EP0811049B1 - Cleaning composition comprising saturated dialkyl cationic surfactants - Google Patents

Cleaning composition comprising saturated dialkyl cationic surfactants Download PDF

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Publication number
EP0811049B1
EP0811049B1 EP96904036A EP96904036A EP0811049B1 EP 0811049 B1 EP0811049 B1 EP 0811049B1 EP 96904036 A EP96904036 A EP 96904036A EP 96904036 A EP96904036 A EP 96904036A EP 0811049 B1 EP0811049 B1 EP 0811049B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
composition according
surfactant
hydrogen
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96904036A
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German (de)
English (en)
French (fr)
Other versions
EP0811049A1 (en
Inventor
Matthew James Leach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0811049A1 publication Critical patent/EP0811049A1/en
Application granted granted Critical
Publication of EP0811049B1 publication Critical patent/EP0811049B1/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • 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

Definitions

  • the present invention relates to a cleaning composition for hard surfaces, wherein said composition comprises both a fully saturated dialkyl cationic surfactant and a nonionic surfactant.
  • GB 1528592 (1978) discloses alkaline, floor cleaning compositions which comprise an organic, polycarboxylic acid co-polymer having a molecular weight in the range 100,000-2,500,000 which is soluble in aqueous solutions having a pH of 8.5 or above. These polymers are readily available in commercial quantities.
  • GB 1534722 (1978) discloses granular hard surface cleaning compositions which comprise surfactant and, as "a soil removal improvement mixture", a polyvinyl alcohol or pyrrolidone and a biopolysaccharide. These polymers have molecular weights ranging from around 5000 to around 360,000 and are available in industrially useful quantities. The compositions form alkaline solutions.
  • EP 0467472 A2 discloses that soil release promoting polymers such as, but not limited to, the cationic poly[beta(methyl diethyl-ammonium) ethyl-methacrylate] are also effective in combination with anionic and cationic surfactant.
  • 'said adsorbed polymer forms a residual anti-soiling hydrophillic layer of said soil release promoting polymer on said surface, whereby removal of soils subsequently deposited thereupon requires less work than in the absence of said residual layer'.
  • the molecular weight range of the polymers falls into the range 4,000-100,000 although the use of polymers having a molecular weight above 50,000 is discouraged for solubility reasons.
  • EP 0379256 discloses similar compositions to the above-mentioned document, having up to 2%wt of an optional quaternised, anti-static, polymer of molecular weight in the range of 2,000 - 500,000, and being characterised by an acidic pH of 2-4 and a 2-4%wt of a nonionic surfactant system. Specific examples relate to compositions having a pH of 2.5 and comprising 2.2%wt of a mixed nonionic system and 0.07% of the specified cationic polymer. The modified polymer is again said to function as a soil release agent.
  • US-A-4065409 discloses a detergent mixture for cleaning hard surfaces which comprises a low level of nonionic detergent (which can include ethoxylated alcohol) and a quat. (such as dimethyl didecyl ammonium chloride: DDAC). There is no mention of any soil release benefit in this document.
  • nonionic detergent which can include ethoxylated alcohol
  • quat. such as dimethyl didecyl ammonium chloride: DDAC
  • WO-A-8605199 discloses compositions which comprise glycoside nonionics. It is noted that the compositions of the prior art disclosed in this citation are said to leave essentially no residues on the surface and it is believed that the compositions of the reference are also intended to leave no residues.
  • WO-A-9406899 also discloses compositions which comprise quaternised mono and di tallow acid esters in combination with glycoside nonionics
  • WO 91/09930 discloses the use 'ETHOQUAT' (TM) on aluminium e.g. metal surfaces such as those found on vehicles.
  • an aqueous, hard-surface cleaning composition comprising a surfactant mixture, wherein said surfactant mixture comprises:
  • An aqueous, hard-surface cleaning composition comprising a surfactant mixture, wherein said surfactant mixture comprises:
  • the cationic surfactant comprises a cation of the formula given above wherein -OOCR 4 and -OOCR 5 are independently C 12 -C 20 .
  • Alternative fully saturated dialkyl quaternary ammonium compounds include X - [CH 3 (CH 2 ) n CO.NH(CH 2 ) m ] 2 .N + R 1 R 2 wherein R 1 and R 2 are independently selected from hydrogen, C1-C4 alkyl, C1-C4 hydroxy alkyl and alkylene glycol residues or polymers thereof, n is 8-26 and m is 1-4 and X is an monovalent anion equivalent.
  • R 1 is methyl
  • R 2 is - (CH 2 CH 2 O) x H, or methyl.
  • dialkyl quaternary ammonium compounds include X - [CH 3 (CH 2 ) n COO(CH 2 ) m ] 2 .N + R 1 R 2 wherein R 1 and R 2 are independently selected from hydrogen, C1-C4 alkyl, C1-C4 hydroxy alkyl and alkylene glycol residues or polymers thereof, n is 8-26 and m is 1-4 and X is an monovalent anion equivalent.
  • R 1 is methyl
  • R 2 is - (CH 2 CH 2 O) x H (where x is on average 1-2), or methyl
  • m is 2.
  • dialkyl quaternary ammonium compounds which may optionally be present include X - [CH 3 (CH 2 ) n ] 2 .N + R 1 R 2 wherein R 1 and R 2 are independently selected from hydrogen, C1-C4 alkyl, C1-C4 hydroxy alkyl and alkylene glycol residues or polymers thereof, n is 8-26 and X is an monovalent anion equivalent.
  • R 1 is methyl
  • R 2 is - (CH 2 CH 2 O) x H (where x is 1-2), or methyl.
  • n is selected such that the longer alkyl chains have a chain length distribution similar to that of tallow.
  • the pH of the compositions according to the present invention is acidic, alkaline or neutral.
  • Typical compositions according to the present invention have a pH of less than 7.5 where ester groups are used. Where ester groups are absent as linkages in the optional cationic surfactant the pH can be higher than 7.5.
  • a preferred cationic surfactant is: X - [(CH 3 ) 3 N-CH 2 -CH(OOCR 4 )-CH 2 OOCR 5 ] + wherein, -OOCR 4 and -OOCR 5 are independently C 12 -C 20 and the composition is essentially free of anionic surfactant. Materials falling within this general class are available from Hoechst. Most preferably, -OOCR 4 and -OOCR 5 are fatty acid residue having a chain length distribution corresponding to that of tallow.
  • Another preferred cationic is: X - [CH 3 (CH 2 ) n CO.NH(CH 2 ) 2 ] 2 .N + R 1 R 2 wherein n is 11-19, R 1 is methyl and R 2 is-(CH 2 CH 2 O) x (where x is 1-2), H, or methyl. Materials falling within this general description are available in the marketplace as ACCOSOFT 440/75 (TM) from Stepan.
  • the ethoxylation number x is close to 1.7, i.e. 1.5-2.0.
  • the cationic surfactants present in the compositions of the present invention modify the surface energy of surfaces to which the composition is applied so as to raise the contact angle of soil subsequently deposited on the modified surface.
  • Preferred cationics have a marked effect on the contact angle of test liquids which are applied to surfaces which have been treated with said cationics.
  • the contact angle of a 10 microlitre dodecane droplet is less than 10 degrees.
  • the contact angle of the dodecane droplet is increased to typically above 20 degrees.
  • the present invention also extends to a method for cleaning a hard surface with a net negative charge which comprises the step of treating said surface with a composition as described herein.
  • compositions of the present invention comprise an alkoxylated alcohol nonionic surfactant.
  • nonionic surfactant is believed to contribute significantly to the cleaning effectiveness of the compositions of the invention.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophillic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophillic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophillic and hydrophobic elements.
  • the nonionic surfactant is thus chosen from the group consisting of the condensation product of aliphatic alcohols having from 6 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide (such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol) and condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol.
  • ethylene oxide such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol
  • alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol.
  • nonionic surfactants are the ethoxylated alcohols having 6-14 carbons and 2-9 moles of ethoxylation.
  • Suitable materials include IMBENTIN 91/35 OFA (TM), a C 10 nonionic having on average five moles of ethoxylation.
  • nonionic surfactants produced by condensation of alkylene oxides with aliphatic or alkyl-aromatic compounds are known to the skilled worker, as set forth in M.J.Schick 'Nonionic Surfactants', Marcel Dekker (1967) and subsequent editions of the same work.
  • the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 1 to 30%wt, preferably from 2 to 20%wt, and most preferably from 5 to 10%wt.
  • the ratio of nonionic surfactant to anionic and cationic surfactant is such that > 75% of the total surfactant present in the composition is nonionic.
  • compositions of the present invention only comprise low levels of anionic detergent actives or that these actives are absent in so far as is practical. It is believed that the presence of anionic detergents will cause the formation of a complex between the cationic and anionic detergents which will reduce the effectiveness of the compositions.
  • the overall surfactant content of compositions according to the present invention will generally be 1 to 30%.
  • Hydrophobic oils are optional components of compositions according to the present invention. Suitable oils include oils which rapidly dissolve triglyceride. When oils are present preferred oils include limonene, para-cymene, dibutyl ether and butyl butyrate.
  • composition according to the invention can contain other ingredients which aid in their cleaning performance.
  • the composition can contain detergent builders.
  • Suitable builders include materials such as carbonates and bicarbonates, nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho- and pyrophosphate, zeolites and mixtures thereof.
  • Such builders can additionally function as abrasives if present in an amount in excess of their solubility in water: although it is preferable that the compositions of the present invention are essentially free of abrasive particles.
  • the builder will form from 0.1 to 25% by weight of the composition.
  • Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST R ) and phosphates and a wide variety of other polyfunctional organic acids and salts, can also optionally be employed.
  • a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in those compositions according to the invention which have a tendency to produce excessive suds in use.
  • suds regulating materials are organic solvents, hydrophobic silica and silicone oils or hydrocarbons.
  • Solvents are optional components of compositions according to the present invention. Where solvents are present, preferred solvents are of the form R 1 -0-(E0) m -(PO) n -R 2 , wherein R 1 and R 2 are independently C2-6 alkyl or H, but not both hydrogen, m and n are independently 0-5. More preferably, the solvent is selected from the group comprising di-ethylene glycol mono n-butyl ether, monoethylene glycol mono n-butyl ether, propylene glycol n-butyl ether, isopropanol, ethanol, butanol and mixtures thereof.
  • Alternative solvents include the pyrrolid(in)ones, for example N-methyl pyrrolidinone.
  • compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, perfumes and opacifiers.
  • various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, perfumes and opacifiers.
  • the composition comprises 1-10% of an alkanolamine, with levels of 2-6%wt being particularly preferred.
  • alkanolamines include: 2-amino-2-methyl-1-propanol(AMP), mono-ethanolamine and diethanolamine.
  • Suitable polymers include polyvinyl pyrrolidone, available in the marketplace as Polymer PVP K-90.
  • Suitable levels of PVP polymer range upwards from 50ppm. Levels of 300-2000ppm are particularly preferred.
  • compositions of the present invention can be alkaline, acidic or neutral, it is preferred for kitchen soils that the compositions are generally alkaline, having a preferred pH >6.
  • compositions have a pH of >10 and comprise, in admixture with water,:
  • Aqueous compositions comprising nonionic surfactant, and a relatively low level of cationic surfactant were prepared as in Tables 1 and 2 below: using the following materials (all compositions are given in terms of wt% unless otherwise stated): NONI IMBENTIN 91/35 OFA (TM), CTAB Cetyl trimethyl ammonium bromide, HEQ [(CH 3 ) 3 N-CH.OOCR 4 -CH2.OOCR 5 ] + Cl - wherein OOCR 4 and OOCR 5 are fatty acid residues having a fatty acid chain length corresponding to tallow (manufactured by Hoechst). ACCO ACCOSOFT 440/75 ex. Stepan. AMP amino-2-methyl-1-propanol digol Butyl Digol (TM)
  • compositions were prepared at room temperature by mixing except where HEQ and ACCO were used, these latter material being dissolved in three parts propylene glycol at 70 celcius and added to water, also at 70 celcius, while stirring.
  • CTAB a typical mono-alkyl cationic surfactant was selected as a control as it has a significantly lower effect on the contact angle of a dodecane droplet placed on a glass (microscope) slide which has been treated with a 1% solution of the dialkyl cationic in a 5% aqueous solution of NONI.
  • the surface energy gamma s /mN.m -1 of the CTAB treated glass (microscope slide) surface is believed to be of the order of 25 mN.m -1 (as measured by the method of Grifalco, Good, Fowkes and Young (see Physical chemistry of Surfaces, A. A. Adamson, Wiley, New York [1990])), whereas the surface energy of surfaces treated with similar solutions of the cationics used in the compositions of the present invention was less than 25 mN.m -1 .
  • EXAMPLE Comp: 1 2 3 4 5 NONI 5% 5% 5% 5% 5% 5% CTAB - 1% - - - HEQ - - .01% 0.1% 1.0% ETh 2140 2119 EPh 2634 1697 - 896 776 Gamma s >25 25 - - 23.1
  • Vitreous enamel times (380x300mm) were cleaned using a fresh damp J-CLOTH (TM) using, in sequence, JIF LAC (TM), a commercially available brand of hand dishwashing liquid and calcite powder. After drying residual calcite was removed by buffing with a paper towel.
  • the effort required to clean the tiles was determined as 'ETh' in table 1 for thermally aged tiles and 'EPh' for photochemically aged tiles.
  • compositions according to the present invention show a marked reduction in the cleaning effort required as compared with comparable compositions which either contain no cationic surfactant or contain a cationic surfactant which is not a saturated dialkyl cationic.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Cosmetics (AREA)
EP96904036A 1995-02-23 1996-02-07 Cleaning composition comprising saturated dialkyl cationic surfactants Expired - Lifetime EP0811049B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9503594 1995-02-23
GBGB9503594.5A GB9503594D0 (en) 1995-02-23 1995-02-23 Cleaning composition comprising dialkyl cationic surfactants
PCT/EP1996/000542 WO1996026257A1 (en) 1995-02-23 1996-02-07 Cleaning composition comprising saturated dialkyl cationic surfactants

Publications (2)

Publication Number Publication Date
EP0811049A1 EP0811049A1 (en) 1997-12-10
EP0811049B1 true EP0811049B1 (en) 2001-04-18

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Family Applications (1)

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EP96904036A Expired - Lifetime EP0811049B1 (en) 1995-02-23 1996-02-07 Cleaning composition comprising saturated dialkyl cationic surfactants

Country Status (16)

Country Link
EP (1) EP0811049B1 (es)
JP (1) JP3207432B2 (es)
KR (1) KR19980702441A (es)
CN (1) CN1175974A (es)
AR (1) AR001004A1 (es)
AU (1) AU719466B2 (es)
BR (1) BR9607341A (es)
CA (1) CA2211346C (es)
DE (1) DE69612549T2 (es)
ES (1) ES2158286T3 (es)
GB (1) GB9503594D0 (es)
HU (1) HU226238B1 (es)
IN (2) IN187431B (es)
TR (1) TR199700840T1 (es)
WO (1) WO1996026257A1 (es)
ZA (1) ZA961118B (es)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2151230B1 (en) * 2007-04-26 2014-07-23 Shiseido Company, Ltd. Oil-in-water emulsion composition and method for producing the same
CN104871289B (zh) * 2012-12-14 2017-10-10 巴斯夫欧洲公司 包含表面活性剂和疏水化剂的组合物在处理线间距尺寸为50nm或更低的图案化材料时避免图案崩塌的用途
CN103510100B (zh) * 2013-09-26 2018-12-28 大连三星五洲化工有限公司 金属清洗剂
CN105671581A (zh) * 2016-02-24 2016-06-15 苏州龙腾万里化工科技有限公司 一种高效乳液脱脂剂

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065409A (en) * 1975-08-01 1977-12-27 Corporate Brands, Inc. Hard surface detergent composition
EP0021491A1 (en) * 1979-06-18 1981-01-07 THE PROCTER & GAMBLE COMPANY Detergent containing nonionic/cationic surfactant and builder mixture
US4540505A (en) * 1981-05-22 1985-09-10 American Cyanamid Company Disinfectant spray cleanser containing glycol ethers
US4606850A (en) * 1985-02-28 1986-08-19 A. E. Staley Manufacturing Company Hard surface cleaning composition and cleaning method using same
US5061395A (en) * 1990-01-04 1991-10-29 Ques Industries, Inc. Hard surface cleaning composition
DE4014859A1 (de) * 1990-05-09 1991-11-14 Henkel Kgaa Verwendung einer kombination ionischer und nichtionischer tenside
SE500534C2 (sv) * 1990-11-12 1994-07-11 Eriksson Tord Utveckling Förfarande för rengöring och avfettning
EP0838518B1 (de) * 1992-09-11 2002-11-13 Cognis Deutschland GmbH & Co. KG Detergensgemische

Also Published As

Publication number Publication date
DE69612549D1 (de) 2001-05-23
ES2158286T3 (es) 2001-09-01
CN1175974A (zh) 1998-03-11
AU4789396A (en) 1996-09-11
BR9607341A (pt) 1997-11-25
HUP9801722A2 (hu) 1999-01-28
GB9503594D0 (en) 1995-04-12
CA2211346C (en) 2002-10-08
TR199700840T1 (xx) 1998-02-21
ZA961118B (en) 1997-08-12
DE69612549T2 (de) 2001-08-23
AR001004A1 (es) 1997-08-27
AU719466B2 (en) 2000-05-11
HU226238B1 (en) 2008-07-28
CA2211346A1 (en) 1996-08-29
HUP9801722A3 (en) 1999-03-01
WO1996026257A1 (en) 1996-08-29
IN187431B (es) 2002-04-27
JPH11500478A (ja) 1999-01-12
KR19980702441A (ko) 1998-07-15
EP0811049A1 (en) 1997-12-10
JP3207432B2 (ja) 2001-09-10
IN187275B (es) 2002-03-16

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