DK160771B - CONCENTRATED, SINGLE-PHASE, BUILDER-CONTAINING, LIQUID DETERGENT - Google Patents
CONCENTRATED, SINGLE-PHASE, BUILDER-CONTAINING, LIQUID DETERGENT Download PDFInfo
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- DK160771B DK160771B DK591785A DK591785A DK160771B DK 160771 B DK160771 B DK 160771B DK 591785 A DK591785 A DK 591785A DK 591785 A DK591785 A DK 591785A DK 160771 B DK160771 B DK 160771B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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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
- 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
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Description
1 DK 160771B1 DK 160771B
Den foreliggende opfindelse angår, vandige, builderholdige, flydende vaskemidler, der er egnede til vaskemiddelformuleringer eller iblødsætningsmiddelformuleringer. Nærmere bestemt angår ' den foreliggende opfindelse vandige, builderholdige, flydende 5 vaskemidler, som er højkoncentrerede med hensyn til overfladeaktivt stof og builder og er tilvejebragt som homogene, klare enkelt-fasede flydende opløsninger.The present invention relates to aqueous builder-containing liquid detergents suitable for detergent formulations or softener formulations. More particularly, the present invention relates to aqueous builder-containing liquid detergents which are highly concentrated in surfactant and builder and are provided as homogeneous, clear single-phase liquid solutions.
Formulering af koncentrerede builderholdige vandige flydende 10 vaskemidler har været et mål for de kommercielle bestræbelser inden for. vaskemiddel teknikken i de senere år. Det kræves generelt, at sådanne vaskemidler giver god vaskeevne ved lav koncentration af produktet i et bad, indeholder vand som det principielle opløsningsmiddel og er i form af homogene en-fasede op-15 løsninger, som giver lang lagerlevetid, uden at der sker faseadskillelse. Konventionelle flydende vaskemidler, der indeholder en detergent-builder, er i almindelighed ikke højkoncentrerede. Det vil sige, de er formuleret som forholdsvis fortyndede vandige opløsninger, således at builderen og det overfladeaktive 20 stof er opløseliggjort i det flydende vaskemiddel. Til opnåelse af den ønskede vaskeevne kræves der forholdsvis høje koncentrationer af et sådant produkt i badet.Formulation of concentrated builder-containing aqueous liquid detergents has been a target of the commercial endeavors within. detergent technique in recent years. Generally, such detergents are required to provide good washability at low concentration of the product in a bath, contain water as the principal solvent, and are in the form of homogeneous single-phase solutions which provide long shelf life without phase separation. Conventional liquid detergents containing a detergent builder are generally not highly concentrated. That is, they are formulated as relatively dilute aqueous solutions so that the builder and the surfactant are solubilized in the liquid detergent. To achieve the desired washability, relatively high concentrations of such a product are required in the bath.
Betegnelsen "koncentreret" som anvendt i nærværende beskrivelse 25 og krav, refererer til flydende vaskemidler, der kan give en effektiv vaskevirkning ved en produktkoncentration ækvivalent med ca. "1/4 kop" under US-vaskebetinge Iser, nemlig ca. 60 ml vaskemiddel pr. standard vaskeportion (ca. 17 US-gallon (ca.The term "concentrated" as used in this specification 25 and claims, refers to liquid detergents which can provide an effective washing effect at a product concentration equivalent to approx. "1/4 cup" under US washing condition Iser, namely approx. 60 ml of detergent per standard wash portion (about 17 US gallons (ca.
65 liter] til en vaskemaskine, der ifyldes fra oven], hvilket 30 svarer til en koncentration på ca. 0,1% flydende vaskemiddel i vaskebadet. For at opnå en vaskeeffekt på et økonomisk acceptabelt niveau ved en så lav produktkoncentration er det nødvendigt, at vaskemidlet indeholder en høj andel af aktive ingredienser, navnlig overfladeaktivt stof og builder. Således define-35 res den i nærværende beskrivelse og krav anvendte betegnelse "koncentreret" flydende vaskemiddel som et vaskemiddel, der ikke indeholder mere end ca. 65 vægt% vand.65 liters] for a washing machine loaded from above], which 30 corresponds to a concentration of approx. 0.1% liquid detergent in the wash bath. In order to achieve a washing effect at an economically acceptable level at such a low product concentration, it is necessary that the detergent contains a high proportion of active ingredients, in particular surfactant and builder. Thus, the term "concentrated" liquid detergent used in the present specification and claims is defined as a detergent containing no more than approx. 65% by weight water.
2 DK 160771B2 DK 160771B
Af praktiske grunde er det vigtigt at der anvendes vand som det principielle, men ikke eneste opløsningsmiddel i et sådant koncentreret flydende vaskemiddel under, tindgåelse af anvendelsen af kosthare opløsningsmidler, såsom glycoler Så-5 ledes indeholder de her omhandlede flydende vaskemidler mindst ca. 35 vægt% vand regnet på det flydende vaskemiddel, idet der i almindelighed foretrækkes et vandindhold på ca. 45% til 60%.For practical reasons, it is important that water be used as the principal, but not the only, solvent in such a concentrated liquid detergent, to prevent the use of dietary solvents such as glycols. 35% by weight of water based on the liquid detergent, generally having a water content of approx. 45% to 60%.
Builderholdige flydende vaskemidler er kendte. Som følge af jQ builderes og overfladeaktive stoffers begrænsede opløselighed i vand fremstilles sådanne vaskemidler imidlertid generelt som forholdsvis fortyndede vandige vaskemidler, der for størstedelens vedkommende indeholder over 65_vægt% vand og ofte så meget som 93 vægt%. Ofte anvendes et alkylenglycol-coopløsnings-lg middel for at forøge det builderholdige vaskemiddels opløselighed. I de vandige vaskemidler, der indeholder mindre end 65% vand, holdes andelen af builder sædvanligvis lavt, dvs. ikke over ca. 10 vægt%, for derved at forøge opløseligheden af den builderholdige detergent i vand. For at tilvejebringe 2ø acceptabel vaskeeffekt, når sådanne kendte flydende vaskemidler anvendes under vaskebetingelser ifølge US-standard anven- .....- des de konventionelt ved produktkoncentrationer, der ligger væsentligt over koncentrationen "1/4 kop" (ca. 0,1 vægt%), ved hvilken de flydende vaskemidler ifølge opfindelsen er effekti-25 ve. Desuden foreligger de- konventionelle vaskemidler i almindelighed som emulsioner eller suspensioner og ikke som klare homogene opløsninger, der er stabile mod faseadskillelse.Builder-containing liquid detergents are known. However, due to the limited solubility of water and surfactants in water, such detergents are generally prepared as relatively dilute aqueous detergents which, for the most part, contain more than 65% by weight of water and often as much as 93% by weight. Frequently, an alkylene glycol co-solvent is used to increase the solubility of the builder-containing detergent. In the aqueous detergents containing less than 65% water, the proportion of builder is usually kept low, ie. not more than approx. 10 wt%, thereby increasing the solubility of the builder-containing detergent in water. To provide 2o acceptable washing effect when such known liquid detergents are used under washing conditions of US standard, they are conventionally used at product concentrations substantially above the "1/4 cup" concentration (about 0.1 wt%) by which the liquid detergents of the invention are effective. In addition, conventional detergents are generally available as emulsions or suspensions and not as clear homogeneous solutions that are stable to phase separation.
Illustrerende for den kendte teknik er de vaskemidler, der er 30 beskrevet i US-Patentskrifterne nr. 3.912.662 og 4.021,377.Illustrative of the prior art are the detergents disclosed in U.S. Patent Nos. 3,912,662 and 4,021,377.
Det førstnævnte patentskrift beskriver et vandigt vaskemiddel, der indeholder ikke-ionisk detergent og betain-detergent samt en polyphosphatbuilder. I eksempel 1 beskrives et vaskemiddel, der indeholder 66% vand og 12% alkylenglycol som opløsnings·** 35 midlet. US-Patentskrift nr. 4.021,377 beskriver et phosphatfrit flydende vaskemiddel, som indeholder citratbuilder og overfladeaktivt stof i et vand-glycol-opløsningsmiddel. Mængden af vand i hvert af de syv vaskemidler, der er beskrevet i tabel 1The former patent discloses an aqueous detergent containing nonionic detergent and betaine detergent as well as a polyphosphate builder. Example 1 describes a detergent containing 66% water and 12% alkylene glycol as the solvent. U.S. Patent No. 4,021,377 discloses a phosphate-free liquid detergent containing citrate builder and surfactant in a water-glycol solvent. The amount of water in each of the seven detergents described in Table 1
3 DK 160771B3 DK 160771B
i det nævnte patentskrift, er mindre end 26 vægt%, idet størstedelen af opløsningsmidlet udgøres af en alkylenglycol. Muligheden for at tilvejebringe et økonomisk flydende vaskemiddel, der anvender vand som hovedopløsningsmidlet, samtidigt med 5 at det foreligger i form af en koncentreret, klar, en-faset opløsning, forbliver' således stadig et uløst problem ved formulering af et økonomisk acceptabelt, builderholdigt, koncentreret, flydende vaskemiddel.in said patent is less than 26% by weight, the majority of the solvent being an alkylene glycol. Thus, the possibility of providing an economically liquid detergent using water as the main solvent, while being in the form of a concentrated, clear, single-phase solution, still remains an unsolved problem in formulating an economically acceptable builder-containing solution. concentrated, liquid detergent.
Den foreliggende opfindelse anviser et koncentreret, vandigt, en-faset, homogent, builderholdigt flydende vaskemiddel, der omfatter: (a) fra ca. 15 til 18 vægt% vandopløseligt ikke-phosphat-deter-gentbuildersalt, (b) fra ca. 15 til 23 vsgt% overfladeaktiv ikke-ionisk detergent forbinde Ise, der er et kondensationsprodukt af 5 til 9 mol ethylenoxid og 1 mol alifatisk alkohol indeholdende 20 12 til 15 carbonatomer, (c) fra ca. 1 til 6 vægt% af mindst én amfoter detergentforbindelse valgt blandt (i) betain-detergentforbindelser med formlen 25 R2 1 I 4 - R — CH2--N+ — R — COO ; og ί 3 Λ 30 (ii) alkylamidobetain-detergentforbindelser med formlen R2The present invention provides a concentrated, aqueous, single-phase, homogeneous builder-containing liquid detergent comprising: (a) from ca. 15 to 18% by weight of water-soluble non-phosphate detergent builder salt; 15 to 23% by weight of surfactant nonionic detergent linking Ise, which is a condensation product of 5 to 9 moles of ethylene oxide and 1 mole of aliphatic alcohol containing 20 to 15 to 15 carbon atoms, 1 to 6% by weight of at least one amphoteric detergent compound selected from (i) betaine-detergent compounds of formula 25 R 2 1 4 - R - CH 2 - N + - R - COO; and (3) 30 (ii) alkylamidobetaine detergent compounds of formula R2
35 0 I35 0 I
1 " 5 41 "5 4
R — C — NH-R -N+-R4-COOR - C - NH-R -N + -R4-COO
i3 4 ·i3 4 ·
; DK 160771 B; DK 160771 B
hvor er en alkylgruppe eller en blanding af alkylgrupper 2 3 indeholdende 9 til 13 carbonatomer, R og R uafhængigt 4 5 af hinanden er methyl eller ethyl, og R og R uafhængigt af hinanden er methylen, ethylen eller propylen, 5 (d) fra ca. 5 til 8 vægt% opløseliggørende stof valgt blandt alkalimetalsalte dannet ' af (i) nonylravsyre- anhydrid og (ii) nonylmaleinsyreanhydrid, og 10 (e) fra ca. 35 til 65 vægt% vand.wherein is an alkyl group or a mixture of alkyl groups 21 containing 9 to 13 carbon atoms, R and R are independently methyl or ethyl, and R and R are independently methylene, ethylene or propylene; . 5 to 8 wt.% Solubilizing agent selected from alkali metal salts formed from (i) nonylsuccinic anhydride and (ii) nonylmaleic anhydride; and 10 (e) from ca. 35 to 65% by weight water.
• I overensstemmelse med fremgangsmåden ifølge opfindelsen påvirkes vask af plettede og/eller tilsmudsede materialer ved at sådanne materialer bringes i kontakt med en vandig opløsning af !5 det ovenfor definerede flydende vaskemiddel, I modsætning til de kendte builderholdige flydende vaskemidler indeholder vaskemidlerne ifølge opfindelsen en høj koncentration af builder og overfladeaktivt stof, samtidigt med at de stadig 20 er karakteristisk klare, en-fasede, homogene opløsninger, der., er fysisk stabile ved længere lagringsperioder og inden for et bredt temperaturområde. De særlige kombinationer af ikke-ionisk detergent og betain-detergent med ikke-phosphat-buildersalt og opløseliggørende stof i overensstemmelse med opfindelsen danner 25 uventet klare, en-fasede, vandige opløsninger, der er højkoncentreret med hensyn til såvel overfladeaktivt stof som builder.In accordance with the process of the invention, washing of stained and / or soiled materials is affected by contacting such materials with an aqueous solution of the above-defined liquid detergent. In contrast to the known builder-containing liquid detergents, the detergents of the invention contain a high builder and surfactant concentration, while still being characteristically clear, single-phase, homogeneous solutions that are physically stable at longer storage periods and over a wide temperature range. The particular combinations of nonionic detergent and betaine detergent with non-phosphate builder salt and solubilizing agent in accordance with the invention form unexpectedly clear, single-phase, aqueous solutions which are highly concentrated in both surfactant and builder.
Fra et kommercielt standpunkt er de her omhandlede vaskemidler særligt fordelagtige, da de er phosphatfrie i overensstemmelse med myndighedernes bestemmelser i mange områder, hvor anvendelse af 30 phosphatholdige vaskemidler er forbudt; de er forholdsvis økonomiske at formulere, da de anvender vand som hovedopløsningsmidlet og undgår anvendelse af kostbare med-opløsningsmidler, såsom alkyl-englycoler i andet end mindre mængder; de giver effektiv vaskevirkning ved lave produktkoncentrationer i vaskebadet, navnlig ved 35 en såkaldt 1/4 kop koncentration, der er en ønskelig lav koncentration under US-vaskebetingelser; og de er homogene opløsninger, hvorved man undgår problemer med manglende ensartethed og faseadskillelse forbundet med lagringen og anvendelsen af emulsioner oq dispersioner.From a commercial standpoint, the detergents in question are particularly advantageous, as they are phosphate-free in accordance with government regulations in many areas where the use of 30 phosphate-containing detergents is prohibited; they are relatively economical to formulate as they use water as the main solvent and avoid the use of expensive co-solvents such as alkyl englycols in other than minor amounts; they provide effective washing action at low product concentrations in the wash bath, especially at a so-called 1/4 cup concentration, which is a desirable low concentration under US washing conditions; and they are homogeneous solutions, avoiding problems of lack of uniformity and phase separation associated with the storage and use of emulsions and dispersions.
5 DK 160771 B5 DK 160771 B
Den ikke-ioniske detergentforbindelse i de beskrevne flydende vaskemidler udgør fra ca. 15 til 23 og fortrinsvis fra 17 til 19 vægt% af vaskemidlet. Den amfotare detergentforbin^ delse varierer - fra ca. 1 til 6, fortrinsvis g fra 2 til 4 vægt% af sådanne vaskemidler. De relative mængder af hver af de førnævnte detergenter bestemmes i almindelighed af den anvendte mængde buildersalt. Jo højere builderkoncentra-tioner inden for området fra 15 til 18% jo lavere er den maksimale koncentration af ikke-ionisk detergent, der kan anvendes 10 i vaskemidlet, når der stadig skal dannes en stabil en-faset opløsning. Ved højere koncentrationer af buildersalt bliver derimod koncentrationen af amfoter detergent og opløseliggø-rende stof fortrinsvis forøget inden for de ovenfor angivne koncentrationsgrænser, således at blandingen derved opløselig-15 gøres og danner en klar en-faset opløsning med den ønskede vaskeeffekt. Ved en builderkoncentration på ca. 17% eller derover er f.eks. således den foretrukne koncentration af ikke-ion'isk overfladeaktivt stof fra ca. 16 til 18%, koncentrationen af amfoter detergent er fra ca. 2 til 4% og mest ønsket mindst 20 3%, og koncentrationen af opløseliggørende stof er ca. 7 til 8%, idet alle procentangivelser er i vægt% af det samlede vaskemiddel.The nonionic detergent compound in the liquid detergents described is from about 15 to 23 and preferably 17 to 19% by weight of the detergent. The amphoteric detergent compound varies - from approx. 1 to 6, preferably g from 2 to 4% by weight of such detergents. The relative amounts of each of the aforementioned detergents are generally determined by the amount of builder salt used. The higher builder concentrations in the range of 15 to 18%, the lower is the maximum concentration of non-ionic detergent that can be used in the detergent when a stable single-phase solution is still to be formed. On the other hand, at higher concentrations of builder salt, the concentration of amphoteric detergent and solubilizing agent is preferably increased within the above concentration limits so that the mixture is thereby solubilized to form a clear single-phase solution with the desired washing effect. At a builder concentration of approx. 17% or more is e.g. thus, the preferred concentration of non-ionic surfactant from ca. 16 to 18%, the concentration of amphoteric detergent is from approx. 2 to 4% and most preferably at least 20 3%, and the concentration of solubilizing agent is approx. 7 to 8%, all percentages being by weight% of the total detergent.
Den syntetiske ikke-ioniske detergent, der anvendes ved udø-25 velse af opfindeIsen,er specifik for de forbindelser, dér er kondensationsproduktet af 5 til 9 mol 'ethylenoxid og en ali-fatisk alkohol, der indeholder 12 til 15 carbonatomer. Den alifatiske alkohol er fortrinsvis en ligekædet alkohol og mest foretrukket en fedtalkohol eller en blanding deraf indeholden-30 de gennemsnitlig 12 til 13 carbonatomer pr. mol. Antallet af ethylenoxidgrupper pr. mol alkohol ligger fortrinsvis gennemsnitlig på ca. 6,5 eller 7, og særlig foretrukne til anvendelse her er "Neodol" ® 23-6,5 og "Neodol"® 25-7, der begge er produkter, der fremstilles af Shell Chemical Company, Inc.The synthetic nonionic detergent used in the practice of the invention is specific to the compounds there being the condensation product of 5 to 9 moles of ethylene oxide and an aliphatic alcohol containing 12 to 15 carbon atoms. The aliphatic alcohol is preferably a straight chain alcohol and most preferably a fatty alcohol or a mixture thereof containing an average of 12 to 13 carbon atoms per minute. moth. The number of ethylene oxide groups per mole of alcohol is preferably an average of approx. 6.5 or 7, and particularly preferred for use herein are "Neodol" ® 23-6.5 and "Neodol" ® 25-7, both of which are manufactured by Shell Chemical Company, Inc.
De amfotere detergentforbindelser, der er mest anvendelige i vaskemidlerne ifølge opfindelsen, er betain-detergentforbindel- 35The amphoteric detergent compounds most useful in the detergents of the invention are betaine detergent compounds.
6 DK 160771B6 DK 160771B
seme og alkylamidobetain-detargentforbindelseme med følgende formler: (i] betain 5 r2 ,seme and the alkylamidobetaine detergent compounds having the following formulas: (i] betaine 5 r 2,
X IX I
R--CH--N+-COO , og R3 10 (ii) alkylamidobetain H2 1 5? 5 1 4R - CH - N + -COO, and R3 (ii) alkylamidobetaine H215? 5 1 4
R~-C-NH-R-N+-R COOR ~ -C-NH-R-N + -R COO
15 I315 I3
RJRJ
hvor i hver af de ovenfor viste formler repræsenterer en alkylkæde eller en blanding af alkylkæder,. der indehol- 2 3 20 der 9 til 13 carbonatomer, R og R uafhængigt af hinanden u 4 5 er methyl eller ethyl, og R og R uafhængigt af hinanden er methylen, ethylen eller propylen.wherein in each of the formulas shown above represents an alkyl chain or a mixture of alkyl chains. containing 9 to 13 carbon atoms, R and R are independently u 4 5 are methyl or ethyl, and R and R are independently methylene, ethylene or propylene.
Når R3- er en blanding af alkylgrupper med varierende kædelængder, foretrækkes det, at en sådan blanding overvejende omfattes 25 af alkylgrupper med 9 til 13 carbonatomer, selvom det er tilstrækkeligt, omend mindre foretrukket, hvis blot den fremherskende alkylgruppe i blandingen indeholder 9 til 13 carbonatomer, og de øvrige alkylkæder ligger uden for et sådant område.When R 3 - is a mixture of alkyl groups of varying chain lengths, it is preferred that such a mixture is predominantly comprised of alkyl groups of 9 to 13 carbon atoms, although sufficient, albeit less preferred, if only the predominant alkyl group in the mixture contains 9 to 13 carbon atoms, and the other alkyl chains are outside such an area.
R^ er fortrinsvis afledt fra kokosnøddeolie.Preferably, R 2 is derived from coconut oil.
30 2 3 4 5 R , R og R er fortrinsvis methylgrupper og R er fortrinsvis en propylengruppe. Således er de til anvendelse her foretrukne betainer kokosdimethylammoniumacetat (kokosbetainl og kokos- amidopropyldimethylammoniumacetat (kokosamidobetainl.Preferably, R, R and R are methyl groups and R is preferably a propylene group. Thus, the betainees preferred for use herein are coconut dimethylammonium acetate (coconut betainl and coconut amidopropyldimethylammonium acetate (cocosamidobetainl).
En ani'onisk detergent kan valgfrit anvendes i mindre mængder til supplering af den ikke-ioniske og den amfotere detergent- 35An anionic detergent can optionally be used in smaller amounts to supplement the nonionic and the amphoteric detergent.
7 DK 160771B7 DK 160771B
forbindelse i de omhandlede flydende vaskemidler. Generelt vil mængden af anionisk detergent være under ca. 3 vægt% af det samlede vaskemiddel som følge af sådanne detergenters be-grænsede opløselighed i det builderholdige flydende vaskemid-5 del. Alkylbenzénsulfonatsalte, hvori alkylgruppen indeholder 10 til 18 carbonatomer,har særligt begrænset opløselighed i de omhandlede vaskemidler, og derfor foretrækkes det,at de omhandlede vaskemidler er i det væsentlige frie for sådanne forbindelser for at undgå muligheden for produktadskillelse.compound in the present liquid detergents. Generally, the amount of anionic detergent will be less than approx. 3% by weight of the total detergent due to the limited solubility of such detergents in the builder-containing liquid detergent. Alkylbenzene sulfonate salts, wherein the alkyl group contains 10 to 18 carbon atoms, have particularly limited solubility in the detergents of the present invention and therefore, the detergents of the present invention are substantially free of such compounds to avoid the possibility of product separation.
1010
De foretrukne anioniske detergenter til anvendelse her er sulfate rede ethoxylerede højere fedtalkoholer med formlen R0(C2H40)mS03M, hvor R er en fedtalkylgruppe med 10 til 18 eller 20 carbonatomer, m er fra 2 til 6 eller 8 (fortrinsvis med 15 en værdi fra ca. 1/5 til 1/2 af antallet af carbonatomer i R) og M er en opløseliggørende saltdannende kation, såsom et alkalimetal, ammonium, lavere alkylamino eller lavere alkanolamino. En foretrukket polyethoxyleret alkoholsulfatdetergent kan fås fra Shell Chemical Company og sælges som "Neodol'® 25-3S.The preferred anionic detergents for use herein are sulfated ethoxylated higher fatty alcohols of the formula R0 (C2H40) mSO3M, wherein R is a fatty alkyl group having 10 to 18 or 20 carbon atoms, m is from 2 to 6 or 8 (preferably having a value of about 1/5 to 1/2 of the number of carbon atoms in R) and M is a solubilizing salt-forming cation such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino. A preferred polyethoxylated alcohol sulfate detergent is available from Shell Chemical Company and is sold as "Neodol'® 25-3S.
2020
Vand er hovedopløsningsmidlet i de koncentrerede flydende vaskemidler. Koncentrationen af vand kan variere fra ca. 35 til 65%, idet der i almindelighed foretrækkes en koncentration i området fra 45 til 60 vægt%. Et med-opløsningsmiddel, såsom 25 en alkylenglycol, f.eks. ethylenglycol eller propylenglycol, kan valgfrit anvendes i mindre mængder for at forøge opløseligheden af det overfladeaktive stof og builderen i opløsningen. Koncentrationen af alkylenglycol i vaskemidlet bør, hvis det er til stede, være under ca. 10 vægt% af det samlede vaskemid-30 del, fortrinsvis under ca. 5% og mest foretrukket er vaskemidlet i det væsentlige fri for en sådan alkylenglycol.Water is the main solvent in the concentrated liquid detergents. The concentration of water can vary from approx. 35 to 65%, generally having a concentration in the range of 45 to 60% by weight. A co-solvent such as an alkylene glycol, e.g. ethylene glycol or propylene glycol, may optionally be used in smaller amounts to increase the solubility of the surfactant and builder in the solution. The concentration of alkylene glycol in the detergent, if present, should be less than ca. 10% by weight of the total detergent, preferably less than about 10%. 5% and most preferably the detergent is substantially free of such alkylene glycol.
Et eller flere alkalimetalsalte af nonylravsyreanhydrid eller nonylmaleinsyreanhydrid er indbefattet i vaskemidlet på grund 35 af deres opløseliggørende egenskaber med hensyn til ikke-ioniske, overfladeaktive stoffer og buildersalte. Sådanne opløseliggørende stoffer anvendes i en mængde fra 5 til 8 vægt% afOne or more alkali metal salts of nonyl succinic anhydride or nonyl maleic anhydride are included in the detergent because of their solubilizing properties with respect to nonionic surfactants and builder salts. Such solubilizers are used in an amount of from 5 to 8% by weight
DK 160771 BDK 160771 B
s det samlede vaskemiddel, idet der foretrækkes en koncentration på mindst 7%, når buildersaltkoncentrationen er ca. 17% eller derover.s the total detergent, with a concentration of at least 7% being preferred when the builder salt concentration is approx. 17% or more.
s Nonylravsyreanhydrid er repræsenteret med formlens Nonyl succinic anhydride is represented by the formula
OISLAND
c9 - c - CNc9 - c - CN
I /° 10 c — cI / ° 10 c - c
IIII
o hvor Cg repræsenterer en alifatisk kæde med 9 carbonatomer, fortrinsvis en alkylgruppe. Nonylmaleinsyreanhydrid defineres 15 på tilsvarende måde, idet formlerne for ravsyreanhydrid og maleinsyreanhydrid kun adskiller sig ved maleinsyres umættede natur.wherein Cg represents an aliphatic chain of 9 carbon atoms, preferably an alkyl group. Nonylmaleic anhydride is similarly defined in that the succinic anhydride and maleic anhydride formulas differ only by the unsaturated nature of maleic acid.
De ikke-phosphat-detergentbuildersalte anvendes i de omhandle-20 de vaskemidler i mængder, der ligger fra ca. 15 til 18 vægt%. Specifikke eksempler på ikke-phosphatholdige, vandopløselige, uorganiske buildere indbefatter vandopløselige, uorganiske carbonatsalte, bicarbonatsalte og silikatsalte. Særligt anvendelige her er carbonater, bicarbonater og silika-25 ter af alkalimetal (f.eks. natrium og kalium).The non-phosphate detergent builder salts are used in the present detergents in amounts ranging from approx. 15 to 18% by weight. Specific examples of non-phosphate-containing, water-soluble, inorganic builders include water-soluble, inorganic carbonate salts, bicarbonate salts and silicate salts. Particularly useful herein are carbonates, bicarbonates, and alkali metal silicates (e.g., sodium and potassium).
Vandopløselige, organiske buildere kan også anvendes og indbefatter polyacetater, carboxylater, polycarboxylater og polyhy-droxysulfonater af alkalimetal, ammonium eller substitueret 30 ammonium. Specifikke eksempler på polyacetatbuildere og poly-carboxylatbuildere indbefatter natriumsalte, kaliumsalte, li-thiumsalte, ammoniumalte og substituerede ammoniumsalte af e-thylendiamintetraeddikesyre, nitrilotrieddikesyre, benzenpo-lycarboxylsyrer (dvs. penta- og tetrasyre), carboxymethoxyrav-35 syre og citronsyre. Ved anvendelsen i nærværende beskrivelse og krav indbefatter betegnelsen "builder" ikke overfaldeaktive stoffer og sæber, såsom de vandopløselige salte af højere fedtsyrer indeholdende fra ca. 8' til 2Q carbonatomer.Water-soluble organic builders may also be used and include polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates of alkali metal, ammonium or substituted ammonium. Specific examples of polyacetate builders and polycarboxylate builders include sodium salts, potassium salts, lithium salts, ammonium salts and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polylcarboxylic acid, As used herein, the term "builder" does not include surfactants and soaps, such as the water-soluble salts of higher fatty acids containing from ca. 8 'to 2Q carbon atoms.
9 . DK 16077 1 B9. DK 16077 1 B
Optiske fluorescerende klaringsmidler eller optisk fluorescerende hvidt, der anvendes i de flydende vaskemidler, er vigtige bestanddele i moderne vaskemidler, der giyer det vaskede vasketøj og de vaskede materialer et klart udseende, således at vasketøjet ikke blot er rent men også ser rent ud. Skønt 5 det er muligt at anvende et enkelt klaringsmiddel til et spe·*-cielt formål i det omhandlede flydende vaskemidler, er det i almindelighed ønskeligt at anvende blandinger af klaringsmidler, som vil have gode klarende virkninger på bomuld, nylon, polyester og blandinger af sådanne materialer, og som også 10 er stabile over for blegemidler. En god beskrivelse af sådanne typer optiske klaringsmidler er givet i artiklen "The Re- quirements of Present day Detergent Fluorescent Whitening A-gents" af A. E. Siegrist, J. Am. Oil Chemists Soc., Januar 1978 (bind 55). Denne artikel samt US-Patentskrift nr. 3.812.041, 15 indeholder detaillerede beskrivelser af et bredt område af forskellige velegnede optiske klaringsmidler.Optical fluorescent detergents or optical fluorescent whites used in liquid detergents are important components of modern detergents that give the washed laundry and the washed materials a clear appearance so that the laundry is not only clean but also looks clean. Although it is possible to use a single detergent for a special purpose in the liquid detergent in question, it is generally desirable to use blends of detergents which will have good clarifying effects on cotton, nylon, polyester and blends of such materials and which are also stable to bleach. A good description of such types of optical brighteners is given in the article "The Requirements of Present Day Detergent Fluorescent Whitening A-gents" by A. E. Siegrist, J. Am. Oil Chemists Soc., January 1978 (Vol. 55). This article, as well as U.S. Patent No. 3,812,041, 15, contain detailed descriptions of a wide range of various suitable optical clarifiers.
Blandt de klaringsmidler, der kan anvendes i de her omhandle- 20 de flydende vaskemidler, er "Calcofluor" 5 BM (American Cyanamid) ; "Tinopal" LPW (CibaJ ; SOF A-2001 (Ciba); CDW (Hilton-Davis); "Phorwite” RKH; "Phorwite" BBH; "Phorwite" BHC (Verona); CSL, pulver, syre (American Cyanamid) ; FB 766 (Verona) ; "Blancophor" PB (GAF); UNPA (Geigy); og "Tinopal" RBS 200 (Geigy).Among the detergents that can be used in the liquid detergents of this invention are "Calcofluor" 5 BM (American Cyanamid); "Tinopal" LPW (CibaJ; SOF A-2001 (Ciba); CDW (Hilton-Davis); "Phorwite" RKH; "Phorwite" BBH; "Phorwite" BHC (Verona); CSL, Powder, Acid (American Cyanamid); FB 766 (Verona); "Blancophor" PB (GAF); UNPA (Geigy); and "Tinopal" RBS 200 (Geigy).
2525
Der kan være hjælpestoffer til stede i de flydende vaskemidler ^ for at give yderligere egenskaber, enten funktionelle eller æstetiske. Indbefattet blandt de anvendelige hjælpestoffer er smudssuspenderings-eller antigenlejringsmidler, såsom polyvi-30 nylalkohol, natriumcarboxymethylcellulose, hydroxypropylmethyl- cellulose; fortykningsmidler, f.eks. gummier, alginater, agaragar; skumforbedringsmidler, f.eks. laurin-myristin-diethanola-mid; antiskummidler, f.eks. silikoner; baktericider, f.eks. tri-bromsalicylanilid, hexachlorophen; farvestoffer; pigmenter (vand-35 dispergerbare); konserveringsmidler; ultraviolette absorberings midler; tøjblødgørende midler; enzymer; opacificeringsmidler, f.eks. polystyrensuspensicner; og parfumer. Naturligvis vil så-Adjuvants may be present in the liquid detergents to provide additional properties, either functional or aesthetic. Included among the auxiliaries useful are dirt suspending or antigen storage agents such as polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose; thickeners, e.g. rubber, alginates, agar agar; foam enhancers, e.g. lauric myristic diethanolamine bromide; antifoaming agents, e.g. silicones; bactericides, e.g. tribromosalicylanilide, hexachlorophen; dyes; pigments (water-dispersible); preservatives; ultraviolet absorbents; fabric softeners; enzymes; opacifiers, e.g. polystyrensuspensicner; and perfumes. Of course, so-
10 DK 160771 B10 DK 160771 B
danne materialer blive udvalgt baseret på de egenskaber, der ønskes i det færdige produkt, deres forligelighed med de øvrige bestanddele, og deres cpløselighed i det flydende vaskemiddel.forming materials are selected based on the properties desired in the finished product, their compatibility with the other ingredients, and their solubility in the liquid detergent.
55
De omhandlede flydende vaskemidler er effektive og lette at anvende. Sammenlignet med højtydende vaskepulvere kan der anvendes betydeligt mindre rumfang af de her omhandlede væsker til opnåelse af en sammenlignelig rengøring af snavset vasketøj.The liquid detergents in question are effective and easy to use. Compared to high-performance washing powders, considerably less volume of the liquids in question can be used to achieve a comparable cleaning of dirty laundry.
10 F.eks. er det ved anvendelse af en typisk foretrukket formulering ifølge opfindelsen kun nødvendigt at anvende 71;g eller • 1/4 kop af det flydende vaskemiddel til et fyldt, vaskekar i en automatisk vaskemaskine med påfyldning foroven, hvori vandrumfanget er ca. 64 liter (17 gallon), og der behøves endog endnu 15 mindre til vaskemaskiner med påfyldning fra forsiden. Således er koncentrationen af det flydende vaskemiddel i vaskevandet i størrelsesordenen på ca. 0,1%. Sædvanligvis vil andelen af det flydende vaskemiddel i vaskeopløsningen ligge i området fra ca. 0,05 til 0,3%, fortrinsvis fra 0,10 til 0,20. Andelene af de 20 forskellige bestanddele i det flydende vaskemiddel kan variere i overensstemmelse hermed. Ækvivalente resultater kan opnås ved anvendelse af større mængder af en mere fortyndet formulering, men den større mængde, der behøves, vil kræve yderligere emballage og vil generelt være mindre bekvem for forbrugeren.For example, for example, using a typical preferred formulation according to the invention, it is only necessary to use 71; g or 1/4 cup of the liquid detergent for a pre-filled washing vessel in an automatic top-loading washing machine wherein the volume of water is approx. 64 liters (17 gallons), and even 15 smaller ones are needed for front-loading washers. Thus, the concentration of the liquid detergent in the wash water is on the order of approx. 0.1%. Generally, the proportion of the liquid detergent in the wash solution will be in the range of from about. 0.05 to 0.3%, preferably from 0.10 to 0.20. The proportions of the 20 different components of the liquid detergent may vary accordingly. Equivalent results can be obtained by using larger amounts of a more diluted formulation, but the larger quantity needed will require additional packaging and will generally be less convenient for the consumer.
25 .25.
Eksempel 1Example 1
Et koncentreret, builderholdigt, flydende vaskemiddel ifølge opfindelsen formuleredes som angivet nedenfor. De viste procentan-30 „ / givelser refererer til den 100% aktive bestanddel.A concentrated builder-containing liquid detergent according to the invention was formulated as indicated below. The percentages shown below represent the 100% active ingredient.
3535
XI DK 160771 BXI DK 160771 B
Bestanddel yægt%Ingredient%
Natriumcitrat 17,2 5 Ethoxyleret C12_C13 alkohol (6,5 mol EO/mol alkohol) 17,6Sodium citrate 17.2 Ethoxylated C12-C13 alcohol (6.5 mol EO / mol alcohol) 17.6
Kokosamidobetain ^ 3,1 (2)Coconamidobetane 3.1 (2)
Nonylravsyreanhydrid (kaliumsalt) 770Nonyl succinic anhydride (potassium salt) 770
Klaringsmiddel og farvestof 0,2 10 Vand " resten (1) Leveret som "Varion CADG", en yandig opløsning af kokos^ amidobetain leveret af Sherex Chemical Company.Detergent and Dye 0.2 10 Water "The residue (1) Delivered as" Varion CADG ", a coconut amidobetain solution supplied by Sherex Chemical Company.
(2) Anhydridet leveres som "Hoe S-2817" af American 15 Hoechst Company, og omsættes derefter- med kalium- hydroxid til dannelse af kaliumsaltet.(2) The anhydride is supplied as "Hoe S-2817" by the American 15 Hoechst Company, and then reacted with potassium hydroxide to form the potassium salt.
Det ovenfor beskrevne flydende vaskemiddel var et klart, blåtfarvet, en-faset, homogent flydende vaskemiddel med en visko-sitet på ca. 80 cp ved 24°C, og som på tilfredsstillende måde kunne udhældes fra en plastvaskemiddelflaske med en udtømningsåbning på ca. 2,5 cm. Det flydende vaskemiddel anvendtes til at vaske en blandet portion af snavset vasketøj, som indbefattede bomuldsprøveklude og polyester/bomulds-prøveklude tilsmudset med partikelformet smuds og med hudfedt. Vasketempera-The liquid detergent described above was a clear, blue-colored, single-phase, homogeneous liquid detergent having a viscosity of approx. 80 cp at 24 ° C and which could be satisfactorily poured from a plastic detergent bottle with a discharge opening of approx. 2.5 cm. The liquid detergent was used to wash a mixed batch of dirty laundry, which included cotton test cloths and polyester / cotton test cloths soiled with particulate dirt and with skin grease. Vasketempera-
OISLAND
turen var 49 C, og koncentrationen af det flydende vaskemiddel i vaskebadet var ca. 0,1 vægt%. Efter vask blev de vaskede genstande skyllet i ledningsvand, hvorpå de tørredes. Pletfjernelsesgraden måltes ved at tage reflektansaflæsninger for hver af de plettede prøveklude før og efter vask under anvendelse af 30 et Gardner XL-20 kolorimeter.the trip was 49 C and the concentration of the liquid detergent in the wash bath was approx. 0.1% by weight. After washing, the washed items were rinsed in tap water and then dried. The degree of stain removal was measured by taking reflectance readings for each of the stained sample cloths before and after washing using a Gardner XL-20 colorimeter.
Den ovenfor beskrevne vaskeproces blev gentaget med et kontrol^ vaskemiddel, et i handelen tilgængeligt vandigt builderholdigt, 3g flydende vaskemiddel indeholdende 19% dodecylbenzensulfonat, 10% natriumcitrat, 7% overfladeaktiv- ethoxyleret alkohol og 5% natriumtoluensulfonat-hydrotrop anvendt som en koncentra-The above-described washing process was repeated with a control detergent, a commercially available aqueous builder-containing, 3g liquid detergent containing 19% dodecylbenzenesulfonate, 10% sodium citrate, 7% surfactant ethoxylated alcohol and 5% sodium toluene sulfonate hydrotrope used as a concentrate.
12 DK 160771 B12 DK 160771 B
tion på "1/2 kop" på ca. 0/2 v«gt% i vaskebadet. De to vasken midlers vaskeevne saromlignedes på basis af de målte pletfjernelser opnået ved vasken. Vaskeevnen for det flydende vaskemiddel ifølge opfindelsen i en koncentration på "1/4 kop" viste sig 5 at være enten ækvivalent med eller bedre end den, der blev opnået med kontrolvaskemidlet i en koncentration på "1/2 kop” med hensyn til vaskede tilsmudsede og plettede tekstiler.tion of "1/2 cup" of approx. 0/2 v «gt% in the wash bath. The washing ability of the two washing agents was compared on the basis of the measured stain removal obtained by the washing. The washing ability of the liquid detergent of the invention at a concentration of "1/4 cup" was found to be either equivalent to or better than that obtained with the control detergent at a concentration of "1/2 cup" with respect to washed soiled and spotted fabrics.
Eksempel 2 1°Example 2 1 °
Virkningen af at inkorporere en betain-de-tergent, der ikke er i . overensstemmelse med den foreliggende opfindelse, i et builder-holdigt, flydende vaskemiddel, der indeholder ikke-ionisk overfladeaktivt stof og en høj koncentration af builder, demonstre-25 redes ved at fremstille to flydende vaskemidler som beskrevet i eksempel 1, bortset fra at kokosamidobetainen i vaskemidlet ifølge eksempel 1 erstattedes i et vaskemiddel med stearylbe-tain og i et andet vaskemiddel med palmytylbetain. Begge de resulterende vaskemidler var ustabile og dannede adskilte faser 20 i modsætning til den stabile klare opløsning, der var karakteristisk for vaskemidlet ifølge eksempel 1.The effect of incorporating a non-betaine-de-tergent. In accordance with the present invention, in a builder-containing liquid detergent containing nonionic surfactant and a high concentration of builder, is demonstrated by preparing two liquid detergents as described in Example 1 except that the cocosamidobetaine in the detergent of Example 1 was replaced in a detergent with stearyl betaine and in another detergent with palmytyl betaine. Both of the resulting detergents were unstable and formed separate phases 20 in contrast to the stable clear solution characteristic of the detergent of Example 1.
Eksempel 3Example 3
Der gennemførtes prøver for vaskeeffekt med vaskemidler A, B og C formuleret som vist nedenfor. Tallene i tabellen repræsenterer mængden i vægt% for hver bestanddel i det flydende vaskemiddel.Washing effect tests were performed with detergents A, B and C formulated as shown below. The figures in the table represent the amount by weight% of each ingredient in the liquid detergent.
Bestanddel Λ B CComponent Λ B C
Natriumcitrat 17,2 17,2 17,2 3 0Sodium citrate 17.2 17.2 17.2 3 0
Ethoxy leret C,9-c,alkohol (6,5 mol EO/molAlkohol) 17,6 22,0 7,0Ethoxy clay C, 9-c, alcohol (6.5 mol EO / mol Alcohol) 17.6 22.0 7.0
Kokos amidobe tain 3,1 " 9,0 ' Nonylravsyreanhvdrid (kaliumsalt) 7,0 14,0Coconut amidobic acid 3.1 "9.0" Nonyl succinic anhydride (potassium salt) 7.0 14.0
Vand resten resten resten 35 13Water the remainder the remainder 35 13
DK 160771 BDK 160771 B
Alle tre vaskemidler var klare, en-fasede opløsninger. Vaskemiddel A er et vaskemiddel ifølge opfindelsen som tidligere beskrevet i eksempel 1. Vaskemiddel B repræsenterer den bedst ydende formulering med hensyn til vaskeevne målt ved en koncentration på 0,1% i vaskebadet blandt vaskemidler, der inde-5 holder de samme bestanddele som vaskemiddel A, bortset fra at betaindetergenten er udeladt, og som dannede en klar en-faset opløsning. Tilsvarende repræsenterer vaskemiddel C den bedst ydende formulering med hensyn til vaskeevne målt ved en koncentration på 0,1% i vaskebadet blandt vaskemidler, der inde-10 * holder de samme komponenter som vaskemiddel A, bortset fra at de ikke indeholder opløseliggørende stof, og som dannede en klar en-faset opløsning. Vaskemidlerne B og C er ikke i overensstemmelse med opfindelsen.All three detergents were clear, single-phase solutions. Detergent A is a detergent according to the invention as previously described in Example 1. Detergent B represents the best performing formulation in terms of detergent as measured at a concentration of 0.1% in the detergent bath among detergents containing the same ingredients as detergent A , except that the betaindetergent is omitted and which formed a clear single-phase solution. Similarly, detergent C represents the best-performing detergent formulation measured at a concentration of 0.1% in the detergent bath among detergents containing the same components as detergent A, except that they do not contain solubilizing agent and which formed a clear single-phase solution. The detergents B and C are not in accordance with the invention.
1515
Vaskeevnen hos vaskemidlerne A, B og C bestemtes i et Tergoto-meterkar fremstillet af US Testing Company på følgende tekstilprøveklude under de angivne betingelser: 20 Prøveklude TFN: Prøvetekstilsmuds på nylon PCC: Piscataway-ler på bomuld SC: Partikelformet hudfedt på bomuld 25 SDC: Partikelformet hudfedt på Dacronbomuld EMPA: EMPA 101 på svært bomuldThe washability of the detergents A, B and C was determined in a Tergoto meter vessel manufactured by the US Testing Company on the following textile test cloths under the conditions specified: Particulate skin grease on Dacron cotton EMPA: EMPA 101 on heavy cotton
Vaskebetinqelser 3ø Koncentration af flydende vaskemiddel 0,10%Washing conditions 3ø Liquid detergent concentration 0.10%
Vandtemperatur 49°CWater temperature 49 ° C
Vandhårdhed ca. 150 ppm (dele per million) som calcium-carbonat 35Water hardness approx. 150 ppm (parts per million) as calcium carbonate 35
Ved afslutningen af vasken, blev prøvekludene skyllet med ledningsvand, hvorefter de tørredes. En reflektansaflæsning blev taget for hver prøveklud før og efter vask under anvendelse 14At the end of the wash, the sample cloths were rinsed with tap water and then dried. A reflectance reading was taken for each sample cloth before and after washing using 14
DK 160771 BDK 160771 B
af et Gardner XL-2O kolorimeter. Værdierne for forandringerne i reflektans (ARd) er vist nedenfor i tabel 1 for hver af de førnævnte prøveklude. En forskel på mere end 0,8 mellem de to værdier for ARd anses som signifikant for alle de vaskede 5 prøveklude, bortset fra målinger på EMPA, hvor kun ARd-værdier over 1,3 anses som signifikante.of a Gardner XL-2O colorimeter. The values of the changes in reflectance (ARd) are shown below in Table 1 for each of the aforementioned sample cloths. A difference of more than 0.8 between the two values of ARd is considered significant for all the washed 5 sample cloths, except for measurements on EMPA, where only ARd values above 1.3 are considered significant.
Tabel 1 !0 ARd-værdier for prøveklude vasket med _vaskemidlerne A, B og C_Table 10.0 ARd values for sample cloths washed with the detergents A, B and C_
Vaskemiddel TFN PCC EMPA SC SDCDetergent TFN PCC EMPA SC SDC
A 37 24 18 10 44 15 B 35 24 17 8 42 C 29 21 15 4 34A 37 24 18 10 44 15 B 35 24 17 8 42 C 29 21 15 4 34
Tabel 1 viser en uventet forbedret vaskeevne forbundet med anvendelsen af et vaskemiddel ifølge opfindelsen i forhold 20 til to en-fasede, flydende vaskemidler, der ligner det, men som ikke er formuleret i overensstemmelse med opfindelsen. Vaskemiddel A ses at være bedre end vaskemiddel B med hensyn til størstedelen af de vaskede prøveklude og bedre end vaskemiddel C med hensyn til alle de vaskede prøveklude.Table 1 shows an unexpectedly improved washability associated with the use of a detergent according to the invention in relation to two single-phase liquid detergents similar to it, but not formulated in accordance with the invention. Detergent A is seen to be better than detergent B for the majority of the washed sample cloths and better than detergent C for all the washed sample cloths.
25 30 3525 30 35
Claims (25)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68297184A | 1984-12-18 | 1984-12-18 | |
| US68297184 | 1984-12-18 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK591785D0 DK591785D0 (en) | 1985-12-18 |
| DK591785A DK591785A (en) | 1986-06-19 |
| DK160771B true DK160771B (en) | 1991-04-15 |
| DK160771C DK160771C (en) | 1991-09-30 |
Family
ID=24742015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK591785A DK160771C (en) | 1984-12-18 | 1985-12-18 | CONCENTRATED, SINGLE-PHASE, BUILDER-CONTAINING, LIQUID DETERGENT |
Country Status (32)
| Country | Link |
|---|---|
| JP (1) | JPS61145298A (en) |
| KR (1) | KR930003937B1 (en) |
| AR (1) | AR240336A1 (en) |
| AT (1) | AT394378B (en) |
| AU (1) | AU578333B2 (en) |
| BE (1) | BE903874A (en) |
| BR (1) | BR8506327A (en) |
| CA (1) | CA1255182A (en) |
| CH (1) | CH668078A5 (en) |
| DE (1) | DE3544236A1 (en) |
| DK (1) | DK160771C (en) |
| EG (1) | EG17366A (en) |
| FI (1) | FI79135C (en) |
| FR (1) | FR2574813B1 (en) |
| GB (1) | GB2170816B (en) |
| GR (1) | GR853046B (en) |
| HK (1) | HK41191A (en) |
| IE (1) | IE58699B1 (en) |
| IN (1) | IN165674B (en) |
| IT (1) | IT1182083B (en) |
| LU (1) | LU86213A1 (en) |
| MX (1) | MX162411A (en) |
| NL (1) | NL8503482A (en) |
| NO (1) | NO165926C (en) |
| NZ (1) | NZ214410A (en) |
| PH (1) | PH24520A (en) |
| PT (1) | PT81670B (en) |
| SE (1) | SE466262B (en) |
| TR (1) | TR23505A (en) |
| ZA (1) | ZA859267B (en) |
| ZM (1) | ZM9885A1 (en) |
| ZW (1) | ZW22085A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8511303D0 (en) * | 1985-05-03 | 1985-06-12 | Procter & Gamble | Liquid detergent compositions |
| US4908147A (en) * | 1986-02-19 | 1990-03-13 | Ciba-Geigy Corporation | Aqueous self preserving soft contact lens solution and method |
| IN169730B (en) * | 1986-02-19 | 1991-12-14 | Ciba Geigy Ag | |
| FR2603601B1 (en) * | 1986-09-08 | 1988-11-10 | Lesieur Cotelle | COMPOSITION FOR CLEANING SANITARY FACILITIES |
| US4830782A (en) * | 1987-08-31 | 1989-05-16 | Colgate-Palmolive Company | Hot water wash cycle built nonaqueous liquid nonionic laundry detergent composition containing amphoteric surfactant and method of use |
| US4900467A (en) * | 1988-05-20 | 1990-02-13 | The Clorox Company | Viscoelastic cleaning compositions with long relaxation times |
| US5063084A (en) * | 1990-05-31 | 1991-11-05 | Nelson Riley H | Method of preventing adherence of insect residues to vehicular surfaces |
| EP0476212A1 (en) * | 1990-09-17 | 1992-03-25 | The Procter & Gamble Company | Liquid detergent compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3579453A (en) * | 1968-11-12 | 1971-05-18 | Rohm & Haas | Alkali-soluble surfactant consisting of substituted succinic acid-nonionic ethoxylate blends |
| SE380751B (en) * | 1971-11-12 | 1975-11-17 | Seco Tools Ab | FRIENDS |
| FR2208976B1 (en) * | 1972-11-30 | 1978-02-24 | Modokemi Ab | |
| US4122043A (en) * | 1973-12-19 | 1978-10-24 | Polytrol Chemical Corporation | Amidobetaine containing detergent composition non-toxic to aquatic life |
| AT344301B (en) * | 1974-08-01 | 1978-07-10 | Hoechst Ag | CLEANING SUPPLIES |
| CA1115618A (en) * | 1977-07-01 | 1982-01-05 | Unilever Limited | Detergent compositions |
| US4375421A (en) * | 1981-10-19 | 1983-03-01 | Lever Brothers Company | Viscous compositions containing amido betaines and salts |
| JPS6039719B2 (en) * | 1982-05-11 | 1985-09-07 | 花王株式会社 | liquid cleaning composition |
-
1985
- 1985-12-02 NZ NZ214410A patent/NZ214410A/en unknown
- 1985-12-02 IN IN1013/DEL/85A patent/IN165674B/en unknown
- 1985-12-03 ZA ZA859267A patent/ZA859267B/en unknown
- 1985-12-05 ZW ZW220/85A patent/ZW22085A1/en unknown
- 1985-12-06 MX MX856A patent/MX162411A/en unknown
- 1985-12-06 AU AU50844/85A patent/AU578333B2/en not_active Ceased
- 1985-12-10 FI FI854875A patent/FI79135C/en not_active IP Right Cessation
- 1985-12-11 IT IT48909/85A patent/IT1182083B/en active
- 1985-12-12 PT PT81670A patent/PT81670B/en not_active IP Right Cessation
- 1985-12-12 FR FR8518433A patent/FR2574813B1/en not_active Expired
- 1985-12-13 SE SE8505909A patent/SE466262B/en not_active IP Right Cessation
- 1985-12-14 DE DE19853544236 patent/DE3544236A1/en not_active Ceased
- 1985-12-16 TR TR50127/85A patent/TR23505A/en unknown
- 1985-12-16 PH PH33179A patent/PH24520A/en unknown
- 1985-12-17 CA CA000497898A patent/CA1255182A/en not_active Expired
- 1985-12-17 GR GR853046A patent/GR853046B/el unknown
- 1985-12-17 IE IE319185A patent/IE58699B1/en not_active IP Right Cessation
- 1985-12-17 NO NO855083A patent/NO165926C/en unknown
- 1985-12-17 BR BR8506327A patent/BR8506327A/en not_active IP Right Cessation
- 1985-12-17 AR AR302608A patent/AR240336A1/en active
- 1985-12-17 BE BE0/216022A patent/BE903874A/en not_active IP Right Cessation
- 1985-12-17 ZM ZM98/85A patent/ZM9885A1/en unknown
- 1985-12-17 LU LU86213A patent/LU86213A1/en unknown
- 1985-12-17 KR KR1019850009487A patent/KR930003937B1/en not_active IP Right Cessation
- 1985-12-18 AT AT0365685A patent/AT394378B/en not_active IP Right Cessation
- 1985-12-18 JP JP60285395A patent/JPS61145298A/en active Pending
- 1985-12-18 EG EG810/85A patent/EG17366A/en active
- 1985-12-18 GB GB08531144A patent/GB2170816B/en not_active Expired
- 1985-12-18 DK DK591785A patent/DK160771C/en not_active IP Right Cessation
- 1985-12-18 CH CH5421/85A patent/CH668078A5/en not_active IP Right Cessation
- 1985-12-18 NL NL8503482A patent/NL8503482A/en not_active Application Discontinuation
-
1991
- 1991-05-30 HK HK411/91A patent/HK41191A/en unknown
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |