CN101970631B - Laundry treatment compositions - Google Patents

Laundry treatment compositions Download PDF

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CN101970631B
CN101970631B CN2009801087457A CN200980108745A CN101970631B CN 101970631 B CN101970631 B CN 101970631B CN 2009801087457 A CN2009801087457 A CN 2009801087457A CN 200980108745 A CN200980108745 A CN 200980108745A CN 101970631 B CN101970631 B CN 101970631B
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laundry treatment
treatment compositions
particle
sio
granular laundry
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CN101970631A (en
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S·N·巴彻洛尔
A·P·帕克
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Unilever NV
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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
    • C11D3/12—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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
  • Silicon Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

According to the invention there is provided a granular laundry treatment composition including a spherical SiO2 particle for use in the wash cycle. A method for applying these compositions during the wash cycle of a laundry process as well as the use of these particles to reduce clothes damage is also included.

Description

Laundry treatment compositions
Invention field
The method that the present invention relates to wash the laundry detergent composition of interpolation and during the cycles of washing of human consumer's laundry processes, use it.
Background technology
Colour clothes gets consumer reception very much.In order to remove the spot on the washes, clothing is adopted detergent compositions vigorous stirring in water.This process causes the damage to the clothing surface, and this has reduced their aesthstic attractive force.This damage especially becomes problem when using the granular laundry compsn.
WO 2007/111887 (Proctor & Gamble) discloses the liquid compsn that comprises dope dye and pearling agent.Add this pearling agent to offset of the darken of this dope dye to the outward appearance of this liquid compsn.Itself can be organic or inorganic for this pearling agent, discloses the glass of glass or metal oxide-coated.
US 4,051, and 046 (Procter & Gamble) discloses the detergent composition that comprises the tensio-active agent and the water-fast particulate material basically of 1～50 micrometer range of the lower concentration that is used to provide the fabric benefit.This document also discloses and has used the particulate state water-insoluble material that has greater than about 50 microns mean diameter can not obtain the above-mentioned fabrics benefit.
Summary of the invention
We have found that SiO 2Particle provides improved color protection through reducing the damage that is caused by fabric washing.
In one aspect, the invention provides and comprise the phosphatic granular laundry treatment compositions that is less than 1wt%, comprising:
(i) 0.1wt%～40wt%, the spherical SiO of preferred 0.5～5wt% 2Particle, this SiO 2Particle has the size at 0.1～5000 micrometer range;
The (ii) tensio-active agent of 2～70wt%; With
The (iii) washing assistant of 1～50wt%.
Preferably, this spherical SiO 2Particle is selected from wherein to have at the sand of the size of 1～2000 micrometer range and/or wherein has the glass in the size of 100～2000 micrometer ranges.
Second aspect of the present invention provides the home method of handling fabric, and this method may further comprise the steps:
(i) handle fabric with the aqueous solution of the compsn of the first aspect of 1～20g/l; With
(ii) rinsing and dry this fabric.
The third aspect of the invention provides spherical SiO 2Particle is used for being reduced in the purposes of family expenses master washing process to the damage of washing clothes.
Preferably in aforementioned applications, this spherical SiO 2Particle is selected from wherein to have at the sand of the size of 1～2000 micrometer range and/or wherein has the glass in the size of 100～2000 micrometer ranges.
Detailed Description Of The Invention
Only if different statements is arranged, components contents is all in the wt% of total compsn in this granular laundry treatment compositions that this paper quotes.
This spherical SiO 2Particle should have＞and 80%, the sphericity (axial ratio) of preferred＞94%.This sphericity (axial ratio) measuring that be numerical value in the length/width relation of 0～1 scope.This length is the shortest axle, and width is the most normal axle.Perfectly circle has 1.0 sphericity value, and thin rectangle value is near 0.In order to calculate this sphericity, should take pictures to this particle, preferably with the microscope that is fit to, for example can be available from Malvern TMPharmaVision 830.
This spherical SiO 2Particle is preferably selected from wherein to have at the sand of the size of 1～2000 micrometer range and/or wherein has the glass in the size of 100～2000 micrometer ranges.
Preferably, this spherical SiO 2Particulate is of a size of 100～2000 microns, and more preferably 100～1000 microns, even more preferably 100～500 microns, for example 100～200 microns.
This spherical SiO 2The particulate size is to use sizing screen to measure, and it is reservation or passes through this sieve.
This spherical SiO 2Particle comprises that content is 50～100wt%, preferred 55～100wt%, the more preferably SiO of 65～100wt% 2Alternately, this SiO 2Particle can comprise other components, and the example is Na 2O, CaO and MgO.If really exist, these other components are preferably with based on this SiO so 2Particulate wt% is 45wt% or still less, more preferably 35wt% or still less exist.
Tensio-active agent
Said compsn comprises 2～70wt%, most preferably the tensio-active agent of 10～30wt%.Generally, the nonionic of surfactant system and AS can be selected from " Surface Active Agents " Vol.1, Schwartz & Perry; Interscience 1949, Vol.2, Schwartz; Perry & Berch, Interscience 1958; Current version or " Tenside-Taschenbuch " of " McCutcheon ' s Emulsifiers and Detergents " that Manufacturing Confectioners Company publishes; H.Stache; 2nd Edn., Carl Hauser Verlag, the tensio-active agent of describing in 1981.Preferably, used tensio-active agent is saturated.
Operable suitable nonionic detergent compounds is particularly including the reaction product of the compound with hydrophobic grouping and active hydrogen atom (for example fatty alcohol, acid, acid amides or alkylphenol) and oxirane (particularly separately or with the oxyethane of propylene oxide).Specific nonionic detergent compounds is C 6～C 22Alkylphenol-ethylene oxide condensate, 5～25EO normally, i.e. 5～25 ethylene oxide units of each molecule, and aliphatic C 8～C 18The condensation product of straight or branched uncle or secondary alcohol and oxyethane (normally 5～40 EO).
Operable suitable anionic detergent immunomodulator compounds normally has the organic sulfate of the alkyl that comprises about 8～about 22 carbon atoms and the water-soluble alkali metal salts of sulphonate, and term alkyl is used to comprise the moieties of senior acyl group.The instance of the synthetic anionic detergent compound that is fit to is sodium alkyl sulfate and potassium, especially through the senior C of sulfation 8～C 18Those that alcohol obtains are by for example tallow oil (tallow oil) or Oleum Cocois preparation; Alkyl C 9～C 20Supragil GN and potassium, particularly linear secondary alkyl C 10～C 15Supragil GN; With alkyl glycerol base ether sodium sulfate, especially be derived from the higher alcohols and those ethers that are derived from the synthol of oil of tallow oil or Oleum Cocois.The preferred anionic surfactants detergent compound is C 11～C 15Sodium alkyl benzene sulfonate and C 12～C 18Sodium alkyl sulfate.Also operable is following tensio-active agent, those that for example describe among the EP-A-328177 (Unilever), and it demonstrates has resistance, the alkyl polyglycoside tensio-active agent of describing among the EP-A-070074 and alkyl list glycosides to saltouing.
The preferred surfactants system is the mixture of negatively charged ion and nonionogenic tenside active material, the negatively charged ion of particularly pointing out among the EP-A-346 995 (Unilever) and the group and the instance of nonionogenic tenside.Especially preferred is such surfactant system, and it is C 16～C 18An alkali metal salt of primary alcohol sulfate, and C 12～C 15The mixture of primary alconol 3～7EO ethoxylate.
This nonionogenic tenside preferably with surfactant system greater than 10%, for example the amount of 25～90wt% exists.AS can be for example exists with the amount of about 5wt%～about 40wt% scope of said surfactant system.
Washing assistant or complexing agent
Said compsn comprises the washing assistant of 1～50wt%.
The washing assistant material can be selected from 1) the calcium sequestrant material, 2) the precipitation threshold material, 3) calcium ion-exchanged material and 4) their mixture.
Preferably when using insoluble inorganic builders (for example zeolite), this size at 0.1～10 micrometer range (by from Malvern TMThe Mastersizer 2000 grain size analysis appearance use determination of laser diffraction).
The instance of calcium sequestrant washing assistant material comprises alkali metal polyphosphates, for example tripoly phosphate sodium STPP, and organic sequestering agent, for example YD 30.
The instance of precipitation threshold washing assistant material comprises sodium orthophosphate and yellow soda ash.
The instance of calcium ion-exchanged washing assistant material comprises various types of water-insoluble crystal or amorphous aluminosilicate; Zeolite is its most known representative; For example zeolite A, zeolite B (being also referred to as zeolite P), zeolite C, X zeolite, zeolite Y and EP-A-0; P type zeolite disclosed in 384,070.
Said compsn also can comprise washing assistant or the complexing agent of 0～50wt%, for example YD 30, diethylene triaminepentaacetic acid(DTPA), alkyl or alkenyl succsinic acid, NTA or other following washing assistants.A lot of washing assistants are because therefore the ability of their complexation of metal ions also is bleaching stibilizer.
Zeolite and carbonate (carbonate (comprising supercarbonate and sesquicarbonate)) are preferred washing assistants.
Said compsn can comprise crystalline aluminosilicate as washing assistant, preferred as alkali aluminosilicate, more preferably sodium aluminium silicate.It typically exists with the content that is less than 15wt%.Aluminosilicate is the material with following general formula:
0.8-1.5?M 2O.Al 2O 3.0.8-6?SiO 2
Wherein M is a monovalent cation, is preferably sodium.These materials contain some combination water, and need have the calcium ion-exchanged capacity of 50mg CaO/g at least.Preferred sodium aluminium silicate comprises 1.5～3.5 SiO in following formula 2The unit.They can easily prepare through the reaction between water glass and the sodium aluminate as describing in detail in the document.The ratio of tensio-active agent and aluminosilicate (under situation about existing) was preferably greater than 5: 2, more preferably greater than 3: 1.
Alternately, or except that this aluminosilicate washing assistant, can use phosphate builders.Term " phosphoric acid salt " comprises diphosphate, triphosphate and phosphonate species in the art.Yet said composition comprises this phosphate builders that is less than 1wt%.Preferably, this laundry detergent formulations is the laundry detergent formulations of nonphosphate builders.
Other forms of washing assistant comprise silicate, for example soluble silicate, metasilicate, layered silicate (for example from Hoechst SKS-6).
We find that also the existence of inorganic builders (particularly zeolite or other insoluble inorganic particles) facilitated the wearing and tearing of fabric under wash conditions.This spherical SiO 2Particulate uses and has improved this problem.
Screening agent (shading agent)
Said granular laundry treatment compositions is preferably included in the blueness or the purple screening agent of 0.0001～0.01wt% scope.Said screening agent has reduced the whiteness of the infringement of a lot of colour clothes being felt and improved white garments.
Said screening agent is preferably selected from the blueness and the purple of alkaline, the direct and acid type of solvent dispersion listed in the Colour Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002).
Preferably, there are direct purple or sun blue dyestuff.Preferred said dyestuff is tetrazo, trisazo dye or three benzos two
Figure GSB00000774259300051
piperazine (triphendioxazine) dyestuff.Carcinogenic p-diaminodiphenyl (benzidene) radical dye is not preferred.
Can use the tetrazo cupriferous dye, for example direct purple 66.
Most preferred disazo dyes has following structure:
Figure GSB00000774259300052
Figure GSB00000774259300061
Wherein:
Ring D and E independently can for shown in naphthyl or phenyl;
R 1Be selected from: hydrogen and C 1～C 4Alkyl, preferred hydrogen;
R 2Be selected from: hydrogen, C 1～C 4Alkyl, replacement or unsubstituted phenyl and replacement or unsubstituted naphthyl, preferred phenyl;
R 3And R 4Be independently selected from: hydrogen and C 1～C 4Alkyl, preferred hydrogen or methyl;
X and Y are independently selected from: hydrogen, C 1～C 4Alkyl and C 1～C 4Alkoxyl group; Preferred said dyestuff has the X=methyl; With the Y=methoxyl group, and n is 0,1 or 2, preferred 1 or 2.
Preferred disazo dyes is directly purple 7, directly purple 9, directly purple 11, directly purple 26, directly purple 31, directly purple 35, directly purple 40, directly purple 41, directly purple 51 and directly purple 99.
Preferred solvent and dispersed dye are selected from monoazo or anthraquinone dye, most preferred solvent purple 13,63 ,DIS,PER,SE ,Vio,let, 63 27,63 ,DIS,PER,SE ,Vio,let, 63 26,63 ,DIS,PER,SE ,Vio,let, 63 28,63 ,DIS,PER,SE ,Vio,let, 63 63 and 63 ,DIS,PER,SE ,Vio,let, 63 77.
A kind of preferred pigment is pigment Violet 23.
Enzyme
Said granular laundry treatment compositions preferably includes one or more enzymes, and it provides clean-up performance and/or fabric nursing benefit.The instance of the enzyme that is fit to is including, but not limited to hemicellulase; Px; Proteolytic enzyme; Cellulase; Zytase; Lypase; Phospholipid hydrolase; Esterase; At; Polygalacturonase; Mannase; Pectin lyase; M-Zyme; Reductase enzyme; Oxydase; Phenol oxidase; Lipoxygenase; Ligninase; Starch debranching enzyme; Tannase; Pentosanase; Malanases; Arabinofuranosidase/xylosidase; Unidasa; Chondroitinase; Laccase and glycase or their mixture.Typical combination is for example can comprise proteolytic enzyme and lypase and combine diastatic enzyme mixture.In the time of in being present in cleaning compsns, aforesaid extra enzyme can be with about 0.00001wt%～about 2wt% of said composition weight, about 0.0001wt%～about 1wt% or even the content of about 0.001wt%～about 0.5wt% zymoprotein exist.
Preferred enzyme is a cellulase.
Fluorescent agent
Said compsn preferably includes fluorescent agent (white dyes).Fluorescent agent is that known and a lot of this fluorescent agents are commercially available getting.Usually, these fluorescent agents are that form with its an alkali metal salt (for example sodium salt) provides and uses.The use total amount of said one or more fluorescent agents in compsn is generally 0.005～2wt%, more preferably 0.01～0.1wt%.Preferred white dyes kind is: two-styrylbiphenyl compounds, for example Tinopal (trade mark) CBS-X; Diamines Stilbene disulfonic acid compound, for example Tinopal DMS pure Xtra and Blankophor (trade mark) HRH; And pyrazoline compounds, for example Blankophor SN.Preferred white dyes is: { [(4-anilino-6-(N-methyl-N-2-hydroxyethyl) amino 1 for 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1,2-d] triazole sodium, 4,4 '-two; 3; 5-triazine-2-yl)] amino } Stilbene-2-2 ' disulfonic acid disodium, 4,4 '-two { [(4-anilinos-6-morpholino-1,3; 5-triazine-2-yl)] amino } Stilbene-2-2 ' disulfonic acid disodium and 4,4 '-two (2-sulfo group styryl (sulfoslyryl)) biphenyl disodium.
Perfume compound
Preferably, said compsn comprises perfume compound.This perfume compound is preferably at 0.001～3wt% scope, most preferably 0.1～1wt%.The instance of a lot of perfume compound that are fit to is provided in the OPD 1993 Chemicals Buyers Directory 80th Annual Edition that CTFA (Cosmetic, Toiletry and Fragrance Association) the 1992 International Buyers Guide and the Schnell Publishing Co of CFTA Publications publication publish.
It is common in prescription, having multiple fragrance components.In compsn of the present invention, expection will have four kinds or more kinds of, and preferred five kinds or more kinds of, more preferably six kinds or more kinds of, or even seven kinds or more kinds of different fragrance components.
In the perfume compound mixture, preferred 15～25wt% is preceding flavor (top notes).Preceding flavor is by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]) definition.Flavor is selected from citrus oil, phantol, phanteine, lavandula angustifolia, dihydromyrcenol, rose oxide and cis-3-hexenol before preferred.
Perfume compound and preceding flavor can be used to point out fabric nursing benefit of the present invention.
Preferred said laundry treatment compositions does not comprise peroxygen bleach, for example SPC-D, Sodium peroxoborate and peracid.
Polymkeric substance
Said compsn can comprise one or more polymkeric substance.Instance is CMC 99.5, polyoxyethylene glycol, Z 150PH, polycarboxylate/salt for example polyacrylic ester/salt, toxilic acid/PEMULEN TR2 and lauryl methacrylate(LMA)/PEMULEN TR2.
Be not used in the polymkeric substance that prevents deposition of dye in the screening formulation, for example gather (vinyl pyrrolidone), gather (vinyl pyridine-N-oxide compound) and gather (vinyl imidazole).
Experiment
Embodiment 1
At Quickwash Plus TMWashing is with Vat Blue 4 painted three knitted cotton fabric samples (20 * 20cm) in the compartment of fabric test system (SDL international).In independent compartment, place identical knitted cotton sample, but these are the dyestuffs with Reactive Orange16.This machine is filled 3.5 liters of 26 ° of French hard water and 24.5g Persil Colour Powder (from UK), with zeolite and carbonate Las/ nonionogenic tenside powder as auxiliary agent.To wherein adding the 0.5g skimmer.Washing cost 15 minutes, machine draining then, draining and rotation are carried out in rotation, and the rinsing of carrying out three times 90 seconds then afterwards at every turn.After washing, with the fabric roller drying.This program is repeated 5 times.Repeat whole experiment then, but add the various additives of 1g/L.
After washing, on Murakami Goniospectrophotometer, measure this VAT Blue cloth at 430nm and the reflectivity of this Reactive Orange cloth at 650nm with 65 ° input angle and 55 ° test angles.The reflectivity of new cloth is 27.20 for Vat Blue and is 65.13 for reactive Orange.The reflectivity of this reflectivity and new unwashed fabric is compared, is expressed as Δ R=|R (newly)-R (washing) |.Δ R (powder contrast) is 6.06 for Vat Blue and is 5.36 for Reactive Orange.In the result shown in the table 1, the average delta R of said blueness and orange colour cloth is given to 1 decimal place.
Table 1
Product ΔR On average
The powder contrast 5.7
Granulated glass sphere diameter 100～200 μ m 4.5
Granulated glass sphere diameter 400～800 μ m 4.6
Sand, mean diameter 180 μ m 4.5
Grey silicon-dioxide-aluminium ceramic microsphere, diameter 1～40 μ m 5.2
White silicon-dioxide-aluminium ceramic microsphere, mean diameter 1～40 μ m 5.1
Granulated glass sphere is obtained by Sigmund Lindner, has 72.5% SiO 2Content.
Sand is obtained by Schlingmeier Quartz sand, has 98.9% SiO 2Content.
Silicon-dioxide-aluminium ceramic microsphere particle is obtained by 3M.
This silicon-dioxide-aluminium ceramic microsphere embodiment is a comparative, demonstrates this SiO 2The advantage that particle is compared with other spherical inorganic particles.
By littler Δ R 430Shown in the value, this SiO 2Particle is maintained this fabric and more approaches new fabric.
Embodiment 2
Exemplary granular laundry prescription A, B, C, D
Figure GSB00000774259300101
Enzyme content provides as the per-cent of pure enzyme.Directly the content of purple 9, solvent violet 13 and sulfonation zinc phthalocyanine phthalocyanine optical white provides as pure dye.NI (7EO) is meant R-(OCH 2CH 2) nOH, wherein R is C 12～C 15Alkyl chain, n is 7.
Through adding in the slurries with the sulfonation zinc phthalocyanine phthalocyanine optical white, then its spraying drying is prepared said prescription with direct purple 9.Alternately, said dyestuff and optical white can be through (post-dosed) MgSO for preparing later 4Particle adds.
Solvent violet 13 is dissolved in the nonionogenic tenside (7EO) to produce on the 0.5wt% solution and the POLARGEL NF of granulating, to provide the particle that comprises the 0.2wt% dyestuff.Be formulated in the said prescription behind its quilt.
Add this granulated glass sphere (Sigmund Lindner) in two ways through adding in these slurries and through back preparation.Notice that this pearl helps flowing of this powder.

Claims (14)

1. comprise the phosphatic granular laundry treatment compositions that is less than 1wt%, comprising:
(i) spherical SiO of 0.1wt%～40wt% 2Particle, this SiO 2Particle has the size at 100～2000 micrometer ranges;
The (ii) tensio-active agent of 2～70wt%; With
The (iii) washing assistant of 1～50wt%.
2. the granular laundry treatment compositions of claim 1, wherein this spherical SiO 2Particle has＞80% sphericity.
3. the granular laundry treatment compositions of claim 2, wherein this spherical SiO 2Particle has＞94% sphericity.
4. each granular laundry treatment compositions, wherein this spherical SiO in the claim 1～3 2Particle exists with the content of 0.5～5wt%.
5. each granular laundry treatment compositions, wherein this spherical SiO in the claim 1～3 2Particle comprises the SiO of 50～100wt% 2
6. each granular laundry treatment compositions, wherein this spherical SiO in the claim 1～3 2Particle comprises the SiO of 55～100wt% 2
7. each granular laundry treatment compositions, wherein this spherical SiO in the claim 1～3 2Particle comprises the SiO of 65～100wt% 2
8. each granular laundry treatment compositions in the claim 1～3, wherein this washing assistant comprises zeolite, this zeolite has the size at 0.1～10 micrometer range.
9. each granular laundry treatment compositions in the claim 1～3, wherein this laundry treatment compositions is included in the blueness or the purple screening agent of 0.0001～0.01wt% scope.
10. each granular laundry treatment compositions in the claim 1～3, wherein this laundry treatment compositions comprises that content is one or more enzymes of 0.00001wt%～2wt%.
11. the granular laundry treatment compositions of claim 10, wherein this enzyme is a cellulase.
12. handle the home method of fabric, this method may further comprise the steps:
(i) handle fabric with the aqueous solution of each compsn in the claim 1～11 of 1～20g/L; With
(ii) rinsing and dry this fabric.
13. be of a size of the spherical SiO of 100～2000 micrometer ranges 2Particle is used for being reduced in the purposes of family expenses master washing process to the damage of the clothing of washing.
14. the purposes of claim 13, wherein this spherical SiO 2Particle is selected from sand and/or glass.
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