WO2009019135A1 - Nanoparticules fluorescentes de blanchiment - Google Patents

Nanoparticules fluorescentes de blanchiment Download PDF

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Publication number
WO2009019135A1
WO2009019135A1 PCT/EP2008/059678 EP2008059678W WO2009019135A1 WO 2009019135 A1 WO2009019135 A1 WO 2009019135A1 EP 2008059678 W EP2008059678 W EP 2008059678W WO 2009019135 A1 WO2009019135 A1 WO 2009019135A1
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formula
functionalized nanoparticles
nanoparticles
hydrogen
alkyl
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PCT/EP2008/059678
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English (en)
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Christian Cremer
Mario Dubini
Robert Hochberg
Gerhard Merkle
Richard Lewis Riggs
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the current invention relates to functionalized nanoparticles suitable for the fluorescent whitening of natural and synthetic organic materials, a process for their preparation and compositions containing them, especially suitable for incorporation into detergent compositions for treatment of textile materials.
  • the instant invention relates to functionalized nanoparticles comprising on the surface a covalently bound radical of formula
  • nanoparticles are SiO 2 , AI 2 O 3 or mixed SiO 2 and AI 2 O 3 nanoparticles
  • R 1 and R 2 are independently of each other hydrogen; C- ⁇ -C 25 alkyl which may be interrupted by -O- or -S-; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 phenylalkyl; -OR 5 ; — 0-Si-O-R 5
  • R 5 is hydrogen; Ci-C 25 alkyl which may be interrupted by -O- or -S-; C 2 -C 24 alkenyl; phenyl;
  • R 10 R 6 and R 7 independently of each other are hydrogen; Ci-C 25 alkyl which may be interrupted by -O- or -S-; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 phenylalkyl; or -OR 5 , and R 8 , Rg and Ri 0 independently of each other are hydrogen; Ci-C 25 alkyl which may be interrupted by -O- or -S-; C 2 -C 24 alkenyl; phenyl; or C 7 -C 9 phenylalkyl.
  • n is 1 , 2, 3, 4, 5, 6, 7 or 8, preferably, 2, 3 or 4, most preferably 3,
  • Ci-C 25 alkyl may be a branched or unbranched radical, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl
  • alkyl radicals may be uninterrupted or be interrupted by -O- or -S-.
  • Alkyl radicals like C 2 -C 25 alkyl, especially C 3 -C 25 alkyl, which are interrupted by -O- or -S- are, for example, CH 3 -O-CH 2 CH 2 -, CH 3 -S-CH 2 CH 2 -, CH 3 -O-CH 2 CH 2 -O-CH 2 CH 2 - , CH 3 -O-CH 2 CH 2 -O-CH 2 CH 2 -, CH 3 -(O-CH 2 CH 2 -) 2 O-CH 2 CH 2 - , CH 3 -(O-CH 2 CH 2 -) 3 O-CH 2 CH 2 - or CH 3 -(O-CH 2 CH 2 -) 4 O-CH 2 CH 2 -.
  • Ci-Ci 2 alkyl especially Ci-C 8 alkyl, which alkyl radicals may be uninterrupted or be interrupted by -0-.
  • Ri, R 2 , R 5 , R 6 , R 7 , R 8 , R9 and R 1 0 as alkenyl having 2 to 24 carbon atoms may be a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2- octadecenyl or n-4-octadecenyl.
  • Ri > R2, Rs, Re, R7, Re, R9 and R10 as C 7 -C 9 phenylalkyl are, for example, benzyl, ⁇ - methylbenzyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl.
  • R 5 is preferably hydrogen, d-C 4 alkyl, or AI 2 O 3 surface or SiO 2 surface, especially the AI 2 O 3 surface or SiO 2 surface.
  • a highly preferred meaning for R 5 is the SiO 2 surface.
  • R 6 , R 7 , Re, R9 and R 1 0 are preferably Ci-C 4 alkyl, especially methyl.
  • Ri and R 2 are -OR 5 ; — 0-Si-O-R 5 ; — 0-Si-O-Si-O-R 5 ; or
  • Ri and R 2 are a radical of formula -OR 5 , wherein R 5 is the AI 2 O 3 surface or SiO 2 surface, especially the SiO 2 surface.
  • B 1 is a direct bond or a bridging member
  • D 1 is a radical of a fluorescent whitening agent
  • the bridging member B 1 is preferably a direct bond, -NH-SO 2 -, -NH-CO-, -NH-CO-NH-CO- or C r C 25 alkylene, which may be bound and/or be interrupted by at least one of the radicals selected from the group consisting of -0-, -S-, - NH-, -CO-, -0-C0-, -CO-O-, -NH-CO- and -CO-NH-, most preferably B 1 is the direct bond or a group of the formula -NH-SO 2 -, -NH-CO-(CH 2 )L 6 -, -NH-(CH 2 ) 1-6 -CO-O-(CH 2 ) 1-6 -, -NH-CO-(CH 2 ) 1-6 -CO-NH-, -NH-CO-(CH 2 ) 1-6 -CO-O- or -NH-(CH 2 ) 1-6 -
  • the residue of a fluorescent whitening agent D 1 is preferably of the formula
  • Rii, Ri 2 and Ri 3 independently of each other represent an -NH 2 , Ci-C 4 alkylamino, di(d- C 4 )alkylamino, C 2 -C 4 hydroxyalkylamino, di(C 2 -C 4 hydroxyalkyl)amino, Ci-C 4 alkoxy, substituted or unsubstituted anilino or a morpholino residue or an amino acid or amino acid amide residue from which a hydrogen atom has been abstracted from the amino group and M represents hydrogen, an alkaline or alkaline earth metal cation, ammonium or ammonium that is mono-, di, tri- or tetrasubstituted by CrC 4 alkyl or C 2 -C 4 hydoxyalkyl or mixtures of these ammonium salts.
  • Rn, Ri 2 and Ri 3 as a residue containing Ci-C 4 alkyl may contain alkyl as a branched or unbranched radical, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, whilst C 2 -C 4 hydroxyalkyl may be 2-hydroxyethyl, 2- or 3- hydroxypropyl or hydroxybutyl.
  • Ci-C 4 alkoxy may, for example be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec- butoxy, isobutoxy or tert-butoxy radicals.
  • Rn, Ri 2 and Ri 3 independently of each other represent an -NH 2 , C 2 -C 4 hydroxy-alkylamino, di(C 2 -C 4 hydroxyalkyl)amino, aniline which is unsubstituted or substituted by 1 or 2 sulphonic acid groups, a morpholino residue or an amino acid or amino acid amide residue from which a hydrogen atom has been abstracted from the amino group selected from the group consisting of iminodiacetic acid or the mono or diacidamide thereof, aspartic acid, glycine, taurine and 2-hydroxyethylaminopropionamide and M represents hydrogen, lithium, potassium or sodium.
  • Rn and Ri 3 are identical and especially represent an aniline, morpholino, monoethanolamino or diethanolamino residue, whilst Ri 2 is especially mono- or diethanolamino and M represents sodium.
  • the functionalized nanoparticles according to the present invention have preferably a spherical shape.
  • the particle size of the nanoparticles is, for example, 10 to 1000 nm, preferably 10 to 500 nm, and more preferably 40 to 500 nm. Highly preferred is a particle size of 40 to 400 nm.
  • the organic content of the nanoparticles according to the present invention is, for example, 5 to 80 percent by weight, especially 10 to 70 percent by weight, based on the total weight of the nanoparticle.
  • Nanoparticles are typically silicon dioxide, aluminum oxide, a heterogeneous mixture thereof or silicon aluminum oxide as mixed oxides.
  • the silicon aluminum oxide nanoparticles according to the present invention can show silicon contents in between 1 to 99 metal- atom %.
  • the functionalized nanoparticles are silica nanoparticles.
  • the expert would preferably use particles showing an index of refraction close to the matrix material.
  • pure silicon dioxide (n D 1.48 to 1.50) or pure aluminum oxide (n D 1.61 ) or silicon aluminum oxides with the whole range of silicon to aluminum ratio covers material with an index of refraction from 1.48 to 1.61.
  • Unmodified nanoparticles are commercially available from different suppliers such as Degussa, Hanse Chemie, Nissan Chemicals, Clariant, H. C. Starck, Nanoproducts or Nyacol Nano Technologies as powder or as dispersions.
  • silica nanoparticles are Aerosil ® from Degussa, Ludox ® from DuPont, Snowtex ® from Nissan Chemical, Levasil ® from Bayer, or Sylysia ® from Fuji Silysia Chemical.
  • Examples of commercially available AI 2 O 3 nanoparticles are Nyacol ® products from Nyacol Nano Technologies Inc., or Disperal ® products from Sasol.
  • the invention relates to a process for the preparation of the functionalized nanoparticles comprising reaction of corresponding unmodified nanoparticles, such as commercially available silica Or AI 2 O 3 nanoparticles, with a compound of the formula (1 a)
  • R 0 is Ci-C 25 alkyl
  • R 1 and R 2 are hydrogen or a substituent as defined above under formula (1 ), n is as defined above under formula (1 ), and X is a functional group selected from -O-, -S- or -N(R 3 )-, wherein
  • R 3 is hydrogen, d-C 8 alkyl or hydroxyl-substituted Ci-C 8 alkyl and subsequently reacting the nanoparticles so obtained with a compound of formula
  • D 1 is as defined in claim 1 and X 1 represents a leaving group capable of undergoing nucleophilic substitution.
  • a compound of formula (1a), in which R 0 , R 1 and R 2 represent hydrogen or a CrC 4 alkyl group, preferably a methyl group, n represents 2, 3 or 4, most preferably 3 and X represents -NR 3 , especially -NH is initially reacted with commercially available silica or AI 2 O 3 nanoparticles, especially silica nanoparticles in aqueous or aqueous/organic solvent media. Subsequently, the resulting reaction product is treated with a compound of formula (1a), in which R 0 , R 1 and R 2 represent hydrogen or a CrC 4 alkyl group, preferably a methyl group, n represents 2, 3 or 4, most preferably 3 and X represents -NR 3 , especially -NH is initially reacted with commercially available silica or AI 2 O 3 nanoparticles, especially silica nanoparticles in aqueous or aqueous/organic solvent media. Subsequently, the resulting reaction product is treated with a
  • R 11 , R 12 , R 13 and M and their preferences are as defined previously, and X 1 is a halogen atom such as bromine, fluorine or chlorine, especially chlorine, to yield the functionalized nanoparticles of the invention.
  • Compounds of formulae (1a) and (2a) are known compounds or may be obtained using known procedures.
  • the functionalized nanoparticles of the invention are useful for fluorescent whitening of natural or synthetic organic materials, in particular, for fluorescent whitening of textile materials.
  • the functionalized nanoparticles of the invention are useful as fluorescent whitening agents for addition to detergent compositions for washing textile fiber materials.
  • the invention relates to a detergent composition
  • a detergent composition comprising i) 1 -75% of an anionic or nonionic surfactant, ii) 1-75% of a builder, iii) 0.001-5% of at least one of the functionalized nanoparticles as disclosed above, iv) 0-30% of a peroxide, v) 0-10% of a peroxide activator, vi) 0-5% of a bleaching catalyst and vii) 0-5% of an enzyme, each component by weight, based on the total weight of the detergent composition.
  • the detergent compositions used comprise i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.01-5%, especially 0.05-5%, of at least one of the functionalized nanoparticles as disclosed above, iv) 0.5-30% of a peroxide, v) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; each by weight, based on the total weight of the detergent.
  • the detergent may be formulated as a solid, as an aqueous liquid comprising, e.g., 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454.
  • the anionic surfactant component may be, e.g., an alkylbenzenesulphonate, an alkylsulphate, an alkylethersulphate, an olefinsulphonate, an alkanesulphonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an ⁇ -sulphofatty acid salt or an ester thereof.
  • alkylbenzenesulphonates having 10 to 20 carbon atoms in the alkyl group, alkylsulphates having 8 to 18 carbon atoms, alkylethersulphates having 8 to 18 carbon atoms, and fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms.
  • the average molar number of ethylene oxide added in the alkylethersulphate is preferably 1 to 20, preferably 1 to 10.
  • the salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium.
  • Highly preferred carboxylates are alkali metal sarcosinates of formula R-CO(R 1 )CH 2 COOM 1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is CrC 4 alkyl and M 1 is alkali metal, especially sodium.
  • the nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates, especially the C 8 -C 2 O aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Ci 0 -Ci 5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • the total amount of anionic surfactant and nonionic surfactant is preferably 5-50% by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As to these surfactants it is preferred that the lower limit is 10% by weight.
  • the builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
  • Preferred silicates are crystalline layered sodium silicates of the formula NaHSi m ⁇ 2m +i-pH 2 O or Na 2 Si m ⁇ 2m +i-pH 2 O in which m is a number from 1.9 to 4 and p is 0 to 20.
  • Preferred aluminosilicates are the commercially-available synthetic materials designated as
  • Zeolites A, B, X, and HS or mixtures of these.
  • Zeolite A is preferred.
  • Preferred polycarboxylates include hydroxypolycarboxylat.es, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
  • Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
  • Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1 -hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the amount of builders is preferably 5-70% by weight, more preferably 5-60% by weight and most preferably 10-60% by weight. As to the builders it is preferred that the lower limit is 15% by weight, especially 20% by weight.
  • Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 95°C.
  • the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest.
  • very active inorganic peroxides such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides.
  • the amount of peroxide is preferably 0.5-30% by weight, more preferably 1-20% by weight and most preferably 1-15% by weight.
  • the lower limit is preferably 2% by weight, especially 5% by weight.
  • the peroxides are preferably activated by the inclusion of a bleach activator.
  • a bleach activator Preferred are such compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
  • Suitable compounds include those that carry O- and/or N-acyl groups having the said number of carbon atoms and/or unsubstituted or substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), compounds of formula wherein R is a sulphonate group, a carboxylic acid group or a carboxylate group, and wherein R' is linear or branched (C 7 -Ci 5 )alkyl; also activators that are known under the names SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-di
  • the amount of bleach activator is preferably 0-10% by weight, more preferably 0-8% by weight.
  • the lower limit is preferably 0.5% by weight, especially 1 % by weight.
  • Bleaching catalysts which may be added, include, e.g., enzymatic peroxide precursors and/or metal complexes.
  • Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A- 0509787.
  • the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, especially 0.05 to 2% by weight. Highly preferred is an amount of 0.1-2% by weight.
  • bleaching catalysts As examples for bleaching catalysts the following are mentioned:
  • the detergent can optionally contain enzymes. Enzymes can be added to detergents for stain removal.
  • the enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices.
  • Preferred enzymes are cellulases, proteases, amylases and lipases.
  • Preferred enzymes are cellulases and proteases, especially proteases.
  • Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose and cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch.
  • enzymes to be used include, but are by no means limited to, the following: proteases as given in US-B-6,242,405, column 14, lines 21 to 32; lipases as given in US-B-6,242,405, column 14, lines 33 to 46; amylases as given in US-B-6,242,405, column 14, lines 47 to 56; and cellulases as given in US-B-6,242,405, column 14, lines 57 to 64.
  • the enzymes can optionally be present in the detergent.
  • the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the detergent.
  • Further preferred additives for the detergents according to the invention are polymers that, during the washing of textiles, inhibit staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions (dye fixing agents, dye transfer inhibitors).
  • Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000.
  • Such polymers are usually used in an amount of from 0.01 to 5 %, preferably 0.05 to 5 % by weight, especially 0.1 to 2 % by weight, based on the total weight of the detergent.
  • Preferred polymers are those given in WO-A-02/02865 (see especially page 1 , last paragraph and page 2, first paragraph).
  • the detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching agents; pigments; and/or shading agents.
  • auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10 % by weight, especially 0.5 to 5 % by weight, based on the total weight of the detergent.
  • the detergent compositions can take a variety of physical forms including powder, granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty detergent tablets.
  • One important physical form is the so-called concentrated granular form adapted to be added to a washing machine.
  • compact detergents Of importance are also the so-called compact (or super compact) detergents.
  • compact detergents In the field of detergent manufacture, a trend has developed recently towards the production of compact detergents, which contain increased amounts of active substance.
  • the compact detergents In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40 0 C, or even at room temperatures, e.g. at 25°C.
  • Such detergents usually contain only low amounts of fillers or processing aids, like sodium sulphate or sodium chloride.
  • the amount of such fillers is usually 0-10% by weight, preferably 0-5 % by weight, especially 0-1 % by weight, based on the total weight of the detergent.
  • Such detergents usually have a bulk density of 650-1000 g/l, preferably 700- 1000 g/l and especially 750-1000 g/l.
  • the detergents can also be present in the form of tablets. Relevant characteristics of tablets are ease of dispensing and convenience in handling. Tablets are the most compact delivery of solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg/litre. To enable fast disintegration laundry detergent tablets generally contain special disintegrants: - Effervescents such as carbonate/hydrogencarbonate/citric acid;
  • the tablets can also contain combinations of any of the above disintegrants.
  • the detergent may also be formulated as an aqueous liquid comprising 5-50, preferably 10- 35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt. % of water.
  • Non-aqueous liquid detergent compositions can contain other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergents can also be present as the so-called "unit liquid dose" form.
  • This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines.
  • the textile fibers treated may be natural or synthetic fibers or mixtures thereof.
  • natural fibers include vegetable fibers such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibers such as wool, mohair, cashmere, angora and silk, preferably wool.
  • Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers.
  • Preferred textile fibers are cotton, polyamide and wool fibers, especially cotton fibers.
  • textile fibers treated according to the method of the present invention have a density of less than 200 g/m 2 .
  • the process usually an amount of 0.01 to 3.0% by weight, especially 0.05 to 3.0% by weight, based on the weight of the textile fiber material, of the functionalized nanoparticles described above is used.
  • the process is usually conducted in the temperature range of from 5 to 100 0 C, especially 5 to 60 0 C.
  • Preferred is a temperature range of 5 to 40 0 C, especially 5 to 35°C and more preferably 5 to 30 0 C.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1 , preferably between about 7.5 and 11. Laundry products are typically at pH 9-1 1. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention.
  • an effective amount of the detergent composition it is meant, e.g., from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are
  • the liquor ratio is preferably 1 :4 to 1 :40, especially 1 :4 to 1 :15. Highly preferred is a liquor ratio of 1 :4 to 1 :10, especially 1 :5 to 1 :9.
  • a further object of the present invention is to provide a process for the domestic washing treatment of a textile fiber material wherein the textile fiber material is contacted with an aqueous solution of a detergent comprising at least one functionalized nanoparticle as defined above, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5°C and 40 0 C, preferably between 5°C and 30 0 C, throughout the process.
  • the invention provides a process for the domestic washing of a textile fiber material, wherein the aqueous detergent solution contains, in addition to the functionalized nanoparticle as defined above, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst, and wherein the temperature of the solution is between 5°C and 40 0 C, preferably between 5°C and 30 0 C, throughout the process.
  • the textile fiber materials are treated with a total of from 0.05 to 3.0% by weight, based on the weight of textile fiber material, of the functionalized nanoparticles described above.
  • the invention relates to textile materials which have been treated with a detergent composition or been subjected to a washing process as described above.
  • the functionalized nanoparticles used for the compositions and processes according to the present invention are particularly advantageous in that they exhibit not only extremely high whitening ability, but, in addition, in many cases highly desirable water solubilities and also possess excellent white aspects in the solid state.
  • a further advantage of the present invention is that the detergent composition delivers improved whiteness performance and fabric feel. Furthermore the compounds show very good results with respect to exhaustion properties.
  • the functionalized nanoparticles have the advantage that they are also effective in the presence of active chlorine donors, such as, for example, hypochlorite and can be used without substantial loss of the effects in washing baths with non-ionic washing agents, for example alkylphenol polyglycol ethers.
  • active chlorine donors such as, for example, hypochlorite
  • non-ionic washing agents for example alkylphenol polyglycol ethers.
  • perborate or peracids and activators for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.
  • perborate or peracids and activators for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.
  • Ludox ® TMA a 34% nanosilica dispersion in water, available from Helm AG
  • 249Og of ethyl alcohol and 345g of 3-aminopropyl trimethoxysilane added dropwise with stirring to the homogeneous mixture.
  • the reaction mixture is heated to 5O 0 C and stirring continued for a further 18 hours at this temperature.
  • the volume of the mixture is then reduced to approximately 1 liter by evaporation on a rotary evaporator.
  • the mixture is vigorously shaken and the two resulting phases separated in a seperatory funnel to remove unreacted aminosilane.
  • the lower aqueous/ethanolic phase is concentrated to a wet paste in vacuo and then resuspended in 1 liter of ethyl alcohol. A total of 1199g of solution is obtained with a solids content of 27.3% of 3-aminopropyl silane modified silica nanoparticles.
  • Thermogravimetric analysis (TGA; heating rate: 10°C/min from 50 to 600 0 C): Weight loss of 25.2%, corresponding to the organic material.
  • TEM Transmission Electron Microscopy
  • DLS Dynamic Light scattering
  • a solution of 64g of 4-amino-4'-nitrostilbene-2,2'-disulphonic acid in 900ml of water is added to a mixture of 15Og of methyl ethyl ketone, 173g of ice and 3Og of cyanuric chloride.
  • the temperature is maintained below 1 O 0 C by external cooling and the pH maintained at between 4.5 and 5.0 by addition of a total of 53ml of 15% aqueous sodium carbonate solution.
  • a solution of 18g of diethanolamine in 30ml of water is added and the pH adjusted to between 7.0 and 7.5 by addition of 81 ml of 15% aqueous sodium carbonate solution.
  • the resulting solution is then stirred for 1 hour at 4O 0 C and then for 1 further hour at 6O 0 C.
  • 22g of diethanolamine are then added and the solution heated to 98 0 C, the pH being adjusted to between 9.0 and 9.3 by addition of 49ml of 4N aqueous sodium hydroxide solution, whilst 200ml of the methyl ethyl ketone/water mixture are distilled off.
  • the reaction solution is then stirred for a further 2 hours at 98 0 C and subsequently cooled to room temperature. Following the addition of 20Og of sodium chloride, the resulting suspension is stirred for a further 30 minutes and the precipitated solids filtered off.
  • the resulting 30Og of product are suspended in 400ml of water and added in portions to a stirred mixture of 4Og of iron filings and 10ml of glacial acetic acid in 600ml of water, previously heated to 100 0 C.
  • the resulting mixture is stirred for a further 1.5 hours at this temperature, rendered alkaline by addition of 32% aqueous sodium hydroxide solution and then filtered.
  • the filtrate is treated with sodium dithionite, acidified with 125ml of concentrated hydrochloric acid and cooled to room temperature.
  • the precipitated solids are filtered, washed with 100ml of water and dried under vacuum to yield 94g of yellow crystals.
  • 36g of the material thus obtained are dissolved in 360ml of water and the solution added over 1 hour to a mixture of 110ml of methyl ethyl ketone, 9.9g of cyanuric chloride, 130ml of water and 20Og of ice.
  • the pH is maintained at between 4.0 and 4.5 by addition of a total of 12ml of 15% aqueous sodium carbonate solution.
  • the mixture is heated to and maintained at 4O 0 C for 40 minutes and then at 6O 0 C for 30 minutes, the pH being maintained at between 7.0 and 7.7 by addition of 15% aqueous sodium carbonate solution.
  • Analogous products may be similarly obtained by replacement of the diethanolamine with equivalent amounts of other primary or secondary amines.
  • a mixture of 10g of an ethyl alcohol dispersion of the 3-aminopropyl silane modified silica nanoparticles, obtained as described in Example 1 , and 5.78g of the compound of formula (201 ) in a mixture of 50ml of water and 50ml of isopropanol is heated to 9O 0 C with stirring, the pH being maintained at 9.0 by addition of triethylamine. After stirring for 5.5 hours at this temperature, the mixture is cooled to room temperature, 300ml of acetone added and the precipitated solids filtered, washed with acetone and isopropanol and dried to yield functionalized nanoparticles of an off-white fluorescent solid which may be represented by formula (301 ).
  • TGA 54.935% of organic material.
  • 4Og of a standard detergent according to ECE 77 per kg of textile material is used to wash the swatches at a liquor ratio of 10:1 at temperatures of 25, 40 and 6O 0 C for a period of 15 minutes after which they are rinsed for 30 seconds under running tap water. After spinning, the swatches are dried in an oven at 6O 0 C in the dark.
  • This process is performed in the absence of fluorescent whitening agent (FWA), in the presence of 0.1% by weight, based on the weight of the detergent, of the functionalized nano particle FWA of formula (301 ) and in the presence of the non-functionalized FWA of formula (201 ).
  • FWA fluorescent whitening agent
  • the reflectance of the resulting swatches was measured using a Datacolor SF 500 spectrophotometer and the degree of whiteness according to Ganz (W G ) and also the degree of exhaustion (E x ) of the FWA onto the fabric after one wash were calculated.
  • the FWA in the form of functionalized nanoparticles 01 results in superior degrees of whiteness on both substrates and at all washing temperatures in comparison to the non-functionalized FWA (201 ). Additionally, in almost all cases, the degree of exhaustion of the functionalized FWA of the invention is superior to that of the non-functionalized analog.
  • the superior whiteness of the fiber treated with the FWA of the invention after radiation as compared with that of the fiber treated with the non-functionalized FWA is clearly advantageous.

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  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention porte sur des nanoparticules fonctionnalisées comprenant, sur la surface, un radical lié de façon covalente de formule (1). Les nanoparticules sont des nanoparticules de SiO2, Al2O3 ou des nanoparticules mixtes de SiO2 et Al2O3, R1 et R2 représentent chacun indépendamment l'un de l'autre hydrogène ; alkyle en C1-C25 qui peut être interrompu par -O- ou -S- ; alcényle en C2-C24, phényle, phénylalkyle en C7-C9 ; -OR5 ; R5 représente hydrogène ; alkyle en C1-C25 qui peut être interrompu par -O- ou -S- ; alcényle en C2-C24 ; phényle, phénylalkyle en C7-C9 ; R6 et R7 représentant chacun indépendamment l'un de l'autre hydrogène ; alkyle en C1-C25 qui peut être interrompu par -O- ou -S- ; alcényle en C2-C24 ; phényle, phénylalkyle en C7-C9 ; ou -OR5, et R8, R9 et R10 représentent chacun indépendamment l'un de l'autre hydrogène ; alkyle en C1-C25 qui peut être interrompu par -O- ou -S- ; alcényle en C2-C24 ; phényle ; ou phénylalkyle en C7-C9 ; n vaut 1, 2, 3, 4, 5, 6, 7 ou 8, B1 est une liaison directe ou un élément pontant, et D1 est un radical d'un agent de blanchiment fluorescent. L'invention porte également sur un procédé permettant de préparer les nanoparticules et sur l'utilisation de celles-ci comme agents fluorescents de blanchiment, en particulier dans des compositions détergentes.
PCT/EP2008/059678 2007-08-03 2008-07-24 Nanoparticules fluorescentes de blanchiment WO2009019135A1 (fr)

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EP07113766 2007-08-03
EP07113766.5 2007-08-03

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WO2009019135A1 true WO2009019135A1 (fr) 2009-02-12

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001032820A1 (fr) * 1999-10-30 2001-05-10 Henkel Kommanditgesellschaft Auf Aktien Detergents ou nettoyants
WO2001083662A1 (fr) * 2000-05-04 2001-11-08 Henkel Kommanditgesellschaft Auf Aktien Utilisation de particules nanoscopiques pour faciliter l'enlevement des salissures
WO2003089108A1 (fr) * 2002-04-19 2003-10-30 Ciba Specialty Chemicals Holding Inc. Agents de regulation de mousse
WO2006008239A2 (fr) * 2004-07-16 2006-01-26 Ciba Specialty Chemicals Holding Inc. Paillettes d'oxyde de silicium luminescentes
WO2006125736A1 (fr) * 2005-05-27 2006-11-30 Ciba Specialty Chemicals Holding Inc. Nanoparticules fonctionnalisees

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001032820A1 (fr) * 1999-10-30 2001-05-10 Henkel Kommanditgesellschaft Auf Aktien Detergents ou nettoyants
WO2001083662A1 (fr) * 2000-05-04 2001-11-08 Henkel Kommanditgesellschaft Auf Aktien Utilisation de particules nanoscopiques pour faciliter l'enlevement des salissures
WO2003089108A1 (fr) * 2002-04-19 2003-10-30 Ciba Specialty Chemicals Holding Inc. Agents de regulation de mousse
WO2006008239A2 (fr) * 2004-07-16 2006-01-26 Ciba Specialty Chemicals Holding Inc. Paillettes d'oxyde de silicium luminescentes
WO2006125736A1 (fr) * 2005-05-27 2006-11-30 Ciba Specialty Chemicals Holding Inc. Nanoparticules fonctionnalisees

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