Alkyl, m are 2, and n is about 1-10, and M is sodium, potassium, ammonium, alkylammonium or alkanol ammonium.R most preferably 2Be C 12-C 16, m is 2, and n is about 1-6, and M is a sodium.When being used for the present composition, since incompatible with peroxygen bleach, preferably avoid using ammonium, alkylammonium and alkanol ammonium counter ion.
If use, about 1%-30% that the polyalkoxylated vitriol of alkyl also can account for composition weight usually more preferably presses the about 5%-25% of composition weight meter.Contain with the non-aqueous liquid detergent compositions of the polyalkoxylated vitriol of polyhydroxy fatty acid amide blended alkyl and describe in detail in the PCT/US96/04223 of Boutique etc., this application is classified this paper reference as.
The anion surfactant that is used as the most preferred type of structural agent in composition of the present invention comprises linear alkylbenzene sulfonate (LAS) tensio-active agent.This LAS especially can be formulated in the powder of the anion surfactant that contains specific type, and it is particularly useful for adding in the non-aqueous liquid detergent compositions of the present invention.This powder contains two kinds of different phases.A kind of being not dissolved in mutually is used for non-water organic liquid diluent of the present invention, and another kind of phased soln is in non-water organic liquid.Just this preferably contain tensio-active agent powder do not dissolve phase, it can be dispersed in the non-water liquid phase of preferred composition of the present invention, and form the little micellar network of accumulative, just make the finished product stably other solia particle material to be suspended in the composition.
This powder that preferably contains anion surfactant forms by common dry aqueous slurry, and soup compound mainly contains a) one or more C 10-16An alkali metal salt of linear alkyl benzene sulphonic acid; And b) one or more nonsurfactant diluting salts.This soup compound drying is a solid matter, and it is powder type normally, and contains dissolving simultaneously with mutually undissolved.
The linear alkylbenzene sulfonate (LAS) that is used to form the powder that preferably contains anion surfactant is a known substances, and this material and their preparation method describe in for example US2220099 and 2477383, classify this paper reference as.Especially preferred linear alkylbenzene sulphonic acid and potassium, wherein the average carbon atom number in the alkyl is about 11-14, sodium C 11-14, C for example 12, LAS is especially preferred.The alkyl benzene sulphonate (ABS) salt anionic surfactant is usually in by the about 20-70% of soup compound weight, and more preferably the amount by the about 20%-60% of soup compound weight is used to form in the soup compound of powder.
The soup compound that forms powder also contains nonsurfactant, organic or inorganic salt component, and it and the common drying of LAS are to form the powder that biphase contains anion surfactant.This salt can be any in sodium, potassium or the magnesium salts of known halogenide, vitriol, Citrate trianion, carbonate, borate, succinate, sulfosuccinate etc.Sodium sulfate is to be used for preferred nonsurfactant thinner salt of the present invention, and it is the by product in the LAS production process normally.Play the salt of solubilizing agent effect, for example sodium sulfosuccinate also can comprise.Nonsurfactant salt usually with LAS in by the about 1%-50% of soup compound weight, more preferably be used for aqueous slurry by the quantity of the about 5%-40% of soup compound weight.The salt that plays the solubilizing agent effect can preferably account at the most 3% of soup compound weight.
But the aqueous slurry drying that contains above-mentioned LAS and thinner salt component contains the powder of anion surfactant with formation, preferably adds in the non-diluent water with the structurized liquid phase in the preparation present composition.Can adopt the dry technology of any routine, for example the combination of spraying drying, drum dried etc. or dry technology.Dry residual moisture content until the solid matter that forms be should carry out and about 0.5%-4%, more preferably from about 1%-3% by weight are.
By two kinds of different phases of the powder constituent that contains anion surfactant that drying operation produces, one of them is dissolved in and is used for inorganic liquid thinner of the present invention, and another is not dissolved in the thinner.The undissolved about 10%-45% that accounts for powder weight mutually usually in containing the powder of anion surfactant more preferably accounts for about 15%-35% of powder weight.
The powder that contains anion surfactant that dry back produces can contain by the about 45%-94% of powder weight, the more preferably from about alkylbenzene sulfonate of 60%-94%.This concentration is enough to the about 0.5%-60% of total detergent composition weight by final preparation, the more preferably from about alkylbenzene sulfonate of 15%-60% usually.The powder itself that contains anion surfactant can account for about 0.45%-45% of the total composition weight of final preparation.After drying, the powder that contains anion surfactant also will contain usually by the about 2%-50% of powder weight, more preferably from about the nonsurfactant salt of 2%-25%.
After being dried to required content, blended LAS/ salt material can be converted into thin slice or powder type by any suitable grinding or crushing process.At this moment, this material mixes to form the structurized liquid phase of composition of the present invention with non-aqueous organic solvent usually, and this particles of powder size will be the 0.1-2000 micron, more preferably from about the 0.1-1000 micron.
The liquid phase that contains surfactant structureization of preferred detergent composition of the present invention can be by mixing above-mentioned non-water organic thinner and the above-mentioned powdered preparation that contains anion surfactant.This mixing process form contain surfactant structureization liquid phase.Prepare this preferred construction liquid phase component mixture condition hereinafter " preparation of compositions and purposes " part describe in detail.As mentioned above, contain the formation of the liquid phase of surfactant structureization can be in preferred detergent composition of the present invention stable suspersion the fine-particle solid material of color spot decorations and other function is arranged.
Be used for other suitable tensio-active agent of the present invention and comprise nonionogenic tenside, especially the polyhydroxy fatty acid amide of following formula: Wherein R is C 9-17Alkyl or alkenyl, R 1Be methyl, Z is the glycosyl that is obtained by reducing sugar or its alkoxy derivative.Example is N-methyl N-1-deoxy-glucose base coconut monoethanolamide and N-methyl N-1-deoxy-glucose base oil acid amides.The method for preparing polyhydroxy fatty acid amide is known, can find in the US2703798 of the US2965576 of for example Wilson and Schwartz, and they classify this paper reference as.The preparation method of material itself and they also describes in detail in the US5174937 of the Honsa of promulgation on December 26th, 1992, and this patent is also classified this paper reference as.
The preferred surfactant that is used for said detergent composition of the present invention is the amido tensio-active agent that comprises following formula:
R 1-X-(CH 2) n-N (R 3) (R 4) R wherein 1Be C 6-C 12Alkyl; N is that about 2-is about 4, and X is that the abutment or the X that are selected from NH, CONH, COO or O are non-existent; And R 3And R 4Be selected from H, C respectively 1-C 4Alkyl or (CH 2-CH 2-O (R 5)), R wherein 5Be H or methyl.Especially preferred amido tensio-active agent comprises as follows:
R 1-(CH 2) 2-NH 2
R 1-O-(CH 2) 3-NH 2
R 1-C(O)-NH-(CH 2) 3-N(CH 3) 2
R 1-N[CH 2-CH (OH)-R 5] 2R wherein 1Be C 6-C 12Alkyl and R 5Be H or CH 3The especially preferred amine that is used for the tensio-active agent of above-mentioned definition comprises and is selected from octylame, hexylamine, decyl amine, amino dodecane, C 8-C 12Two (hydroxyethyl) amine, C 8-C 12Two (hydroxyl sec.-propyl) amine and C 8-C 12The material of amido propyl-dimethyl amine and their mixture.
In a more preferred embodiment, the amido tensio-active agent is described by following formula:
R 1-C (O)-NH-(CH 2) 3-N (CH 3) 2R wherein 1Be C 8-C 12Alkyl.
The solia particle material
Nonaqueous detergent composition of the present invention preferably contains about by weight 0.01%-50%, 0.1%-30% solid phase particulate matter more preferably from about, and its disperses and is suspended in the liquid phase.Usually this particulate matter has about 0.1-1500 micron, the size of 0.1-900 micron more preferably from about, most preferably will the have an appointment size of 5-200 micron of this material.
Be used for the detergent composition component that particulate matter of the present invention can contain one or more types, it is a particulate form, is not dissolved in the non-water liquid phase of composition basically, and the type of spendable particulate matter is in following detailed description:
(A) peroxygen bleach and optionally bleach activator
The particulate matter that is used for the most preferred type of detergent composition of the present invention contains the peroxygen bleach particulate.This peroxygen bleach can be an organic or inorganic in nature.The inorganic peroxy SYNTHETIC OPTICAL WHITNER is used in combination with bleach activator usually.
Useful organic peroxy SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and their salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-nonyl amino-4-oxygen Perbutyric Acid and diperoxy dodecanedioic acid.This SYNTHETIC OPTICAL WHITNER is at the US4483781 of the Hartman of promulgation on November 20th, 1984; Open among the US4412934 of the Chung of EP-A-133354 that on February 20th, 1985 was disclosed Banks and promulgation on November 1 nineteen eighty-three etc.Preferred SYNTHETIC OPTICAL WHITNER comprises that also 4-nonyl amino-4-oxygen of describing among the US4634551 as the Burns of on January 6th, 1987 promulgation etc. crosses oxy hexanoic acid (NAPAA).
The inorganic peroxy SYNTHETIC OPTICAL WHITNER also can particulate form be used for detergent composition of the present invention.In fact inorganic SYNTHETIC OPTICAL WHITNER is preferred.This inorganic peroxy compounds comprises alkali metal perborate and percarbonate, most preferably percarbonate.For example can use Sodium peroxoborate (single-or tetrahydrate).Suitable inorganic SYNTHETIC OPTICAL WHITNER also can comprise yellow soda ash or potassium peroxyhydrate and suitable " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example OXONE that produces by E.I.Du Pont Company).The inorganic peroxy SYNTHETIC OPTICAL WHITNER scribbles silicate, borate, vitriol or water soluble surfactant active usually.For example the percarbonate particulate of Tu Fuing is by different commercial source, and for example FMC, Solvay Interox, Tokai Denka and Degussa obtain.
The inorganic peroxy SYNTHETIC OPTICAL WHITNER, promptly perborate, percarbonate etc. preferably combine with bleach activator, and it causes producing on the spot the peroxy acid corresponding to bleach activator in the aqueous solution (promptly being used for washing/bleaching process at composition of the present invention).The US4915854 of the Mao that the various limiting examples of promoting agent were issued in April 10 nineteen ninety etc.; Open among the US4412934 of the Chung of promulgation on November 1 nineteen eighty-three etc.Be typically nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) promoting agent, also can use their mixture, referring to SYNTHETIC OPTICAL WHITNER that is used for other type of the present invention and the promoting agent among the US4634551 mentioned above.
Other useful amido deutero-bleach activator has following formula:
R 1N (R 5) C (O) R 2C (O) L or R 1C (O) N (R 5) R 2C (O) L is R wherein 1Be the alkyl that contains about 12 carbon atoms of the 6-that has an appointment, R 2Be the alkylidene group that contains about 6 carbon atoms of 1-, R 6Be H or alkyl, aryl or the alkaryl that contains about 10 carbon atoms of the 1-that has an appointment, L is any suitable leavings group.Leavings group be by the nucleophillic attack of crossing hydrolysis negatively charged ion bleach activator from bleach activator replaced any group, leavings group is phenolsulfonate preferably.
The preferred embodiment of the bleach activator of following formula is included in (6-decoyl amino-caproyl) oxygen benzene sulfonate, (6-nonanoyl amino-caproyl) oxygen benzene sulfonate and (6-caprinoyl amino-caproyl) oxygen benzene sulfonate of describing among the above-mentioned US4634551 and their mixture.This mixture is expressed as (6-C in the present invention 6-C 8Alkyl amido-caproyl) phenolsulfonate.
Another kind of useful bleach activator is included in the benzo-oxazine derivative of describing among the US4966723 of the Hodge of October 30 nineteen ninety promulgation etc., classifies this paper reference as.Preferred benzoxazine type promoting agent is:
Figure 9881214600281
Another kind of useful bleach activator comprises the acyl lactam promoting agent, especially the acyl caprolactam of following formula and acyl group Valerolactim: R wherein 6Be H or alkyl, aryl, alkoxy aryl or the alkaryl that contains about 12 carbon atoms of 1-.Preferred lactan promoting agent comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethylammonium hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, 3; 5,5-three caproyl Valerolactims and their mixture.Referring to for example US4545784 of the Sanderson of promulgation on October 8th, 1985, classify this paper reference as.It discloses the acyl caprolactam that is absorbed in the Sodium peroxoborate, comprises benzoyl caprolactam.
If peroxygen bleach is as all or part of particulate matter, they account for about 1%-30% of composition weight usually.Peroxygen bleach more preferably accounts for about 1%-20% of composition weight.Peroxygen bleach most preferably exists with the content by the about 5%-20% of composition weight meter.If use, bleach activator can account for about 0.5%-20% of composition weight, more preferably from about 3%-10%.Usually use promoting agent, make that the mol ratio of SYNTHETIC OPTICAL WHITNER and promoting agent is about 1: 1-10: 1, more preferably from about 1.5: 1-5: 1.
In addition, we find that when bleach activator and some acid, when for example citric acid was reunited, it was more chemically stable.
(B) organic washing-assisting detergent material
Can be suspended in particulate matter that in the non-aqueous liquid detergent compositions of the present invention another may type and include machine washing and washs the agent aid material, the calcium that it runs in composition laundry/bleaching application of the present invention as antagonism or other ion, the water hardness.The example of this material comprises alkali metal citrate, succinate, malonate, lipid acid, carboxymethyl succinate, carboxylate salt, multi-carboxylate and poly-ethanoyl carboxylate salt.Specific examples comprises sodium, potassium and the lithium salts of oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.Other example of organic phosphonate type sequestrant comprises material and the alkane hydroxy phosphonate of being sold with the Dequest trade(brand)name by Monsanto Company.Citrate trianion is preferred.
Other suitable organic washing-assisting detergent comprises known polymkeric substance and multipolymer with washing assistant character.For example this material comprises suitable polyacrylic acid, polymaleic acid and poly propenoic acid maleic acid and their salt, and for example by the material of BASF with trade(brand)name Sokalan sale, it has the molecular weight of about 5000-100000.
The organic washing-assisting detergent of another adequate types comprises the water-soluble salt of higher fatty acid, i.e. " soap ".It comprises alkali metal soap, for example contains 8-Yue 24 carbon atoms of having an appointment, sodium, potassium, ammonium and the alkanol ammonium salts of the higher fatty acid of about 18 carbon atoms of preferably about 12-.Soap can be by the direct saponification or the preparation of the neutralization by free fatty acids of fat and oil.What be particularly useful is the sodium and the sylvite of the fatty acid mixt that obtained by Oleum Cocois and Tallow, beef, sodium or potassium animal and Oleum Cocois soap.
If as all or part of particulate matter, undissolved organic detergent auxiliary agent can account for about 2%-20% of composition weight usually, this auxiliary material more preferably accounts for about 4%-10% of composition weight.
(C) inorganic alkaline source
Can be suspended in particulate matter that in the non-aqueous liquid detergent compositions of the present invention another may type comprises and is used to make the aqueous cleaning solution that is formed by said composition to be alkaline material usually.This material can also also maybe cannot also be used as detergent builder, and the water hardness of promptly contending with is to the material of the disadvantageous effect of scourability.
The example of suitable alkaline source comprises water soluble alkali metal carbonate, supercarbonate, borate, silicate and metasilicate.Although because ecological consideration is not preferred, water-soluble phosphate also can be used as alkaline source.It comprises alkali metal pyrophosphate, orthophosphoric acid salt, poly-phosphate and phosphonate.In these alkaline sources, alkaline carbonate, for example yellow soda ash is most preferred.
Alkaline source, if but exist with the salt of hydration, also can in non-aqueous liquid detergent compositions, be used as siccative.Exist simultaneously still the alkaline source of siccative can be in composition component, for example the chemically stable aspect to the peroxygen bleach of water sensitive inactivation provides effect.
If as all or part of particulate matter component, alkaline source accounts for about 1%-25% of present composition weight usually.Alkaline source more preferably accounts for about 2%-15% of composition weight.This material although be water miscible, is not dissolved in the nonaqueous detergent composition of the present invention usually.Therefore, this material will be scattered in the non-water liquid phase with independent particle form usually.
(D) the color spot decorations are arranged
Non-aqueous liquid detergent compositions of the present invention also contains about 0.05%-2% of composition, and most preferably the color spot that has of 0.1%-1% is adornd.This has the color spot decorations itself is the mixture of the carrier substance of conventional dyestuff or pigment material and some type that gives spot decorations special characteristics.Being used for " coloured " of the present invention spot decorations is coloured materials, can be observed different with the color of disperseing liquid detergent composition wherein.
The coloring matter that can be used for being formed with the color spot decorations can comprise any known and be used for the conventional dyestuff and the pigment of household detergent product, this material can comprise, for example Ultramarine Blue dyestuff, Acid 80 Blue dyestuffs, Red HP Liquitint, Blue Liquitint etc.
Dyestuff or pigment can combine with the carrier substance of specific type with the color spot that has that is formed for detergent composition of the present invention and adorn.Select carrier substance to give the density and the water-soluble characteristic of the certain regulation of spot decorations.Be suitable for comprising polyacrylate, polysaccharide, for example starch, Mierocrystalline cellulose, glue and their derivative as the material of the carrier that the color spot decorations are arranged; And polyoxyethylene glycol.Especially preferred carrier substance comprises the about 4000-20000 of molecular weight, the more preferably from about polyoxyethylene glycol of 4000-10000.
There are color spot decorations to prepare by dyestuff or pigment material are dispersed in the carrier substance.This can be by for example a) fusion carrier, and dispersed dye or pigment therein under mixing b) mix dyes/pigments powder and support powder, or c) dissolving dye/pigment and carrier carry out in the aqueous solution.Pigment/carrier mixture subsequently can be by compressing tablet, spraying drying, granulation, extrude or other routine techniques is made particle.There are the color spot decorations to contain pigment (dyestuff or the pigment) material of adoring the about 0.1%-5% of weight by spot usually.
The color spot decorations that have with this method preparation have about 400-1500 micron, the more preferably from about size of 400-1200 micron usually.Spot decorations by the preparation of specific support material will have less than about 1.4g/cc, preferably the density of about 1.0-1.4g/cc.These spot decorations also will be not dissolved in the non-water liquid phase of liquid detergent composition of the present invention basically.Therefore, there are the color spot decorations can stably be suspended in the non-water base body of liquid detergent composition of the present invention, and can not dissolve therein.Yet these spot decorations are dissolved in rapidly in the aqueous cleaning mother liquor for preparing with liquid detergent composition of the present invention.
Other selectivity composition component
Except composition liquid phase and solid phase as described above, detergent composition of the present invention is passable, and preferably will contain various other optional ingredients.This optional ingredient can be the liquid or solid form.Optional ingredient may be dissolved in the liquid phase, or can fine particle or the form of drop be dispersed in the liquid phase.Some other material that optionally is used for composition of the present invention is in following detailed description;
(a) optionally inorganic detergent builder
Detergent composition of the present invention also optionally contains belonging to of one or more types of the above-mentioned inorganic detergent builder that also can be used as the material of alkaline source.This optionally inorganic builders can comprise for example silico-aluminate, for example zeolite.Go through among the US4605509 of the Corkill that issue on August 12nd, 1986 as the purposes of detergent builder aluminosilicate zeolite and they etc., this patent is classified this paper reference as.Crystalline layered silicate is for example above-mentioned ' those disclosed also is suitable in the detergent composition of the present invention in the 509US patent.If use, optionally inorganic detergent builder can account for about 2%-15% of composition weight.
(c) enzyme optionally
Detergent composition of the present invention also optionally contains the detergent enzyme of one or more types.This enzyme can comprise proteolytic enzyme, amylase, cellulase and lipase.This material is known in the prior art, is commercial available.They can suspension, " ball " or " bead " form adds in the non-water liquid phase of the present invention detergent composition.Another suitable enzyme comprises the material that the form of suspension with the enzyme in nonionogenic tenside exists, for example the enzyme of being sold with trade(brand)name " SL " by Novo Nordisk or little encapsulate capsule enzyme of being sold with trade(brand)name " LDP " by Novo Nordisk.
The enzyme that adds composition with conventional enzyme particle shape formula especially is preferred among the present invention.Usually the size of this grain is about 100-1000 micron, 200-800 micron more preferably from about, and be suspended in the non-water liquid phase of whole composition.Compare with other enzyme form, we find that the enzyme grain in the present composition shows especially required enzyme stability aspect the reservation of enzymic activity.Therefore, use the composition of enzyme grain not need to contain conventional enzyme stabilizers, for example the enzyme stabilizers of normal use when enzyme adds in the aqueous liquid detergent.
If use, enzyme is enough to provide by weight up to 10mg with every gram composition usually, and more preferably from about the content of the about 5mg organized enzyme of 0.01mg-adds in the non-aqueous liquid compositions of the present invention.In other words, non-aqueous liquid detergent compositions of the present invention will contain about by weight 0.001%-5% usually, preferably about 0.01%-1% commercial enzyme preparation.For example, proteolytic enzyme is usually to be enough to the providing active content of every gram composition 0.005-0.1Anson unit (AU) to be present in this commercial formulation.
(c) sequestrant optionally
Detergent composition of the present invention can also optionally contain sequestrant, and it is used for being sequestered in the metal ion of nonaqueous detergent composition of the present invention, for example iron and/or manganese.Therefore this sequestrant is used for forming title complex with the metallic impurity of composition, and metallic impurity trend towards deactivation composition component, for example peroxygen bleach.Useful chelating agents can comprise aminocarboxylate, phosphonate, amino phosphonates do, the fragrant chelating agent of polyfunctional group replacement and their mixture.
Being used as optionally, the aminocarboxylate of sequestrant comprises edetate, N-hydroxyethyl-ethylene diamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, ethylenediamine disuccinate and ethanol Diglycocol salt.An alkali metal salt of these materials is preferred.
When detergent composition allowed the total phosphorus of low levels at least, amino phosphonates do was adapted at being used as sequestrant in the composition of the present invention, and comprises the ethylenediamine tetraacetic (methylene phosphonic acid salt) that is called DEQUEST.These amino phosphonates do preferably do not contain the alkyl or alkenyl that surpasses 6 carbon atoms.
Preferred sequestrant comprises hydroxyethyl di 2 ethylhexyl phosphonic acid (HEDP), diethylene triaminepentaacetic acid(DTPA) (DTPA), ethylenediamine disuccinic acid (EDDS) and pyridine dicarboxylic acid (DPA) and salt thereof.Certainly, sequestrant also can be used as detergent builder in fabric washing/bleaching process in composition of the present invention.If use, sequestrant can account for about 0.1%-4% of present composition weight.Sequestrant more preferably accounts for about 0.2%-2% of detergent composition weight of the present invention.
(d) optionally thickening material, viscosity control agent and/or dispersion agent
Detergent composition of the present invention optionally contains polymkeric substance, and it is used to improve the composition ability that to keep its solia particle component be suspended state.Therefore this material can be used as thickening material, viscosity control agent and/or dispersion agent.This material is the polymeric polycarboxylate normally, but can comprise other polymkeric substance, as Polyvinylpyrolidone (PVP) (PVP) or polyamide resin.
Polymeric polycarboxylate material can be preferably its sour form preparation by polymerization or the suitable unsaturated monomer of copolymerization.The unsaturated monomer acid that polymerizable forms 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.Have not carboxylate-containing group in polymeric polycarboxylate of the present invention, for example the monomer fragment of vinyl methyl ether, vinylbenzene, ethene etc. is suitable, its condition be this fragment be no more than polymer weight about 40%.
Especially suitable polymeric polycarboxylate can be obtained by vinylformic acid.Being used for of the present invention should be polyacrylic water-soluble salt based on the polymerizing acrylic acid thing.The molecular-weight average of the polymkeric substance of this acid form is preferably about 2000-100000, more preferably about 2000-10000, also preferred about 4000-7000, most preferably from about 4000-5000.The water-soluble salt of this acrylate copolymer can comprise for example an alkali metal salt.The water miscible polymkeric substance of this class is a known substances.Use this class polyacrylate to be disclosed among the US3308067 of the Diehl that for example issued on March 7th, 1967 in detergent composition, this material also can play the washing assistant effect.
If use, optionally thickening material, viscosity control agent and/or dispersion agent should be present in composition of the present invention with the content of about 0.1%-4% by weight.This material more preferably can account for about 0.5%-2% of detergent composition weight of the present invention.
(e) remove clay soil/anti redeposition agent
Composition of the present invention can also optionally contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.If use, decontamination dirt material can account for about 0.01% to about 5% of present composition weight.
Most preferred decontamination and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine is described in the US4597898 of the VanderMeer of promulgation on July 1st, 1986.Another kind of preferred removal clay soil-anti redeposition agent be on June 27th, 1984 disclosed Oh and the EP111965 of Gosselink in disclosed cation compound.Operable other are removed disclosed ethoxylated amine polymer among the EP111984 that clay soil/anti redeposition agents comprise disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th EP112592 in disclosed amphoteric ion polymer; With disclosed amine oxide among the US4548744 of the Connor of on October 22nd, 1985 promulgation.As known in the art other are removed clay soil/anti redeposition agent and also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.
(f) liquid bleaching promoting agent optionally
Detergent composition of the present invention also optionally contains bleach activator, and it at room temperature is a liquid form, and can be used as liquid and add in the non-water liquid phase of detergent composition of the present invention.A kind of liquid bleaching promoting agent is acetyl triethyl Citrate trianion (ATC).Other example comprises triacetin and nonanoyl Valerolactim.The liquid bleaching promoting agent is dissolvable in water in the non-water liquid phase of the present composition.
(g) bleaching catalyst optionally
If desired, bleaching compounds can carry out catalysis with manganic compound.This compound is well known in the art, and comprises, for example, is disclosed in the manganese-based catalyst among US5246621, US5244594, US5194416, US5114606 and EP549271A1,549272A1,544440A2 and the 544490A1.The preferred embodiment of this catalyzer comprises Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(OCH 3) 3(PF 6) and composition thereof.Other metal matrix bleaching catalyst comprises those disclosed in US4430243 and the US5114611.Following US4728455,5284944,5246612,5256779,5280117,5274147,5153161 and 5227084 has reported that also use manganese and various complex coordination body are to improve bleachability.
In fact, but not in order to limit, can adjust to provide the compositions and methods of the invention and contain at least one ten million/a active bleaching catalyst material in the wash water solution, and preferably in washings, contain the about 700ppm of the 0.1ppm-that has an appointment, the catalyst substance of the about 500ppm of more preferably about 1ppm-.
It is known being used for cobalt bleaching catalyst of the present invention, at for example M.L.Tobe, and " alkaline hydrolysis of transition metal complex " Adv.Inorg.Bioinorg.Mech., (1983), and 2, describe in the 1-94 page or leaf.Being used for most preferred cobalt catalyst of the present invention is formula [Co (NH 3) 5OAc] T yCobalt five amine acetates, " OAc " expression acetate part wherein, " T y" be negatively charged ion, five amine acetate cobalt chloride especially, [Co (NH 3) 5OAc] Cl 2And [Co (NH 3) 5OAc] (OAc) 2, [Co (NH 3) 5OAc] (PF 6) 2, [Co (NH 3) 5OAc] (SO 4), [Co (NH 3) 5OAc] (BF 4) 2[Co (NH 3) 5OAc] (NO 3) 2(being called " PAC " herein).
These cobalt catalyst easily prepare by currently known methods, for example at Tobe paper and the document wherein quoted/at US4810410, the J.Chem.Ed. (1989) of the Diakun of promulgation on March 7th, 1989 etc., 66 (12), 1043-45, " the synthetic and sign of mineral compound ", W.L.Jolly (Prentice-hall; 1970), 461-3 page or leaf; Inorg.Chem., 18,1497-1502 (1979); Inorg.Chem., 21,2881-2885 (1982), Inorg.Chem., 18,2023-2025 (1979), Inorg.Synthesis, 173-176 (1960) and Journal of PhysicalChemistry, 56, discuss among the 22-25 (1952).
In fact, but not in order to limit, can adjust to provide the compositions and methods of the invention and contain at least one hundred million/a active bleaching catalyst material in the wash water solution, and preferably in washings, contain the about 25ppm of the 0.01ppm-that has an appointment, the about 10ppm of more preferably about 0.05ppm-, the bleaching catalyst material of the about 5ppm of most preferably from about about 0.1ppm-.Obtain this content in the washing mother liquor of automatic washing process, composition contains by the about 0.0005%-of detergent composition weight about 0.2% usually, more preferably from about bleaching catalyst, especially manganese or the cobalt catalyst of 0.004%-about 0.08%.
(h) optionally whitening agent, suds suppressor, dyestuff and/or spices
Detergent composition of the present invention also optionally contains conventional whitening agent, suds suppressor, dyestuff and/or spices.Certainly, these whitening agent, suds suppressor, dyestuff and/or spices must be in non-water surrounding be compatible and nonreactive activity with other composition component.If exist, whitening agent, suds suppressor, dyestuff and/or spices account for about 0.0001%-2% of present composition weight usually.
(ⅰ) structure elasticizer
Non-aqueous liquid detergent compositions of the present invention also can contain about by weight 0.1%-5%, the broken solia particle material of fine powder of preferred about 0.1%-2%, it can comprise silicon-dioxide, for example the broken carbon of baking silicon-dioxide, titanium dioxide, undissolved carbonate, fine powder or the mixture of these materials.This class fine particles material plays the structure elasticizer in product of the present invention.This material has about 7-40 nanometer, the particle size of 7-15 nanometer more preferably from about, and this material has about 40-400m 2The specific surface area of/g.
The broken elasticizer material of fine powder does not increase the transportation stability that product viscosity can be improved the non-aqueous liquid detergent product by the elasticity of the liquid phase of increase surfactant structureization.This can not be subjected to undesirable structure deteriorate when making the HF oscillation that this product carries out can running in transportation, and the structure deteriorate meeting causes the sedimentation in the product.
Under the situation of titanium dioxide, use this material also to improve the whiteness of particulate matter in suspension liquid in detergent composition of the present invention, the overall appearance of product that this is effect improved.
Composition forms
As mentioned above, non-aqueous liquid detergent compositions of the present invention is SYNTHETIC OPTICAL WHITNER and/or other material with particulate form as solid suspension be dispersed in the whole tensio-active agent that contains, the form of the non-water liquid phase of preferred structureization.Structurized non-water liquid phase will account for about 45%-95% of composition weight usually, more preferably account for about 50%-90%, and the dispersed solids material accounts for about 5%-55% of composition weight, more preferably from about 10%-50%.
The particle liquid detergent composition that contains of the present invention is non-water (or anhydrous) basically on feature.Although very a spot of water can add in the said composition as the impurity of component mainly or optionally, the content of water should not surpass about 5% of detergent composition of the present invention.The content of the water of nonaqueous detergent composition of the present invention more preferably will be less than about by weight 1%.
The non-aqueous liquid detergent compositions that contains particulate of the present invention is that relative heavy-gravity is with mutually stable under the condition of commercial distribution and composition use.The viscosity of the present composition is generally about 300-5000cps, more preferably from about 500-3000cps.In the present invention, viscosity uses Carrimed CSL2 rheometer with 20s -1Shearing rate under measure.
Preparation of compositions and purposes
Non-aqueous liquid detergent compositions of the present invention can contain tensio-active agent by at first forming, the non-water liquid phase of preferred structureization, structurized add particulate constituent and mixing in mutually with any order easily at this subsequently, for example stir the component mixture that obtains and prepare to form phase stable composition of the present invention.Typically preparing in the method for said composition, main and some preferred optional ingredient are with specific order and mix under certain conditions.
In the first step of preferred preparation method, preparation is used to form the structurized powder that contains anion surfactant that contains the liquid of tensio-active agent.This pre-preparation step comprises that formation contains one or more straight chain C of 30%-60% of having an appointment 10-16The aqueous slurry of one or more thinner nonsurfactant salt of an alkali metal salt of alkyl benzene sulphonate (ABS) and about 2%-30%, in step subsequently, dry this soup compound is to forming the required degree that contains the solid matter that is less than about 4% residual water by weight.
After this solid surfactant materials of preparation, this material can mix with one or more non-water organic thinners to form the structurized liquid phase that contains tensio-active agent of detergent composition of the present invention.This can be reduced into powder type by the material that contains anion surfactant that above-mentioned pre-preparation step is formed, with mix this powder and contain one or more non-water organic thinners, be that tensio-active agent or nonsurfactant or both stirred liq media carry out as mentioned above.Be blended under the agitation condition and carry out, it is enough to form the well-mixed dispersion liquid of particle in non-water organic liquid diluent of common exsiccant LAS/ salt material.
In procedure of processing subsequently, prepared on-aqueous liquid dispersion liquid under the condition of the structurized liquid phase that contains tensio-active agent that is enough to obtain detergent composition of the present invention through grinding or high-shear is stirred.It is about 10 ℃-90 ℃ that this grinding or high-shear agitation condition generally include the maintenance temperature, preferred about 20 ℃-60 ℃; Be enough to form the gathering small-particle network that does not dissolve part of the powder mass that contains anion surfactant process period.The suitable equipment that is used for this purposes comprises: the ball mill of stirring, common ball mill (Fryma), colloidal mill, high-pressure homogenate device, high-shear mixer etc.Colloidal mill and high-shear mixer are because its high yield and low investment and maintenance cost thereby be preferred.The small-particle that produces in each equipment is generally the size of about 0.4-2 micron.The grinding of liquid/solid mixtures and high-shear are stirred usually the yield value of the structurized liquid phase of increase to about 1Pa-8Pa, more preferably from about 1Pa-4Pa.
In on-aqueous liquid, form after the dispersion liquid of the common dry substance of LAS/ salt,, can add the particulate matter that is used for detergent composition of the present invention grinding or stir with before or after increasing yield value.This component that can add under high-shear is stirred comprises silicon-dioxide or titanium dioxide elasticizer; Basically all organic washing-assisting detergents, for example Citrate trianion and/or lipid acid.And/or alkaline source, for example yellow soda ash can be to add under the shear agitation continuing to keep the mixture of said composition component.Continue to stir the mixture, and the point of the homodisperse liquid that does not dissolve solid phase particle that if desired can be in being formed on liquid phase increases and stirs.
Part or all of above-mentioned solid matter add this stir the mixture in after, have the particle of color spot decorations and preferred peroxygen bleach can add in the mixture, mixture is kept shear agitation equally.By last adding peroxygen bleach material, or after all or other component of great majority, especially after the alkaline source particle adds, can obtain the stabilizing effect of required peroxygen bleach.If the adding enzyme granulate, their preferred last adding in the on-aqueous liquid matrix.
As last procedure of processing, after adding all particulate matters, continue to stir the mixture have required viscosity to being enough to form, the time of yield value and phase stability combination of features thing, this comprises stir about 1-30 minute time usually.
When in on-aqueous liquid, adding solid ingredient according to above-mentioned method, advantageously keep these solid matters free, combined moisture content is not lower than some restriction.Free water content usually with 0.8% or higher content exist.Before adding washing composition matrix,,, can obtain the tangible stability advantages of resultant composition for example by fluidised bed drying solia particle material to 0.5% or lower free water content by reducing free water content.
Zhi Bei composition of the present invention can be used for being formed on the aqueous cleaning solution that uses in laundry and the bleached woven fabric as mentioned above.Usually the said composition with significant quantity adds in the entry, preferably in the fabric washing automatic washing machine of routine, to form this moisture laundry/liquid lime chloride.Formed moisture laundry/liquid lime chloride subsequently with fabric, preferably under agitation the contact, with the washing and bleached woven fabric.
The significant quantity that adds in the entry with the liquid detergent composition of the present invention that forms aqueous cleaning/liquid lime chloride can comprise the amount that is enough to form about 500-7000ppm composition in aqueous solution.About 800-3000ppm detergent composition more preferably is provided in aqueous cleaning/liquid lime chloride.
Following embodiment illustrates preparation method and the feature performance benefit that contains the non-aqueous liquid detergent compositions of medium chain branched chain surfactant of the present invention.Yet this embodiment is not restriction or defines scope of the present invention in addition.
The embodiment I
The preparation of 7-methyl tridecyl ethoxylation (E2)
Synthesizing of (6-hydroxyl hexyl) three phenyl phosphonium bromides
In the 5L three neck round-bottomed flasks that nitrogen inlet, condenser, thermometer, mechanical stirrer and nitrogen outlet are housed, in nitrogen, add 6-bromo-1-hexanol (500g, 2.76mol), triphenylphosphine (768g, 2.9mol) and acetonitrile (1800ml).Reaction mixture refluxed heating 72 hours, reaction mixture is transferred in the 5L beaker to room temperature, product under 10 ℃ in anhydrous diethyl ether (1.5L) recrystallization.Vacuum filtration with the ether washing, 50 ℃ of following vacuum-dryings 2 hours, obtains the required product of 1140g subsequently in baking oven, be white crystals.
Synthesizing of 7-methyl tridecylene-1-alcohol
In the exsiccant 5L three neck round-bottomed flasks that mechanical stirrer, nitrogen inlet, addition funnel, thermometer and nitrogen outlet are housed, add 60% sodium hydride (1.76mol) of 70.2g in mineral oil.By removing mineral oil with hexane wash, in flask, add anhydrous dimethyl sulphoxide (500ml), mixture heating up to 70 ℃ is emitted until hydrogen and to be stopped.With the reaction mixture cool to room temperature, add the 1L anhydrous tetrahydro furan subsequently.(443.4g, 1mol) (50 ℃, 500ml) pulping slowly adds in the reaction mixture by addition funnel (6-hydroxyl hexyl) three phenyl phosphonium bromides, keeps reaction mixture at 25-30 ℃ simultaneously with warm anhydrous dimethyl sulphoxide.At room temperature stirred the mixture 30 minutes, simultaneously by addition funnel slowly add methyln-hexyl ketone (140.8g, 1.1mol).The reaction slight exotherm needs the temperature of cooling with 25-30 ℃ of maintenance.Mixture stirred 18 hours, and impouring under agitation subsequently contains in the 5L beaker of 1L pure water, isolates oil phase (top layer) in separating funnel, removes water.Water is isolated organic phase with hexane (500ml) washing, mixes with the oil phase that washs from water.Organic mixture is used water extraction 3 times (each 500ml) subsequently, subsequently under 140 ℃ and 1mmHg vacuum distilling to collect transparent oily product (110g).
The hydrogenation of 7-methyl tridecylene-1-alcohol
Wave adding 7-methyl tridecylene-1-alcohol (108g in the autoclave sleeve at 3L, 0.508mol), methyl alcohol (300ml) and be stated from the platinum (by weight 10% of carbon, 35g), mixture hydrogenation 13 hours in 180 ℃ and 1200psig hydrogen, cooling is also passed through the Celite545 vacuum filtration, uses washed with dichloromethane Celite545.If desired, can repeat to filter to remove the Pt catalyzer of trace, available dried over mgso product.Product solution concentrates in rotatory evaporator and obtains transparent oily matter (104g).
The alkoxylate of 7-methyl tridecyl alcohol
Nitrogen inlet, mechanical stirrer are housed and have thermometer and the 1L three neck round-bottomed flasks of the y type pipe of pneumatic outlet in add the rapid alcohol of previous step.For removing the moisture of trace, alcohol under 80-100 ℃ about 30 minutes with nitrogen purging.Continue nitrogen purging, add the sodium Metal 99.5 catalyzer, under agitation 120-140 ℃ of slowly fusing down.Under violent stirring, fed ethylene oxide gas 140 minutes, keeping temperature of reaction simultaneously is 120-140 ℃.After accurately weight (equaling 2 equivalent oxyethane) adds, use nitrogen purging device 20-30 minute, make the sample cooling.Collect required 7-methyl tridecyl ethoxylate (average 2 ethoxylates of per molecule) subsequently.
The embodiment II
By the Sasol alcohol specimen preparation medium chain side chain C12 of experiment inclusion compound, 13 and C14,15 alcohol ethoxylates
Experimental test medium chain branched-chain alcoho sample is by the C12 of Sasol, and 13 and C14, the urea inclusion of the pure sample of 15 detergent ranges obtains, and alcohol ethoxylate is by the preparation of experiment alcohol.Urea inclusion process is used for by separation medium chain branched-chain alcoho in the conventional straight chain alcohol of the high-content (35-45% by weight) that exists at Sasol alcohol sample.The urea that uses in sepn process is 10 with the mol ratio of alcohol: 1-20: 1.Urea inclusion process by J.March at Advanced Organic Chemistry, 4th ed., Wileyand Sons, 1992, the 87-88 page or leaf neutralizes by Takemoto; Sonoda,, in Atwood; Davies; The MacNicol paper, name is called Inclusion Compounds, and vol.2 describes in the 47-67 page or leaf.The carbonylation of the alpha-olefin for preparing by Fischer Trosch method described in original Sasol alcohol sample such as the patent WO 97/01521 prepares and announces according to the Sasol R﹠K technical products on October 1st, 1996, is called SASOL DETERGENT ALCOHOLS.The inclusion process is reduced to straight chain content about by weight 5% by 35-45% according to sample, stay C12, and 13 and C14,15 alcohol, it contains 95% the branched-chain alcoho of having an appointment.In branched-chain alcoho, about 70% is medium chain branched-chain alcoho of the present invention, and other 30% is the alcohol of oxygen counting side chain on the 2-carbon location from alcohol.
SasolC12, the urea inclusion of 13 alcohol
In the dry 12L three neck round-bottomed flasks that mechanical stirrer is housed, add SasolC12,13 alcohol (399.8g, 2.05mol) and urea (2398.8g, 39.98mol) and methyl alcohol (7L).Make reagent stir about 20 hours at room temperature.During this period, the straight chain component of urea and Sasol alcohol, but do not form title complex with branched fraction.After about 20 hours, by medium porous funnel filtering suspension liquid, vacuum-evaporation methyl alcohol is used the hexane wash urea subsequently, and the vacuum-evaporation hexane obtains the almost colourless liquid of 189g.GC analyzes and shows that the alcohol that reclaims is 5.4% straight chain and 94.6% side chain.In branched-chain alcoho, the 67.4%th, the medium chain side chain, the 32.6%th, at the side chain of counting by the oxygen in the alcohol on the 2-carbon location.
The alcohol of SasolC12.13 inclusion is to the ethoxylation of E5
Gas inlet, mechanical stirrer are housed and have thermometer and the dry 500ml flask of the y type pipe of pneumatic outlet in add SasolC12,13 inclusion alcohol (134.4g, 0.7mol).For removing the moisture of trace, alcohol under 60-80 ℃ about 30 minutes with nitrogen purging.Continue nitrogen purging, (0.8g, 0.04mol) catalyzer is under agitation 120-140 ℃ of slowly fusing down to add sodium Metal 99.5.Under violent stirring, (154g, 3.5mol), keeping temperature of reaction simultaneously is 120-140 ℃ to feed ethylene oxide gas in 60 minutes.After accurately the oxyethane of weight adds, use nitrogen purging device 20-30 minute, make the sample cooling, the golden product liquid of bottling in nitrogen (285g, 0.69mol).
SasolC14, the urea inclusion of 15 alcohol
In the dry 12L three neck round-bottomed flasks that mechanical stirrer is housed, add SasolC14,15 alcohol (414.0g, 1.90mol) and urea (2220.0g, 37.0mol) and methyl alcohol (3.5L).Make reagent stir about 48 hours at room temperature.During this period, the straight chain component of urea and Sasol alcohol, but do not form title complex with branched fraction.After about 48 hours, by medium porous funnel filtering suspension liquid, vacuum-evaporation methyl alcohol is used the hexane wash urea subsequently, and the vacuum-evaporation hexane obtains the almost colourless liquid of 220g.GC analyzes and shows that the alcohol that reclaims is 2.9% straight chain and 97.1% side chain.In branched-chain alcoho, the 70.4%th, the medium chain side chain, the 29.6%th, at the side chain of counting by the oxygen in the alcohol on the 2-carbon location.
SasolC14, the alcohol of 15 inclusions is to the ethoxylation of E7
Gas inlet, mechanical stirrer are housed and have thermometer and the dry 500ml flask of the y type pipe of pneumatic outlet in add SasolC14,15 inclusion alcohol (76.3g, 0.35mol).For removing the moisture of trace, alcohol under 60-80 ℃ about 30 minutes with nitrogen purging.Continue nitrogen purging, (0.4g, 0.02mol) catalyzer is under agitation 120-140 ℃ of slowly fusing down to add sodium Metal 99.5.Under violent stirring, (37.7g, 2.45mol), keeping temperature of reaction simultaneously is 120-140 ℃ to feed ethylene oxide gas in 35 minutes.After accurately the oxyethane of weight adds, use nitrogen purging device 20-30 minute, make the sample cooling, the golden product liquid of bottling in nitrogen (179.9g, 0.34mol).
The embodiment III
The preparation of 7-methyl dodecyl ethoxylate (E5)
Synthesizing of 7-methyl dodecylene-1-alcohol
In the exsiccant 5L three neck round-bottomed flasks that mechanical stirrer, nitrogen inlet, addition funnel, thermometer and nitrogen outlet are housed, add 60% sodium hydride (1.76mol) of 70.2g in mineral oil.By removing mineral oil with hexane wash, in flask, add anhydrous dimethyl sulphoxide (500ml), mixture heating up to 70 ℃ is emitted until hydrogen and to be stopped.With the reaction mixture cool to room temperature, add the 1L anhydrous tetrahydro furan subsequently.(6-hydroxyl hexyl) three phenyl phosphonium bromides (443.4g, 1mol), preparation as mentioned above) (50 ℃, 500ml) pulping slowly adds in the reaction mixture by addition funnel, keeps reaction mixture at 25-30 ℃ simultaneously with warm anhydrous dimethyl sulphoxide.At room temperature stirred the mixture 30 minutes, simultaneously by addition funnel slowly add 2-heptanone (125.4g, 1.1mol).The reaction slight exotherm needs the temperature of cooling with 25-30 ℃ of maintenance.Mixture stirred 18 hours, and impouring under agitation subsequently contains in the 5L beaker of 1L pure water, isolates oil phase (top layer) in separating funnel, removes water.Water is isolated organic phase with hexane (500ml) washing, mixes with the oil phase that washs from water.Organic mixture is used water extraction 3 times (each 500ml) subsequently, subsequently under 140 ℃ and 1mmHg vacuum distilling to collect transparent oily product.
The hydrogenation of 7-methyl dodecylene-1-alcohol
Wave adding 7-methyl dodecylene-1-alcohol (100.6g in the autoclave sleeve at 3L, 0.508mol), methyl alcohol (300ml) and be stated from the platinum (by weight 10% of carbon, 35g), mixture hydrogenation 13 hours in 180 ℃ and 1200psig hydrogen, cooling is also passed through the Celite545 vacuum filtration, uses washed with dichloromethane Celite545.If desired, can repeat to filter to remove the Pt catalyzer of trace, available dried over mgso product.Product solution concentrates in rotatory evaporator and obtains transparent oily matter.
The alkoxylate of 7-methyl dodecyl alcohol
Nitrogen inlet, mechanical stirrer are housed and have thermometer and the 1L three neck round-bottomed flasks of the y type pipe of pneumatic outlet in add 7-methyl dodecyl alcohol.For removing the moisture of trace, alcohol under 80-100 ℃ about 30 minutes with nitrogen purging.Continue nitrogen purging, add the sodium Metal 99.5 catalyzer, under agitation 120-140 ℃ of slowly fusing down.Under violent stirring, fed ethylene oxide gas 140 minutes, keeping temperature of reaction simultaneously is 120-140 ℃.After accurately weight (equaling 5 equivalent oxyethane) adds, use nitrogen purging device 20-30 minute, make the sample cooling.Collect required 7-methyl dodecyl ethoxylate (average 5 ethoxylates of per molecule) subsequently.
The embodiment IV
By experiment Shell Research alcohol specimen preparation medium chain side chain C13 alcohol ethoxylate
Shell Research experimental test C13 alcohol sample is used to prepare alcohol ethoxylate.These experiment alcohol are according to following method ethoxylation.Experiment alcohol is prepared by the C12 alhpa olefin in this case.The C12 alhpa olefin is reset by skeleton and is obtained branched-chain alkene.Skeleton is reset and is produced the side chain that limits the number, preferred medium chain.Reset to produce the C1-C3 side chain, more preferably ethyl, most preferable.The branched-chain alkene mixture produces required branched-chain alcoho mixture through catalyzed carbonylation.
ShellC13 experiment alcohol is to the ethoxylation of E9
Gas inlet, mechanical stirrer are housed and have thermometer and the dry 250m1 three-necked flask of the y type pipe of pneumatic outlet in add ShellC13 experiment alcohol (50.0g, 0.25mol).For removing the moisture of trace, alcohol under 60-80 ℃ about 30 minutes with nitrogen purging.Continue nitrogen purging, (0.3g, 0.01mol) catalyzer is under agitation 120-140 ℃ of fusing down to add sodium Metal 99.5.Under violent stirring, (99.0g, 2.25mol), keeping temperature of reaction simultaneously is 120-140 ℃ to feed ethylene oxide gas in 35 minutes.After accurately the oxyethane of weight adds, use nitrogen purging device 20-30 minute, make the sample cooling, the golden product liquid of bottling in nitrogen (143g, 0.24mol).
Adopt following analytical procedure to characterize side chain in the surfactant mixture of the present invention: the separation of component and evaluation in the Fatty Alcohol(C12-C14 and C12-C18) (before alkoxylate or after the alcohol sulfate hydrolysis that is used to analyze).The position of the side chain of in the precursor fatty alcohol material, finding and length by the GC/MS technical measurement [referring to D.J.Harvey, bio-pharmaceutical, environment mass spectrum (1989) 18 (9), 719-23; D.J.Harvey, J.M.GIFfany, chromatogram magazine (1984) 301 (1), 173-87; K.A.Karlsson, B.E.Samuelsson, G.O.Steen, fat physical chemistry (1973), 11 (1), 17-38].
The embodiment V
Be used as the preparation of the LAS powder of structural agent
C 12Linear alkylbenzene sulphonic acid (NaLAS) is processed into and contains the biphase powder.The a kind of of these phases is dissolved in the non-aqueous liquid detergent compositions, other be undissolved mutually.Undissolved part is used for increasing structure and particle suspension ability to the nonaqueous phase of composition of the present invention.
The NaLAS powder prepares NaLAS soup compound (about 40-50% activity) preparation by at dissolving sodium sulfate (3-15%) and solubilizing agent in the water of sodium sulfosuccinate (1-3%).Solubilizing agent and vitriol are used to improve the feature of dry powder.With rotary drum dryer soup compound is dried to thin slice.The undissolved network structure of assembling small-particle (0.4-2um) that produces mutually, it makes final nonaqueous detergent product become the solid of stable suspersion.
NaLAS powder according to the embodiment preparation has the following composition shown in the table 1.
The table V
The LAS powder
Form % by weight
NaLAS ????85％
Vitriol ????11％
Sulfosuccinate ????2％
Water ????2.5％
Unreacted reactant, etc. Balance to 100%
Undissolved LAS% ????17％
The # of phase (through X-ray diffraction) ????2
The embodiment VI is following to be the non-water heavy-filth liquid laundry detergent composition that contains medium chain branched chain surfactant of the present invention.
The table VI contains the SYNTHETIC OPTICAL WHITNER non-aqueous liquid detergent compositions
Component ????Wt％ ????A ????Wt％ ????B ????Wt％ ????Wt％ ????D ????Wt％ ????E
LAS is obtained by embodiment 1 ???16 ????13 ????8 ????8 ????2
C 12-14The EO=5 alcohol ethoxylate ???21 ????20 ????18 ????10 ????4
The branched-chain alcoho alcohol ethoxylate surfactant ????1 ????5 ????10 ????20 ????30
BPP ???19 ????19 ????19 ????19 ????19
Trisodium citrate dihydrate ????3 ????3 ????3 ?????3 ????3
Bleach activator ??5.9 ????5.9 ???5.9 ???5.9 ????5.9
Yellow soda ash ????9 ?????9 ????9 ?????9 ??????9
Maleic acid-acrylic acid copolymer ????3 ?????3 ????3 ?????3 ??????3
The color spot decorations are arranged ??0.4 ???0.4 ???0.4 ????0.4 ????0.4
EDDS ????1 ????1 ????1 ?????1 ????1
The cellulase bead ??0.1 ????0.1 ???0.1 ????0.1 ????0.1
The amylase bead ??0.4 ????0.4 ???0.4 ????0.4 ????0.4
Ethoxylation diamines quat ??1.3 ????1.3 ???1.3 ????1.3 ????1.3
Sodium peroxoborate ??15 ?????15 ???15 ????15 ????15
Optional ingredient comprises: whitening agent, pigment, spices, thickening material, suds suppressor, color spot decorations etc. are arranged Equal amount Equal amount Equal amount Equal amount Equal amount
????100％ ??100％ ???100％ ????100％ ???100％
The table VI composition that obtains is stable anhydrous heavy-filth liquid detergent for washing clothes, and it is used for providing when normal fabric washing is operated outstanding removal spot and fouling performance.

Claims (10)

1. non-water, liquid, heavy-dirty liquid-detergent composition, it is solid, the stable suspension form of undissolved particulate matter basically, described particulate matter is dispersed in structure, contains in whole liquid phases of tensio-active agent, and wherein said composition is characterised in that:
By weight at least about 10% branched chain surfactant mixture, described branched chain surfactant mixture is characterised in that and contains medium chain side chain and straight chain surfactant compounds, be less than 25% by the described straight chain compound of branched chain surfactant mixture weight, described medium chain branched compound has following formula:
A b-(EO/PO/BO) mOH is wherein:
A bBe the hydrophobic medium chain branched-chain alkyl of total carbon number C9-C18 in group, it contains be connected in (EO/PO/BO) of (1) 8-17 carbon atom mThe long linear carbochain of OH part; (2) the one or more C that stretch out by long linear carbochain 1-C 3Moieties; (3) at least one branched-chain alkyl partly is directly connected in the carbon of long linear carbochain, and the position of this carbon is by being connected in (EO/PO/BO) mPosition 3 carbon of the carbon #1 counting of OH part are to position ω-2 carbon, and end carbon deducts in 2 carbon ranges; (4) A of surfactant composition in above-mentioned formula bPart has the average the total number of carbon atoms greater than 12-about 14.5; With
EO/PO/BO is the alkoxyl group part that is selected from oxyethyl group, propoxy-, butoxy and their mixture, and m is at least about 1-about 30.
2. the detergent composition of claim 1, the wherein A of medium chain branched chain surfactant compound bPart is the branched-chain alkyl part of following formula: The integer of w=0-10 wherein; The integer of x=0-10; The integer of y=0-10; The integer of z=0-10; And w+x+y+z=3-10; In addition, comprising R, R 1And R 2The sum of carbon atom is 10-17 in the branched-chain alkyl part of side chain; R, R 1And R 2Be selected from hydrogen and C respectively 1-C 3Alkyl, its condition are R, R 1And R 2Be not hydrogen simultaneously, in addition, when z=0, R or R at least 1Not hydrogen.
3. the detergent composition of claim 1, the wherein A of medium chain branched chain surfactant component bPart is branched-chain alkyl part and their mixture that is selected from following formula:
Figure 9881214600031
Wherein a, b, d and e are integers, and a+b is 6-13, and d+e is 4-11; With
When a+b=6, a is the integer of 2-5, and b is the integer of 1-4;
When a+b=7, a is the integer of 2-6, and b is the integer of 1-5;
When a+b=8, a is the integer of 2-7, and b is the integer of 1-6;
When a+b=9, a is the integer of 2-8, and b is the integer of 1-7;
When a+b=10, a is the integer of 2-9, and b is the integer of 1-8;
When a+b=11, a is the integer of 2-10, and b is the integer of 1-9;
When a+b=12, a is the integer of 2-11, and b is the integer of 1-10;
When a+b=13, a is the integer of 2-12, and b is the integer of 1-11;
When d+e=4, d is the integer of 2-3, and e is the integer of 1-2;
When d+e=5, d is the integer of 2-4, and e is the integer of 1-3;
When d+e=6, d is the integer of 2-5, and e is the integer of 1-4;
When d+e=7, d is the integer of 2-6, and e is the integer of 1-5;
When d+e=8, d is the integer of 2-7, and e is the integer of 1-6;
When d+e=9, d is the integer of 2-8, and e is the integer of 1-7;
When d+e=10, d is the integer of 2-9, and e is the integer of 1-8;
When d+e=11, d is the integer of 2-10, and e is the integer of 1-9.
4. the detergent composition of claim 1, wherein detergent composition also contains by composition weight meter 55%-98.9% structurizedly, contains the liquid phase of tensio-active agent, and it forms by mixing following component:
ⅰ) by one or more non-water organic thinners of described liquid phase weight 1%-80%; With
ⅱ) by the surfactant system of described liquid phase weight 20%-99%, it is characterized in that tensio-active agent is selected from negatively charged ion, nonionic, cats product and their mixture.
5. the detergent composition of claim 1, wherein detergent composition also contains the alkyl polyhydroxy fatty acid amide of 0.1-8%.
6. the detergent composition of claim 1, wherein said particulate matter accounts for the 0.01%-50% of composition weight, described particulate is the 0.1-1500 micron, and it is selected from peroxygen bleach, bleach activator, color spot decorations, organic detergent auxiliary agent, inorganic alkaline source and their mixture are arranged.
7. the detergent composition of claim 1, wherein said surfactant system is characterised in that branched chain surfactant mixture weight at least 20%, preferably at least 50%.
8. the detergent composition of claim 1, wherein A bHydrophobic part has 10-17, preferred 11-15 total carbon atom.
9. the detergent composition of claim 1, wherein A in the branched chain surfactant mixture bAverage the total number of carbon atoms of part is greater than 12-14.
10. the detergent composition of claim 2 is wherein worked as R 2Be C 1-C 3During alkyl, the tensio-active agent of z=0 and z=1 or be at least 1: 1, preferably at least 1: 10 greater than the mol ratio of 1 tensio-active agent.
CN 98812146 1997-10-14 1998-10-14 Non-aqueous liquid detergent compositions comprising mid-chain branched surfactants Pending CN1281502A (en)

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US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US8809392B2 (en) 2008-03-28 2014-08-19 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
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US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
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US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
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