CN103282477A - Top-loading laundry vessel method - Google Patents
Top-loading laundry vessel method Download PDFInfo
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- CN103282477A CN103282477A CN2011800490857A CN201180049085A CN103282477A CN 103282477 A CN103282477 A CN 103282477A CN 2011800490857 A CN2011800490857 A CN 2011800490857A CN 201180049085 A CN201180049085 A CN 201180049085A CN 103282477 A CN103282477 A CN 103282477A
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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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/08—Silicates
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A laundry process which comprises the steps of: a)providing a coated detergent particle having perpendicular dimensions x, y and z, wherein x is from 1mm to less than 2 mm, y is from more than 2mm to 8mm and z is from more than 2mm to 8 mm, wherein the particle comprises: (i) from 50 to 90 wt% surfactant selected from anionic surfactant and/or non-ionic surfactant; (ii)from 1 to 40 wt% water-soluble inorganic salts; (iii) from 0 to 20 wt% other ingredients, including less than 15wt% water insoluble materials including fragrance, and, wherein the inorganic salts are present on the laundry detergent particle as a coating and the surfactant is present as a core; b)dissolving said coated detergent particle in water to form a wash liquor c)treating articles with said wash liquor, d)separating said articles from said wash liquor, and e)rinsing and drying said articles wherein at least step (c) is performed in a top-loading washing vessel.
Description
Invention field
The present invention relates to use the laundry cleaning method of the detergent for washing clothes particle of shaping.
Background of invention
A lot of different customs of cleaning are arranged on the known world.Though it is common in West Europe to have " front loading ", " automatically ", the horizontal axis washer of complex control system, a lot of people especially in the emerging market of development neutralization, still use " (top-loading) loaded at the top " clean container.Its scope is from loading machine by cylinder and the bucket that some machine stirring device (for example Brazilian's " Tanquinho ") is provided to more complicated top.
Except thin slice, paste and the tablet of relatively small amount with in the world some local detergent bar, most of detergent composition are sold with liquid or powder type and are used.Powder is the form of many local traditions, and the user payes attention to effective cleaning that they provide.Yet people can realize some negative issues that caused by the accumulation of residue on the goods that are washed.These residue parts are by ash, other insoluble solid (for example zeolite synergistic agent) and/or are owing to the precipitation synergistic agent produces.The net result of this accumulation can be that the color of the goods that have been washed changes.
Liquid washing agent does not have these same residue problems, but because its major part is the system of non-synergy, they may clean the power deficiency, especially in hard water areas.Liquid has another advantage that is better than powder, and for example they do not have the agglomeration problems of solid.
Yet many users do not believe that still liquid has the cleaning effectiveness identical with powder.The laundry that the residue problem of powder is loaded at the top is especially remarkable under being accustomed to, and wherein rinses the solid existing problems of precipitation or deposition, is especially lacking water or the water area to costliness.
WO1999/32599 has described the method for making the detergent for washing clothes particle, by synergistic agent and tensio-active agent are extruded the formation bar.To have the forcing machine that sulfation or Sulfonated aniorfic surfactant are fed to as the composition of main ingredient, and at few 40 ℃, carry out mechanical work under preferred at least 60 ℃ the temperature, and extrude by the extruder head with a plurality of extrusion cavities.In most of example, tensio-active agent is fed in the forcing machine than the weight ratio of 2 parts of tensio-active agents to surpass 1 part of synergistic agent with synergistic agent.Extrudate obviously needs further dry.In embodiment 6, that the PAS mashed prod is dry and extrude.Such PAS bar is to know in the prior art.The strip material is normally columniform, and their length is above their diameter, as described in example 2 above.
EP application 09158717.0 (WO2010/122051) discloses the high active detergent granules with low surface roughness, it is to extrude by the composition that will be rich in aniorfic surfactant, and the product cutting of extruding is formed the thin slice thinner than their width prepares.Then, with for example aqueous sodium carbonate these thin slices of spraying, to form ganoid, the free flowing granule that may look like " French beans ".In its specification sheets, illustrate, for example use that the builder salts of yellow soda ash is useful, because it is buffered in especially effectively level of aniorfic surfactant with pH, and increase ionic strength.It is said that particle also dissolves finely in water, and be suitable for being used in the washing machine of front loading (the 6th page, 19 row).
We relevant but undocumented EP application 09158718.8 discloses the high-activity particle of the linear alkylbenzene sulfonate that comprises main amount.
The invention summary
We determine, in comprising the method for using the top to load the laundry container, the coating with specified shape and prescription is extruded particle and demonstrated by unusual good cleaning and the nursing role of the perception of one group of user institute.
In especially preferred embodiment, use in coating under the situation of crystal carbonate preparation, particle does not have to show the sensation of " scorching hot on hand " in use.
Therefore, the invention provides clothes washing method, it comprises following steps:
A) provide a kind of coated detergent particle, it has orthogonal dimension x, y and z, and wherein x is 1mm to less than 2mm, and y is greater than 2mm to 8mm, and z is greater than 2mm to 8mm, and wherein said particle comprises:
I) tensio-active agent that is selected from aniorfic surfactant and nonionic surface active agent of 50-90 weight %;
The ii) water-soluble inorganic salt of 1-40 weight %;
Iii) other component of 0-20 weight %, it comprise the water-insoluble material that comprises spices that is less than 15 weight % and,
Wherein said inorganic salt are present on the described detergent for washing clothes particle as coating, and described tensio-active agent exists as nuclear,
B) described coated detergent particle is dissolved into forms washings in the water
C) with described washings treatment articles,
D) described goods are separated with described washings and
E) rinsing and dry described goods;
Wherein step c) is carried out in the laundry container that load at the top at least.
Group study shows that aforesaid method makes clothing more soft, has more bright color, and residue still less still has the cleaning action equal with conventional powder.It is most preferred that tensio-active agent and synergistic agent ratio are 1.5-2.5 in the detergent particles: 1, more preferably be 1.8-2.2: 1.When ratio further moves horizontally to high synergistic agent, the washings alkalescence that becomes too, and when it moves horizontally to high surfactant, then buffer loss ability.By synergistic agent is existed as the coating of the tensio-active agent of parcel softness and viscosity, can provide the concentrated granular with preferred surfactant and synergistic agent ratio.Do not exist other material (supporting surfactant, filler etc.) to reduce and once cleaned needed unitary dose, and therefore reduced transportation cost and increased the shelf utilization ratio.
Also reduced the influence of chemical to environment.Dosage will usually the product than routine be littler significantly, and the machine that loads for the top is approximately the product of preparation fully of 0.5-1g/L, is approximately 1-3g/L for the hand washing container.
It may be noted that by size applying the detergent for washing clothes particle has aspheric surface.Preferably, this surface portion is crooked.Apply the detergent for washing clothes particle and can be described as dish type, lenticular shaped, oblate sphere/spheroid, wherein z and y are equatorial diameters, and x is polar diameter.Preferably, similar on y and the z numerical value, but under some manufacture method since during the extruded product cutting institute's applied pressure, they may be different slightly.Generally speaking, particle has along the rotationally symmetric axis of pole axis line.
Preferably, apply the detergent for washing clothes particle and do not have any hole, that is, the topological genus that applies the detergent for washing clothes particle is 0.
Preferably y and z are 3-8mm independently.This makes and has improved solvability by the ratio that its shape further departs from spheroid and increased surface-area and volume.Use short and fat rather than long and thin particle to improve flowing and the dosage control performance of product.By applying big relatively detergent particles of the present invention, by the coat-thickness that uses the available coat-thickness of specific coating level significantly will reach greater than the washing composition particulate (0.5-2mm diameter sphere) of general size.This has obtained firm coating, and has reduced tensio-active agent and ooze out the trend that particle is become sticky by coating.In addition, in this case, significantly the synergistic agent of ratio tensio-active agent begins to dissolve before, dissolve consequently washings before surfactant dissolves at least in part by synergy.
These big relatively particles further advantage in the loading of top is that their sink rapidly and contacting with impeller in early days in cleaning.
For obtaining best solubility property, the ratio of this surface-area and volume must be greater than 3mm
-1Yet coat-thickness and this coefficient are inversely proportional to, therefore should be less than 15mm divided by the ratio of " coated particle volume " for coating " surface-area of coated particle "
-1
Preferably, it is such applying the detergent for washing clothes particle: at least 90 to 100% the coating detergent for washing clothes particle, maximum with minimum coating detergent for washing clothes particle in average x, the y of individual particle and the variation on the z size in 20%, preferred 10%.These agglomeration of particles with similar size have shown good flowing property, can be packaged in the bottle and also can give amount as liquid.
Compatibly, detergent particles comprises 0.0001-0.1 weight %, the dyestuff of preferred 0.001-0.01 weight %, and wherein said dyestuff is selected from: anionic dyestuff and nonionic dye.Dyestuff provides several useful functions.Dyestuff can help the user to identify variant production, and/or can bring into play the effect of screening agent, to cover the yellow that is washed goods.Preferably, not all particle all is same color, but has two or more colors, for example white and blueness, white and pink colour or white and orange.
Unless otherwise mentioned, all weight % refer in particle with the dry weight percent of total of (under situation about existing, comprising water of hydration).
Detailed Description Of The Invention
For can be further and understand the present invention better, will further describe with reference to various preferred and/or optional features.
The washing container that load at the top
For present specification and in the context of the present invention, the clean container that loads of top is any container that is used for washing clothes by terminal user.Usually, the capacity of such container is greater than 4 liters.
Such container comprises and preferably comprises that the semi-automatic and automatic washing machine that load at the top preferably has stirring at the device of the washings of their inside, with, in addition or alternatively, be other containers under the manual situation in stirring, preferred basin, cylinder, bucket, pond, bowl or groove.Machine for example comprises or is similar to the machine of " Tanquinho " of Brazil.
In a preferred embodiment of this invention, container is opened on top in cleaning operation process, and at least part of stirring is provided by hand.
Tensio-active agent
Apply the detergent for washing clothes particle and comprise 50-90 weight %, the most preferably tensio-active agent of 70-90 weight %.Generally speaking, the non-ionic type of surfactant system and aniorfic surfactant can be selected from " Surface Active Agents ", the 1st volume, Schwartz﹠amp; Perry, Interscience 1949, the 2 volumes, Schwartz, Perry﹠amp; Berch, Interscience 1958; The current edition that Manufacturing Confectioners Company publishes " McCutecheon ' s Emulsifiers and Detergents " or " Tenside-Taschenbuch ", H.Stache, the 2nd edition, Carl Hauser Verlag, the tensio-active agent described in 1981.Preferably, used tensio-active agent is saturated.
Aniorfic surfactant
Operable suitable anionic detergent compound normally has to contain has an appointment 8 to the organic sulfate of the alkyl of about 22 carbon atoms and the water-soluble alkali metal salts of sulfonate, and the term alkyl is used for comprising the moieties of senior acyl group.The example of suitable synthetic anionic detergent compound is sodium alkyl sulfate and potassium, especially by originating from the senior C of tallow for example or Oleum Cocois
8To C
18Those that the alcohol sulfation obtains, alkyl C
9-C
20Benzene sulfonic acid sodium salt and potassium, particularly linear secondary alkyl C
10-C
15Benzene sulfonic acid sodium salt; With the alkyl glycerol ether sodium sulfate, especially be derived from the higher alcohols and those ethers that are derived from the synthol of oil of tallow or Oleum Cocois.
Most preferred aniorfic surfactant is Zetesol NL (SLES) (especially preferably having 1-3 oxyethyl group), C
10-C
15Sodium alkyl benzene sulfonate (LAS) and C
12-C
18Sodium alkyl sulfate (PAS).Alkyl ester sulfonate such as methyl ester sulfonate (MES) can all or part ofly be used for substituting other aniorfic surfactant.
Those tensio-active agents, the alkyglycosides tensio-active agent described in the EP-A-070 074 and the alkyl monoglycosides that demonstrate anti-saltouing property described in EP-A-328 177 (Unilever) also are suitable.The chain of tensio-active agent can be side chain or straight chain.
Can also there be soap.Used fatty acid soaps preferably contains has an appointment 16 to about 22 carbon atoms, preferably linear configuration.Preferably account for the 0-30 weight % of total negatively charged ion from the negatively charged ion contribution of soap.
Preferably, the aniorfic surfactant of at least 50 weight % is selected from: C
11-C
15Sodium alkyl benzene sulfonate and C
12-C
18Sodium alkyl sulfate.Even more preferably, aniorfic surfactant is C
11-C
15Sodium alkyl benzene sulfonate
Preferably, aniorfic surfactant is present in the coating detergent for washing clothes particle with the level of total surfactant 15-85 weight %, more preferably 50-80 weight %.
Nonionogenic tenside
Particularly, operable suitable non-ionic detergent compound comprises that compound (for example, Fatty Alcohol(C12-C14 and C12-C18), acid, acid amides or alkylphenol) with hydrophobic group and active hydrogen atom is with the reaction product of oxirane (especially independent oxyethane or itself and propylene oxide).Preferred non-ionic detergent compound is C
6-C
22Alkylphenol-ethylene oxide condensate is generally 5-25EO, i.e. each molecule 5-25 ethylene oxide unit, and aliphatic C
8-C
18The condensation product of uncle or secondary straight or branched alcohol and oxyethane is generally 5-50EO.Preferably, non-ionic type is 10-50EO, more preferably 20-35EO.Special preferred alkyl ethoxylate is the most especially for having those of 25-35EO, because these provide good especially foaming properties.
Preferably, nonionic surface active agent is with the 5-75 weight % of total surfactant, and more preferably the level of total surfactant 10 to 40 weight % is present in the coating detergent for washing clothes particle.
Cationic surfactant can be used as submember and preferably exists with the level of total surfactant 0-5 weight %.
Preferably, before drying, all surface promoting agent is mixed.Can use conventional mixing equipment.The tensio-active agent of detergent for washing clothes particle is endorsed with by extruding or roller is suppressed to form, and coating inorganic salt subsequently.
Profoamer is to choose wantonly as betaines, oxidation Ammonia and/or other zwitter-ions and amphoterics, because composition of the present invention shows enough forming processs usually.
The lime-resistant surfactant system
In one aspect of the method, used surfactant system is anti-calcium, and this is preferred aspect, because this has reduced the demand to synergistic agent.
Preferably do not need to exist the surfactant mixture of synergistic agent for effective washing in the hard water.If their tests by hereinafter listing are called the lime-resistant surfactant mixture with such mixture.Yet the present invention also can be used for using washing natural generation or the soft water that the use water-softening agent makes.In this case, the calcium tolerance recedes into the background and can use anti-calcium compounds mixture in addition.
The calcium tolerance of following test surfaces active agent intermixture:
Concentration with every premium on currency 0.7g solid surfactant prepares the surfactant mixture of being tested, and it contains the capacity calcium ion so that French hardness is 40 (4 * 10
-3Mole Ca
2+).With other do not contain hardness ions ionogen (as, sodium-chlor, sodium sulfate and sodium hydroxide) add in the solution, ionic strength is adjusted to 0.05M and with pH regulator to 10.After 15 minutes, measure the light of 540nm wavelength by the absorption of 4mm sample in specimen preparation.Carrying out ten times measures and calculating mean value.Generation is considered to anti-calcium less than the sample of 0.08 absorption value.
The example that satisfies the surfactant mixture of above-mentioned calcium tolerance test comprises having the LAS tensio-active agent (himself not being anti-calcium) mixes as other lime-resistant surfactants of major portion and one or more (cosurfactant), with generation almost less than those of mixture that use and passed through the enough anti-calcium of given test with synergistic agent.The suitable cosurfactant of anti-calcium comprises that SLES 1-7EO and alkyl-ethoxylate nonionic surface active agent, particularly fusing point are lower than those of 40 ℃.
The LAS/SELS surfactant mixture has the foaming properties that is better than the LAS honionic surfactant mixture and is preferred for the hand washing preparation of needs high level foam therefore.Can use SLES with the level of the 30 weight % that are up to surfactant mixture.
Water-soluble inorganic salt
Water-soluble inorganic salt is preferably selected from water miscible carbonate, chloride salt, silicate and vitriol, or its mixture, and most preferably based on total water-soluble inorganic salt, 70-100% is yellow soda ash.Water-soluble inorganic salt is present on the particle as coating.
Although those skilled in the art will recognize that the laminated coating that can use identical or different coated material, for easy and simple to handle, and the thickness of maximization coating, the preferred single layer coating.For making detergent particles obtain best anti-caking performance, the content of coating should be at the 1-40 of particle weight %, and preferred 20-40 weight % is more preferably in the scope of 25-35 weight %.
Preferably the deposition of the aqueous solution by water-soluble inorganic salt puts on coating on the surface of tensio-active agent nuclear.Perhaps, coating can use slurry to carry out.The aqueous solution preferably contains greater than 50g/L, more preferably greater than the salt of 200g/L.The water-based injection that has now had been found that the coating solution in the fluidized-bed has produced good result, and can also produce the slight rounding of detergent particles in fluid mapper process.May need drying and/or cooling to finish this method.
The tensio-active agent of the coating detergent for washing clothes particle of preferred anti-calcium contains the anion surfactant of 15-100 weight % based on surfactant package, and wherein surfactants based 20-30 weight % is Zetesol NL.
The water-soluble inorganic salt that is included in the coating very preferably is crystal carbonate.The coated detergent particle touches under water and user's the situation of skin simultaneously in cleaning process, and this will have obvious benefit, because when being exposed to water, the heat that particle produces can be not many producing under the anhydrous situation as carbonate.This is important preferred feature, because user's warp hand cleaning composition product commonly used and water, and will adopt the product description of anhydrous sodium carbonate to feel for having " scorching hot on hand ".
Preferably the inorganic salt in the coating are crystal carbonates of 100 weight %.This provides best protection to protection against the tide.The level of crystal carbonate can be low to moderate 50 weight % of inorganic salt in the coating.
Dyestuff
Dyestuff is the present invention's composition very preferably.The dyestuff that is fit to is described among the Industrial Dyes 2003 Wiley-VCH ISBN 3-527-30426-6 that K.Hunger edits.
Dyestuff used in this invention is selected from anionic and nonionic dye.The anionic dyestuff is electronegative in the aqueous medium of pH 7.The example of anionic dyestuff can be referring in the acid and substantive dyestuff classification in the color index (Colour Index) (the dyer person of being and colorist association (Society of Dyers and Colourists) and U.S. textile chemist and printing and dyeing Shi Xiehui 2002 (American Association of Textile Chemists and Colorists 2002)).The anionic dyestuff preferably contains at least one sulfonate or carboxylate groups.Nonionic dye is uncharged in the aqueous medium of pH7, and example is found in the dispersed dye classification in the color index (Colour Index).
Dyestuff can alkoxylate.The alkoxylate dyestuff preferably has following general formula: dyestuff-NR
1R
2NR
1R
2Group is connected to the aromatic nucleus of dyestuff.R
1And R
2Be independently selected from the polyoxyalkylene chain with 2 or more repeating units, and preferably have 2-20 repeating unit.The example of polyoxyalkylene chain comprises oxyethane, propylene oxide, glycidyl ether (glycidol oxide), oxybutylene and composition thereof.
Preferred polyoxyalkylene chain is [(CH
2CR
3HO)
x(CH
2CR
4HO)
yR
5), x+y≤5 wherein, wherein y 〉=1, and z=0-5, R
3Be selected from: H, CH
3, CH
2O (CH
2CH
2O)
zH and composition thereof; R
4Be selected from: H, CH
2O (CH
2CH
2O)
zH and composition thereof; And R
5Be selected from: H and CH
3
The preferred alkoxylate dyestuff that is used for the present invention is:
Preferably, dyestuff is selected from matching stain, dispersed dye and alkoxylate dyestuff.
Most preferably, dyestuff is nonionic dye.
Preferably, dyestuff be selected from have anthraquinone, list-azo, two-azo, xanthene, phthalocyanine and azophenlyene chromophoric those.More preferably, dyestuff is selected from and has: those of anthraquinone and list-azo chromophore.
In order to obtain painted particle, add in coating solution or the slurry dyestuff and stirring, be applied over the nuclear of particle afterwards.Apply and preferably to be sprayed on the nuclear particle as described in detail above by any suitable method.
Dyestuff can be any color, and preferred coloring agent is blueness, purple, green or red.Most preferably, dyestuff is blueness or purple.
Preferably, dyestuff is selected from: acid blue 80, acid blue 62, acid violet 43, ACID GREEN 25, sun blue 86, acid blue 59, acid blue 98, direct purple 9, direct purple 99, direct purple 35, direct purple 51, acid violet 50, quinoline yellow, Xylene Red 94, Xylene Red 51, Xylene Red 95, acid red 92, Xylene Red 98, acid red 87, turmeric yellow 73, Xylene Red 50, acid violet 9, Xylene Red 52, food black 1, food black 2, azogeramine 63, Acid Black 1, von Muller's indicator 24, acid yellow 23, turmeric yellow 40, acid yellow 11, acid red 18 0, azogeramine 55, azogeramine, Xylene Red 33, Xylene Red 41, azogeramine 9, von Muller's indicator 10, Xylene Red 27, Xylene Red 26, von Muller's indicator 20, von Muller's indicator 6, Sulfonated Al and Zn phthalocyanine, solvent violet 13,63 ,DIS,PER,SE ,Vio,let, 63 26,63 ,DIS,PER,SE ,Vio,let, 63 28, solvent green 3, solvent blue 63, Disperse Blue-56,63 ,DIS,PER,SE ,Vio,let, 63 27, solvent yellow 33, Disperse Blue-79: 1.
What dyestuff was preferred for that the laundry fabric gives pure white sense covers dyestuff (shading dye).Dyestuff can be covalently bound on the polymeric material.Can use dye combinations.
Water content
Under 293K and 50% relative humidity, particle preferably comprises the water of 0-15 weight %, more preferably 0-10 weight %, the most preferably water of 1-5 weight %.This helps stability in storage and the mechanical property thereof of particle.
Other auxiliary agent
Hereinafter described auxiliary agent may reside in the coating or nuclear of particle.
Fluorescent agent
Apply the detergent for washing clothes particle and preferably comprise fluorescent agent (white dyes).Fluorescent agent is that such fluorescent agents that know and many can be buied.Usually, these fluorescent agents are supplied with the form of its an alkali metal salt and are used, for example, and sodium salt.The total amount of one or more used fluorescent agents is generally 0.005-2 weight %, more preferably 0.01-0.1 weight % in the composition.Be applicable to the 7th chapter of the Industrial Dyes that the fluorescent agent among the present invention is edited at K.Hunger, among the 2003Wiley-VCH ISBN 3-527-30426-6 description arranged.
Preferred fluorescent agent is selected from toluylene biphenyl class, triazine radical amido stilbene class, two (1,2,3-triazoles-2-yl) stilbene class, two (benzo [b] furans-2-yl) biphenyl class, 1,3-phenylbenzene-2-pyrazolines and coumarins.Preferred fluorescent agent is Sulfonated.
Preferred fluorescent agent classification is: the toluylene biphenol compound, for example, Tinopal (trade mark) CBS-X, diamines stilbene disulfonic acid compound, for example, Tinopal DMS pure Xtra and Blankphor (trade mark) HRH, and pyrazoline compounds, for example, Blankophor SN.Preferred fluorescent agent is: 2-(4-styryl-3-sulfophenyl)-2H-naphthols [1,2-d] triazole sodium, 4,4 '-it is two that { [(4-anilino-6-(N-methyl-N-2 hydroxyethyl) amino 1,3,5-triazine-2-yl)] amino } stilbene-2-2 ' disulfonic acid disodium, 4,4 '-two { [(4-anilino-6-morpholino-1,3,5-triazine-2-yl)] amino } stilbene-2-2 ' disulfonic acid disodium and 4,4 '-two (2-thio phenyl vinyl) biphenyl disodium.
Tinopal
DMS is 4, the disodium salt of 4 '-two { [(4-anilino-6-morpholino-1,3,5-triazines-2-yl)] amino } stilbene-2-2 ' disulfonic acid disodium.Tinopal
CBS is 4, the disodium salt of 4 '-two (2-sulfonated phenylethylene base) biphenyl disodium.
Spices
Preferably, composition comprises spices.Spices is preferably at 0.001-3 weight %, most preferably in the scope of 0.1-1 weight %.At CTFA (Cosmetic, Toiletry and Fragrance Association) the 1992 International Buyers Guide of CFTA Publications publication and the OPD 1993 Chemicals Buyers Directory 80 of Schnell Publishing Co publication
ThMany suitable spices examples are provided among the Annual Edition.
It is common having multiple fragrance component in preparation.In composition of the present invention, can there be four kinds or more kinds of, preferred five kinds or more kinds of, more preferably six kinds or more kinds of, so that seven kinds or more kinds of different fragrance component.
In spice mixt, preferred 15-25 weight % is that head is fragrant.Head is fragrant by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80[1955]) definition.Preferred perfume (or spice) is selected from tangerine oil, linalool, linalyl acetate, lavandula angustifolia, dihydromyrcenol, rose oxide and suitable-3-hexanol.
Polymkeric substance
Composition can comprise one or more other polymkeric substance.Example is carboxymethyl cellulose, poly-(ethylene glycol), poly-(vinyl alcohol), polymine, ethoxylation polymine, water-soluble polyester polymer poly carboxylicesters, as polyacrylic ester, toxilic acid/acrylic copolymer and methacrylic acid Lauryl Ester/acrylic copolymer.
Enzyme
There are one or more enzymes in the preferred composition of the present invention.
Preferably, the level of every kind of enzyme is based on product meter 0.0001 weight % to 0.5 weight % protein.
Especially the enzyme of Kao Lving comprises proteolytic enzyme, α-Dian Fenmei, cellulase, lipase, peroxidase/oxydase, pectate lyase and mannase, or its mixture.
Suitable lipase comprises those of bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.Useful lipase example comprises the lipase from Humicola (Humicola) (the thermophilic trichosporon spp of synonym (Thermomyces)), for example described in EP 258 068 and the EP 305 216 from pubescence humicola lanuginosa (H.lanuginosa (T.lanuginosus)) or described in WO96/13580 from special humicola lanuginosa (H.insolens); Rhodopseudomonas (Pseudomonas) lipase, for example from Pseudomonas alcaligenes (P.alcaligenes) or pseudomonas pseudoalcaligenes (P.pseudoalcaligenes) (EP 218 272), pseudomonas cepacia (P.cepacia) (EP 331 376), (GB 1 for pseudomonas stanieri (P.stutzeri), 372,034), Pseudomonas fluorescens (P.fluorescens), pseudomonas strain SD 705 (WO 95/06720 and WO 96/27002), Wisconsin pseudomonas (P.wisconsinensis) (WO 96/12012); Bacillus (Bacillus) lipase, for example from subtilis (B.subtilis) (Dartois etc. (1993), Biochemica et Biophysica Acta, 1131,253-360), bacillus acidocldarius (B.stearothermophilus) (JP 64/744992) or bacillus pumilus (B.pumilus) (WO 91/16422).
Other examples are lipase Variant, those described in WO92/05249, WO 94/01541, EP 407 225, EP 260 105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063, WO 09/107091 and WO09/111258.
Preferred commercially available lipase comprises Lipolase
TMWith Lipolase Ultra
TM, Lipex
TM(Novozymes A/S) and Lipoclean
TM
Method of the present invention can be carried out in the presence of the Phospholipid hydrolase that classifies as EC 3.1.1.4 and/or EC 3.1.1.32.As used in this article, the term Phospholipid hydrolase is that phosphatide is had active enzyme.
Phosphatide, as Yelkin TTS or phosphatidylcholine, its by with two lipid acid externally (sn-1) and middle (sn-2) the position esterification and form at the glycerine of the 3rd position esterification with phosphoric acid; Phosphoric acid and then can esterification become amino alcohol.Phospholipid hydrolase is the enzyme that participates in the phosphatide hydrolysis.Can distinguish the type of several phospholipase activity, comprise phospholipase A
1And A
2, fatty acyl group of its hydrolysis (respectively in sn-1 and sn-2 position) is to form lysophospholipid; And lysophospholipase (or phospholipase B), its can the hydrolysis lysophospholipid in remaining fatty acyl group.Phospholipase C and Phospholipase D (phosphodiesterase) discharge DG or phosphatidic acid respectively.
Suitable proteolytic enzyme comprises animal, plant or microbe-derived those.The preferred microorganism source.Comprise chemically modified or protein engineering mutant.Proteolytic enzyme can be serine protease or metalloprotease, preferred alkaline microbial protease or tryptase.Preferably the proteolytic enzyme that can buy comprises Alcalase
TM, Savinase
TM, Primase
TM, Duralase
TM, Dyrazym
TM, Esperase
TM, Everlase
TM, Polarzyme
TMAnd Kannase
TM(Novozymes A/S), Maxatase
TM, Maxacal
TM, Maxapem
TM, Properase
TM, Purafect
TM, PurafectOxP
TM, FN2
TMAnd FN3
TM(Genencor International Inc.)
Method of the present invention can be carried out in the presence of the at that classifies as EC 3.1.1.74.At used according to the invention can be any source.Preferred at is microbe-derived, particularly bacterium, fungi or yeast source.
Suitable amylase (α and/or β) comprises those of bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.Amylase comprises, for example, α-Dian Fenmei available from bacillus (Bacillus), for example, be described in more detail in GB 1, the specific bacterial strain of Bacillus licheniformis in 296,839 (B.licheniformis), or disclosed bacillus (Bacillus sp.) bacterial strain among WO 95/026397 or the WO 00/060060.The amylase that can buy is Duramyl
TM, Termamyl
TM, Termamyl Ultra
TM, Natalase
TM, Stainzyme
TM, Fungamyl
TMAnd BAN
TM(Novozymes A/S), Rapidase
TMAnd Purastar
TM(from Genencor International Inc.).
Suitable cellulase comprises those of bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.Suitable cellulase comprises from bacillus (Bacillus), Rhodopseudomonas (Pseudomonas), Humicola (Humicola), fusarium (Fusarium), Thielavia (Thielavia), the cellulase of Acremonium (Acremonium), for example, by special humicola lanuginosa (Humicola insolens), autochthonal shuttle spore mould (Thielavia terrestris), thermophilicly ruin the fungal cellulase that silk mould (Myceliophthora thermophila) and Fusarium oxysporum (Fusarium oxysporum) produce, it is disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, among WO 96/029397 and the WO 98/012307.The cellulase that can buy comprises Celluzyme
TM, Carezyme
TM, Endolase
TM, Renozyme
TM(Novozymes A/S), Clazinase
TMWith Puradax HA
TM(Genencor International Inc.), and KAC-500 (B)
TM(Kao Corporation).
Suitable peroxidase/oxydase comprises those of plant, bacterium or originated from fungus.Comprise chemically modified or protein engineering mutant.Useful peroxidase example comprises the peroxidase from Coprinus (Coprinus), for example from Coprinus cinereus (C.cinereus) and variant thereof, and those described in WO 93/24618, WO 95/10602 and WO 98/15257.The peroxidase that can buy comprises Guardzyme
TMAnd Novozym
TM51004 (Novozymes A/S).
How suitable enzyme is disclosed among WO2009/087524, WO2009/090576, WO2009/148983 and the WO2008/007318.
Can use the enzyme combination.Particularly preferred be to use lipase, proteolytic enzyme and be selected from amylase and mannase in a kind of or the two combination.
Enzyme stabilizers
Any enzyme that exists in the composition can use conventional stablizer to stablize; for example; polyvalent alcohol (as propylene glycol or glycerine), sugar or sugar alcohol, lactic acid, boric acid or boric acid derivatives are (for example; and composition can be as preparing described in for example WO 92/19709 and WO 92/19708 aromatic borate) or phenyl-boron dihydroxide derivative (as 4-formyl radical phenyl-boron dihydroxide).
Sequestrant
The sequestrant of the ion except calcium ion and magnesium ion may reside in and applies in the detergent for washing clothes particle.A kind of suitable sequestrant (it also plays a part as the synergistic agent of removing iron) is citrate.Citrate preferably exists with the level based on the 5-15 weight % of total particle.Citrate can exist with the form of salt or acid.When existing with acid, when being exposed to water, particle can produce evolving gas.This can produce local turbulence, the indicator that it has promoted dissolving and has been used as cleaning.Phosphoric acid salt, for example Dequest
TM2010 also can be used as sequestrant.
Preferably, apply the detergent for washing clothes particle and do not contain peroxide bleaching agent, for example percarbonate, perborate and other peracid.
Pei Zhi product fully
Preferably " basis (chassis) " preparation comprises:
LAS/NI base (more low foaming scheme):
(i) the LAS sodium of 50-70 weight % and 7-35EO non-ionic type,
The (ii) yellow soda ash of 20-30 weight %,
The (iii) carboxymethyl cellulose of 1-3 weight %,
(iv) the spices of 1-3 weight % and
(the v) moisture of 0-2 weight %.
In above-mentioned preparation, some LAS can replace with PAS.
LAS/PAS/SLES base (high foam method case):
(i) LAS sodium, PAS and the SLES of 50-70 weight %,
The (ii) yellow soda ash of 20-30 weight %,
The (iii) carboxymethyl cellulose of 1-3 weight %,
(iv) the spices of 1-3 weight % and
(the v) moisture of 0-2 weight %.
Can be with the Citrate trianion/citric acid in combination of the scheme LAS/NI base or the LAS/PAS/SLES base and 5-10 weight % level.
Arbitrary preparation can comprise soil release polymer, is preferably polyester material, for example the Texcare SRN170 of 1-5 weight % level.
In order further to be understood and to implement the present invention in practice, will further be described by the mode of embodiment.
Embodiment
Embodiment 1: granule manufacture
Surfactant mixture drying, that grind (LAS/PAS/NI is 68/17/15 by weight) and the 37.38g spice oil of 1962.5g are fully mixed.Use ThermoFisher 24HC twin screw extruder then, under 8 kilograms/hour speed, operate, mixture is extruded.The temperature in of forcing machine is set to 20 ℃, is warmed up to 40 ℃ before being about to arrive Die and mould plate.The Die and mould plate that uses is drilled with the circular port of 6 5mm diameters.
Use the high-speed cutting machine, after Die and mould plate, will extrude product cutting, have～particle of 1.1mm thickness with generation.Cutting machine deforms the dish that downcuts from extruded product, produces difference slightly between y and z size.
The above-mentioned extrudate of 764g is loaded in the fluidising chamber of Strea 1 laboratory fluidized bed dryer (Aeromatic-Fielder AG), and uses the solution that in 748.3g water, contains 320.7g yellow soda ash of top-spray structure spraying 1069g to apply.
Coating solution is fed in the nozzle of Strea 1 by peristaltic pump (Watson-Marlow model 101U/R), and original speed is 3.3 gram/minute, is elevated to 9.1 gram/minute in the process of coated test.
In the fluidized-bed spreader operational process, the initial air temperature in is 55 ℃, is increased to 90 ℃ in the process of coated test, is 45-50 ℃ and keep temperature out in whole coating procedure.
The particle of gained is oblate sphere, and it has following mean sizes: x=1.1mm, y=4.0mm, z=5.0mm.Each particle weight is～0.013g.
Embodiment 2: wash studies
Washing composition research is carried out in the washing machine that load at the Whirlpool top of Brazil, is set to cold medium washing, charges into 12FH water (45L).Load comprises cotton and 31% the knitting polyester of 31% knitted cotton, 38% the polymerization of 3kg.Use the product dosage of 20-25g, carry out repeated washing six times.But use is provided with the extensive test set of particulate matter, fat and grease, enzyme susceptibility and bleach spot and measures detergent power.The result provides in following table.
The result of higher numerical value demonstrates " Skip " with respect to the standard of being set to
TMThe better score of powder.
As can be seen, composition of the present invention has shown significant improvement with respect to standard from these results, although and they are dumpable compositions, also show better than conventional liq significantly.
Embodiment 3: the test of black pouch
With Skip
TMPowder (from Argentina) and composition of the present invention stitch in the black cotton pouch.Use the cycle of mentioning in the following table to wash.Before preparing pouch the black cotton 60 ℃ of following prewashing 3 times to avoid dyestuff in black pouch test process, to shift (Miele professional 350gRobijn, 8kg black cotton).Pouch loads with the different Betengent product of 10g, and the result is as shown in the table.
| ? | Skip (comparison) | The present invention |
| 40 degree cotton circulations | Some residues | Noresidue |
| 30 degree woolen knitwear circulations | A lot of residues | Slight residue |
The result has shown embodiments of the present invention, although size begins with the particle bigger than powder, has still obtained residue still less.
Example 4: group's test
Invite one group from 80 human consumers in Thailand and South Africa product of the present invention and powder-product that they are current to be compared secretly.
Statistically evident discovery is product of the present invention " dissolving thoroughly ", " effectively cleaning ", " clothing is become clear ", " making the clothing softness " and " making the easier flatiron of clothing ".
In this technology observational study, the consumer alert is to comparing with their current powder-product, and product according to the present invention is not " scorching hot on hand ".
Embodiment 5: the heating contrast
Temperature when the present composition is dissolved rises to raise with the temperature that is purchased laundry composition and compares in the two at plastic tank and glass pot.In both cases, the product with 75g joins in the water of 70g.Rise with 300 seconds time interval monitoring temperature.In all cases, use the temperature rising of particle of the present invention to be markedly inferior to the temperature rising that use is purchased product.
Result given below is the temperature of the product that list on the left side when using bucket.
The rising of the initial temperature of embodiment of the present invention is purchased product far below contrast as can be seen.
Claims (15)
1. clothes washing method, it comprises following steps:
A) provide the coated detergent particle, it has orthogonal dimension x, y and z, and wherein x is 1mm to less than 2mm, and y is greater than 2mm to 8mm, and z is greater than 2mm to 8mm, and wherein said particle comprises:
I) tensio-active agent that is selected from aniorfic surfactant, nonionic surface active agent and composition thereof of 50-90 weight %;
The ii) water-soluble inorganic salt of 1-40 weight %;
Iii) other component of 0-20 weight %, it comprise the water-insoluble material that comprises spices that is less than 15 weight % and,
Wherein said inorganic salt are present on the described detergent for washing clothes particle as coating, and described tensio-active agent exists as nuclear;
B) described coated detergent particle is dissolved into forms washings in the water;
C) with described washings treatment articles;
D) described goods are separated with described washings; With
E) rinsing and dry described goods;
Wherein step c) is carried out in the laundry container that load at the top at least.
2. according to the method for claim 1, wherein said coated detergent particle further comprises one or more dyestuffs, be preferably selected from matching stain, dispersed dye and alkoxylate dyestuff, more preferably be selected from have anthraquinone, list-azo, two-azo, xanthene, phthalocyanine and azophenlyene chromophoric those, most preferably be selected from have anthraquinone and list-azo-group chromophoric those.
3. according to the method for claim 1 or 2, wherein the described inorganic salt that are present on the described detergent for washing clothes particle as coating comprise yellow soda ash.
4. according to each method of aforementioned claim, wherein said aniorfic surfactant comprises alkylbenzene sulfonate, preferred C
10-C
15Sodium alkyl benzene sulfonate; Sulfated alkyl ether preferably has the Zetesol NL of 1-3 oxyethyl group; And/or alkyl-sulphate, preferred C
12-C
18Sodium alkyl sulfate.
5. according to each method of claim 1-4, wherein said tensio-active agent comprises the aniorfic surfactant of 15-100 weight %, and wherein 20-30 weight % is Zetesol NL, based on the total surfactant meter.
6. according to each method of claim 1-4, wherein said tensio-active agent comprises based on the aniorfic surfactant of the 15-85 weight % of total surfactant and the nonionic surface active agent of 5-75 weight %.
7. according to claim 1-4 and 6 each methods, wherein said nonionic surface active agent is the alcohol ethoxylate of 10-50EO.
8. according to the method for claim 7, wherein said nonionic surface active agent is the aliphatic C of straight or branched
8-C
18The condensation product of uncle or secondary alcohol and 20-35 ethylene oxide group.
9. according to each method of aforementioned claim, wherein said coated detergent particle comprises 20-40 weight %, and the inorganic salt synergistic agent of preferred 25-35 weight % is as coating.
10. according to each method of aforementioned claim, wherein said particle comprises 0-15 weight %, the water of preferred 1-5 weight %.
11. according to each method of aforementioned claim, in the coating detergent for washing clothes particle of at least 90 quantity % to 100 quantity % maximum with minimum coating detergent for washing clothes particle in the variation on x, y and the z size in 20 quantity %, preferred 10 quantity %.
12. according to each method of aforementioned claim, the laundry container that load at wherein said top is selected from the semi-automatic or automatic washing machine that load at the top.
13. according to the method for claim 12, wherein said machine has the device that stirs described washings.
14. according to each method of claim 1-11, the laundry container that load at wherein said top comprises basin, cylinder, bucket, pond, bowl or groove.
15. according to each method of aforementioned claim, wherein at coated detergent particle described in the described cleaning process simultaneously and water and user's skin contact.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10187500.3 | 2010-10-14 | ||
| EP10187500 | 2010-10-14 | ||
| PCT/EP2011/067159 WO2012049033A1 (en) | 2010-10-14 | 2011-09-30 | Top-loading laundry vessel method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103282477A true CN103282477A (en) | 2013-09-04 |
| CN103282477B CN103282477B (en) | 2015-04-01 |
Family
ID=43759466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180049085.7A Active CN103282477B (en) | 2010-10-14 | 2011-09-30 | Top-loading laundry vessel method |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2627751B1 (en) |
| CN (1) | CN103282477B (en) |
| BR (1) | BR112013009127B1 (en) |
| WO (1) | WO2012049033A1 (en) |
| ZA (1) | ZA201302655B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020109227A1 (en) | 2018-11-28 | 2020-06-04 | Unilever N.V. | Large particles |
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Also Published As
| Publication number | Publication date |
|---|---|
| BR112013009127B1 (en) | 2020-05-26 |
| BR112013009127A2 (en) | 2016-07-19 |
| CN103282477B (en) | 2015-04-01 |
| WO2012049033A1 (en) | 2012-04-19 |
| EP2627751A1 (en) | 2013-08-21 |
| EP2627751B1 (en) | 2015-06-03 |
| ZA201302655B (en) | 2014-06-25 |
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