EP0811049A1 - Composition de nettoyage comprenant des tensioactifs cationiques de dialkyle sature - Google Patents

Composition de nettoyage comprenant des tensioactifs cationiques de dialkyle sature

Info

Publication number
EP0811049A1
EP0811049A1 EP96904036A EP96904036A EP0811049A1 EP 0811049 A1 EP0811049 A1 EP 0811049A1 EP 96904036 A EP96904036 A EP 96904036A EP 96904036 A EP96904036 A EP 96904036A EP 0811049 A1 EP0811049 A1 EP 0811049A1
Authority
EP
European Patent Office
Prior art keywords
surfactant
composition according
alkyl
oor
compositions
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.)
Granted
Application number
EP96904036A
Other languages
German (de)
English (en)
Other versions
EP0811049B1 (fr
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
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0811049A1 publication Critical patent/EP0811049A1/fr
Application granted granted Critical
Publication of EP0811049B1 publication Critical patent/EP0811049B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 surfactan .
  • 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.
  • WO 91/09930 discloses the use 'ETHOQUAT' (TM) on aluminium e.g. metal surfaces such as those found on vehicles.
  • the present invention provides an aqueous, hard-surface cleaning composition
  • a surfactant mixture comprising:
  • a cationic surfactant which is a substantially ethyleneically saturated dialkyl quaternary ammonium compound.
  • the cationic surfactant is of the general formula:
  • the cationic surfactant comprises a cation of the formula given above wherein R 4 and R 5 are independently
  • R x 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 0) X H, or methyl.
  • R : 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 0) ⁇ H (where x is on average 1-2), or methyl
  • m is 2.
  • Further fully saturated dialkyl quaternary ammonium compounds include
  • R. 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* ⁇ is methyl
  • R 2 is -(CH 2 CH 2 0) 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 cationic surfactant the pH can be higher than 7.5.
  • a preferred cationic surfactant is:
  • R 4 and R 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, R 4 and R 5 are fatty acid residues having a chain length distribution corresponding to that of tallow.
  • Another preferred cationic is:
  • 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 a nonionic surfactan .
  • 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.
  • Particular examples include 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; 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; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxy-ethyl groups, for instance dimethyldodecyla ine oxide; tertiary phosphine oxides
  • 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 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.
  • 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, di- butyl 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
  • 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 ⁇ O- (EO) m - (PO) n -R 2 , wherein R x and R 2 are independently C2-6 alkyl or H, but not both hydrogen, m and n are independently 0-5.
  • the solvent is selected from the group comprising di-ethylene glycol mono n-butyl ether, mono- ethylene 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-l-propanol, mono-ethanolamine and di- ethanolamine.
  • 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, :
  • nonionic surfactant preferably, C9-C12 E05-8 nonionic surfactant
  • solvent preferably, diethylene glycol mono-n- butyl ether
  • buffer/alkali preferably, an alkali metal carbonate
  • a cationic surfactant comprises a cation of the general formula:
  • R. 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, said composition being packaged in a container adapted to produce a spray of 0.1- 1.5ml of product per spraying operation, said spray having an average drop size in the range 30-300 microns.
  • 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.COOR 4 -CH2.COOR*-,] * Cl ⁇
  • OOR 4 and OOR 5 are fatty acid residues having a fatty acid chain length corresponding to tallow (manufactured by Hoechst ) .
  • ACCO ACCOSOFT 440/75 ex. Stepan.
  • 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./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 .
  • lOOg dehydrated castor oil (ex. UNICHEMA) was weighed into a glass jar. To this was added 0.2g Fat Red (TM) dye (ex. SIMGA) and the mixture was stirred vigorously (2000 RPM) for 6 hours using a Heidolph stirrer. The stirred mixture was refrigerated when not in use.
  • TM Fat Red
  • SIMGA Fat Red
  • 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.
  • TM fresh damp J-CLOTH
  • TM JIF LAC
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Cosmetics (AREA)

Abstract

La description concerne des compositions améliorées qui à la fois nettoient une surface et sont censées déposer sur celle-ci une couche de tensioactif cationique, lequel aide à l'enlèvement de salissures se déposant par la suite sur cette surface. Ces compositions comprennent un mélange de tensioactifs, lequel mélange comporte: a) au moins 65 % en poids, par rapport au poids total du tensioactif, d'un tensioactif non ionique, b) moins de 1 % en poids, par rapport au poids total du tensioactif, d'un tensioactif anionique, et c) 0,1 à 35 % en poids, par rapport au poids total du tensioactif, d'un tensioactif cationique qui est un composé de dialkyle ammonium quaternaire à saturation éthylénique.
EP96904036A 1995-02-23 1996-02-07 Composition de nettoyage comprenant des tensioactifs cationiques de dialkyle sature Expired - Lifetime EP0811049B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9503594.5A GB9503594D0 (en) 1995-02-23 1995-02-23 Cleaning composition comprising dialkyl cationic surfactants
GB9503594 1995-02-23
PCT/EP1996/000542 WO1996026257A1 (fr) 1995-02-23 1996-02-07 Composition de nettoyage comprenant des tensioactifs cationiques de dialkyle sature

Publications (2)

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

Family

ID=10770102

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96904036A Expired - Lifetime EP0811049B1 (fr) 1995-02-23 1996-02-07 Composition de nettoyage comprenant des tensioactifs cationiques de dialkyle sature

Country Status (16)

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

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5352116B2 (ja) * 2007-04-26 2013-11-27 株式会社 資生堂 水中油型乳化組成物及びその製造方法
SG11201504607QA (en) * 2012-12-14 2015-07-30 Basf Se Use of compositions comprising a surfactant and a hydrophobizer for avoiding anti pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below
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 (fr) * 1979-06-18 1981-01-07 THE PROCTER & GAMBLE COMPANY Composition détergente contenant un mélange non-ionique et cationique d'agents tensioactifs et un mélange d'agents renforçateurs
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 (fr) * 1992-09-11 2002-11-13 Cognis Deutschland GmbH & Co. KG Mélanges de détergents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9626257A1 *

Also Published As

Publication number Publication date
AU719466B2 (en) 2000-05-11
GB9503594D0 (en) 1995-04-12
AU4789396A (en) 1996-09-11
JP3207432B2 (ja) 2001-09-10
HUP9801722A3 (en) 1999-03-01
HU226238B1 (en) 2008-07-28
ZA961118B (en) 1997-08-12
HUP9801722A2 (hu) 1999-01-28
DE69612549T2 (de) 2001-08-23
DE69612549D1 (de) 2001-05-23
CN1175974A (zh) 1998-03-11
AR001004A1 (es) 1997-08-27
KR19980702441A (ko) 1998-07-15
CA2211346A1 (fr) 1996-08-29
IN187431B (fr) 2002-04-27
BR9607341A (pt) 1997-11-25
IN187275B (fr) 2002-03-16
WO1996026257A1 (fr) 1996-08-29
JPH11500478A (ja) 1999-01-12
EP0811049B1 (fr) 2001-04-18
ES2158286T3 (es) 2001-09-01
CA2211346C (fr) 2002-10-08
TR199700840T1 (xx) 1998-02-21

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