NO173662B - TOYVI DETAILS MIXTURE WITH IMPROVED ANTI-REPOSITIONING CHARACTERISTICS INCLUDING DIPICOLIC ACID DERIVATIVES AND A PODE COPOLYMER OF POLYALKYL OXYDE AND VINYL ACETATE - Google Patents
TOYVI DETAILS MIXTURE WITH IMPROVED ANTI-REPOSITIONING CHARACTERISTICS INCLUDING DIPICOLIC ACID DERIVATIVES AND A PODE COPOLYMER OF POLYALKYL OXYDE AND VINYL ACETATE Download PDFInfo
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- NO173662B NO173662B NO89893537A NO893537A NO173662B NO 173662 B NO173662 B NO 173662B NO 89893537 A NO89893537 A NO 89893537A NO 893537 A NO893537 A NO 893537A NO 173662 B NO173662 B NO 173662B
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- vinyl acetate
- mixture according
- detergent mixture
- detergent
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- 239000000203 mixture Substances 0.000 title claims description 42
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 16
- 239000002253 acid Substances 0.000 title description 5
- 229920001577 copolymer Polymers 0.000 title description 3
- 239000003599 detergent Substances 0.000 claims description 47
- -1 polyethylene Polymers 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229920000578 graft copolymer Polymers 0.000 claims description 14
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- FYWQWZBZNHKKSQ-UHFFFAOYSA-M sodium;6-carboxypyridine-2-carboxylate Chemical compound [Na+].OC(=O)C1=CC=CC(C([O-])=O)=N1 FYWQWZBZNHKKSQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Classifications
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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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
Landscapes
- 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)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
Description
Den foreliggende oppfinnelse angår tøyvaskemiddelblandinger med forbedrede anti-gjenavsettingsegenskaper. The present invention relates to laundry detergent compositions with improved anti-redeposition properties.
Gjenavsetting av smuss som er fjernet fra vaskede artikler tilbake på artiklene, er et velkjent problem som er av spesiell betydning når det gjelder tekstilstoffer, og mange løsninger på dette problem er blitt foreslått. Den klassiske fremgangsmåte er at natriumkarboksylmetylcellulose er blitt innarbeidet i tøyvaske-middelblandinger, og denne forbindelse anvendes fremdeles i dag. Redeposition of dirt removed from washed articles back onto the articles is a well-known problem which is of particular importance in the case of textile fabrics, and many solutions to this problem have been proposed. The classic method is that sodium carboxyl methyl cellulose has been incorporated into laundry detergent mixtures, and this compound is still used today.
I det aller siste er kopolymerer av etylen eller vinylmetyleter og maleinsyreanhydrid, kopolymerer av akrylsyre og maleinsyreanhydrid og homopolymerer av akrylsyre blitt foreslått i patentlitterat-uren; se for eksempel GB 1 269 848 og GB 1 460 893. More recently, copolymers of ethylene or vinyl methyl ether and maleic anhydride, copolymers of acrylic acid and maleic anhydride, and homopolymers of acrylic acid have been proposed in the patent literature; see, for example, GB 1,269,848 and GB 1,460,893.
EP 219 048 beskriver anvendelse av pode-kopolymerer av polyalkylenoksyd med vinylacetat som grånings-inhibitorer ved vaske- og ettervaske-behandling av syntetiske tekstilstoffer. EP 219 048 describes the use of graft copolymers of polyalkylene oxide with vinyl acetate as graying inhibitors in washing and post-washing treatment of synthetic textile fabrics.
Vi har nå oppdaget at vaskemiddelblandinger som inneholder en pode-kopolymer av denne type i forbindelse med et dipikolin-syresalt, oppviser overraskende forbedret smuss-suspenderings-(anti-gjenavsettings-)egenskaper når det gjelder polyesterstoffer. We have now discovered that detergent compositions containing a graft copolymer of this type in conjunction with a dipicoline acid salt exhibit surprisingly improved soil suspension (anti-redeposition) properties in the case of polyester fabrics.
Anvendelse av dipikolinsyre og dens salter og derivater som vaskeevnebyggere er beskrevet i GB 1 342 095 (Unilever). The use of dipicolinic acid and its salts and derivatives as detergency builders is described in GB 1 342 095 (Unilever).
Den foreliggende oppfinnelse tilveiebringer en vaskemiddelblanding som er karakterisert ved at den omf?tter: (a) fra 2 til 50 vekt% av et vaskeaktivt s; .em som omfatter ett eller flere anioniske, ikke-ioniske, kationiske, zwitterioniske eller amfotære overflateaktive materialer; (b) fra 0,5 til 60 vekt% av en forbindelse med den generelle formel I og/eller et vannløselig eller vann-dispergerbart salt av denne: hvor R representerer et hydrogenatom, et kloratom, et bromatom, en hydroksylgruppe, en aminogruppe, en alkyl-substituert aminogruppe, en karboksylgruppe eller en C1.4-alkylgruppe; og (c) fra 0,1 til 3 vekt% av en pode-kopolymer av (i) polyetylen-, The present invention provides a detergent mixture which is characterized in that it comprises: (a) from 2 to 50% by weight of a detergent active s; .em comprising one or more anionic, nonionic, cationic, zwitterionic or amphoteric surfactants; (b) from 0.5 to 60% by weight of a compound of the general formula I and/or a water-soluble or water-dispersible salt thereof: where R represents a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, an alkyl-substituted amino group, a carboxyl group or a C1-4 alkyl group; and (c) from 0.1 to 3% by weight of a graft copolymer of (i) polyethylene-,
polypropylen- eller polybutylenoksyd med (ii) vinylacetat polypropylene or polybutylene oxide with (ii) vinyl acetate
(eventuelt forsåpet i et omfang av opp til 15%) (possibly saponified to an extent of up to 15%)
med et vektforhold mellom (i) og (ii) på fra 1:0,2 til 1:10. with a weight ratio between (i) and (ii) of from 1:0.2 to 1:10.
Oppfinnelsen angår således vaskemiddelblandinger som inneholder tre spesifiserte bestanddeler - et overflateaktivt system, en dipikolinsyreforbindelse og en pode-kopolymer - som i tillegg kan inneholde eventuelle andre konvensjonelle vaskemiddelbestand-deler, for eksempel andre byggere, blekemiddelsystemer, skum-dempende systemer, fluorescerende midler, uorganiske salter og andre materialer som er velkjente for fagfolk på området som angår utforming av vaskemidler. Vaskemiddelblandingene ifølge oppfinnelsen kan ha hvilken som helst egnet form, for eksempel som pulvere, væsker eller stykker. The invention thus relates to detergent mixtures containing three specified components - a surface-active system, a dipicolinic acid compound and a graft copolymer - which may additionally contain any other conventional detergent components, for example other builders, bleach systems, anti-foam systems, fluorescent agents, inorganic salts and other materials well known to those skilled in the art of detergent formulation. The detergent mixtures according to the invention can have any suitable form, for example as powders, liquids or pieces.
Den totale mengde vaskeaktivt materiale (overflateaktivt materiale) i vaskemiddelblandingene ifølge oppfinnelsen er fra 2 til 50 vekt% og er fortrinnsvis fra 5 til 40 vekt%. The total amount of detergent active material (surfactant material) in the detergent mixtures according to the invention is from 2 to 50% by weight and is preferably from 5 to 40% by weight.
Vaskemiddelblandingene ifølge oppfinnelsen kan inneholde ett eller flere anioniske, ikke-ioniske, kationiske, amfotære eller zwitterioniske overflateaktive såpe- eller ikke-såpe-materialer eller kombinasjoner av disse. Mange egnede vaskeaktive forbindelser er tilgjengelige og er fullstendig beskrevet i litteraturen, for eksempel i "Surface-Active Agents and Detergents", volum I og II, av Schwartz, Perry og Berch. The detergent mixtures according to the invention may contain one or more anionic, non-ionic, cationic, amphoteric or zwitterionic surfactant soap or non-soap materials or combinations thereof. Many suitable detergent active compounds are available and are fully described in the literature, for example in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
De foretrukkede vaskeaktive forbindelser som kan anvendes, er såper og syntetiske anioniske overflateaktive ikke-såpe-materialer og ikke-ioniske overflateaktive materialer. The preferred detergent compounds that can be used are soaps and synthetic anionic surfactants, non-soap materials and non-ionic surfactants.
Syntetiske anioniske overflateaktive materialer er velkjente for fagfolk på området. Eksempler innbefatter alkylbenzensulfonater, spesielt rettkjedede natrium-alkylbenzensulfonater med en alkylkjedelengde på C8-C15, primære og sekundære alkylsulfater, spesielt natrium-Cl2-C15-prim. -alkoholsulfater; olef insulfonater ; alkansulfonater; dialkylsulfosuksinater; og fettsyreester-sulfonater. Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulfonates, especially straight chain sodium alkylbenzene sulfonates with an alkyl chain length of C8-C15, primary and secondary alkyl sulfates, especially sodium Cl2-C15-prim. - alcohol sulfates; olef insulfonates ; alkane sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates.
Egnede ikke-ioniske vaskeaktive forbindelser som kan anvendes, innbefatter spesielt produktene fra reaksjonen mellom forbindelser med en hydrofob gruppe og et reaktivt hydrogenatom, for eksempel alifatiske alkoholer, syrer, amider eller alkylfenoler, og alkylenoksyder, særlig etylenoksyd enten alene eller med propylenoksyd. Spesifikke ikke-ioniske vaskeaktive forbindelser er alkyl (C6.22)-fenol-etylenoksyd-kondensater, produkter fra kondensasjonsreaksjonen mellom rettkjedede eller forgrenede alifatiske primære eller sekundære C8.20-alkoholer og etylenoksyd, og produkter dannet ved kondensasjon av etylenoksyd med produkter fra reaksjonen mellom propylenoksyd og etylendiamin. Andre såkalte ikke-ioniske vaskeaktive forbindelser innbefatter langkjedede tert.amin-oksyder, tert.-fosfinoksyder og dialkyl-sulfoksyder. Suitable non-ionic detergent-active compounds which can be used include in particular the products of the reaction between compounds with a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols, and alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detersive compounds are alkyl (C6.22)-phenol-ethylene oxide condensates, products of the condensation reaction between straight or branched-chain aliphatic primary or secondary C8.20 alcohols and ethylene oxide, and products formed by condensation of ethylene oxide with products of the reaction between propylene oxide and ethylenediamine. Other so-called non-ionic detersive compounds include long-chain tert-amine oxides, tert-phosphine oxides and dialkyl sulphoxides.
Særlig foretrukket er prim.- og sek.-alkohol-etoksylatene, særlig de primære og sekundære Cl2.15-alkoholer etoksylert med gjennomsnittlig fra 5 til 20 mol etylenoksyd pr. mol alkohol. Particularly preferred are the primary and secondary alcohol ethoxylates, especially the primary and secondary Cl2.15 alcohols ethoxylated with an average of from 5 to 20 mol of ethylene oxide per moles of alcohol.
Det kan også være ønskelig å innarbeide én eller flere såper av fettsyrer. Disse er fortrinnsvis natriumsåper som stammer fra naturlig forekommende fettsyrer, for eksempel fettsyrene fra kokosolje, oksetalg, solsikke- eller herdet raps-olje. It may also be desirable to incorporate one or more fatty acid soaps. These are preferably sodium soaps derived from naturally occurring fatty acids, for example the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
En foretrukket type vaskemiddelblanding som er egnet for anvendelse i de fleste automatiske tøyvaskemaskiner, inneholder anionisk og ikke-ionisk overflateaktivt materiale sammen i et vektforhold på minst 0,67:1, fortrinnsvis minst 1:1, og mer foretrukket innenfor området fra 1:1 til 10:1. Såpe kan også være tilstede hvis ønskelig. A preferred type of detergent composition suitable for use in most automatic laundry machines contains anionic and nonionic surfactants together in a weight ratio of at least 0.67:1, preferably at least 1:1, and more preferably within the range of 1:1 to 10:1. Soap can also be present if desired.
Forbindelsen med formel (I) i syreform eller fullstendig eller delvis nøytralisert saltform vil i det følgende bli omtalt som dipikolinsyreforbindelsen. Denne forbindelse finnes i vaskemiddelblandingene ifølge oppfinnelsen i en mengde på fra 0,5 til 60%. The compound with formula (I) in acid form or completely or partially neutralized salt form will be referred to below as the dipicolinic acid compound. This compound is found in the detergent mixtures according to the invention in an amount of from 0.5 to 60%.
Fortrinnsvis representerer R i formelen et hydrogenatom, det vil si at forbindelsen er dipikolinsyren selv eller et salt av denne. En annen foretrukket forbindelse er én hvor R er en hydroksylgruppe. Preferably, R in the formula represents a hydrogen atom, that is to say that the compound is dipicolinic acid itself or a salt thereof. Another preferred compound is one where R is a hydroxyl group.
Forbindelsen er hensiktsmessig i form av et alkalimetallsalt, mer foretrukket natriumsaltet. Hvilket som helst passende The compound is conveniently in the form of an alkali metal salt, more preferably the sodium salt. Anything suitable
solubiliserende kation kan imidlertid anvendes. however, solubilizing cation can be used.
Som nevnt tidligere, er disse forbindelser kjente vaskeevnebyggere. De kan anvendes som de eneste byggere i vaskemiddelblandingene ifølge oppfinnelsen, eller de kan anvendes i forbindelse med én eller flere andre byggere. As mentioned earlier, these compounds are known detergency builders. They can be used as the only builders in the detergent mixtures according to the invention, or they can be used in conjunction with one or more other builders.
I henhold til en foretrukket utførelsesform av oppfinnelsen anvendes dipikolinsyreforbindelsen i forbindelse med et krystallinsk eller amorft alkalimetall-aluminiumsilikat. Aluminium-silikatet er fortrinnsvis tilstede i en mengde på fra 10 til 60 vekt%, mer foretrukket fra 20 til 50 vekt%. Ved denne utførel-sesform av oppfinnelsen er dipikolinsyreforbindelsen hensiktsmessig tilstede i en forholdsvis liten mengde, for eksempel fra 1 til 10 vekt%. According to a preferred embodiment of the invention, the dipicolinic acid compound is used in connection with a crystalline or amorphous alkali metal aluminum silicate. The aluminum silicate is preferably present in an amount of from 10 to 60% by weight, more preferably from 20 to 50% by weight. In this embodiment of the invention, the dipicolinic acid compound is suitably present in a relatively small amount, for example from 1 to 10% by weight.
Alkalimetall-(fortrinnsvis natrium-)aluminiumsilikatene som anvendes ved denne utførelsesform av oppfinnelsen, kan enten være krystallinske eller amorfe eller blandinger av disse, og de har den generelle formel: 0,8-1,5 Na20. A1203. 0,8-6 Si02. The alkali metal (preferably sodium) aluminum silicates used in this embodiment of the invention can either be crystalline or amorphous or mixtures thereof, and they have the general formula: 0.8-1.5 Na 2 O. A1203. 0.8-6 SiO 2 .
Disse materialer inneholder en del bundet vann og fordres å ha en kalsium-ionebytterkapasitet på minst ca. 50 mg CaO pr. gram. De foretrukkede natriumaluminiumsilikater inneholder 1,5-3,5 Si02-enheter (i formelen ovenfor). Både de amorfe og de krystallinske materialer kan fremstilles lett ved omsetting av natriumsilikat med natriumaluminat, som er utfyllende beskrevet i litteraturen. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least approx. 50 mg CaO per gram. The preferred sodium aluminum silicates contain 1.5-3.5 SiO 2 units (in the above formula). Both the amorphous and the crystalline materials can be produced easily by reacting sodium silicate with sodium aluminate, which is further described in the literature.
Egnede krystallinske natriumaluminiumsilikat-ionebytter-vaskeevnebyggere er beskrevet for eksempel i GB 1 473 201 Suitable crystalline sodium aluminum silicate ion exchange builders are described for example in GB 1 473 201
og GB 1 429 143. De foretrukkede natriumaluminiumsilikater av denne type er de velkjente kommersielt tilgjengelige zeolitter A og X, og blandinger av disse. Særlig foretrukket er zeolitt. 4A. and GB 1 429 143. The preferred sodium aluminum silicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof. Particularly preferred is zeolite. 4A.
Andre byggere kan også innarbeides i vaskemiddelblandingene ifølge oppfinnelsen hvis nødvendig eller ønskelig: en fagmann på området vil lett kunne finne egnede organiske eller uorganiske vannløselige eller vann-uløselige byggere. Uorganiske byggere som kan være tilstede, innbefatter alkalimetall-(vanligvis natrium-) -orto-, -pyro- og -tripolyfosfat og -karbonat; mens organiske byggere innbefatter nitriltriacetater, citrater og karboksy-metyloksysuksinater. Denne liste er ikke ment å være fullstendig. Det totale vaskeevnebygger-nivå er vanligvis innenfor området fra 20 til 80 vekt%. Other builders can also be incorporated into the detergent mixtures according to the invention if necessary or desired: a person skilled in the art will easily be able to find suitable organic or inorganic water-soluble or water-insoluble builders. Inorganic builders that may be present include alkali metal (usually sodium) ortho, pyro, and tripolyphosphate and carbonate; while organic builders include nitrile triacetates, citrates and carboxymethyloxysuccinates. This list is not intended to be complete. The total detergency builder level is usually within the range of 20 to 80% by weight.
I henhold til en foretrukket utførelsesform av oppfinnelsen inneholder vaskemiddelblandingene mindre enn 10 vekt% uorganiske fosfatbyggere, og er mer foretrukket hovedsakelig fri for uorganisk fosfat. According to a preferred embodiment of the invention, the detergent mixtures contain less than 10% by weight of inorganic phosphate builders, and are more preferably mainly free of inorganic phosphate.
Pode-kopolymerene som anvendes i vaskemiddelblandingene ifølge den foreliggende oppfinnelse, er beskrevet og patentsøkt i EP 219 048. De kan oppnås ved at et polyalkylenoksyd med molekylvekt (antallsmidlere) 2000 - 100 000 podes med vinylacetat, som eventuelt kan være forsåpet, med et vektforhold mellom polyalkylenoksyd og vinylacetat på fra 1:0,2 til 1:10. Vinyl-acetatet er eventuelt forsåpet i et omfang av opp til 15%. Polyalkylenoksydet kan inneholde enheter av etylenoksyd, propylenoksyd og/eller butylenoksyd; polyetylenoksyd er foretrukket. The graft copolymers used in the detergent mixtures according to the present invention are described and patented in EP 219 048. They can be obtained by grafting a polyalkylene oxide with a molecular weight (number average) of 2,000 - 100,000 with vinyl acetate, which may optionally be saponified, with a weight ratio between polyalkylene oxide and vinyl acetate of from 1:0.2 to 1:10. The vinyl acetate is optionally saponified to an extent of up to 15%. The polyalkylene oxide may contain units of ethylene oxide, propylene oxide and/or butylene oxide; polyethylene oxide is preferred.
Polyalkylenoksydet har fortrinnsvis en antallsmidlere molekylvekt på fra 4000 til 50 000, og vektforholdet mellom polyalkylenoksyd og vinylacetat er fra 1:0,5 til 1:6. Særlig foretrukket er polymerer som stammer fra polyetylenoksyd med molekylvekt på 2000-50 000 og som har et vektforhold mellom polyetylenoksyd og vinylacetat på fra 1:0,5 til 1:6. The polyalkylene oxide preferably has a number average molecular weight of from 4,000 to 50,000, and the weight ratio between polyalkylene oxide and vinyl acetate is from 1:0.5 to 1:6. Particularly preferred are polymers derived from polyethylene oxide with a molecular weight of 2,000-50,000 and which have a weight ratio between polyethylene oxide and vinyl acetate of from 1:0.5 to 1:6.
Et materiale innenfor denne definisjon, basert på polyetylenoksyd med molekylvekt 6000 (ekvivalent med 13 6 etylenoksyd-enheter), som inneholder ca. 3 vektdeler vinylacetat-enheter pr. vektdel polyetylenoksyd, og som selv har en molekylvekt på 24 000, er kommersielt tilgjengelig fra BASF som Sokalan (varemerke) HP22. A material within this definition, based on polyethylene oxide with a molecular weight of 6000 (equivalent to 13 6 ethylene oxide units), which contains approx. 3 parts by weight of vinyl acetate units per weight part polyethylene oxide, and which itself has a molecular weight of 24,000, is commercially available from BASF as Sokalan (trademark) HP22.
Polymerene er tilstede i vaskemiddelblandingene ifølge oppfinnelsen i mengder på fra 0,1 til 3 vekt%, fortrinnsvis fra 0,3 til 1 vekt%. The polymers are present in the detergent compositions according to the invention in amounts of from 0.1 to 3% by weight, preferably from 0.3 to 1% by weight.
Såvel som bestanddelene - overflateaktivt system, dipikolin-syref orbindelse , andre byggere og pode-kopolymer - som allerede er omtalt, kan vaskemiddelblandingene ifølge oppfinnelsen inneholde hvilke som helst andre ikke-forstyrrende bestanddeler som er kjent for å være egnet for innarbeidelse i vaskemiddelblandinger. As well as the components - surfactant system, dipicoline acid compound, other builders and graft copolymer - which have already been mentioned, the detergent compositions according to the invention may contain any other non-interfering components which are known to be suitable for incorporation into detergent compositions.
For eksempel kan vaskemiddelblandingene ifølge oppfinnelsen hensiktsmessig inneholde et blekemiddelsystem. Peroksy-bleke-middelforbindelser er foretrukket, for eksempel uorganiske persalter eller organiske peroksysyrer, som kan anvendes i forbindelse med aktivatorer for forbedring av blekevirkningen ved lave vasketemperaturer. En fagmann på vaskemiddelområdet vil ikke ha noen vanskelighet med å anvende de normale prinsipper ved valg av et hensiktsmessig blekemiddelsystem. For example, the detergent mixtures according to the invention can suitably contain a bleaching agent system. Peroxy bleach compounds are preferred, for example inorganic persalts or organic peroxy acids, which can be used in conjunction with activators to improve the bleaching effect at low washing temperatures. A person skilled in the field of detergents will have no difficulty in applying the normal principles when choosing an appropriate bleaching agent system.
Andre materialer som kan være tilstede i vaskemiddelblandingene ifølge oppfinnelsen, innbefatter natriumsilikat, fluorescerende materialer, uorganiske salter såsom natriumsulfat, enzymer, skumregulerende midler eller skumøkende midler ettersom det er hensiktsmessig, pigmenter og parfymer. Igjen er denne liste ikke ment å være fullstendig. Other materials which may be present in the detergent compositions of the invention include sodium silicate, fluorescent materials, inorganic salts such as sodium sulfate, enzymes, suds control agents or suds enhancers as appropriate, pigments and perfumes. Again, this list is not intended to be complete.
Vaskemiddelblandinger ifølge oppfinnelsen kan fremstilles ved hvilken som helst egnet fremgangsmåte. Vaskepulvere fremstilles hensiktsmessig ved sprøytetørking av en oppslemning av forenlige varmestabile betanddeler, og deretter påsprøyting eller etter-dosering av de bestanddeler som er uegnet for bearbeidelse via oppslemningen. En fagmann på vaskemiddelområdet vil vanligvis ikke ha noen vanskelighet med å avgjøre hvilke bestanddeler som bør innarbeides i oppslemningen og hvilke som bør etterdoseres eller påsprøytes. Detergent mixtures according to the invention can be prepared by any suitable method. Washing powders are conveniently produced by spray-drying a slurry of compatible heat-stable dental components, and then spraying or post-dosing the components that are unsuitable for processing via the slurry. A person skilled in the field of detergents will usually have no difficulty in deciding which components should be incorporated into the slurry and which should be dosed or sprayed on.
Pode-kopolymeren er tilgjengelig som en oppløsning med et faststoffinnhold på 20%, som er stabil ved oppslemningsbear-beidelsestemperaturer, og kan innarbeides i oppslemningen uten problemer, under forutsetning av at pH holdes under 12. The graft copolymer is available as a solution with a solids content of 20%, which is stable at slurry processing temperatures, and can be incorporated into the slurry without problems, provided the pH is kept below 12.
Dipikolinsyreforbindelsen kan likeledes normalt innarbeides i oppslemningen. The dipicolinic acid compound can also normally be incorporated into the slurry.
Oppfinnelsen er ytterligere illustrert ved det følgende eksempel, hvor deler og prosentandeler er på vektbasis dersom ikke annet er angitt. The invention is further illustrated by the following example, where parts and percentages are on a weight basis unless otherwise stated.
EKSEMPEL EXAMPLE
Fire vaskemiddelblandinger ble fremstilt med følgende utformning ved konvensjonelle oppslemmingsfremstillings-, sprøytetørkings- og etterdoseringsteknikker: Four detergent compositions were prepared with the following formulation by conventional slurry preparation, spray drying and post-dosing techniques:
Detaljer vedrørende de fire vaskemiddelblandinger er vist i Details regarding the four detergent mixtures are shown in
tabellen nedenfor. the table below.
Smuss-suspensjons-(anti-gjenavsettings)egenskapene hos vaskemiddelblandingene ble sammenliknet ved hjelp av følgende fremgangsmåte. To nye, rene, uvaskede polyester-forsøkstøystykker ble vasket sammen med fem skitne tøystykker i et tergotometer ved 60°C i vann med hardhet 50° (fransk) (forhold mellom Ca og Mg 4:1) ved et forhold mellom vaskevæske og tøy på ca. 50:1, hvor vaske-væsken inneholdt 4 g/l av vaskemiddelblandingen som skulle utprøves. Det skitne tøy hadde mange forskjellige flekker såsom leire-, olje-, fett-, protein- og blekkflekker. Vaskesyklusen ble gjentatt ytterligere ni ganger, og det skitne tøy ble erstattet med nytt skittent tøy (med det samme flekkområde) ved hver vaskesyklus. The soil suspension (anti-redeposition) properties of the detergent compositions were compared using the following procedure. Two new, clean, unwashed polyester test garments were washed together with five soiled garments in a tergotometer at 60°C in water of hardness 50° (French) (Ca to Mg ratio 4:1) at a detergent to fabric ratio of about. 50:1, where the washing liquid contained 4 g/l of the detergent mixture to be tested. The dirty laundry had many different stains such as clay, oil, grease, protein and ink stains. The wash cycle was repeated nine more times, and the soiled laundry was replaced with new soiled laundry (with the same stain area) at each wash cycle.
Refleksjonskoeffisienten for de to nye tøystykker ble målt før vasking, og etter den tiende vaskesyklus. Reduksjonen i refleksjonskoeffisient for de vaskede tøystykker etter ti vaskinger er vist i den følgende tabell; jo mindre reduksjonen i refleksjonskoeffisient var, dess mindre gjenavsetting hadde skjedd. The reflection coefficient for the two new pieces of cloth was measured before washing, and after the tenth washing cycle. The reduction in reflection coefficient for the washed pieces of cloth after ten washings is shown in the following table; the smaller the reduction in reflection coefficient, the less redeposition had occurred.
Det vil kunne ses at Vaskemiddelblanding 1 illustrerer oppfinnelsen, mens Vaskemiddelblandinger A-C er sammenliknings-produkter. Pode-kopolymeren Sokalan HP22 hadde liten virkning i seg selv på gjenavsettingen. Natriumdipikolinatet alene hadde en ganske vesentlig fordelaktig effekt når det gjaldt gjenavsetting, men effekten var meget betydelig forøket ved tilstedeværelsen av pode-kopolymeren. It will be seen that Detergent Mixture 1 illustrates the invention, while Detergent Mixtures A-C are comparative products. The graft copolymer Sokalan HP22 had little effect by itself on redeposition. The sodium dipicolinate alone had a fairly significant beneficial effect when it came to redeposition, but the effect was very significantly increased by the presence of the graft copolymer.
Claims (11)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB888821032A GB8821032D0 (en) | 1988-09-07 | 1988-09-07 | Detergent compositions |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO893537D0 NO893537D0 (en) | 1989-09-04 |
| NO893537L NO893537L (en) | 1990-03-08 |
| NO173662B true NO173662B (en) | 1993-10-04 |
| NO173662C NO173662C (en) | 1994-01-12 |
Family
ID=10643227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO893537A NO173662C (en) | 1988-09-07 | 1989-09-04 | Detergent blend with improved anti-scavenging properties including dipicolic acid derivatives and a graft copolymer of polyalkylene oxide and vinyl acetate |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0358472B1 (en) |
| JP (1) | JPH0689359B2 (en) |
| AU (1) | AU616558B2 (en) |
| BR (1) | BR8904491A (en) |
| CA (1) | CA1323276C (en) |
| DE (1) | DE68919951T2 (en) |
| ES (1) | ES2066857T3 (en) |
| GB (1) | GB8821032D0 (en) |
| NO (1) | NO173662C (en) |
| ZA (1) | ZA896843B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8821035D0 (en) * | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
| US5759989A (en) * | 1993-07-12 | 1998-06-02 | The Procter & Gamble Company | Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent |
| ES2137246T3 (en) * | 1993-07-12 | 1999-12-16 | Procter & Gamble | STABLE AQUEOUS EMULSIONS OF NON-ION SURFACES WITH A VISCOSITY CONTROL AGENT. |
| EP0653482B1 (en) * | 1993-11-11 | 2000-03-15 | The Procter & Gamble Company | Hypochlorite bleaching compositions |
| EP0861318B1 (en) * | 1995-09-04 | 2001-11-14 | Unilever Plc | Detergent compositions and process for preparing them |
| EP0778340A3 (en) | 1995-12-06 | 1999-10-27 | Basf Corporation | Improved non-phosphate machine dishwashing compositions containing copolymers of alkylene oxide adducts of allyl alcohol and acrylic acid |
| US5750483A (en) | 1995-12-06 | 1998-05-12 | Basf Corporation | Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide |
| US6083488A (en) * | 1996-12-04 | 2000-07-04 | The Block Drug Company | Barrier to plaque formation |
| US6511952B1 (en) | 2000-06-12 | 2003-01-28 | Arco Chemical Technology, L.P. | Use of 2-methyl-1, 3-propanediol and polycarboxylate builders in laundry detergents |
| US8519060B2 (en) | 2006-05-31 | 2013-08-27 | Basf Se | Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
| JP5933584B2 (en) * | 2010-12-17 | 2016-06-15 | ザ プロクター アンド ギャンブル カンパニー | Detergent composition having polyoxyalkylene oxide end-capped polyalkylene oxide polycarboxylate graft polymer |
| RU2014133350A (en) | 2012-03-09 | 2016-03-10 | Дзе Проктер Энд Гэмбл Компани | Detergent formulations containing grafted copolymers with a wide range of polar distribution |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1342095A (en) * | 1971-01-05 | 1973-12-25 | Unilever Ltd | Detergent compositions |
| DE3536530A1 (en) * | 1985-10-12 | 1987-04-23 | Basf Ag | USE OF POLYALKYLENE OXIDES AND VINYL ACETATE GRAFT COPOLYMERISATS AS GRAY INHIBITORS IN THE WASHING AND TREATMENT OF TEXTILE GOODS CONTAINING SYNTHESIS FIBERS |
| GB8624050D0 (en) * | 1986-10-07 | 1986-11-12 | Unilever Plc | Machine dishwashing compositions |
-
1988
- 1988-09-07 GB GB888821032A patent/GB8821032D0/en active Pending
-
1989
- 1989-08-31 CA CA000609979A patent/CA1323276C/en not_active Expired - Fee Related
- 1989-09-04 NO NO893537A patent/NO173662C/en unknown
- 1989-09-06 AU AU41079/89A patent/AU616558B2/en not_active Ceased
- 1989-09-06 BR BR898904491A patent/BR8904491A/en not_active Application Discontinuation
- 1989-09-06 JP JP1231339A patent/JPH0689359B2/en not_active Expired - Lifetime
- 1989-09-06 DE DE68919951T patent/DE68919951T2/en not_active Expired - Fee Related
- 1989-09-06 ES ES89309008T patent/ES2066857T3/en not_active Expired - Lifetime
- 1989-09-06 EP EP89309008A patent/EP0358472B1/en not_active Expired - Lifetime
- 1989-09-07 ZA ZA896843A patent/ZA896843B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA1323276C (en) | 1993-10-19 |
| NO893537D0 (en) | 1989-09-04 |
| GB8821032D0 (en) | 1988-10-05 |
| ZA896843B (en) | 1991-05-29 |
| EP0358472A3 (en) | 1990-10-10 |
| EP0358472A2 (en) | 1990-03-14 |
| EP0358472B1 (en) | 1994-12-14 |
| DE68919951D1 (en) | 1995-01-26 |
| ES2066857T3 (en) | 1995-03-16 |
| NO893537L (en) | 1990-03-08 |
| NO173662C (en) | 1994-01-12 |
| DE68919951T2 (en) | 1995-05-04 |
| BR8904491A (en) | 1990-04-24 |
| AU4107989A (en) | 1990-03-15 |
| AU616558B2 (en) | 1991-10-31 |
| JPH02107699A (en) | 1990-04-19 |
| JPH0689359B2 (en) | 1994-11-09 |
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