DK170991B1 - Liquid, bleach-containing detergent - Google Patents
Liquid, bleach-containing detergent Download PDFInfo
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- DK170991B1 DK170991B1 DK292288A DK292288A DK170991B1 DK 170991 B1 DK170991 B1 DK 170991B1 DK 292288 A DK292288 A DK 292288A DK 292288 A DK292288 A DK 292288A DK 170991 B1 DK170991 B1 DK 170991B1
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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
- C11D3/395—Bleaching agents
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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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
- C11D3/39—Organic or inorganic per-compounds
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Abstract
Description
DK 170991 B1 iDK 170991 B1 i
Den foreliggende opfindelse angår væskeformige vaskemidler, som indeholder et fast, vandopløseligt peroxygenblegemiddel. De foreliggende sammensætninger indeholder et opløsningsmiddel system omfattende vand og et vandblandbart organisk opløsningsmiddel.The present invention relates to liquid detergents containing a solid, water-soluble peroxygen bleach. The present compositions contain a solvent system comprising water and a water miscible organic solvent.
5 Opløsningsmiddel systemet er udformet med henblik på at holde mængden af tilgængeligt oxygen i opløsningen på under 0,5%, fortrinsvis under 0,1%. Mængden af tilgængeligt chlor i væskefasen svarer til ikke mere end 1/5 af den totale mængde af peroxygenbl egemi ddel i sammensætningen, fortrinsvis ikke mere end 1/10.The solvent system is designed to keep the amount of oxygen available in the solution below 0.5%, preferably below 0.1%. The amount of chlorine available in the liquid phase corresponds to no more than 1/5 of the total amount of peroxygenic compound in the composition, preferably no more than 1/10.
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De såkaldte kraftigt virkende, væskeformige vaskemidler, der for tiden er kommercielt opnåelige, omfatter typisk organiske surfak-tanter, enzymer og parfumer. Disse bestanddele er almindeligvis inkompatible med peroxygenblegemi dl er. Som et resultat af dette er 15 ingen væskeformige, peroxygenblegemiddelhol dige vaskemidler kommercielt opnåelige i dag.The so-called powerful liquid detergents that are currently commercially available typically comprise organic surfactants, enzymes and perfumes. These components are generally incompatible with peroxygen bleaching. As a result, no liquid peroxygen bleach-containing detergents are commercially available today.
I beskrivelsen til EP patent nr. 0.037.184, udstedt 23. januar 1985 til Interox Chemicals Ltd. beskrives væskeformige vaskemidler 20 omfattende organiske surfaktanter, et buildersystem, mindst 2% hydrogenperoxid og et stabiliserende system omfattende en amino-ethylenphosphonat eller hydroxyalkyldiphosphonat, et polyhydroxy-ali fati sk carboxyl at og/eller en lavmolekylær, al i fati sk mono-hydroxyalkohol.In the specification to EP Patent No. 0.037,184, issued January 23, 1985 to Interox Chemicals Ltd. liquid detergents comprising organic surfactants, a builder system, at least 2% hydrogen peroxide and a stabilizing system comprising an aminoethylene phosphonate or hydroxyalkyl diphosphonate, a polyhydroxy-aliphatic carboxyl and / or a low molecular weight alkoxy-hydroxy alcohol are disclosed.
25 I beskrivelsen til EP patent nr. 0.086.511, udstedt 2. juni 1986 til The Procter & Gamble Company beskrives vandige, væskeformige vaskemidler med et pH på under 9 og omfattende organiske surfaktanter, oxygenblegemiddel, fedtsyre og et vandopløseligt calciumsalt.25 In the specification of EP Patent No. 0.086,511, issued June 2, 1986 to The Procter & Gamble Company, aqueous liquid detergents having a pH of less than 9 and comprising organic surfactants, oxygen bleach, fatty acid and a water-soluble calcium salt are disclosed.
30 I DE offentliggørelsesskrift nr. 35 11 515, publiceret 17. oktober 1985 beskrives ikke-vandige, væskeformige vaskemidler omfattende natriumperboratmonohydrat og en aktivator for perboratet. I beskrivelsen til FR 2.579.615, publiceret 3. oktober 1986, beskrives 35 ligeledes ikke-vandige sammensætninger som yderligere omfatter katalaseinhibitorer. De sammensætninger, der er givet eksempler på i disse to patentbeskrivelser, indeholder ikke anioniske surfaktanter.30 in DE Publication No. 35 11 515, published October 17, 1985, discloses non-aqueous liquid detergents comprising sodium perborate monohydrate and an activator for the perborate. The disclosure of FR 2,579,615, published October 3, 1986, also discloses 35 non-aqueous compositions which further comprise catalase inhibitors. The compositions exemplified in these two patent specifications do not contain anionic surfactants.
Det er et formål med den foreliggende opfindelse at tilvejebringe 2 DK 170991 B1 vandige, væskeformige vaskemidler indeholdende væsentlige mængder af et fast, vandopløseligt peroxygenblegemiddel. Det er yderligere et formål med den foreliggende opfindelse at tilvejebringe sådanne væskeformige, bl egemiddelholdige vaskemidler, som indeholder væ-5 sentlige mængder anionisk surfaktant.It is an object of the present invention to provide aqueous liquid detergents containing substantial amounts of a solid, water-soluble peroxygen bleach. It is a further object of the present invention to provide such liquid, inter alia, detergent-containing detergents which contain substantial amounts of anionic surfactant.
De væskeformige vaskemidler ifølge den foreliggende opfindelse har et pH på midst 8 og omfatter organiske surfaktanter og endvidere en mængde af en fast, vandopløselig peroxygenforbindelse på basis af 10 sammensætningens vægt, hvilken forbindelse er dispergeret i en væskefase, som omfatter et opløsningsmiddel system omfattende vand og mindst et vandblandbart, organisk opløsningsmiddel, således at mængden af tilgængeligt oxygen (AVO, engelsk: available oxygen), som er opløst i væskefasen, ikke er mere end 0,5 vægtprocent, fortrins-15 vis ikke mere end 0,1 vægtprocent af væskefasen. Mængden af tilgængeligt oxygen, som er opløst i væskefasen, svarer til ikke mere end 1/5 af mængden af peroxygenforbindelse i sammensætningen, fortrinsvis til ikke mere end 1/10.The liquid detergents of the present invention have a pH of at least 8 and comprise organic surfactants and, further, an amount of a solid, water-soluble peroxygen compound based on the weight of the composition, which is dispersed in a liquid phase comprising a solvent system comprising water and at least one water-miscible organic solvent such that the amount of available oxygen dissolved in the liquid phase is not more than 0.5% by weight, preferably not more than 0.1% by weight of the liquid phase . The amount of available oxygen dissolved in the liquid phase corresponds to no more than 1/5 of the amount of peroxygen compound in the composition, preferably no more than 1/10.
20 I forbindelse med den foreliggende opfindelse foretrækkes vaskemidler med et pH på mindst 9, mere fortrinsvis mindst 9,5.In the present invention, detergents having a pH of at least 9, more preferably at least 9.5, are preferred.
De foretrukne faste, vandopløselige peroxygenforbindel ser er perbo-rater. De foretrukne vandblandbare, organiske opløsningsmidler er 25 lavmolekylære monovalente alkoholer, og den mest foretrukne blandt disse opløsningsmidler er ethanol.The preferred solid, water-soluble peroxygen compounds are perforates. The preferred water-miscible organic solvents are 25 low molecular weight monovalent alcohols, and the most preferred of these solvents is ethanol.
Der foretrækkes endvidere også væskeformige vaskemidler, som yderligere omfatter vaskemiddel enzymer.Furthermore, liquid detergents which further comprise detergent enzymes are also preferred.
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Den foreliggende opfindelse angår problemet med formulering af væskeformige vaskemidler, som indeholder væsentlige mængder af en organisk surfaktant, inklusiv anioniske surfaktanter, og et fast, vandopløseligt peroxygenblegemiddel, og som er stabile. Det har nu 35 vist sig, at dette kan opnås ved anvendelse af et opløsningsmiddel -system, som omfatter vand og et vandblandbart, organisk opløsningsmiddel. Dette gør det muligt at inkorporere en væsentlig mængde af peroxygenforbindelse i det væskeformige vaskemiddel, samtidig med at mængden af tilgængeligt oxygen i opløsning holdes under 0,5 vægt- DK 170991 B1 3 procent af opløsningsmiddel systemet, fortrinsvis under 0,1%. Mindre end 1/5 af peroxygenforbindel sen er opløst i den væskeformige fase, fortrinsvis mindre end 1/10.The present invention relates to the problem of formulation of liquid detergents containing substantial amounts of an organic surfactant, including anionic surfactants, and a solid, water-soluble peroxygen bleach and which are stable. It has now been found that this can be achieved by using a solvent system comprising water and a water miscible organic solvent. This makes it possible to incorporate a substantial amount of peroxygen compound into the liquid detergent while keeping the amount of available oxygen in solution below 0.5% by weight, preferably below 0.1%. Less than 1/5 of the peroxygen compound is dissolved in the liquid phase, preferably less than 1/10.
5 Tilstedeværelsen af vand i opløsningsmiddel systemet er væsentlig for opløseligheden af f.eks. anioniske surfaktanter. Det lave niveau af tilgængeligt oxygen i opløsningen har vist sig at medføre et bl egemiddel system, som er stabilt ved lagring under typiske lagringsbetingelser.The presence of water in the solvent system is essential for the solubility of e.g. anionic surfactants. The low level of available oxygen in the solution has been shown to cause a bleaching agent system which is stable during storage under typical storage conditions.
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De væskeformige vaskemidler formuleres ved et pH på mindst 8, fortrinsvis mindst 9 og mere fortrinsvis mindst 9,5. Det alkaliske pH bidrager til en god blegevirkning af peroxygenforbindelsen, navnlig når peroxygenforbindelsen er en perborat. Ikke desto mindre 15 er stabiliteten af bl egemiddel systemet i en vandig væske med alkalisk pH overraskende. I det mindste menes noget af det tilgængelige oxygen i opløsning at være til stede i form af hydrogenperoxid. Det har vist sig, at hydrogenperoxid ikke er tilstrækkelig stabilt i opløsningsmiddel systemerne af de væskeformige vaskemidler ifølge den 20 foreliggende opfindelse. Dog har de faste, vandopløselige peroxy-genblegemidler vist sig at være stabile deri. Tilsyneladende er lave indhold af tilgængeligt oxygen i opløsning kritisk for stabiliteten af dette system.The liquid detergents are formulated at a pH of at least 8, preferably at least 9, and more preferably at least 9.5. The alkaline pH contributes to a good bleaching effect of the peroxygen compound, especially when the peroxygen compound is a perborate. Nevertheless, the stability of the bleaching agent system in an aqueous liquid of alkaline pH is surprising. At least some of the available oxygen in solution is believed to be present in the form of hydrogen peroxide. It has been found that hydrogen peroxide is not sufficiently stable in the solvent systems of the liquid detergents of the present invention. However, the solid, water-soluble peroxygen bleaches have been found to be stable therein. Apparently, low content of available oxygen in solution is critical to the stability of this system.
25 Eksempler på passende vandopløselige, faste peroxygenforbindel ser omfatter perborater, persulfater, peroxydisulfater, perphosphater og krystallinske peroxyhydrater, som er dannet ved at omsætte hydrogenperoxid med natriumcarbonat eller urinstof. Foretrukne peroxygen-blegemiddelforbindelser er natriumperboratmononhydrat og natriumper-30 borattetrahydrat.Examples of suitable water-soluble solid peroxygen compounds include perborates, persulfates, peroxide disulfates, perphosphates and crystalline peroxyhydrates, which are formed by reacting hydrogen peroxide with sodium carbonate or urea. Preferred peroxygen bleach compounds are sodium perborate monohydrate and sodium perborate tetrahydrate.
Den iodmetriske standardmetode, (som f.eks. beskrevet i Methoden der Organischen Chemie, Houben Weyl, 1953, bind 2, side 562) er egnet til at bestemme indhold af tilgængelig oxygen (AV0) i sammensæt-35 ningen.The standard iodometric method (as described, for example, in the Methods der Organischen Chemie, Houben Weyl, 1953, Vol. 2, page 562) is suitable for determining the content of available oxygen (AV0) in the composition.
For at sikre fuldstændig ligevægt mellem væskeformige og faste faser opretholdes sammensætningerne efter blanding i tre dage ved stuetemperatur før AVO-titrering. Før måling rystes produkterne omhygge- 4 DK 170991 B1 ligt for at sikre korrekt prøveudtagning.To ensure complete equilibrium between liquid and solid phases, the compositions are maintained after mixing for three days at room temperature before AVO titration. Before measurement, the products are shaken carefully to ensure correct sampling.
Ved bestemmelse af tilgængeligt oxygen (AVO) i væskefasen centrifugeres prøver af sammensætningerne i 10 minutter ved 10.000 omdrej -5 ni nger pr. minut. Væsken adskilles derefter fra det faste stof og titreres for tilgængeligt oxygen.In determining available oxygen (AVO) in the liquid phase, samples of the compositions are centrifuged for 10 minutes at 10,000 rpm for 5 minutes. minute. The liquid is then separated from the solid and titrated for available oxygen.
Det er ikke nødvendigt, at det organiske opløsningsmiddel er fuldstændig blandbart med vand under den forudsætning, at nok af opløs-10 ningsmidlet blandes med vandet i sammensætningen til at bevirke opløseligheden af peroxygenforbindel sen på den beskrevne måde. Der foretrækkes fuldstændig vandopløselige opløsningsmidler til anvendelse i forbindelse med den foreliggende opfindelse.It is not necessary for the organic solvent to be completely miscible with water, provided that enough of the solvent is mixed with the water in the composition to effect the solubility of the peroxygen compound in the manner described. Fully water-soluble solvents are preferred for use in the present invention.
15 Vandblandbare, organiske opløsningsmidler må selvfølgelig være kompatible med peroxygenblegemiddel forbindel sen ved det anvendte pH. Derfor er polyalkoholer med vicinalhydroxygrupper (dvs. 1,2-propandiol og glycerol) mindre ønskelige, når peroxygenblegemiddel-forbindel sen er perborat.Of course, water-miscible organic solvents must be compatible with the peroxygen bleach compound at the pH used. Therefore, polyalcohols with vicinal hydroxy groups (ie 1,2-propanediol and glycerol) are less desirable when the peroxygen bleach compound is perborate.
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Eksempler på egnede vandblandbare, organiske opløsningsmidler omfatter de lavere alifatiske monoalkoholer, ethere af diethylenglycol og lavere monoal i fati ske monoalkoholer, navnlig ethanol, n-propanol, iso-propanol, butanol, polyethylenglycol (f.eks. PRG 150, 200, 300, 25 400), di propylenglycol, hexylenglycol, methoxyethanol, ethoxyetha- nol, butoxyethanol, ethyldiglycolether, benzyl al kohol, butoxypropa-nol, butoxypropoxypropanol og blandinger deraf. Foretrukne opløsningsmidler omfatter ethanol, iso-propanol, l-methoxy-2-propanol og butyldiglycolether. Et foretrukkent opløsningsmiddel system omfatter 30 ethanol og et co-opløsningsmiddel med et højere flammepunkt end ethanol.Examples of suitable water-miscible organic solvents include the lower aliphatic monoalcohols, ethers of diethylene glycol and lower monoal in fatty monoalcohols, in particular ethanol, n-propanol, iso-propanol, butanol, polyethylene glycol (e.g. PRG 150, 200, 300, 25,400), di propylene glycol, hexylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, ethyl diglycol ether, benzyl alcohol, butoxypropanol, butoxypropoxypropanol and mixtures thereof. Preferred solvents include ethanol, iso-propanol, 1-methoxy-2-propanol and butyldiglycol ether. A preferred solvent system comprises 30 ethanol and a co-solvent having a higher flash point than ethanol.
Selv om tilstedeværelse eller mangel på andre bestanddele spiller en rolle bestemmes mængden af tilgængeligt oxygen 1 opløsningen hoved-35 sageligt af forholdet mellem vand og organisk opløsningsmiddel. Jo mindre dette forhold er (dvs. at der anvendes mere organisk opløsningsmiddel i opløsningsmiddel systemet), jo lavere er mængden af tilgængeligt oxygen i opløsning. Selv om dette er godt med henblik på stabilitet af bl egemiddel systemet, er det mindre ønskeligt med DK 170991 Bl 5 henblik på at opnå god opløselighed af andre bestanddele (f.eks. elektrolyt, anioniske surfaktanter). I alle tilfælde er det ikke nødvendigt at anvende mere organisk opløsningsmiddel end det, som er nødvendigt for at holde mængden af tilgængeligt oxygen i opløsningen 5 på under 0,5%, fortrinsvis under 0,1%.Although the presence or absence of other components plays a role, the amount of oxygen available in the solution is mainly determined by the ratio of water to organic solvent. The smaller this ratio (i.e. more organic solvent is used in the solvent system), the lower the amount of oxygen available in solution. While this is good for the stability of the bleaching agent system, it is less desirable for DK 170991 Bl 5 to achieve good solubility of other ingredients (eg electrolyte, anionic surfactants). In all cases, it is not necessary to use more organic solvent than is necessary to keep the amount of oxygen available in solution 5 below 0.5%, preferably below 0.1%.
Udtrykt praktisk, ligger vand:organisk opløsningsmiddel-forholdet for de fleste systemer på fra 8:1 til 1:3, fortrinsvis fra 5:1 til 1:2.In practical terms, water: organic solvent ratio for most systems ranges from 8: 1 to 1: 3, preferably from 5: 1 to 1: 2.
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De væskeformige vaskemidler ifølge den foreliggende opfindelse indeholder fra 5 til 60%, fortrinsvis fra 15 til 40% af et organisk overfladeaktivt middel, der er udvalgt blandt ikke-ioniske, anioniske og zwitterioniske overfladeaktive midler og blandinger deraf 15 på basis af det væskeformige vaskemiddel.The liquid detergents of the present invention contain from 5 to 60%, preferably from 15 to 40%, of an organic surfactant selected from nonionic, anionic and zwitterionic surfactants and mixtures thereof based on the liquid detergent.
Syntetiske, anioniske surfaktanter kan repræsenteres ved den generelle formel R^OjM, hvor R1 betegner en carbonhydridgruppe, der er udvalgt fra gruppen bestående af uforgrenede eller forgrenede 20 al kyl radikal er indeholdende fra ca. 8 til ca. 24 carbonatomer og al kyl phenyl radikal er indeholdende fra ca. 9 til ca. 15 carbonatomer i al kylgruppen. M er en saltdannende kation, som typisk er udvalgt fra gruppen bestående af natrium, kalium, ammonium og blandinger deraf.Synthetic anionic surfactants may be represented by the general formula R RO₂M, wherein R 8 to approx. 24 carbon atoms and all alkyl phenyl radicals contain from ca. 9 to approx. 15 carbon atoms in all of the cooling group. M is a salt-forming cation typically selected from the group consisting of sodium, potassium, ammonium and mixtures thereof.
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En foretrukken syntetisk, anionisk surfaktant er et vandopløseligt salt af en al kyl benzensul fonsyre indeholdende fra 9 til 15 carbonatomer i al kyl gruppen. En anden foretrukken syntetisk, anionisk surfaktant er et vandopløseligt salt af en al kyl sul fat eller en 30 alkylpolyethoxylatethersulfat, hvori al kyl gruppen indeholder fra ca.A preferred synthetic anionic surfactant is a water-soluble salt of an alkyl benzene sulphonic acid containing from 9 to 15 carbon atoms in the alkyl group. Another preferred synthetic anionic surfactant is a water-soluble salt of an all-alkyl sulphate or an alkyl polyethoxylate ether sulphate, wherein all the alkyl group contains from ca.
8 til ca. 24, fortrinsvis fra ca. 10 til ca. 18 carbonatomer, og der er fra ca. 1 til ca. 20, fortrinsvis fra ca. 1 til ca. 12 ethoxy-grupper. Andre egnede anioniske surfaktanter er beskrevet i beskrivelsen til US patent nr. 4.170.565, udstedt 9. oktober 1979 til 35 Flesher et al.8 to approx. 24, preferably from ca. 10 to approx. 18 carbon atoms and there are from approx. 1 to approx. 20, preferably from ca. 1 to approx. 12 ethoxy groups. Other suitable anionic surfactants are described in the specification of U.S. Patent No. 4,170,565, issued October 9, 1979 to Flesher et al.
De ikke-ioniske surfaktanter fremstilles traditionelt ved at kondensere ethylenoxid og et carbonhydrid med et reaktivt hydrogenatom, f.eks. en hydroxyl-, carboxyl- eller amidogruppe, i nærværelse DK 170991 B1 6 af en sur eller basisk katalysator og omfatter forbindelser med den generelle formel RA(CH2CH20)nH, hvor R betegner den hydrofobe enhed, A repræsenterer den gruppe, som bærer det reaktive hydrogenatom, og n betegner gennemsnitsantallet af ethylenoxidenheder. R indeholder 5 typisk fra ca. 8 til 22 carbonatomer. De kan også dannes ved kondensation af propylenoxid og en lavmolekylær forbindelse, n varierer almindeligvis fra ca. 2 til ca. 24.The nonionic surfactants are traditionally prepared by condensing ethylene oxide and a hydrocarbon with a reactive hydrogen atom, e.g. a hydroxyl, carboxyl or amido group, in the presence of an acidic or basic catalyst DK 170991 B1, and comprises compounds of the general formula RA (CH 2 CH 2 O) nH where R represents the hydrophobic moiety, A represents the group bearing the reactive hydrogen atom, and n represents the average number of ethylene oxide units. R typically contains from about 8 to 22 carbon atoms. They can also be formed by condensation of propylene oxide and a low molecular weight compound, n usually varying from approx. 2 to approx. 24th
Den hydrofobe enhed af den ikke-ioniske forbindelse er fortrinsvis 10 en primær eller sekundær, uforgrenet eller forgrenet alifatisk alkohol med fra ca. 8 til ca. 24, fortrinsvis fra ca. 12 til ca. 20 carbonatomer. En mere fuldstændig beskrivelse af egnede ikke-ioniske surfaktanter kan findes i beskrivelsen til US patent nr. 4.111.855. Blandinger af ikke-ioniske surfaktanter kan være ønskelige.Preferably, the hydrophobic unit of the nonionic compound is a primary or secondary, unbranched or branched aliphatic alcohol having from about 1 8 to approx. 24, preferably from ca. 12 to approx. 20 carbon atoms. A more complete description of suitable nonionic surfactants can be found in the specification of U.S. Patent No. 4,111,855. Mixtures of nonionic surfactants may be desirable.
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Zwitterioniske surfaktanter omfatter derivater af alifatiske, kvaternære ammonium-, phosphonium- og sulphoniumforbindelser, hvori den alifatiske enhed kan være uforgrenet eller forgrenet, og hvori en af de alifatiske substituenter indeholder fra ca. 8 til ca. 24 20 carbonatomer, og en anden substituent indeholder mindst en anionisk, vandsol ubi li serende gruppe. Særlig foretrukne zwitterioniske materialer er de ethoxylerede ammoniumsulfonater og -sulfater, som er beskrevet i US patenterne nr. 3.925.262, udstedt 9. december 1975 til Laughlin et al., og nr. 3.929.678, udstedt 30. december 1975 til 25 Laughlin et al.Zwitterionic surfactants include derivatives of aliphatic, quaternary ammonium, phosphonium and sulphonium compounds, wherein the aliphatic moiety may be unbranched or branched and wherein one of the aliphatic substituents contains from ca. 8 to approx. 24 carbon atoms, and another substituent contains at least one anionic, water-solubilizing group. Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patent Nos. 3,925,262 issued December 9, 1975 to Laughlin et al. And No. 3,929,678 issued December 30, 1975 to 25 Laughlin. et al.
Semi-polære, ikke-ioniske surfaktanter omfatter vandopløselige aminoxider indeholdende en al kyl- eller hydroxyalkyl enhed med fra ca. 8 til ca. 28 carbonatomer og to enheder, som er udvalgt fra 30 gruppen bestående af alkylgrupper og hydroxyalkylgrupper indeholdende fra 1 til ca. 3 carbonatomer, og som eventuelt kan være forenet til ringstrukturer.Semi-polar, nonionic surfactants include water-soluble amine oxides containing an alkyl or hydroxyalkyl moiety having from about 8 to approx. 28 carbon atoms and two units selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to ca. 3 carbon atoms and which may optionally be joined to ring structures.
Egnede syntetiske, anioniske overfladeaktive salte er udvalgt fra 35 gruppen af sulfonater og sulfater. Lignende anioniske vaskemidler er velkendte inden for vaskemiddel området og har fundet udbredt anvendelse i kommercielle vaskemidler. Foretrukne syntetiske, anioniske, vandopløselige sul fonat- og sulfatsalte har i deres molekylstruktur et al kyl radikal indeholdende fra ca. 8 til ca. 22 cabonatomer.Suitable synthetic anionic surfactant salts are selected from the group of sulfonates and sulfates. Similar anionic detergents are well known in the detergent field and have found widespread use in commercial detergents. Preferred synthetic, anionic, water-soluble sulphonate and sulphate salts have in their molecular structure an alkyl radical containing from ca. 8 to approx. 22 carbon atoms.
DK 170991 B1 7DK 170991 B1 7
Eksempler på sådanne foretrukne anioniske surfaktantsalte er de reaktionsprodukter, som opnås ved at sulfatere Cg-C^g-fedtalkohol er, der er afledt fra talg og kokosnødolie; al kyl benzensulfonater, hvori alkylgruppen indeholder fra ca. 9 til 15 carbonatomer; natriumal kyl-5 glycerylethersulfonater; ethersulfater af fedtalkoholer afledt fra talg og kokosnødolier; kokosnødfedtsyremonoglyceridsulfater og -sulfonater; og vandopløselige salte af paraffinsulfonater med fra ca. 8 til ca. 22 carbonatomer i alkylkæden. Sulfonerede olefinsur-faktanter, som de er mere fuldstændigt beskrevet i f.eks. beskrivel-10 sen til US patent nr. 3.332.880, kan også anvendes. Den neutraliserende kation til de syntetiske, anioniske sulfonater og/eller sulfater er repræsenteret af traditionelle kationer, som er meget anvendt indenfor vaskemiddel området, såsom natrium og kalium.Examples of such preferred anionic surfactant salts are the reaction products obtained by sulfating C 6 -C 8 fatty alcohol derived from sebum and coconut oil; all cool benzenesulfonates, wherein the alkyl group contains from ca. 9 to 15 carbon atoms; sodium alkyl glyceryl ether sulfonates; ether sulphates of fatty alcohols derived from sebum and coconut oils; coconut fatty acid monoglyceride sulfates and sulfonates; and water-soluble salts of paraffin sulfonates having from ca. 8 to approx. 22 carbon atoms in the alkyl chain. Sulfonated olefin acidic factors, as they are more fully described in e.g. the description of US Patent No. 3,332,880 may also be used. The neutralizing cation for the synthetic, anionic sulfonates and / or sulfates is represented by traditional cations widely used in the detergent field such as sodium and potassium.
15 En særlig foretrukken syntetisk, anionisk surfaktantbestanddel i forbindelse med den foreliggende opfindelse er repræsenteret ved de vandopløselige salte af en al kyl benzensul fonsyre, fortrinsvis natriumbenzensulfonater med fra ca. 10 til 13 carbonatomer i alkylgruppen.A particularly preferred synthetic anionic surfactant component of the present invention is represented by the water-soluble salts of an alkyl benzene sulphonic acid, preferably sodium benzene sulfonates having from about 10 to 13 carbon atoms in the alkyl group.
2020
En foretrukken klasse af ikke-ioniske ethoxylater er repræsenteret ved kondensationsproduktet af et fedtalkohol med fra 12 til 15 carbonatomer og fra ca. 4 til 10 mol ethylenoxid pr. mol fedtalkohol. Passende forbindelser fra denne klasse af ethoxylater omfatter 25 kondensationsproduktet mellem C12'C15 -oxo-al kohol er og 7 mol ethylenoxid pr. mol alkohol, kondensationsproduktet mellem snævert fraktionerede C14-C15-oxo-alkoholer og 7 eller 9 mol ethylenoxid pr. mol fedt(oxo)alkohol; kondensationsproduktet mellem en snævert fraktioneret C12-C13-fedt(oxo)alkohol og 6,5 mol ethylenoxid pr. mol 30 fedtalkohol; og kondensationsprodukter af en C10’C14 -kokosnødfedt-alkohol med en ethoxyleringsgrad (mol E0/mol fedtalkohol) på fra 5 til 8. Fedt-oxo-alkohol er kan, selv om de hovedsagelig er uforgrene-de alt afhængigt af behandlingsbetingelserne og råmaterialeolefiner-ne, have en vis grad af forgrening, navnlig kortkædet, såsom methyl-35 forgrening.A preferred class of non-ionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from ca. 4 to 10 moles of ethylene oxide per moles of fatty alcohol. Suitable compounds from this class of ethoxylates include the condensation product between C12-C15 -oxoalcohol and 7 moles of ethylene oxide per liter. the condensation product between narrowly fractionated C14-C15 oxo alcohols and 7 or 9 moles of ethylene oxide per moles of fat (oxo) alcohol; the condensation product between a narrowly fractionated C12-C13 fat (oxo) alcohol and 6.5 moles of ethylene oxide per liter. moles of fatty alcohol; and condensation products of a C10-C14 coconut fat alcohol having an ethoxylation degree (mol E0 / mol of fatty alcohol) of from 5 to 8. Fat oxo alcohol is can, although essentially unbranched, depending on the processing conditions and feedstock olefins. ne, have some degree of branching, especially the short chain such as methyl branching.
En forgreningsgrad på fra 15 til 50% (vægtprocent) findes ofte i kommercielle oxo-alkohol er.A branching rate of from 15 to 50% (weight percent) is often found in commercial oxo-alcohols.
DK 170991 B1 8DK 170991 B1 8
Foretrukne ikke-ioniske ethoxylerede bestanddele kan også repræsenteres ved en blanding af 2 separat ethoxylerede ikke-ioniske sur-faktanter indeholdende en forskellig ethoxyleringsgrad. F.eks den ikke-ioniske ethoxylatsurfaktant indeholdende fra 3 til 7 mol 5 ethylenoxid pr. mol hydrofob enhed, og en anden ethoxyleret forbin delse indeholdende fra 8 til 14 mol ethylenoxid pr. mol hydrofob enhed. En foretrukken ikke-ionisk ethoxyleret blanding indeholder et lavere ethoxylat, som er kondensationsproduktet af en C12'C15 -0X0-alkohol med op til 50% (vægtprocent) forgrening, og fra ca. 3 til 7 10 mol ethylenoxid pr. mol fedtoxoalkohol, og et højere ethoxylat, som er kondensationsproduktet af en C16'C19 -oxoal kohol med mere end 50% (vægtprocent) forgrening og fra ca. 8 til 14 mol ethylenoxid pr. mol forgrenet oxo-alkohol.Preferred nonionic ethoxylated components may also be represented by a mixture of 2 separately ethoxylated nonionic acidic factors containing a different degree of ethoxylation. For example, the nonionic ethoxylate surfactant containing from 3 to 7 moles of 5 ethylene oxide per and another ethoxylated compound containing from 8 to 14 moles of ethylene oxide per mole. moles of hydrophobic unit. A preferred nonionic ethoxylated mixture contains a lower ethoxylate, which is the condensation product of a C12'C15-OXO alcohol with up to 50% (wt%) branching, and from about 3 to 7 moles of ethylene oxide per and a higher ethoxylate, which is the condensation product of a C16'C19 -oxoal carbon having more than 50% (wt.%) branching and from ca. 8 to 14 moles of ethylene oxide per moles of branched oxo-alcohol.
15 De foreliggende væskeformige vaskemidler indeholder eventuelt en kationisk surfaktant, som fortrinsvis udgør fra 0,1 til 4 vægtprocent af sammensætningen.The present liquid detergents optionally contain a cationic surfactant which preferably constitutes from 0.1 to 4% by weight of the composition.
Eksempler på egnede kationiske surfaktanter omfatter kvaternære 20 ammon i umforbi ndel ser med formlen hvor Rj betegner C^^Q-alkyl eller -hydroxyalkyl, Rg betegner Cj-C^-alkyl eller Cig-CgQ-alKyl eller -hydroxyalkyl eller C-hydroxyal kyl, R3 og R^ betegner hver især Cj-C^-alkyl eller -hydroxyalkyl, eller Cg-Cg-aryl eller alkylaryl, og X" betegner halogen. Der foretrækkes langkædede, 25 kvaternære monoammoniumforbindel ser (f.eks. forbindelser med ovennævnte formel, hvor R£ betegner Cj-C^-alkyl eller -hydroxyalkyl).Examples of suitable cationic surfactants include quaternary ammonia in compounds of the formula wherein R R represents C ^^ Q Qalkyl or hydroxyalkyl, Rg represents Cj-Calk alkyl or Cig--CgQalkyl or hydroxyalkyl or C-hydroxyalkyl , R 3 and R 2 each represent C 1 -C 4 alkyl or hydroxyalkyl, or C 6 -C 8 aryl or alkylaryl, and X "represents halogen. Long-chain, quaternary monoammonium compounds are preferred (e.g., compounds of the above formula) wherein R R represents Cj-C ^ alkyl or hydroxyalkyl).
De væskeformige vaskemidler ifølge opfindelsen indeholder som en builderforbindelse eventuelt en fedtsyrebestanddel. Mængden af 30 fedtsyre ligger imidlertid fortrinsvis på under 5 vægtprocent af sammensætningen, mere fortrinsvis mindre end 4%. Foretrukne, mættede fedtsyrer indeholder fra 10 til 16, mere fortrinsvis 12 eller 14 carbonatomer. Foretrukne, umættede fedtsyrer er oliesyrer og palmitolsyrer.The liquid detergents of the invention optionally contain as a builder compound a fatty acid component. However, the amount of fatty acid is preferably less than 5% by weight of the composition, more preferably less than 4%. Preferred saturated fatty acids contain from 10 to 16, more preferably 12 or 14 carbon atoms. Preferred unsaturated fatty acids are oleic acids and palmitic acids.
3535
Der kan anvendes vaskemiddel enzymer i de væskeformige vaskemidler ifølge nærværende opfindelse. Faktisk er en af de ønskelige egenskaber ved de foreliggende sammensætninger den, at de er kompatible med sådanne vaskemiddelenzymer. Egnede enzymer omfatter vaskemiddel- DK 170991 B1 9 proteaser, -amylaser, -lipaser og -cellulaser. Enzymstabiliserende midler til anvendelse i vandige, væskeformige vaskemidler er velkendte. I forbindelse med den foreliggende opfindelse foretrækkes et salt af myresyre, f.eks. natriumformat. Mængden af dette stabil ise-5 ringsmiddel udgør fortrinsvis fra 0,5 til 2%.Detergent enzymes can be used in the liquid detergents of the present invention. In fact, one of the desirable properties of the present compositions is that they are compatible with such detergent enzymes. Suitable enzymes include detergent proteases, amylases, lipases and cellulases. Enzyme stabilizers for use in aqueous liquid detergents are well known. In the present invention, a salt of formic acid, e.g. sodium formate. The amount of this stable insulating agent is preferably from 0.5 to 2%.
Foretrukne sammensætninger indeholder en uorganisk eller organisk builderforbindelse. Eksempler på uorganiske builderforbindel ser omfatter phosphorbaserede builderforbindel ser, f.eks. natriumtri-10 polyphosphat, natriumpyrophosphat og al umi nosil i cater (zeoliter).Preferred compositions contain an inorganic or organic builder compound. Examples of inorganic builder compounds include phosphorus-based builder compounds, e.g. sodium tri-polyphosphate, sodium pyrophosphate, and aluminum nosil in caterers (zeolites).
Eksempler på organiske builderforbindelser er repræsenteret ved polysyrer, såsom citronsyre, nitrilotrieddikesyre og blandinger af tartratmonosuccinat og tartratdisuccinat. Foretrukne builderforbin-15 delser til anvendelse i forbindelse med den foreliggende opfindelse er citronsyre og alk(en)yl-substituerede ravsyreforbindel ser, hvor alk(en)yl indeholder fra 10 til 16 carbonatomer. Et eksempel på denne gruppe af forbindelser er dodecylravsyre. Der kan også anvendes polymere carboxylatbuilderforbindel ser omfattende polyacrylater, 20 polyhydroxyacrylater og polyacrylat/polymaleatcopolymerer.Examples of organic builder compounds are represented by polyacids such as citric acid, nitrilotriacetic acid, and mixtures of tartrate monosuccinate and tartrate disuccinate. Preferred builder compounds for use in the present invention are citric acid and alk (en) yl-substituted succinic acid compounds, wherein alk (en) yl contains from 10 to 16 carbon atoms. An example of this group of compounds is dodecyl succinic acid. Polymeric carboxylate builder compounds comprising polyacrylates, polyhydroxyacrylates and polyacrylate / polymaleate copolymers can also be used.
De foreliggende sammensætninger kan indeholde en lang række yderligere eventuelle bestanddele, som for det meste anvendes i additive niveauer, almindeligvis under ca. 5%. Eksempler på sådanne tilsæt-25 ningsmidler omfatter: polysyrer, enzymer og enzymstabiliserende midler, skumregulerende midler, opacificerende midler, midler til forbedring af maskinkompatibilitet i forbindelse med emaljebelagte overflader, baktericider, farvestoffer, parfumer, klaringsmidler og 1ignende.The present compositions may contain a wide variety of additional optional ingredients, which are mostly used in additive levels, generally below about 5%. 5%. Examples of such additives include: polysacids, enzymes and enzyme stabilizers, foam regulators, opacifiers, enhancers for machine compatibility with enamel coated surfaces, bactericides, dyes, perfumes, clarifiers and the like.
3030
De væskeformige sammensætninger ifølge den foreliggende opfindelse kan indeholde yderligere tilsætningsmidler i et niveau på fra 0,05 til 2%.The liquid compositions of the present invention may contain additional additives at a level of from 0.05 to 2%.
35 Disse tilsætningsmidler omfatter polyaminocarboxylater, såsom ethylendi ami ntetraeddi kesyre, diethylentri ami nopentaedd i kesyre, ethylendiaminodiravsyre eller vandopløselige alkalimetalsalte deraf. Andre tilsætningsmidler omfatter organophosphonsyrer, særligt foretrukne er ethylendiamintetramethylenphosphonsyre, hexamethylen- DK 170991 B1 10 di ami notetramethylenphosphonsyre, diethylentri aminopentamethy1 en- phosphonsyre og aminotrimethylenphosphonsyre.These additives include polyaminocarboxylates such as ethylenediaminetetraacetic acid, diethylenetriaminopentadecetic acid, ethylenediaminodiracetic acid or water-soluble alkali metal salts thereof. Other additives include organophosphonic acids, especially preferred are ethylenediaminetetramethylene phosphonic acid, hexamethylene phosphate, diethylenetri aminopentamethylene phosphonic acid and aminotrimethylene phosphonic acid.
Bl egemiddel stabilisatorer, såsom ascorbinsyre, dipicoli nsyre, 5 natriumstannater og 8-hydroxyquinolin kan også inkluderes i de foreliggende sammensætninger på niveauer på mellem 0,01 og 1%.Among other things, stabilizers such as ascorbic acid, dipicolic acid, 5 sodium stannates and 8-hydroxyquinoline can also be included in the present compositions at levels of between 0.01 and 1%.
Fordelagtig anvendelse af de foreliggende sammensætninger under forskellige anvendelsesbetingelser kan kræve anvendelse af et 10 skumreguleringsmiddel. Selv om generelt alle vaskemiddel skumreguleringsmidler kan anvendes i forbindelse med den foreliggende opfindelse, foretrækkes alkylerede polysiloxaner, såsom dimethyl poly-siloxan, som ofte betegnes siliconer. Siliconer anvendes ofte i et niveau, som ikke overstiger 1,5% fortrinsvis mellem 0,1 og 1,0%.Advantageous use of the present compositions under various conditions of use may require the use of a foam control agent. Although generally all detergent foam control agents can be used in the present invention, alkylated polysiloxanes such as dimethyl polysiloxane, often referred to as silicones, are preferred. Silicones are often used at a level not exceeding 1.5%, preferably between 0.1 and 1.0%.
1515
Det kan også være ønskeligt at anvende opacificerende midler, idet de bidrager til at skabe et ensartet udseende af de koncentrerede, væskeformige vaskemidler. Eksempler på egnede opacificerende midler omfatter: polystyren, der er kommercielt kendt som LYTR0N 621, og 20 som fremstilles af MONSANTO CHEMICAL CORPORATION. De opacificerende midler anvendes ofte i en mængde på fra 0,3 til 1,5%.It may also be desirable to use opacifying agents as they help to create a uniform appearance of the concentrated liquid detergents. Examples of suitable opacifiers include: polystyrene, commercially known as LYTR0N 621, and 20 manufactured by MONSANTO CHEMICAL CORPORATION. The opacifiers are often used in an amount of from 0.3 to 1.5%.
De væskeformige vaskemidler ifølge den foreliggende opfindelse kan ydermere omfatte et middel til forbedring af vaskemaskinekompatibi-25 litet, navnlig i forhold til emaljebelagte overflader.The liquid detergents of the present invention may further comprise a means for improving washing machine compatibility, especially with respect to enamel-coated surfaces.
Det kan yderligere være ønskeligt at tilsætte fra 0,1 til 5% af de kendte anti-genaflejrings- og/eller kompatibiliseringsmidler. Eksempler på lignende tilsætningsmidler omfatter: natriumcarboxy-30 methyl cellulose, hydroxy-Cj 6-alkylcellulose, polycarboxyliske homo-eller copolymere bestanddele, såsom polymaleinsyre, en copolymer af maleinsyreanhydrid og methyl vinylether i et mol forhold på fra 2:1 til 1:2, og en copolymer af en ethylenisk umættet monocarboxyl-syremonomer med ikke mere end 5, fortrinsvis 3 eller 4 carbonatomer, 35 f.eks. (meth)acrylsyre, og en ethylenisk, umættet di carboxyl syre-monomer med ikke mere end 6, fortrinsvis 4 carbonatomer, hvor molforholdet mellem monomererne ligger på fra 1:4 til 4:1, hvilken copolymer er beskrevet mere detaljeret i beskrivelsen til EP patentansøgning nr. 0.066.915 indleveret 17. maj 1982.It may further be desirable to add from 0.1 to 5% of the known anti-gene deposition and / or compatibility agents. Examples of similar additives include: sodium carboxymethyl cellulose, hydroxy-C 1-6 alkyl cellulose, polycarboxylic homo or copolymeric constituents such as polymaleic acid, a copolymer of maleic anhydride and methyl vinyl ether in a mole ratio of 2: 1 to 1: 2, and a copolymer of an ethylenically unsaturated monocarboxylic acid monomer having no more than 5, preferably 3 or 4 carbon atoms, e.g. (meth) acrylic acid, and an ethylenic, unsaturated di-carboxylic acid monomer having no more than 6, preferably 4 carbon atoms, the mole ratio of the monomers being from 1: 4 to 4: 1, the copolymer being described in more detail in the description of the EP Patent Application No. 0.066,915 filed May 17, 1982.
11 DK 170991 B111 DK 170991 B1
Den fysiske stabilitet af de væskeformige vaskemidler forbedres ved at tilsætte små mængder af mættede Cjg-C22-fedtsyresæber eller derivater af sådanne fedtsyrer, såsom estere eller amider. Der foretrækkes al kalimetal sæber af C18'C22 -fedtsyrer, almindeligvis fra 5 0,1 til 2%. Et passende eksempel er natriumstearat.The physical stability of the liquid detergents is improved by adding small amounts of saturated C Cg-C₂ C fatty acid soaps or derivatives of such fatty acids, such as esters or amides. All potassium metal soaps of C18'C22 fatty acids are generally preferred, usually from 0.1 to 2%. A suitable example is sodium stearate.
Nedenstående eksempler illustrerer opfindelsen og letter yderligere forståelsen af denne.The following examples illustrate the invention and further facilitate the understanding thereof.
10 Der blev fremstillet væskeformige vaskemidler ved at blande de nedenfor anførte bestanddele i de anførte andele: 15 20 25 30 35 12 DK 170991 B1Liquid detergents were prepared by mixing the ingredients listed below in the proportions indicated: 15 20 25 30 35 12 DK 170991 B1
Bestanddele Sammensætning (vægt%)Ingredients Composition (% by weight)
I II III IY VI II III IY V
5 Vand 33 32 26 23 345 Water 33 32 26 23 34
Ethanol 14 15 18 22 11Ethanol 14 15 18 22 11
Uforgrenet dodecylbenzensul fonsyre 12 10 8 8 12Unbranched dodecylbenzene sulphonic acid 12 10 8 8 12
Kondensationsprodukt af 1 mol C13-C15- oxoalkohol og 7 mol ethylenoxid 7 9 10 8 7 10 Natriumcocoylsul fat 2 3 4 2 2Condensation product of 1 mole of C13-C15 oxoalcohol and 7 moles of ethylene oxide 7 9 10 8 7 10 Sodium cocoyl sulphate 2 3 4 2 2
Dodecenylravsyre 13 10 12 15 13Dodecenyl succinic acid 13 10 12 15 13
Citronsyre 0,8 1 1 0,8 0,8Citric acid 0.8 1 1 0.8 0.8
Oliesyre 3,3 4 3 2 3,3Oleic acid 3.3 4 3 2 3.3
Protease 0,3 0,5 - 0,5 - 15 Di ethylentri ami npentamethylen- phosphonsyre 0,05 0,85 0,05 0,05 0,05Protease 0.3 0.5 - 0.5 - 15 Di ethylenetriamine pentamethylene phosphonic acid 0.05 0.85 0.05 0.05 0.05
Natriumformat 0,9 1 - 1Sodium format 0.9 1 - 1
Natriumperboratmonohydrat 10 10 12 10 10)*Sodium perborate monohydrate 10 10 12 10 10
Natriumhydroxid (til justering til) 20 pH 9 10 9 11 8,2Sodium hydroxide (for adjustment to) 20 pH 9 10 9 11 8.2
Parfume, ubetydelige bestanddele ........ balance ........Perfume, insignificant ingredients ........ balance ........
*) Natriumperborattetrahydrat 25 30 35 DK 170991 B1 13*) Sodium perborate tetrahydrate DK 170991 B1 13
Bestanddele Sammensætning (vaqt%) vi m yin ix x m miIngredients Composition (wt%) vi m yin ix x m mi
Vand 31 28 27 32 23 28 22 5 Ethanol 6,5 - 75678 l-Methoxy-2-propanol - 14 3,5 - - 77Water 31 28 27 32 23 28 22 5 Ethanol 6,5 - 75,678 l-Methoxy-2-propanol - 14 3,5 - - 77
Isopropanol 6,5- -- 6--Isopropanol 6.5- - 6--
Butyldiglycolether - - 4,0 5---Butyldiglycol ether - - 4.0 5 ---
Uforgrenet dodecylbenzen- 10 sulfonsyre 11,4 12 7 13 12 10 9Unbranched dodecylbenzene sulfonic acid 11.4 12 7 13 12 10 9
Ikke-ionisk surfaktant 7,2 7 11 3,5 687Nonionic Surfactant 7.2 7 11 3.5 687
Natriumcocoylsul fat 3,1 2,5 2,5 3,0 4,0 3,0 2,0 TMS/TDS* - 6,5 3,5Sodium cocoyl sulphate 3.1 2.5 2.5 3.0 4.0 3.0 2.0 TMS / TDS * - 6.5 3.5
Dodecenylravsyre 13,4 9 - - 7 8,5 9,5 15 Tetradecenylravsyre - 4 .... i,oDodecenyl succinic acid 13.4 9 - 7 8.5 9.5 Tetradecenyl succinic acid - 4 .... i, o
Kokosnødfedtsyre - - 16 1,01,0-Coconut fatty acid - - 16 1.01.0-
Oliesyre 3,6 3,6 4,0 2,0 3,0 2,0 2,5Oleic acid 3.6 3.6 4.0 2.0 3.0 2.0 2.5
Citronsyre 0,8 0,9 0,5 - 3,5 - 0,5 DTPMPA** 0,9 0,5 0,5 - 0,4 0,8 1,5 20 Ethylendiamintetra- eddikesyre ... l,o 0,4 -Citric acid 0.8 0.9 0.5 - 3.5 - 0.5 DTPMPA ** 0.9 0.5 0.5 - 0.4 0.8 1.5 Ethylenediaminetetraacetic acid ... 1.0 0.4 -
Natriumtripolyphosphat ... 15,0 -Sodium Tripolyphosphate ... 15.0 -
Natriumperborat- tetrahydrat - - --17-- 25 Natriumperborat- monohydrat 9,0 10,4 9 13 - 13 19Sodium perborate tetrahydrate - - - 17-- Sodium perborate monohydrate 9.0 10.4 9 13 - 13 19
Natriumformat 0,9 0,8 1,0 1,0 1,5 0,5 1,0Sodium format 0.9 0.8 1.0 1.0 1.5 0.5 1.0
Protease 0,7 0,6 0,8 0,5 1,0 0,5 0,6Protease 0.7 0.6 0.8 0.5 1.0 0.5 0.6
Natriumhydroxid til pH 9 10 11 11 9,5 10,5 10,5 30 Parfume, ubetydelige bestanddele ............... balance...............Sodium hydroxide to pH 9 10 11 11 9.5 10.5 10.5 30 Perfume, negligible ingredients ............... balance ............. ..
* 80:20-blanding af tartratmonosuccinat og tartratdisuccinat 35 ** Di ethylentriaminopentamethylenphosphonsyre DK 170991 B1 14* 80: 20 mixture of tartrate monosuccinate and tartrate disuccinate 35 ** Di ethylenetriaminopentamethylene phosphonic acid DK 170991 B1 14
Bestanddele Sammensætning (væqt%lIngredients Composition (wt% l
XIII XIV XV XVI XVII XVIIIXIII XIV XV XVI XVII XVIII
5 Vand 27 27 27 24 23,5 255 Water 27 27 27 24 23.5 25
Ethanol 13 8 10 13 13 10Ethanol 13 8 10 13 13 10
Co-opløsningsmiddel^ - 53--3Co-solvent ^ - 53--3
Uforgrenet dodecyl- benzensulfonsyre 9 9999 9 10 Kondensationsprodukt af 1 mol Cjj-Cjjj-oxo-alkohol og 7 mol ethylenoxid 7 7777 7Unbranched dodecylbenzenesulfonic acid 9 9999 9 10 Condensation product of 1 mole of C
Natriumcocoylsul fat 1 1111 1 15 Dodecenylravsyre 13 13 13 13 13 13Sodium cocoylsul fat 1 1111 1 15 Dodecenyl succinic acid 13 13 13 13 13 13
Citronsyre 0,8 0,8 0,8 0,8 0,8 0,8Citric acid 0.8 0.8 0.8 0.8 0.8 0.8 0.8
Oliesyre 3 3333 3Oleic acid 3 3333 3
Protease 0,8 0,5 0,5 0,5 0,5 0,5Protease 0.8 0.5 0.5 0.5 0.5 0.5 0.5
Di ethylentri ami npenta- 20 methylenphosphonsyre 0,7 0,7 0,7 0,7 0,7 0,7Diethylenetriaminepentimethylene phosphonic acid 0.7 0.7 0.7 0.7 0.7 0.7
Natriumstearat - - 0,3 1,0 1,5 0,6Sodium stearate - - 0.3 1.0 1.5 0.6
Natriumformat 1,0 1,0 1,0 1,0 1,0 1,0Sodium format 1.0 1.0 1.0 1.0 1.0 1.0
Natriumperborat- monohydrat 14,0 14,0 14,0 14,0 14,0 14,0 25 C12-Cj4-trimethyl- ammoniumchlorid - - - 2,0 - C12'C14'(2"hydroxy' ethyl)dimethyl- ammoniumchlorid - - - - 2,0 30 Cjg(2-hydroxyethyl)-dimethylammoniumchlorid - .... 2,0Sodium perborate monohydrate 14.0 14.0 14.0 14.0 14.0 14.0 C 12 -C 4 trimethyl ammonium chloride - - - 2.0 - C 12 2.0 - 30 µg (2-hydroxyethyl) dimethylammonium chloride - .... 2.0
Natriumhydroxid (til justering til) pH 10 10 10 10 10 10 35 Parfume, ubetydelige bestanddele -................ balance................Sodium hydroxide (for adjustment to) pH 10 10 10 10 10 10 35 Perfume, negligible ingredients ------------------ balance .............. ..
1) udvalgt blandt 15 DK 170991 B1 - PEG 150, 200, 300, 400/dipropylenglycol, hexylenglycol, n-propa-nol, iso-propanol, Methoxyethanol, Ethoxyethanol, Butoxyethanol, Ethyldiglycol, Butyldiglycolether, Benzyl al kohol, Butoxypropanol, ButoxyPropoxypropanol.1) selected from DK 170991 B1 - PEG 150, 200, 300, 400 / dipropylene glycol, hexylene glycol, n-propanol, iso-propanol, methoxyethanol, ethoxyethanol, butoxyethanol, ethyldiglycol, butyldiglycol ether, benzylalcohol, butoxypropanol, butoxypropoxypropoxyl.
5 10 15 20 25 30 355 10 15 20 25 30 35
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8712430 | 1987-05-27 | ||
| GB878712430A GB8712430D0 (en) | 1987-05-27 | 1987-05-27 | Liquid detergent |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK292288D0 DK292288D0 (en) | 1988-05-27 |
| DK292288A DK292288A (en) | 1988-11-28 |
| DK170991B1 true DK170991B1 (en) | 1996-04-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK292288A DK170991B1 (en) | 1987-05-27 | 1988-05-27 | Liquid, bleach-containing detergent |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0293040B2 (en) |
| JP (1) | JP2721176B2 (en) |
| KR (1) | KR880014094A (en) |
| CN (1) | CN1026125C (en) |
| AT (1) | ATE70296T1 (en) |
| AU (1) | AU625049B2 (en) |
| CA (1) | CA1319077C (en) |
| DE (1) | DE3866778D1 (en) |
| DK (1) | DK170991B1 (en) |
| EG (1) | EG18585A (en) |
| FI (1) | FI89721C (en) |
| GB (1) | GB8712430D0 (en) |
| GR (1) | GR3003434T3 (en) |
| IE (1) | IE63070B1 (en) |
| MX (1) | MX169169B (en) |
| NZ (1) | NZ224799A (en) |
| PH (1) | PH25142A (en) |
| TR (1) | TR25691A (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8713756D0 (en) * | 1987-06-12 | 1987-07-15 | Procter & Gamble | Liquid detergent |
| CA1335646C (en) * | 1988-06-13 | 1995-05-23 | Guido Clemens Van Den Brom | Liquid detergent compositions |
| CA1327503C (en) * | 1988-06-14 | 1994-03-08 | Charles Randolph Minns | Carpet cleaning composition and method of use |
| GB8900525D0 (en) * | 1989-01-10 | 1989-03-08 | Procter & Gamble | Liquid detergent composition containing enzyme and enzyme stabilization system |
| GB8900496D0 (en) * | 1989-01-10 | 1989-03-08 | Procter & Gamble | Liquid detergent composition containing enzyme and enzyme stabilization system |
| GB8904007D0 (en) * | 1989-02-22 | 1989-04-05 | Procter & Gamble | Stabilized,bleach containing,liquid detergent compositions |
| US5160655A (en) * | 1989-02-27 | 1992-11-03 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds |
| EP0385522B1 (en) * | 1989-02-27 | 2001-08-29 | Unilever N.V. | Liquid detergent composition |
| US5279772A (en) * | 1989-04-28 | 1994-01-18 | Ciba-Geigy Corporation | Liquid detergents containing specifically disulfonated dibenzofuranyl-biphenyls as flourescent whitening agents |
| US4992194A (en) * | 1989-06-12 | 1991-02-12 | Lever Brothers Company, Division Of Conopco Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
| GB8916094D0 (en) * | 1989-07-13 | 1989-08-31 | Unilever Plc | Liquid bleach composition |
| GB8924294D0 (en) * | 1989-10-27 | 1989-12-13 | Unilever Plc | Detergent compositions |
| EP0429124A1 (en) * | 1989-11-21 | 1991-05-29 | The Procter & Gamble Company | Chlorine-free liquid automatic dishwashing compositions |
| EP0430330A3 (en) * | 1989-11-24 | 1991-12-18 | The Procter & Gamble Company | Suspending liquid detergent compositions |
| DE69029190T2 (en) * | 1989-11-30 | 1997-03-20 | Clorox Co | Stable aqueous oxidation detergent |
| GB8928631D0 (en) * | 1989-12-19 | 1990-02-21 | Procter & Gamble | Concentrated aqueous liquid bleach compositions |
| WO1991012309A2 (en) * | 1990-02-08 | 1991-08-22 | Unilever N.V. | Liquid bleach composition |
| EP0476212A1 (en) * | 1990-09-17 | 1992-03-25 | The Procter & Gamble Company | Liquid detergent compositions |
| TW230784B (en) * | 1990-10-22 | 1994-09-21 | Procter & Gamble | |
| DE69027774T2 (en) * | 1990-10-22 | 1997-02-20 | Procter & Gamble | Stable, liquid detergent containing a bleach |
| US5264142A (en) * | 1991-11-25 | 1993-11-23 | Lever Brothers Company, Division Of Conopco, Inc. | Stabilization of peroxygen bleach in enzyme-containing heavy duty liquids |
| MX9207050A (en) * | 1991-12-19 | 1993-06-01 | Ciba Geigy Ag | STABLE BLEACH DISPERSION DURING STORAGE |
| CH684485A5 (en) * | 1992-11-17 | 1994-09-30 | Ciba Geigy Ag | Liquid detergent. |
| EP0619368A1 (en) * | 1993-04-06 | 1994-10-12 | The Procter & Gamble Company | Concentrated liquid detergent compositions |
| US5731275A (en) * | 1994-04-05 | 1998-03-24 | Universite De Montreal | Synergistic detergent and disinfectant combinations for decontaminating biofilm-coated surfaces |
| US5776877A (en) * | 1995-05-25 | 1998-07-07 | The Clorox Company | Liquid peracid precursor colloidal dispersions: macroemulsions |
| US5792385A (en) * | 1995-05-25 | 1998-08-11 | The Clorox Company | Liquid peracid precursor colloidal dispersions: liquid crystals |
| US5681805A (en) * | 1995-05-25 | 1997-10-28 | The Clorox Company | Liquid peracid precursor colloidal dispersions: microemulsions |
| US5954998A (en) * | 1995-05-25 | 1999-09-21 | The Clorox Company | Liquid peracid precursor colloidal dispersions: oil-core vesicles |
| DE69627847T2 (en) * | 1996-09-13 | 2004-03-11 | The Procter & Gamble Company, Cincinnati | Methods and compositions for bleaching laundry |
| EP0906950A1 (en) * | 1997-10-03 | 1999-04-07 | The Procter & Gamble Company | Peroxygen bleach-containing compositions comprising a particular chelating agent system |
| AU764340B2 (en) | 1998-11-06 | 2003-08-14 | Universite De Montreal | Improved bactericidal and non-bactericidal solutions for removing biofilms |
| US8143309B2 (en) * | 2006-07-14 | 2012-03-27 | Urthtech, Llc | Methods and composition for treating a material |
| AR119948A1 (en) * | 2019-09-12 | 2022-01-19 | Stella Pharma Corp | PHARMACEUTICAL COMPOSITION AND METHOD FOR PRODUCING THE SAME |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE381672B (en) * | 1971-07-15 | 1975-12-15 | Mo Och Domsjoe Ab | LIQUID DETERGENT COMPOSITION |
| US4347149A (en) * | 1980-04-01 | 1982-08-31 | Interox Chemicals Limited | Aqueous bleach compositions |
| US4377489A (en) * | 1981-03-16 | 1983-03-22 | Ceil Clean Corporation, Inc. | Inorganic persulfate cleaning solution for acoustic materials |
| EP0217454B1 (en) * | 1985-09-30 | 1992-03-11 | Unilever N.V. | Non-aqueous liquid detergent composition and perborate anhydrous |
-
1987
- 1987-05-27 GB GB878712430A patent/GB8712430D0/en active Pending
-
1988
- 1988-05-20 AT AT88201009T patent/ATE70296T1/en not_active IP Right Cessation
- 1988-05-20 EP EP88201009A patent/EP0293040B2/en not_active Expired - Lifetime
- 1988-05-20 DE DE8888201009T patent/DE3866778D1/en not_active Expired - Fee Related
- 1988-05-24 PH PH36964A patent/PH25142A/en unknown
- 1988-05-25 EG EG279/88A patent/EG18585A/en active
- 1988-05-26 CA CA000567834A patent/CA1319077C/en not_active Expired - Fee Related
- 1988-05-26 IE IE158688A patent/IE63070B1/en not_active IP Right Cessation
- 1988-05-26 AU AU16684/88A patent/AU625049B2/en not_active Ceased
- 1988-05-26 NZ NZ224799A patent/NZ224799A/en unknown
- 1988-05-26 FI FI882486A patent/FI89721C/en not_active IP Right Cessation
- 1988-05-27 DK DK292288A patent/DK170991B1/en active
- 1988-05-27 MX MX011681A patent/MX169169B/en unknown
- 1988-05-27 JP JP63130026A patent/JP2721176B2/en not_active Expired - Fee Related
- 1988-05-27 CN CN88103670A patent/CN1026125C/en not_active Expired - Fee Related
- 1988-05-27 TR TR88/0361A patent/TR25691A/en unknown
- 1988-05-27 KR KR1019880006239A patent/KR880014094A/en not_active Application Discontinuation
-
1991
- 1991-12-24 GR GR91402149T patent/GR3003434T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3866778D1 (en) | 1992-01-23 |
| CN88103670A (en) | 1988-12-14 |
| JP2721176B2 (en) | 1998-03-04 |
| FI89721C (en) | 1993-11-10 |
| IE63070B1 (en) | 1995-03-22 |
| FI89721B (en) | 1993-07-30 |
| FI882486A (en) | 1988-11-28 |
| IE881586L (en) | 1988-11-27 |
| GR3003434T3 (en) | 1993-02-17 |
| TR25691A (en) | 1993-06-15 |
| CA1319077C (en) | 1993-06-15 |
| JPS6438499A (en) | 1989-02-08 |
| NZ224799A (en) | 1990-11-27 |
| FI882486A0 (en) | 1988-05-26 |
| AU625049B2 (en) | 1992-07-02 |
| KR880014094A (en) | 1988-12-22 |
| EG18585A (en) | 1993-08-30 |
| ATE70296T1 (en) | 1991-12-15 |
| DK292288A (en) | 1988-11-28 |
| GB8712430D0 (en) | 1987-07-01 |
| MX169169B (en) | 1993-06-23 |
| EP0293040B1 (en) | 1991-12-11 |
| EP0293040A1 (en) | 1988-11-30 |
| DK292288D0 (en) | 1988-05-27 |
| CN1026125C (en) | 1994-10-05 |
| PH25142A (en) | 1991-02-19 |
| AU1668488A (en) | 1988-12-01 |
| EP0293040B2 (en) | 1999-06-09 |
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