NO172854B - TOYSY DETAILS MIXTURES WITH IMPROVED ANTI-ANTI-DEPOSIT CHARACTERISTICS CONTAINING A PODE COPOLYMER OF AN ALKYL OXIDE AND VINYL ACETATE - Google Patents
TOYSY DETAILS MIXTURES WITH IMPROVED ANTI-ANTI-DEPOSIT CHARACTERISTICS CONTAINING A PODE COPOLYMER OF AN ALKYL OXIDE AND VINYL ACETATE Download PDFInfo
- Publication number
- NO172854B NO172854B NO893535A NO893535A NO172854B NO 172854 B NO172854 B NO 172854B NO 893535 A NO893535 A NO 893535A NO 893535 A NO893535 A NO 893535A NO 172854 B NO172854 B NO 172854B
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- Prior art keywords
- vinyl acetate
- detergent
- weight
- mixture according
- ionic surfactant
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 48
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims description 16
- 229920001577 copolymer Polymers 0.000 title description 4
- 239000003599 detergent Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 23
- 239000002736 nonionic surfactant Substances 0.000 claims description 23
- -1 polyethylene Polymers 0.000 claims description 13
- 229920000578 graft copolymer Polymers 0.000 claims description 12
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000004743 Polypropylene Substances 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
- 239000004094 surface-active agent Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Chemical group 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 238000007046 ethoxylation reaction Methods 0.000 description 5
- 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 4
- 125000002947 alkylene group Chemical group 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
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 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
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000725 suspension 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 229930182556 Polyacetal Natural products 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 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 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 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
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000011976 maleic acid Substances 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 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
- 238000000926 separation method Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 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
- 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
Description
Den foreliggende oppfinnelse angår tøyvaskemiddel-blandinger med forbedrede anti-gjenavsetningsegenskaper. The present invention relates to laundry detergent compositions with improved anti-redeposition properties.
Gjenavsetning 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 natriumkarboksymetylcellulose er blitt innarbeidet i tøy-vaskemiddelblandinger, og denne forbindelse anvendes fremdeles i dag. I det aller siste er kopolymerer av etylen eller vinyl-metyleter og maleinsyreanhydrid, kopolymerer av akrylsyre og maleinsyreanhydrid og homopolymerer av akrylsyre blitt foreslått i patentlitteraturen; se for eksempel GB 1 269 848 (Procter & Gamble) og GB 1 460 893 (Unilever). 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 carboxymethyl cellulose has been incorporated into laundry detergent mixtures, and this compound is still used today. 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 (Procter & Gamble) and GB 1,460,893 (Unilever).
Et annet polymert materiale som er blitt foreslått for forbedring av smuss-suspendering, er polyvinylpyrrolidon. Another polymeric material that has been suggested for improving soil suspension is polyvinylpyrrolidone.
EP 262 897A (Unilever) beskriver vaskemiddelblandinger som inneholder polyvinylpyrrolidon, et anionisk overflateaktivt middel, og et ikke-ionisk overflateaktivt system med en hydrofil-lipofil-balanse (HLB) på ikke mer enn 10,5. EP 262 897A (Unilever) describes detergent compositions containing polyvinylpyrrolidone, an anionic surfactant, and a nonionic surfactant system with a hydrophilic-lipophilic balance (HLB) of not more than 10.5.
EP 219 048A (BASF) beskriver anvendelse av pode-kopolymerer av polyalkylenoksyd med vinylacetat som grånings-inhibitorer ved vaske- og ettervaske-behandling av syntetiske tekstilstoffer. EP 219 048A (BASF) 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 ikke-ionisk overflateaktivt system med lavt innhold av HLB, viser over-raskende forbedret smussbærende (anti-gjenavsetnings-)egenskaper når det gjelder polyester/bomullsstoffer. We have now discovered that detergent compositions containing a graft copolymer of this type in conjunction with a low HLB non-ionic surfactant system show surprisingly improved soil-carrying (anti-redeposition) properties for polyester/cotton fabrics.
Den foreliggende oppfinnelse tilveiebringer en vaskemiddelblanding som omfatter: (a) fra 2 til 50 vekt% av et vaskeaktivt system, hvilken mengde innbefatter et ikke-ionisk overflateaktivt system som består av ett eller flere ikke-ionisk overflateaktive midler, hvor det ikke-ionisk overflateaktive system har et tåkepunkt (som definert i det følgende) som ikke er høyere The present invention provides a detergent composition comprising: (a) from 2 to 50% by weight of a detergent system, which amount includes a non-ionic surfactant system consisting of one or more non-ionic surfactants, wherein the non-ionic surfactant system has a cloud point (as defined below) that is not higher
enn 40°C; og than 40°C; and
(b) fra 0,1 til 3 vekt% av en pode-kopolymer av (i) polyetylen-, (b) from 0.1 to 3% by weight of a graft copolymer of (i) polyethylene-,
polypropylen- eller polybutylenoksyd med (ii) vinylacetat med et vektforhold mellom (i) og (ii) på fra 1:0,2 til 1:10. polypropylene or polybutylene oxide with (ii) vinyl acetate with a weight ratio between (i) and (ii) of from 1:0.2 to 1:10.
Oppfinnelsen angår altså vaskemiddelblandinger som inneholder to spesifiserte bestanddeler - et ikke-ionisk overflateaktivt system og en pode-kopolymer - som i tillegg kan inneholde eventuelle andre konvensjonelle vaskemiddelbestanddeler, for eksempel andre overflateaktive midler, byggere, blekemiddel-systemer, skumdempende 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 therefore relates to detergent mixtures containing two specified components - a non-ionic surface-active system and a graft copolymer - which may additionally contain any other conventional detergent components, for example other surface-active agents, 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.
Det ikke-ionisk overflateaktive system som inngår i oppfinnelsen finnes som en uklar fase ett eller annet sted i tempe-ra turområdet 0-40°C, fortrinnsvis 0-15°C, i destillert vann ved en konsentrasjon på 1%. I praksis betyr dette at systemet har et tåkepunkt på ikke over 40°C, fortrinnsvis ikke over 15°C. Tåkepunktet er en betegnelse som er velkjent på fagområdet, The non-ionic surface-active system included in the invention is found as a cloudy phase somewhere in the temperature range 0-40°C, preferably 0-15°C, in distilled water at a concentration of 1%. In practice, this means that the system has a cloud point of no more than 40°C, preferably no more than 15°C. The fog point is a term that is well known in the field,
for eksempel fra "Surface Active Ethylene Oxide Adducts" av N. Schonfeldt, Pergamon Press 1969, sider 145-154. Generelt angitt er tåkepunktet for et overflateaktivt materiale den temperatur ved hvilken forbindelsen mellom molekylene i det overflateaktive materiale og vannmolekyler ved hydrogenbinding brytes ned, hvilket fører til atskillelse av fasen som har høyt innhold av overflateaktivt middel, og fasen som har høyt innhold av vann, og en derav følgende økning i turbiditet eller uklarhet. for example from "Surface Active Ethylene Oxide Adducts" by N. Schonfeldt, Pergamon Press 1969, pages 145-154. Generally stated, the cloud point of a surfactant is the temperature at which the connection between the molecules of the surfactant and water molecules breaks down by hydrogen bonding, which leads to the separation of the phase that has a high content of surfactant, and the phase that has a high content of water, and a consequent increase in turbidity or turbidity.
Tåkepunktet svarer omtrent til hydrofil-lipofil-balansen (HLB) hos overflateaktivt-middel-systemet, og det er derfor foretrukket at HLB ikke er høyere enn 10,5 og mer foretrukket ikke høyere enn 9,5. HLB bør imidlertid fortrinnsvis være over 6,0, mer foretrukket over 8,0, for tilveiebringelse av tilstrekkelig vaskeevne. The cloud point roughly corresponds to the hydrophilic-lipophilic balance (HLB) of the surfactant system, and it is therefore preferred that the HLB is not higher than 10.5 and more preferably not higher than 9.5. However, the HLB should preferably be above 6.0, more preferably above 8.0, to provide sufficient detergency.
Egnede ikke-ionisk 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 alkyl-fenoler, og alkylenoksyder, særlig etylenoksyd enten alene eller med propylenoksyd. Spesifikke ikke-ionisk 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-ionisk 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 alkyl phenols, and alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific non-ionic detergent active 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 detergent-active compounds include long-chain tert-amine oxides, tert-phosphine oxides and dialkyl sulphoxides.
Hvor for eksempel alkylenoksyd-addisjonsprodukter av fettaktige materialer (alifatiske alkoholer, syrer eller amider) anvendes som de ikke-ionisk vaskeaktive forbindelser, har antallet alkylenoksydgrupper pr. molekyl en betydelig effekt på tåkepunktet som angitt ved Schonfeldt-referansen nevnt ovenfor. Det fettaktige materiales kjedelengde og beskaffenhet har også innvirkning, og således avhenger det foretrukkede antall alkylenoksydgrupper pr. molekyl av det fettaktige materiales beskaffenhet og kjedelengde. Vi har for eksempel funnet at når det fettaktige materiale er en alkohol med ca. 12-15 karbon-atomer, har addisjonsproduktene med 3 og 4 etylenoksydgrupper pr. molekyl (i det følgende betegnet 3E0- og 4E0-materialene) begge tåkepunkt på under 0°C og er derfor egnet for anvendelse ved den foreliggende oppfinnelse. De tilsvarende overflateaktive 5EO- og 6E0-materialer har tåkepunkt på henholdsvis ca. 12 og ca. 3 0°C; begge er derfor egnet for anvendelse ved den foreliggende oppfinnelse, men 5E0-materialet er foretrukket fremfor 6E0-materialet. Where, for example, alkylene oxide addition products of fatty materials (aliphatic alcohols, acids or amides) are used as the non-ionically detergent-active compounds, the number of alkylene oxide groups per molecule a significant effect on the cloud point as indicated by the Schonfeldt reference mentioned above. The chain length and nature of the fatty material also have an impact, and thus the preferred number of alkylene oxide groups per molecule of the nature and chain length of the fatty material. We have found, for example, that when the fatty material is an alcohol with approx. 12-15 carbon atoms, the addition products have 3 and 4 ethylene oxide groups per molecule (hereinafter referred to as the 3E0 and 4E0 materials) both have a cloud point below 0°C and are therefore suitable for use in the present invention. The corresponding surface-active 5EO and 6E0 materials have cloud points of approx. 12 and approx. 30°C; both are therefore suitable for use in the present invention, but the 5E0 material is preferred over the 6E0 material.
Det tilsvarende overflateaktive 7E0-materiale har et tåkepunkt på ca. 48°C og er derfor uegnet for anvendelse ved den foreliggende oppfinnelse, dersom det ikke er blandet med et annet overflateaktivt middel med lavere tåkepunkt: for eksempel har en blanding av 1 vektdel av 7E0-materialet med 3 vektdeler av 3E0-materialet et tilstrekkelig lavt tåkepunkt til at den er egnet ved den foreliggende oppfinnelse. Ytterligere etoksylering hever tåkepunktet enda mer: således har det tilsvarende llEO-materiale et tåkepunkt som er høyere enn 80°C, og er uegnet for anvendelse ved den foreliggende oppfinnelse. The corresponding surfactant 7E0 material has a cloud point of approx. 48°C and is therefore unsuitable for use in the present invention, if it is not mixed with another surfactant with a lower cloud point: for example, a mixture of 1 part by weight of the 7E0 material with 3 parts by weight of the 3E0 material has a sufficiently low cloud point to be suitable in the present invention. Further ethoxylation raises the cloud point even more: thus the corresponding llEO material has a cloud point higher than 80°C, and is unsuitable for use in the present invention.
Således er foretrukkede ikke-ionisk overflateaktive materialer for anvendelse i vaskemiddelblandingene ifølge oppfinnelsen alifatiske C12.15-alkoholer med en etoksyleringsgrad som ikke overstiger 6, fortrinnsvis 3-5. Thus, preferred non-ionic surfactant materials for use in the detergent compositions according to the invention are aliphatic C12.15 alcohols with a degree of ethoxylation not exceeding 6, preferably 3-5.
Det ikke-ionisk overflateaktive system i vaskemiddelblandingene ifølge oppfinnelsen kan bestå av et enkelt ikke-ionisk overflateaktivt materiale med hensiktsmessig tåkepunkt, skjønt man må huske at selv et enkelt kommersielt ikke-ionisk overflateaktivt materiale er en blanding av materialer med for-skjellig kjedelengde og etoksyleringsgrad: kjedelengdene og etoksyleringsgradene som er angitt i denne beskrivelse, er gjennomsnittlige verdier. Alternativt kan det oppnås et ikke-ionisk overflateaktivt system med passende tåkepunkt og HLB-verdi ved blanding av to eller flere ikke-ionisk overflateaktive materialer, som eksemplifisert ved 7EO/3EO-blandingen nevnt i foregående avsnitt. The non-ionic surface-active system in the detergent mixtures according to the invention can consist of a single non-ionic surface-active material with an appropriate cloud point, although it must be remembered that even a single commercial non-ionic surface-active material is a mixture of materials with different chain length and degree of ethoxylation : the chain lengths and degrees of ethoxylation given in this specification are average values. Alternatively, a non-ionic surfactant system with suitable cloud point and HLB value can be obtained by mixing two or more non-ionic surfactant materials, as exemplified by the 7EO/3EO mixture mentioned in the previous section.
Det ikke-ionisk overflateaktive system er fortrinnsvis tilstede i en mengde på fra 2 til 20 vekt%, mer foretrukket fra 3 til 10 vekt%, basert på den totale vaskemiddelblanding. Som angitt nedenfor, kan andre overflateaktive midler, av andre ione-typer, også være tilstede hvis ønskelig, og den totale mengde overflateaktivt materiale av alle ionetyper som er tilstede, er innenfor området fra 2 til 50 vekt%, fortrinnsvis fra 5 til 40 vekt%, basert på den endelige vaskemiddelblanding. The nonionic surfactant system is preferably present in an amount of from 2 to 20% by weight, more preferably from 3 to 10% by weight, based on the total detergent composition. As indicated below, other surface-active agents, of other ion types, may also be present if desired, and the total amount of surface-active material of all ion types present is within the range of from 2 to 50% by weight, preferably from 5 to 40% by weight %, based on the final detergent mixture.
Pode-kopolymerene som anvendes i vaskemiddelblandingene ifølge den foreliggende oppfinnelse, er beskrevet i EP 219 048A (BASF). De kan oppnås ved at et polyalkylenoksyd med molekylvekt (antallsmidlere) 2000 - 100 000 podes med vinylacetat, som kan være delvis forsåpet, med et vektforhold mellom polyalkylenoksyd og vinylacetat på fra 1:0,2 til 1:10. Vinylacetatet kan for eksempel være forsåpet i et omfang på 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 in EP 219 048A (BASF). 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 be partially saponified, with a weight ratio between polyalkylene oxide and vinyl acetate of from 1:0.2 to 1:10. The vinyl acetate can, for example, be 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 136 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 A material within this definition, based on polyethylene oxide with a molecular weight of 6000 (equivalent to 136 ethylene oxide units), which contains approx. 3 parts by weight of vinyl acetate units per part by weight polyethylene oxide, and which itself has a molecular weight of 24,000, is commercially available from BASF
som Sokalan<®> HP22. such as Sokalan<®> 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.
Vaskemiddelblandingene ifølge oppfinnelsen kan, likesom det spesifiserte ikke-ionisk overflateaktive system og pode-kopolymeren, inneholde hvilke som helst andre ikke-forstyrrende bestanddeler som er kjent for å være egnet for innarbeidelse i vaskemiddelblandinger. The detergent compositions according to the invention may, like the specified nonionic surfactant system and the graft copolymer, contain any other non-interfering ingredients known to be suitable for incorporation into detergent compositions.
Vaskemiddelblandingene kan passende inneholde ett eller flere anioniske, kationiske, amfotære eller zwitterioniske, overflateaktive såpe- eller ikke-såpe-materialer, eller kombina-sjoner av disse. Mange egnede vaskeaktive forbindelser er til-gjengelige 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 compositions may suitably contain one or more anionic, 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, i tillegg til det spesifiserte ikke-ionisk overflateaktive system, er såper og syntetiske anionisk overflateaktive ikke-såpe-materialer. The preferred detergent compounds that can be used, in addition to the specified nonionic surfactant system, are soaps and synthetic anionic surfactant nonsoap materials.
Syntetiske anionisk overflateaktive materialer er velkjente for fagfolk på området. Eksempler innbefatter alkylbenzensulfo-nater, spesielt rettkjedede natriumalkylbenzensulfonater med en alkylkjedelengde på C8.c15; primære og sekundære alkylsulfater, spesielt natrium-C12-C15-prim. -alkoholsulfater; olef insulfonater; alkansulfonater; dialkylsulfosuksinater; og fettsyreester-sulfonater. Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzenesulfonates, especially straight chain sodium alkylbenzenesulfonates with an alkyl chain length of C8-C15; primary and secondary alkyl sulfates, especially sodium C12-C15-prim. - alcohol sulfates; olef insulfonates; alkane sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates.
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 fett-syrene fra kokosolje, oksetalg, solsikke- eller herdet rapsolje. 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 vaskemiddelblanding-type som er egnet for anvendelse i de fleste automatiske tøyvaskemaskiner, inneholder anionisk og ikke-ionisk overflateaktivt middel 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 detergent blend type suitable for use in most automatic laundry machines contains anionic and nonionic surfactant 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.
Som tidligere angitt, er den totale mengde overflateaktivt materiale i vaskemiddelblandingene ifølge oppfinnelsen fra 2 til 50 vekt%, og er fortrinnsvis fra 5 til 40 vekt%. As previously indicated, the total amount of surface-active 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.
Vaskemiddelblandinger ifølge oppfinnelsen vil også vanligvis inneholde én eller flere vaskeevnebyggere. Disse er likeså velkjente for en fagmann på området som de overflateaktive materialer som er oppregnet ovenfor. Uorganiske byggere som kan være tilstede, innbefatter alkalimetall-(vanligvis natrium-)-orto-, -pyro- og -tripolyfosfat og -karbonat, og krystallinske og amorfe aluminiumsilikater; mens organiske byggere innbefatter polykarboksylat-polymerer såsom poly-akrylater, akrylsyre/maleinsyre-kopolymerer, og polyacetal-karboksylater, og monomere polykarboksylater såsom nitriltri-acetater, citrater og karboksymetyloksysuksinater. Denne liste er ikke ment å være fullstendig. Det totale vaskeevnebygger-nivå er vanligvis innenfor området fra 20 til 80 vekt%. Detergent mixtures according to the invention will also usually contain one or more detergent builders. These are as well known to a person skilled in the art as the surfactants listed above. Inorganic builders that may be present include alkali metal (usually sodium) ortho, pyro, and tripolyphosphate and carbonate, and crystalline and amorphous aluminosilicates; while organic builders include polycarboxylate polymers such as polyacrylates, acrylic acid/maleic acid copolymers, and polyacetal carboxylates, and monomeric polycarboxylates such as 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.
Ved denne foretrukkede utførelsesform omfatter bygger-systemet fortrinnsvis krystallinsk eller amorft alkalimetall-aluminiumsilikat, eventuelt i forbindelse med en tilleggsbygger. Aluminiumsilikatet er hensiktsmessig tilstede i en mengde på fra 10 til 60 vekt%. In this preferred embodiment, the builder system preferably comprises crystalline or amorphous alkali metal aluminum silicate, possibly in connection with an additional builder. The aluminum silicate is conveniently present in an amount of from 10 to 60% by weight.
Vaskemiddelblandinger ifølge oppfinnelsen kan også hensiktsmessig inneholde et blekemiddelsystem. Peroksy-bleke-middelforbindelser, for eksempel uorganiske persalter eller organiske peroksysyrer, som kan anvendes i forbindelse med aktivatorer for forbedring av blekevirkningen ved lave vaske-temperaturer, er foretrukket. En fagmann på området vaskemiddelblandinger vil ikke ha noen vanskelighet med å anvende de normale prinsipper til utvelging av et passende blekemiddelsystem. Detergent mixtures according to the invention can also appropriately contain a bleaching agent system. Peroxy bleach compounds, 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, are preferred. One skilled in the art of detergent compositions will have no difficulty in applying the normal principles for selecting a suitable bleach system.
Andre materialer som kan være tilstede i vaskemiddelblandinger ifølge oppfinnelsen, innbefatter natriumsilikat, fluorescerende midler, 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 detergent compositions of the invention include sodium silicate, fluorescent agents, 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 bestanddeler, og deretter påsprøyting eller etterdosering av de bestanddeler som er uegnet for bearbeidelse via oppslemningen. En fagmann på vaskemiddel-området 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 components, and then spraying on 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 oppslemnings-bearbeidelsestemperaturer, og kan innarbeides i oppslemningen uten problemer, under forutsetning av at pH holdes på 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.
Det ikke-ionisk overflateaktive system innarbeides fortrinnsvis ikke via oppslemningen, Hvis det imidlertid anvendes et blandet system som innbefatter en forholdsvis sterkt etoksylert bestanddel, kan denne bestanddel hvis ønskelig bearbeides via oppslemningen mens materiale med lavere etoksylering påsprøytes eller etter-doseres på en fast bærer. The non-ionic surfactant system is preferably not incorporated via the slurry. If, however, a mixed system is used which includes a relatively strongly ethoxylated component, this component can, if desired, be processed via the slurry while material with lower ethoxylation is sprayed on or post-dosed onto a solid carrier.
Oppfinnelsen er ytterligere illustrert ved de følgende eksempler, hvor deler og prosentandeler er på vektbasis dersom ikke annet er angitt. The invention is further illustrated by the following examples, where parts and percentages are on a weight basis unless otherwise stated.
Eksempel 1 Example 1
Fire vaskemiddelblandinger ble fremstilt med følgende utformning ved vanlige oppslemnings-fremstillings-, sprøyte-tørkings- og etterdoserings-teknikker: Four detergent mixtures were prepared with the following formulation by conventional slurry-making, spray-drying and post-dosing techniques:
De fremstilte vaskemiddelblandinger inneholdt følgende mengder av ikke-ioniske overflateaktive materialer og Sokalan HP22: The manufactured detergent mixtures contained the following amounts of non-ionic surface-active materials and Sokalan HP22:
Det vil kunne sees at vaskemiddelblanding 1 illustrerer oppfinnelsen, mens blandingene A-C er sammenlikningsprodukter. It will be seen that detergent mixture 1 illustrates the invention, while the mixtures A-C are comparative products.
Smuss-suspensjons-(anti-gjenavsetnings)egenskapene hos de fire vaskemiddelblandinger ble sammenliknet ved hjelp av føl-gende fremgangsmåte. To nye, rene, uvaskede polyester/bomull-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 vaskevæsken inneholdt 4 g/l av vaske-middelblandingen 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 four detergent mixtures were compared using the following method. Two new, clean, unwashed polyester/cotton test garments were washed together with five soiled garments in a tergotometer at 60°C in 50° (French) hardness water (Ca to Mg ratio 4:1) at a ratio of detergent to cloth of approx. 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.
Refleksjonskoéffisienten for de to nye tøystykker ble målt før vasking, og etter den tiende vaskesyklus. Reduksjonen i refleksjonskoéffisient for de vaskede tøystykker etter ti vaskinger er vist i følgende tabell; jo mindre reduksjonen i refleksjonskoéffisient var, dess mindre gjenavsetning 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.
Claims (12)
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| GB888821035A GB8821035D0 (en) | 1988-09-07 | 1988-09-07 | Detergent compositions |
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| NO893535L NO893535L (en) | 1990-03-08 |
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| NO893535A NO172854C (en) | 1988-09-07 | 1989-09-04 | TOYSY DETAILS MIXTURES WITH IMPROVED ANTI-ANTI-DEPOSIT CHARACTERISTICS CONTAINING A PODE COPOLYMER OF AN ALKYL OXIDE AND VINYL ACETATE |
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| US5698510A (en) * | 1993-09-13 | 1997-12-16 | The Procter & Gamble Company | Process for making granular detergent compositions comprising nonionic surfactant |
| GB9403155D0 (en) * | 1994-02-18 | 1994-04-06 | Unilever Plc | Detergent compositions |
| DE4424818A1 (en) * | 1994-07-14 | 1996-01-18 | Basf Ag | Low-viscosity mixtures of amphiphilic nonionic graft copolymers and viscosity-reducing additives |
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| US5728672A (en) * | 1995-08-04 | 1998-03-17 | Reckitt & Colman Inc. | Pine oil hard surface cleaning compositions |
| TR199800380T1 (en) * | 1995-09-04 | 1998-05-21 | Unilever N.V. | Detergent compositions and a process for their preparation. |
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| JP3325830B2 (en) * | 1998-03-30 | 2002-09-17 | 株式会社日本触媒 | Bleach composition |
| JP2002003890A (en) * | 2000-06-20 | 2002-01-09 | Kao Corp | Detergent composition |
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| MX2007007318A (en) | 2004-12-17 | 2007-07-09 | Procter & Gamble | Hydrophilically modified polyols for improved hydrophobic soil cleaning. |
| US7465701B2 (en) | 2006-05-31 | 2008-12-16 | The Procter & Gamble Company | Detergent composition |
| WO2007138054A1 (en) † | 2006-05-31 | 2007-12-06 | The Procter & Gamble Company | Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
| JP5535903B2 (en) | 2007-06-29 | 2014-07-02 | ザ プロクター アンド ギャンブル カンパニー | Laundry detergent composition comprising an amphiphilic graft polymer based on polyalkylene oxide and vinyl ester |
| JP4933487B2 (en) * | 2008-05-21 | 2012-05-16 | 旭洋造船株式会社 | Fuel efficient transport ship |
| JP4873388B2 (en) * | 2008-07-28 | 2012-02-08 | 上野 康男 | Starting device |
| US20110152161A1 (en) * | 2009-12-18 | 2011-06-23 | Rohan Govind Murkunde | Granular detergent compositions comprising amphiphilic graft copolymers |
| US8334250B2 (en) | 2009-12-18 | 2012-12-18 | The Procter & Gamble Company | Method of making granular detergent compositions comprising amphiphilic graft copolymers |
| US8859484B2 (en) | 2012-03-09 | 2014-10-14 | The Procter & Gamble Company | Detergent compositions comprising graft polymers having broad polarity distributions |
| ES2713084T3 (en) | 2013-07-30 | 2019-05-17 | Procter & Gamble | Method for preparing granular detergent compositions comprising surfactants |
| EP2832843B1 (en) | 2013-07-30 | 2019-08-21 | The Procter & Gamble Company | Method of making granular detergent compositions comprising polymers |
| EP2899259A1 (en) * | 2014-01-22 | 2015-07-29 | The Procter and Gamble Company | Detergent compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH644394A5 (en) * | 1977-11-17 | 1984-07-31 | Procter & Gamble | GRAINY DETERGENT AND DETERGENT COMPOSITION. |
| 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 |
| GB8623586D0 (en) * | 1986-10-01 | 1986-11-05 | Unilever Plc | Detergent composition |
| GB8821032D0 (en) * | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
| GB8821034D0 (en) * | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
-
1988
- 1988-09-07 GB GB888821035A patent/GB8821035D0/en active Pending
-
1989
- 1989-08-31 CA CA000609975A patent/CA1328065C/en not_active Expired - Fee Related
- 1989-09-04 NO NO893535A patent/NO172854C/en unknown
- 1989-09-06 BR BR898904489A patent/BR8904489A/en not_active Application Discontinuation
- 1989-09-06 DE DE68919392T patent/DE68919392T2/en not_active Expired - Fee Related
- 1989-09-06 AU AU41080/89A patent/AU619892B2/en not_active Ceased
- 1989-09-06 JP JP1231337A patent/JPH02117999A/en active Pending
- 1989-09-06 ES ES89309010T patent/ES2063139T3/en not_active Expired - Lifetime
- 1989-09-06 EP EP89309010A patent/EP0358474B1/en not_active Expired - Lifetime
- 1989-09-07 ZA ZA896841A patent/ZA896841B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02117999A (en) | 1990-05-02 |
| NO893535L (en) | 1990-03-08 |
| EP0358474A2 (en) | 1990-03-14 |
| CA1328065C (en) | 1994-03-29 |
| AU619892B2 (en) | 1992-02-06 |
| EP0358474A3 (en) | 1990-10-10 |
| ZA896841B (en) | 1991-05-29 |
| BR8904489A (en) | 1990-04-24 |
| NO893535D0 (en) | 1989-09-04 |
| EP0358474B1 (en) | 1994-11-17 |
| NO172854C (en) | 1993-09-15 |
| DE68919392D1 (en) | 1994-12-22 |
| GB8821035D0 (en) | 1988-10-05 |
| DE68919392T2 (en) | 1995-03-30 |
| AU4108089A (en) | 1990-03-15 |
| ES2063139T3 (en) | 1995-01-01 |
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