CN101743299A - A solid detergent composition - Google Patents
A solid detergent composition Download PDFInfo
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- CN101743299A CN101743299A CN200880024761A CN200880024761A CN101743299A CN 101743299 A CN101743299 A CN 101743299A CN 200880024761 A CN200880024761 A CN 200880024761A CN 200880024761 A CN200880024761 A CN 200880024761A CN 101743299 A CN101743299 A CN 101743299A
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- solid detergent
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1233—Carbonates, e.g. calcite or dolomite
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Detergent Compositions (AREA)
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Abstract
A solid detergent composition comprising: (i) 5 to 90 wt% magnesium salt of linear alkyl benzene sulphonic acid; (ii) 10 to 70 wt% water soluble alkali metal carbonate; and (iii) 3 to 50 wt% seed for precipitating calcium carbonate and (iv) an optionalco-builder which is a di-carboxylic acid or a salt thereof.
Description
Technical field
The present invention relates to a kind of solid detergent composition that comprises the carbonate builders system.
Background and correlation technique
Traditionally soap (its for an alkali metal salt of lipid acid) is used for the personal cleansing purpose.Also soap is used for washing clothes.When washing clothing with soaping, detersive efficiency is lower when washing in hard water.Hard water is meant the water with high-load lysed calcium and magnesium salts.Lysed calcium and magnesium ion very apace with the reaction of the alkali metal cation (sodium or potassium) of soap, cause forming water-fast calcium soap, therefore cause bad detersive power.Still there is same problem in appearance along with synthetic detergent (it is an alkali metal salt that comes from the long chain acid of oil).Most popular synthetic detergent comprises linear alkylbenzene sulfonate, sulfonated and the primary alkyl sulphates that belongs to the anionic species tensio-active agent.The tensio-active agent of also known nonionic, positively charged ion, both sexes and zwitter-ion character.The clean-up performance of most of synthetic surfactants also is subjected to wash in hard water to be influenced.
In detergent composition, used the lysed calcium and the magnesium ion reaction that exist in preferential and the hard water therefore to keep the washing composition of the high density of wanting to be in the compound of its activity form.The mixture of this compounds or compound is called washing assistant.Common known washing assistant has alkaline carbonate, silicate, phosphoric acid salt and structurized compound such as zeolite.Alkaline carbonate such as yellow soda ash (being commonly referred to soda) are being dirt cheap and widely used washing assistant in low-cost detergent formulations.The washing composition that valency of fine quality is high uses washing assistant such as phosphoric acid salt and/or zeolite, washes character because they have better to help, but expensive more.Carried out continuous firing develop use less expensive material more effectively and faster help the system of washing.In addition, many people think that use phosphoric acid salt causes the eutrophication in river and other natural water territory in washing composition.Therefore, having carried out many effort develops and uses soda to help the system of washing fast as main raw material(s).
EP0234818 (Unilever, 1987) discloses a kind of detergent composition, and described detergent composition comprises (i) detergent active system, and described detergent active system comprises the mixture of following component: (a) non-the soaping of negatively charged ion washed promoting agent; (b) nonionic detergent active; (c) soap; (ii) water soluble alkali metal carbonate; (iii) water insoluble microparticle carbonate material, it is the crystal seed of lime carbonate; The specified weight that it is characterized in that multiple detergent active is than combination.Builder system in the disclosure case is the mixture of soda and lime carbonate.Existing many improvement and many products of putting on market for this technology, they are the improvement to this basic technology of the combination of using soda and lime carbonate.The inventor determines to use at present yellow soda ash still not provide the desired space to this technological improvement that helps the degree of cleaning aspect of washing and exist in its laundry fast or can be discovered by the human consumer as the system of washing that preferably helps that basic washing assistant obtains with regard to product cost.
US7186677 (Henkel, 2007) method that a kind of preparation has the surfactant granules of good solvability and different stacking densities has been described, described method comprises that (a) provides the mixture of anionic surfactant acid and builder acid, and the weight ratio of builder acid and surfactant acid is 1: 100 to 1: 20; (b) described mixture is contacted with at least a solid neutralizing agent.Described builder acid is selected from citric acid, tartrate, Succinic Acid, propanedioic acid, hexanodioic acid, toxilic acid, fumaric acid, oxalic acid, glyconic acid, nitrilotriacetic acid(NTA), aspartic acid, ethylenediamine tetraacetic acid (EDTA) and a lot of other acid, and wherein the granularity of builder acid is lower than 200 μ m.
The magnesium salts of known linear alkyl benzene sulphonic acid and having used it in the detergent formulations also.US4146551 (Lion, 1979) described a kind of method for preparing the magnesium salts of sulfonic acid and sulfuric ester, described method is included in and is no more than about 6 pH down with in the aqueous dispersion that contains following material and the step of sulfonic acid and sulfuric ester: (1) at least a be selected from the neutralizing agent of magnesium oxide and magnesium hydroxide and (2) at least a be selected from phenylformic acid, citric acid, oxysuccinic acid, phosphoric acid, Tripyrophosphoric acid and its water-soluble salt in and accelerator.Though the disclosure case discloses the purposes of magnesium base anion surfactant, it does not point out the particular combinations of this class tensio-active agent and selected builder system, and described combination provides the detersive power of strengthening in the hard water that helps the power of washing and strengthen thus.
Indian patent application 225/MUM/2000 (Hindustan Lever Ltd, 2003 open) has described collaborative grinding cleaning compositions of a kind of selected combination that contains tensio-active agent and preparation method thereof.Described method comprises the acid precursor of the anion surfactant of the mineral neutralization at least 40% of using at least a rhombspar class; Mixed-abrasive and other conventional ingredient, so that the total amount of tensio-active agent is 0.5-35%, the amount of abrasive is 30-95%; Process described mixture in a usual manner.Rhombspar is a kind of chemical formula CaMg (CO that has
3)
2Mineral.The open case of the prior art relates to hard-surface cleaning compositions, and described composition comprises the calcium-magnesium salts of anion surfactant and do not point out to be used to provide the magnesium salts of linear alkyl benzene sulphonic acid of detersive power of reinforcement and the combination of selected builder system.
A target of the present invention is to provide a kind of solid detergent composition of comparing the staining fabric cleaning that reinforcement is provided under the hard water condition with some prior art compositions.
Another target of the present invention is to provide a kind of solid detergent composition that equal or better staining fabric cleaning is provided at lower cost of comparing with some prior art compositions when cleaning under the hard water condition.
Summary of the invention
According to the present invention, a kind of solid detergent composition is provided, described solid detergent composition comprises
(i) magnesium salts of the linear alkyl benzene sulphonic acid of 5-90% weight;
The (ii) water soluble alkali metal carbonate of 10-70% weight;
The (iii) crystal seed that makes precipitation of calcium carbonate of 3-50% weight; With
(iv) Ren Xuan auxiliary washing assistant, it is dicarboxylic acid or its salt.
Detailed Description Of The Invention
The inventor has found that very fast the helping that the use of disclosed specific builder system among the EP0234818 and specific auxiliary washing assistant had never been realized with similar system before providing wash.
In addition, the inventor has determined to comprise water soluble alkali metal carbonate and make the builder system of crystal seed of precipitation of calcium carbonate and specific anion surfactant when being the magnesium salts of linear alkyl benzene sulphonic acid when using, the helping of this builder system wash character therewith the special properties combination cooperative interaction of tensio-active agent when particularly in hard water, using, to provide the staining fabric of reinforcement to clean.
Solid detergent composition of the present invention comprises the magnesium salts (Mg-LAS) of linear alkyl benzene sulphonic acid.Described solid detergent composition preferably is powder, particle, bar or tablet form.The more preferably form of described detergent composition is powder or particle form.When described detergent composition exists with powder or particle form, Mg-LAS wherein preferably with size range greater than 0.3mm, more preferably greater than 0.5mm, most preferably greater than 1mm, best particle form in the 1-2mm scope exists.Described solid detergent composition comprises Mg-LAS, and it is measured to the 5%-90% of described detergent composition weight, is preferably 10%-50%, most preferably is 15%-35%.
The appropriate method of the Mg-LAS of preparation solid form is open in we copending application 445/MUM/2007.Wherein open and claimed method be included in the presence of the water of the 3%-28% that accounts for described reaction mixture weight, use in the high-shear mixer based in the alkali of magnesium with the step of linear alkyl benzene sulphonic acid.The Mg-LAS that solid form such as powder, particle maybe can be extruded the very high density (up to 90%) of bar can pass through method for preparing.This method has only needs small amount of alkali to be used to finish the neutral advantage.Being used for the neutral preferred amounts is the excessive alkali based on magnesium of 5%-100% stoichiometry.The suitable alkali based on magnesium is one or more in magnesiumcarbonate, Magnesium hydrogen carbonate, magnesium oxide, magnesium basic carbonate or the magnesium hydroxide.
The Mg-LAS particle that the preferred aspect of another of detergent composition of the present invention provides stand-by water-soluble polymers to apply.Described water-soluble polymers can be polyoxyethylene, Xylo-Mucine, Polyvinylpyrolidone (PVP), polyacrylic acid or polyvinyl alcohol, most preferably is polyvinyl alcohol.Can adopt following method to come to apply the Mg-LAS particle with water-soluble polymers.
The preferred method that applies Mg-LAS is included in the pan-type pelletizer step that polymers soln is sprayed on the Mg-LAS.Spray product can be dried to the particle moisture content less than 10% weight by the high temperature that pan-type pelletizer is heated to 60 ℃-90 ℃.Perhaps, spray product can be transferred in the baking oven so that dry.Also can use fluidized-bed to come coated polymer, use warm air with particle drying to want moisture content.The preferred amounts of polymeric coating is the 0.25%-5% of Mg-LAS particle weight, and more preferably 0.5%-2% most preferably is 0.75%-1.25%.
Solid detergent composition of the present invention comprises water soluble alkali metal carbonate.Described basic metal is preferably sodium or potassium, is preferably sodium.Therefore, most preferred alkaline carbonate is a yellow soda ash.The amount of described water soluble alkali metal carbonate is the 10%-70% of described solid detergent composition weight, is preferably 15%-60%, most preferably is 25%-50%.
Another important component of solid detergent composition of the present invention is the crystal seed that makes precipitation of calcium carbonate.Make the crystal seed of precipitation of calcium carbonate be meant the compound that in aqueous medium, has the ability of serving as the crystal seed that is used for precipitation of calcium carbonate.The described crystal seed of lime deposit that makes is water-fast substantially particulate matter.This water-fast particulate matter can be present in the detergent composition or original position generation when being scattered in detergent composition in the water.Preferred aspect provides the water-fast substantially particulate matter that is present in the detergent composition.The example of the crystal seed that makes precipitation of calcium carbonate that original position produces comprises by comprise sodium zincate generation particulate oxide zinc in detergent composition, produces particulate oxide aluminium or produce silicon-dioxide by comprise pure aluminium silicate in detergent composition by comprising sodium aluminate.The suitable water-fast substantially particulate matter that can be present in the detergent composition has silicon-dioxide, zinc oxide, aluminum oxide, titanium oxide, zeolite, magnesium oxide or lime carbonate.Especially preferred water-fast substantially particulate matter is a lime carbonate.Lime carbonate can be calcite or aragonite, most preferably is calcite.Calcite is preferably the calcite of high surface area.Preferred described water-fast particulate carbon hydrochlorate surface of seed is long-pending greater than 20m
2/ g is more preferably greater than 30m
2/ g is most preferably greater than 60m
2/ g.Described to make the amount of the crystal seed of precipitation of calcium carbonate be the 3%-50% of described solid detergent composition weight, and more preferably 5%-40% most preferably is 10%-30%.
Described solid detergent composition is optional and preferably comprise auxiliary washing assistant, and it is dicarboxylic acid or its salt.The water solubility of auxiliary washing assistant under 25 ℃ that is present in the described solid detergent composition is preferably greater than 1g/l.Preferred dicarboxylic acid is oxalic acid, propanedioic acid and Succinic Acid, most preferably is oxalic acid.The preferably salt of described dicarboxylic acid is basic metal or ammonium salt, more preferably an alkali metal salt.Most preferred auxiliary washing assistant is the oxalic acid disodium.Described auxiliary washing assistant preferably is present in the described solid detergent composition with powder type (promptly with low granularity).The mean particle size of described auxiliary washing assistant is more preferably less than 75 microns preferably less than 150 microns.The amount of described auxiliary washing assistant is preferably the 1%-20% of described solid detergent composition weight, and more preferably 5%-15% most preferably is 5%-10%.
Solid detergent composition of the present invention preferably comprises other washing assistant, and it is an alkalimetal silicate.Described alkalimetal silicate is preferably water glass or potassium silicate, more preferably water glass.Water glass is the oxide compound of sodium and the leucocompound of silicon-dioxide.It has sodium oxide (Na
2O) and silicon-dioxide (silicon dioxide or silica) (SiO
2) the different number of chemical formula of content.Its water soluble and it are by making silicon-dioxide (sand) and yellow soda ash prepared in reaction under 1200 ℃-1400 ℃ high temperature.The aqueous solution of water glass is known as water glass.Na
2O: SiO
2The water glass that ratio changed from 1: 1.6 to 1: 4 is called as colloidal silicate.These are sold as the aqueous solution of 20%-50% usually.In available various types of water glass, the preferred compound that is used for composition of the present invention is a neutral sodium silicate.Its concentration in water is 27%-39%, Na
2O: SiO
2Ratio is 3.0-3.5.Preferably with the 5%-50% of described solid detergent composition weight, more preferably 12%-40% exists alkalimetal silicate.Solid detergent composition with the washings of 2g/l-5g/l use therefore guarantee alkalimetal silicate in washings with 0.2g/l-1g/l, preferred 0.5g/l-0.8g/l exists.
According to a further aspect in the invention, a kind of method for preparing granular detergent composition is provided, described method comprise the magnesium salts that mixes linear alkyl benzene sulphonic acid particle and water soluble alkali metal carbonate, to make the crystal seed of precipitation of calcium carbonate and the powder of auxiliary washing assistant, described auxiliary washing assistant be dicarboxylic acid or its salt.
According to a preferred aspect of the present invention, provide a kind of preparing washing agent method for compositions, said method comprising the steps of:
(i) in high-shear mixer in the presence of the water of the 3%-28% that accounts for described reaction mixture weight by use based in the alkali of magnesium and linear alkyl benzene sulphonic acid prepare the particle form of linear alkyl benzene sulphonic acid magnesium salts (Mg-LAS);
(ii) the described Mg-LAS particle of optionally sieving is to the size range greater than 0.3mm; With
(iii) mix described Mg-LAS particle and water soluble alkali metal carbonate, make the crystal seed of precipitation of calcium carbonate and the powder of auxiliary washing assistant, described auxiliary washing assistant is dicarboxylic acid or its salt.
Used Mg-LAS particle coated has water-soluble polymers in the preferred aforesaid method.
Now the present invention is described with regard to following non-limiting examples.
Embodiment
Embodiment 1-4 and Comparative Examples A, B
These embodiment explanations are compared helping of detergent composition of the present invention with conventional products and are washed kinetics-hand washing scheme.
Use option A as described below to prepare the multiple detergent composition shown in the table 1 and it is added in the hard water of 48FH (French hardness).All detergent composition surfactant concentration in use is 0.7g/l.Help and wash kinetics by under a plurality of time points, measuring Ca according to FH
2+Concentration is studied, and data see Table 2.Measure Ca
2+The method of concentration is as follows:
The measurement of calcium ion concn
Described method comprise use EBT (chrome black-T) as indicator with EDTA (disodium salt of ethylenediamine tetraacetic acid (EDTA)) titration.About 2ml ionic calcium soln is pipetted in the 150ml erlenmeyer flask.Described solution is diluted with 10ml water.To wherein adding 5ml ammonia-ammonium chloride pH10 damping fluid.Add the 1%EBT of about 35mg in potassium nitrate solution.Obtain burgundy.Under constant agitation, from drop-burette, dropwise add the EDTA solution of demarcating.Along with added EDTA becomes many, color gradually becomes purple by burgundy.Terminal point sports blue identification by color by purple.Calcium ion concn uses following formula to calculate:
Ca according to FH
2+Concentration uses following formula to calculate:
Ca
2+Concentration (FH)=Ca
2+Ionic concn (ppm) ÷ 4
Option A: the scheme that is used to simulate hand washing
Get FH and be 48 water, to wherein adding detergent composition and manually stirring 45 seconds with about 70-80rpm.Make solution left standstill after about 5 minutes, with the strong stir about of described solution 10 seconds.Shift out sample and use syringe filter to be filled into TARSON at want time point use syringe subsequently
TMIn the pipe.As discussed previously filtrate being used to measured Ca
2+Ionic concn.
Table 1
| Embodiment | Tensio-active agent | Tensio-active agent, granularity, mm | SODA ASH LIGHT 99.2, g/l | ??HSAC，??g/l | ??STPP，??g/l |
| Comparative Examples A | ??NaLAS | ??0.5-1 | ??1.4 | ??0.3 | ??0.16 |
| Comparative example B | ??NaLAS | ??0.5-1 | ??1.5 | ??1.0 | ??- |
| Embodiment 1 | ??MgLAS | ??1-2 | ??1.5 | ??1.0 | ??- |
| Embodiment 2 | ??MgLAS | ??0.5-1 | ??1.5 | ??1.0 | ??- |
| Embodiment 3 | ??MgLAS | 1-2; Scribble PVA | ??1.5 | ??1.0 | ??- |
| Embodiment 4 | ??MgLAS | ??0.3-0.5 | ??1.5 | ??1.0 | ??- |
NaLAS is the sodium salt of linear alkyl benzene sulphonic acid
HSAC: surface-area is (20-30) m
2The High Surface Area Calcite of/g.
STPP: tripoly phosphate sodium STPP
PVA: polyvinyl alcohol
Table 2
| Embodiment | FH, time=5 minute | FH, time=10 minute | FH, time=30 minute |
| Comparative Examples A | ?24.4 | 23.3 | 19.7 |
| Comparative example B | ?19.1 | 10.5 | 8.2 |
| Embodiment 1 | ?0.25 | 0.15 | 0.10 |
| Embodiment 2 | ?0.30 | 0.18 | 0.15 |
| Embodiment 3 | ?0.28 | 0.10 | 0.10 |
| Embodiment 4 | ?4.50 | 6.80 | 6.80 |
Data in the table 2 show that comparing detergent composition of the present invention with prior art products provides faster helping to wash kinetics.
Embodiment 5-7 and Comparative Examples A, B
These embodiment relate to and compare helping of detergent composition of the present invention with conventional sample and wash kinetics (machine washing scheme).
Use Comparative Examples A as following table 3 as shown in and the composition of B and embodiment 5-7 to come preparing washing liquid, described washings uses option b simulation as described below to machine-wash:
Option b: (being used to simulate the scheme of washing machine)
Get FH and be 48 water, to wherein adding detergent composition and by using overhead stirrer to stir with about 160-170rpm.All detergent composition surfactant concentration in use is 0.7g/l.Continuously stirring amounts to 30 minutes.Shift out sample and use syringe filter to be filled into TARSON at want time point use syringe subsequently
TMIn the pipe.As discussed previously filtrate being used to measured Ca
2+Concentration.
Table 3
| Embodiment | Tensio-active agent | Tensio-active agent, granularity, mm | SODA ASH LIGHT 99.2, g/l | ??HSAC??，g/l | ??STPP，??g/l | The oxalic acid disodium, g/l |
| Comparative Examples A | ??NaLAS | ??0.5-1 | ??1.4 | ??0.3 | ??0.16 | ??- |
| Comparative example B | ??NaLAS | ??0.5-1 | ??1.5 | ??1.0 | ??- | ??- |
| Embodiment 5 | ??MgLAS | ??1-2 | ??1.5 | ??0.5 | ??- | ??0.4 |
| Embodiment 6 | ??MgLAS | ??0.5-1.0 | ??1.5 | ??0.5 | ??- | ??0.4 |
| Embodiment 7 | ??MgLAS | 1-2; Scribble PVA | ??1.5 | ??0.5 | ??- | ??0.4 |
Oxalic acid disodium granularity with＜0.075mm in above-mentioned experiment is used.
Composition operational version B for table 3 sees the following form 4 at each time point about washing dynamic (dynamical) data according to helping of FH.
Table 4
| Embodiment | FH, time=5 minute | FH, time=10 minute | FH, time=30 minute |
| Comparative Examples A | ?20.0 | 21.0 | 20.0 |
| Comparative example B | ?19.7 | 10.8 | 9.3 |
| Embodiment 5 | ?4.69 | 0.10 | 0.10 |
| Embodiment 6 | ?15.4 | 14.4 | 8.10 |
| Embodiment 7 | ?0.30 | 0.30 | 0.30 |
Data in the table 4 show that comparing more preferably detergent composition of the present invention (embodiment 5 and 7) with prior art compositions provides faster helping to wash kinetics.
Embodiment 8-12 and Comparative Examples A, B, C
These embodiment relate to the clean-up performance of comparing detergent composition of the present invention with conventional sample.
Use the scheme of simulation hand washing to use the composition of Comparative Examples A-C as shown in table 5 and embodiment 8-12 to wash various tests supervision things.This scheme C is described below.
Scheme C:(hand-washes scheme)
Get FH and be 48 water, to wherein adding detergent composition and with the manual stir about of about 50-60rpm 45 seconds.All detergent composition surfactant concentration in use is 0.7g/l.Made solution left standstill 5 minutes, and after this it was manually stirred 10 seconds.Add fabric test subsequently and monitor thing, it was soaked 10 minutes.Subsequently described test is monitored that thing washed 30 minutes with 90rpm in tergo-to-meter.Test the supervision thing 3 times, subsequent drying with 25 liquid and the rinsing of fabric ratio subsequently.Measure the reflectivity of described supervision thing subsequently.Obtain three different mean values that monitor the reflectivity data of thing.
Table 5
| Embodiment | Tensio-active agent | Tensio-active agent, granularity, mm | SODA ASH LIGHT 99.2, g/l | ??HSAC，??g/l | ??STPP，g/l |
| Comparative Examples A | ??NaLAS | ??0.5-1 | ??1.4 | ??0.3 | ??0.16 |
| Comparative example B | ??NaLAS | ??0.5-1 | ??1.5 | ??1.0 | ??- |
| Comparative example C | ??NaLAS | ??0.5-1 | ??0.89 | ??0.07 | ??1.02 |
| Embodiment 8 | ??MgLAS | ??1-2 | ??1.5 | ??1.0 | ??- |
| Embodiment 9 | ??MgLAS | ??1-2 | ??1.5 | ??0.7 | ??- |
| Embodiment 10 | ??MgLAS | ??0.5-1 | ??1.5 | ??0.7 | ??- |
| Embodiment 11 | ??MgLAS | ??0.3-0.5 | ??1.5 | ??1.0 | ??- |
| Embodiment 12 | ??MgLAS | ??0.3-0.5 | ??1.5 | ??0.7 | ??- |
Monitor the Δ R of the reflectivity of thing with respect to initial test about basis
*Various tests monitor that the data of the clean-up performance of things see Table 6.Used initial (unwashed) test monitors that thing is WFK10D (the complicated dirt on the cotton fabric), and its initial reflectance is about 45; WFK20D (the complicated dirt on synthon-cotton fabric), its initial reflectance is about 40; And WFK30D (the complicated dirt on the polyester textile), its initial reflectance is about 40.
Table 6
| Embodiment | ?ΔR ＊WFK10D | ?ΔR ＊WFK20D | ?ΔR ＊WFK30D |
| Comparative Examples A | ?20.0 | ?18.5 | ?17.6 |
| Comparative example B | ?20.0 | ?15.7 | ?17.2 |
| Comparative example C | ?22.2 | ?22.9 | ?20.5 |
| Embodiment 8 | ?23.6 | ?28.6 | ?22.7 |
| Embodiment 9 | ?21.3 | ?26.1 | ?21.1 |
| Embodiment 10 | ?20.2 | ?29.2 | ?23.2 |
| Embodiment 11 | ?17.8 | ?22.4 | ?20.3 |
| Embodiment 12 | ?15.2 | ?19.6 | ?22.3 |
Data in the table 6 show that comparing detergent composition of the present invention with prior art products monitors that to some tests thing provides similar cleaning and other test monitors that thing provides better cleaning to great majority.Described data show that also the Mg-LAS (embodiment 8-10) of higher granularity provides the cleaning of improving greatly.In addition, compare with the more expensive conventional products based on Na-LAS+STPP, preferred composition of the present invention (embodiment 8-10) provide similar cleaning or better cleaning.
Embodiment 13-16 and Comparative Examples A and C
These embodiment relate to the clean-up performance of comparing preferred detergent composition of the present invention with conventional product.
Use aforesaid scheme C to use the composition of Comparative Examples A as shown in table 7 and C and embodiment 13-16 to wash various tests and monitor thing.
Table 7
| Embodiment | Tensio-active agent | Tensio-active agent, granularity, mm | SODA ASH LIGHT 99.2, g/l | ??HSAC??，g/l | ??STPP，??g/l | Oxalic acid, g/l |
| Comparative Examples A | ??NaLAS | ??0.5-1 | ?1.4 | ??0.3 | ??0.16 | ??- |
| Comparative example C | ??NaLAS | ??0.5-1 | ?0.89 | ??0.07 | ??1.02 | ??- |
| Embodiment 13 | ??MgLAS | ??0.3-0.12 | ?1.5 | ??0.5 | ??- | ??0.42 |
| Embodiment 14 | ??MgLAS | ??1-2 | ?1.5 | ??0.5 | ??- | ??0.42 |
| Embodiment 15 | ??MgLAS | ??0.5-0.3 | ?1.5 | ??0.5 | ??- | ??0.42 |
| Embodiment | Tensio-active agent | Tensio-active agent, granularity, mm | SODA ASH LIGHT 99.2, g/l | ??HSAC??，g/l | ??STPP，??g/l | Oxalic acid, g/l |
| Embodiment 16 | ??MgLAS | ??1-2 | ?1.5 | ??0.5 | ??- | ??0.27 |
The granularity of above-mentioned experiment mesoxalic acid is in＜size range of 0.075mm in.
Monitor the Δ R of the reflectivity of thing with respect to initial test about basis
*Various tests monitor that the data of the clean-up performance of things see Table 8.
Table 8
| Embodiment | ΔR ＊WFK10D | ΔR ＊WFK20D | ?ΔR ＊WFK30D |
| Comparative Examples A | 20.0 | ?18.5 | ?17.6 |
| Comparative example C | 22.2 | ?22.9 | ?20.5 |
| Embodiment 13 | 22.4 | ?22.3 | ?24.2 |
| Embodiment 14 | 24.5 | ?26.8 | ?25.2 |
| Embodiment 15 | 24.0 | ?26.8 | ?23.3 |
| Embodiment 16 | 23.1 | ?27.5 | ?21.6 |
Data in the table 8 show compare with the prior art sample preferred detergent composition of the present invention to some tests monitor things provide similar or better cleaning and to great majority other test monitors that things provide much better cleaning.Data also show have＞Mg-LAS of the higher granularity of 0.5mm provides the cleaning of improving greatly with washing assistant such as oxalic acid combination the time.
Embodiment 17 and 18 and comparative example C
These embodiment relate to the clean-up performance of comparing more preferably detergent composition of the present invention with conventional sample.
Use simulation machine washing scheme to use the various tests of cleaning compositions of comparative example C as shown in table 9 and embodiment 17 and 18 to monitor thing.This scheme D is described below.
Scheme D:(washing machine scheme)
In Tergo-to-meter, put into FH and be 48 water and test and monitor thing, to wherein adding detergent composition and with 90rpm stir about 10 minutes.All detergent composition surfactant concentration in use is 0.7g/l.Add fabric test subsequently and monitor thing, it was soaked 15 minutes.After this, make it with 90rpm running 30 minutes.Test the supervision thing 3 times, subsequent drying with 25 liquid and the rinsing of fabric ratio subsequently.Measure the reflectivity of described supervision thing subsequently.Obtain three different mean values that monitor the reflectivity data of thing.Monitor the Δ R of the reflectivity of thing with respect to initial test about basis
*Various tests monitor that the data of the clean-up performance of things see Table 10.Used initial (unwashed) test monitors that thing is WFK10D (the complicated dirt on the cotton fabric), and its initial reflectance is about 45; WFK20D (the complicated dirt on synthon-cotton fabric), its initial reflectance is about 40; And WFK30D (the complicated dirt on the polyester textile), its initial reflectance is about 40.
Table 9
| Embodiment | Tensio-active agent | The tensio-active agent granularity, mm | SODA ASH LIGHT 99.2, g/l | ?HSAC?，g/l | ??STPP，??g/l | The oxalic acid disodium, g/l |
| Comparative example C | ??NaLAS | ??0.5-1 | ?0.89 | ?0.07 | ??1.02 | ?- |
| Embodiment 18 | ??MgLAS | 1-2; Scribble PVA | ?1.5 | ?0.5 | ??- | ?0.40 |
| Embodiment 19 | ??MgLAS | 1-2; Scribble PVA | ?1.5 | ?0.5 | ??- | ?0.15 |
The granularity of above-mentioned experiment mesoxalic acid disodium is in the size range of＜0.075mm.
Monitor the Δ R of the reflectivity of thing with respect to initial test about basis
*Various tests monitor that the data of the clean-up performance of things see Table 10.
Table 10
| Embodiment | ΔR ＊WFK10D | ΔR ＊WFK20D | ?ΔR ＊WFK30D |
| Comparative example C | 26.3 | ?19.4 | ?20.7 |
| Embodiment 17 | 26.5 | ?26.5 | ?24.2 |
| Embodiment 18 | 25.1 | ?26.2 | ?25.5 |
Data in the table 10 show that comparing preferred detergent composition of the present invention with prior art compositions provides better cleaning to great majority test supervision thing.
Claims (10)
1. solid detergent composition, described solid detergent composition comprises:
(i) account for the magnesium salts of linear alkyl benzene sulphonic acid of the 5%-90% of described detergent composition weight;
(ii) account for the water soluble alkali metal carbonate of the 10-70% of described detergent composition weight;
(iii) account for the crystal seed that makes precipitation of calcium carbonate of the 3-50% of described detergent composition weight; With
(iv) Ren Xuan auxiliary washing assistant, it is dicarboxylic acid or its salt.
2. the solid detergent composition of claim 1, the water solubility of wherein said auxiliary washing assistant under 25 ℃ is greater than 1g/l.
3. claim 1 or 2 solid detergent composition, the mean particle size of wherein said auxiliary washing assistant is less than 150 microns.
4. each solid detergent composition in the aforementioned claim, the amount of wherein said auxiliary washing assistant is the 1%-20% of described detergent composition weight.
5. each solid detergent composition in the aforementioned claim, wherein the magnesium salts of linear alkyl benzene sulphonic acid exists with the particle form greater than the size range of 0.3mm.
6. each solid detergent composition in the aforementioned claim, the magnesium salts of wherein said linear alkyl benzene sulphonic acid is coated with water-soluble polymers.
7. each solid detergent composition in the aforementioned claim, wherein said to make the crystal seed of precipitation of calcium carbonate be that surface-area is greater than 20m
2The lime carbonate of/g.
8. each solid detergent composition in the aforementioned claim, described solid detergent composition comprises other washing assistant, and it is an alkalimetal silicate.
9. method for preparing the solid particulate detergent composition, described method comprises: mix the magnesium salts of linear alkyl benzene sulphonic acid particle and water soluble alkali metal carbonate, to make the crystal seed of precipitation of calcium carbonate and the powder of auxiliary washing assistant, described auxiliary washing assistant be dicarboxylic acid or its salt.
10. the method for claim 13 said method comprising the steps of:
(i) in high-shear mixer in the presence of the water of the 3-28% that accounts for reaction mixture weight by use based in the alkali of magnesium and linear alkyl benzene sulphonic acid prepare the particle form of the magnesium salts (Mg-LAS) of linear alkyl benzene sulphonic acid;
(ii) the described Mg-LAS particle of optionally sieving is to the size range greater than 0.3mm; With
(iii) mix described Mg-LAS particle and water soluble alkali metal carbonate, to make the crystal seed of precipitation of calcium carbonate and the powder of auxiliary washing assistant, described auxiliary washing assistant be dicarboxylic acid or its salt.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1354/MUM/2007 | 2007-07-16 | ||
| IN1354MU2007 | 2007-07-16 | ||
| EP07120954 | 2007-11-19 | ||
| EP07120954.8 | 2007-11-19 | ||
| PCT/EP2008/058137 WO2009010375A1 (en) | 2007-07-16 | 2008-06-26 | A solid detergent composition |
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| CN101743299A true CN101743299A (en) | 2010-06-16 |
| CN101743299B CN101743299B (en) | 2012-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008800247613A Expired - Fee Related CN101743299B (en) | 2007-07-16 | 2008-06-26 | A solid detergent composition |
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|---|---|
| EP (1) | EP2167624B1 (en) |
| CN (1) | CN101743299B (en) |
| AT (1) | ATE490303T1 (en) |
| DE (1) | DE602008003820D1 (en) |
| PL (1) | PL2167624T3 (en) |
| WO (1) | WO2009010375A1 (en) |
| ZA (1) | ZA200908805B (en) |
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- 2008-06-26 DE DE602008003820T patent/DE602008003820D1/en active Active
- 2008-06-26 CN CN2008800247613A patent/CN101743299B/en not_active Expired - Fee Related
- 2008-06-26 EP EP08761382A patent/EP2167624B1/en not_active Not-in-force
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026478A (en) * | 2015-09-15 | 2018-05-11 | 荷兰联合利华有限公司 | Aqueous hard surface Cleasing compositions |
| CN109661459A (en) * | 2016-09-07 | 2019-04-19 | 艺康美国股份有限公司 | The method of solid detergent composition and the distribution rate using solid anionic surfactant adjusting solid detergent |
| CN109661459B (en) * | 2016-09-07 | 2021-07-27 | 艺康美国股份有限公司 | Solid detergent compositions and methods of using solid anionic surfactants to adjust the dispensing rate of solid detergents |
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| Publication number | Publication date |
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| CN101743299B (en) | 2012-03-28 |
| ATE490303T1 (en) | 2010-12-15 |
| PL2167624T3 (en) | 2011-05-31 |
| EP2167624B1 (en) | 2010-12-01 |
| DE602008003820D1 (en) | 2011-01-13 |
| ZA200908805B (en) | 2011-03-30 |
| WO2009010375A1 (en) | 2009-01-22 |
| EP2167624A1 (en) | 2010-03-31 |
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