EP0479826B1 - Cleaning composition - Google Patents

Cleaning composition Download PDF

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Publication number
EP0479826B1
EP0479826B1 EP90909473A EP90909473A EP0479826B1 EP 0479826 B1 EP0479826 B1 EP 0479826B1 EP 90909473 A EP90909473 A EP 90909473A EP 90909473 A EP90909473 A EP 90909473A EP 0479826 B1 EP0479826 B1 EP 0479826B1
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
composition
solvent
cationic polymer
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
EP90909473A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0479826A1 (en
Inventor
Peter Leonard Dawson
Thomas 39 Brookhurst Avenue Stirling
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
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Filing date
Publication date
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Publication of EP0479826A1 publication Critical patent/EP0479826A1/en
Application granted granted Critical
Publication of EP0479826B1 publication Critical patent/EP0479826B1/en
Anticipated expiration legal-status Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • This invention relates to an aqueous cleaning composition intended to be suitable for use undiluted in cleaning various surfaces notably fixed surfaces exemplified by glass, paintwork, ceramic tiles, vinyl flooring, chromium plate, marble and plastic laminates. It is intended that rinsing should be unnecessary.
  • this invention seeks to provide a product which will give a good finish to the surface being cleaned despite usage at higher levels than necessary and/or incomplete removal. It is intended that no visible residue should remain on the surface which has been cleaned.
  • an aqueous cleaning composition comprising:
  • the total amount of surfactant and any other materials which do not boil below 200°C at atmospheric pressure does not exceed 0.2% by weight based on the whole composition.
  • the said organic solvent is present in an amount which is at least 0.05% better from 0.5 to 10% by weight.
  • compositions of this invention have a very large proportion of constituents which are sufficiently volatile for residues of them to evaporate from the surface.
  • the property of boiling below 200°C at normal atmospheric pressure of 760mmHg is an indicator of adequate volatility.
  • the composition When the composition is applied, say with a cloth, the bulk of the composition and solubilised soil will be removed by the cloth with which it is applied and/or a second cloth used subsequently. Most of the residue left on the surface will evaporate.
  • Polar organic compounds with boiling points over 200°C generally do not have sufficient volatility for this: consequently the level of them is preferably very low, as stated above.
  • any organic solvent is sufficiently water soluble to give a single phase solvent system.
  • a solvent of low water solubility and include sufficient solvent that there is a surplus of organic solvent forming a separate phase. This could be dispersed as an emulsion, or distributed through the product by shaking the container before use.
  • the preferred class of organic solvents are those which have both hydroxyl functionality and an alkyl group which is C1 to C5, preferably C3 to C5 alkyl.
  • the solvent will provide a combination of hydrophilic and hydrophobic functions, so that preferred solvents bring about a lowering of surface tension as well as helping to solubilise oily soils.
  • the C3 to C5 alkyl group may be linked directly to hydroxyl as in the case of aliphatic alcohols or it may be connected through a linking group containing both carbon atoms and an atom other than carbon or hydrogen - usually oxygen.
  • Suitable as organic solvents are those of structural formula: R-X-OH where R is C1 to C5 alkyl and X is a covalent bond or -OCH2CH2- or even -OC2H4OC2H4- or -OC3H6OC3H6- but in all cases subject to the requirement for a boiling point below 200°C.
  • Suitable solvents having a formula as defined above include methanol, ethanol and the various isomers of propanol, butanol and pentanol, 2-propoxyethanol, 2-butoxyethanol, 2-pentoxyethanol, 1-propoxypropan-2-ol and 1-butoxypropan-2-ol.
  • Examples of less water soluble solvents which may be included, giving more than one phase, are paraffins, olefins, terpenes and alkyl benzenes, subject in each instance to the requirement that the boiling point is below 200°C.
  • ammonia or alkanolamine serves to render the composition alkaline, which is beneficial for cleaning performance.
  • Alkanolamines are preferred over ammonia; their hydroxy function serves to enhance water solubility and the amino group contributes to the solubilisation of polar fatty soils.
  • An alkanolamine meeting the requirement for boiling point below 200°C will generally be a monoalkanolamine, whose structural formula is: where R1 is hydroxy alkyl and R and R3 are (independently of each other) either hydrogen or alkyl.
  • the number of carbon atoms in the groups R1, R, R3 is restricted by the requirement that the boiling point is not over 200°C. Generally not more than four carbon atoms will be present in total in the groups R1, R and R3.
  • Monoethanolamine is the preferred compound. Further possibilities include 2-amino 2-methyl propanol, 2-aminopropanol, n-propanolamine, 2-amino 1-butanol, N-methyl ethanolamine and N,N-dimethyl ethanolamine.
  • the amount of alkanolamine may be up to 10% by weight of the composition. Preferably, however, the quantity is not greater than 5%, since quantities in excess of 5% produce little additional benefit in return for the extra cost.
  • the amount of alkanolamine is preferably at least 0.5%.
  • the cationic polymer enhances the ability of the composition to remove particulate soils. Without being limited by our hypothesis as to its mode of action, it is believed that the polymer is able to cause aggregation of particulate soil particles without the disadvantage of causing excessive aggregation and interference with detergency, for example by binding the soil particles to the surface. Presumably then the resulting larger particles are more easily picked up by a cloth being used to wipe the surface being cleaned.
  • a variety of cationic polymers can be used. It is preferred that the molecular weight of the polymer is at least 10,000 better at least 50,000 or even better at least 100,000. It may be a high molecular weight of at least 1 million or even at least 5 million up to 20 million or more at the time of adding the polymer to the composition, although there may be some breakdown in the length of polymer chains in the composition.
  • Cationic polymers generally consist of a polymeric chain which does not have cationic character, bearing cationic substitute groups.
  • Certain cationic polymers can interact with anionic or amphoteric surfactants, reducing the effectiveness of both.
  • anionic surfactant is present, within the limit of 0.5% by weight surfactant, then it is desirable to use a cationic polymer with a hydrophilic polymer chain (e.g. polysaccharide or polyacrylamide) and not more than 50% (molar) cationic substitution on this chain.
  • a hydrophilic polymer chain e.g. polysaccharide or polyacrylamide
  • anionic surfactant is absent, a wide range of cationic polymers can be used, including cationic polymers based on hydrophobic polymer chains such as polyethylene or polymethylene.
  • Cationic polymers which may be used in compositions of this invention include:
  • compositions of this invention to include some detergent active.
  • the quantity of detergent active is restricted to at most 0.5% by weight of the composition, e.g. 0.01 to 0.5%, preferably not over 0.2%, while inorganic electrolyte is substantially absent.
  • Detergent actives which are used may be chosen from the conventional classes, that is to say anionic, nonionic, cationic and amphoteric detergents and mixtures thereof.
  • Anionic detergent actives are preferred for the sake of their good detergency, but as stated above, some cationic polymers cannot be used with anionic detergents, for which reason nonionic detergent active may be preferred.
  • anionic, cationic and amphoteric detergent actives contain an alkyl group of 8 to 22 carbon atoms, or an alkyl aromatic group with 6 to 14 carbon atoms in the alkyl portion, and a charged head group.
  • anionic detergent actives sodium C10 ⁇ 12 alkyl benzene sulphonates and sodium C12 ⁇ 15 synthetic alcohol 3EO sulphates. C10 ⁇ 16 secondary alkane sulphonates are further possibilities.
  • Nonionic detergent actives may be compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Particular examples include the condensation product of aliphatic alcohols having from 8 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 synthetic primary or secondary alcohols having 8 to 15 carbon atoms with 3 to 12 moles of ethylene oxide per mole of the synthetic alcohol; also 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, and condensates of synthetic primary or secondary alcohols having 8 to 15 carbon atoms with 3 to 12 moles of ethylene oxide per mole of the synthetic alcohol
  • alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene
  • nonionic surfactants are 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; also block copolymers of ethylene oxide and propylene oxide.
  • Nonionic detergent actives may be compounds containing a C8 to C22 alkyl group and a polar head group (which may or may not be provided by alkylene oxide residues).
  • Examples are tertiary amine oxides of formula RR1R1NO where the group R is an alkyl group of 8 to 18 carbon atoms and the groups R1 are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; glycosides or polyglycosides etherified with at least one C8-C22 alkyl group or esterified with at least one C8-C22 fatty acyl group; fatty acid alkylolamides; and alkylene oxide condensates of fatty acid alkylolamides.
  • Mixtures of two or more nonionic detergent actives can be employed, as can mixtures of nonionic and anionic detergent actives.
  • the involatile constituents of a composition of this invention will be the detergent active and cationic polymer if these are used, together with part of any perfume if used.
  • An approximate working rule is that half of a conventional perfume will class as involatile. It is very desirable that not more than 0.5% by weight of the composition, preferably not more than 0.2% is provided by such involatiles.
  • compositions of this invention can be prepared by simply mixing their constituents into distilled or deionised water, e.g. in a mixing vessel with a stirrer.
  • the invention is illustrated by the following Examples of compositions (including some comparative Examples outside the invention). All percentages are by weight.
  • the nonionic detergent was C9 to C11 synthetic alcohol ethoxylated with average 5 ethylene oxide residues.
  • the cationic polymers used were: Polymer of Source Approx Mol. wt. Approx Degree Substitution (% molar) Acrylamide Floc Aid 300 National Starch 10m 2 Floc Aid 301 National Starch 10m 7 Floc Aid 371 National Starch 6m 2.5 Cationised Guar Jaguar C-13 Meyhall 2m+ 13 Polydimethyldiallylammonium Merquat 100 Merck 1 ⁇ 2 m 100
  • Example B (comparative - non-volatile solvent)
  • Example C (comparative - inorganic alkaline electrolyte)
  • compositions of the Examples were tested for streaking brought about by components of the composition and for effectiveness in cleaning.
  • Streaking is assessed subjectively on high gloss black-coloured ceramic tiles which have been wiped over with a sponge cloth loaded with a standard amount of formulation. The liquid film is allowed to evaporate before assessment is made. High gloss black tiles are a very discriminating surface for judgement of streaking and product residues.
  • Soiled tiles were prepared by a combination of spraying of soil components from a solvent solution/suspension, followed by rubbing of soil into the surface to obtain an even coverage which cannot be easily wiped off with a dry cloth.
  • the predominantly fatty soil consisted of 5 parts kaolin, 0.2 parts carbon black, 19 parts of glycerol trioleate and 1 part oleic acid. This represents a model for kitchen and bathroom soil.
  • the predominantly particulate soil consisted of 8 parts Illite clay, 0.1 parts carbon black and 2 parts glycerol trioleate; this is a model for the soils found on floors and windows.
  • Example 1 The composition of Example 1, and various analogous compositions with different cationic polymer or none at all, were used to demonstrate the value of the cationic polymer in removal of particulate soil.
  • a 30cm x 30cm glass mirror is thoroughly cleaned and its reflectance is measured.
  • a soil consisting of 8 parts of Illite type clay and 0.1 parts of carbon black in ethanol is sprayed lightly and evenly onto the mirror. Reflectance is measured again.
  • One half of the mirror (15cm x 30cm) is cleaned with experimental composition, the other half with a control window cleaning product. Each half is cleaned by placing 1 ⁇ 2 ml of composition on the soiled surface and wiping 32 times over the area with a dry non-woven viscose cloth (approx. 75 g.s.m.) 12 x 15cm. After allowing 1 minute to dry, the reflectance of the cleaned mirror surface is measured again. Knowing the reflectance of the perfectly clean mirror, the % loss due to initial and residual soil coverage can be calculated. Results are as follows:

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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)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
EP90909473A 1989-06-23 1990-06-22 Cleaning composition Expired - Lifetime EP0479826B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB8914462 1989-06-23
GB898914462A GB8914462D0 (en) 1989-06-23 1989-06-23 Cleaning composition
PCT/GB1990/000964 WO1991000332A1 (en) 1989-06-23 1990-06-22 Cleaning composition

Publications (2)

Publication Number Publication Date
EP0479826A1 EP0479826A1 (en) 1992-04-15
EP0479826B1 true EP0479826B1 (en) 1996-01-17

Family

ID=10658955

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90909473A Expired - Lifetime EP0479826B1 (en) 1989-06-23 1990-06-22 Cleaning composition

Country Status (10)

Country Link
EP (1) EP0479826B1 (es)
JP (1) JPH0689360B2 (es)
AU (1) AU630470B2 (es)
BR (1) BR9007469A (es)
CA (1) CA2019642C (es)
DE (1) DE69024957T2 (es)
ES (1) ES2082859T3 (es)
GB (1) GB8914462D0 (es)
WO (1) WO1991000332A1 (es)
ZA (1) ZA904890B (es)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0467472A3 (en) * 1990-07-16 1993-06-02 Colgate-Palmolive Company Hard surface liquid cleaning composition with anti-soiling polymer
EP0503219A1 (en) * 1991-03-11 1992-09-16 THE PROCTER & GAMBLE COMPANY Method and diluted cleaning composition for the cleaning of hard surfaces
ATE116696T1 (de) * 1992-08-07 1995-01-15 Wack O K Chemie Gmbh Reinigungsmittel.
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
JP2952373B1 (ja) * 1998-09-09 1999-09-27 株式会社 羽野組 建造物の清掃方法
JP2002531633A (ja) * 1998-12-01 2002-09-24 ザ、プロクター、エンド、ギャンブル、カンパニー 使い捨て吸収パッドに使用する、汚れ懸濁剤を含有する洗剤組成物
US6653274B1 (en) 1999-09-27 2003-11-25 The Proctor & Gamble Company Detergent composition comprising a soil entrainment system
JP2002060786A (ja) * 2000-08-23 2002-02-26 Kao Corp 硬質表面用殺菌防汚剤
JP4813833B2 (ja) * 2005-07-06 2011-11-09 株式会社Adeka 化学機械的研磨用洗浄剤組成物および該洗浄剤組成物を用いる洗浄方法
WO2012067962A1 (en) * 2010-11-16 2012-05-24 Dow Global Technologies Llc Hard surface cleaners comprising low voc, low odor alkanolamines

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549546A (en) * 1967-10-02 1970-12-22 Procter & Gamble Process for preparing liquid detergent
US3627687A (en) * 1968-02-09 1971-12-14 Dow Chemical Co Cleaning of ferrous metal surfaces
US4102707A (en) * 1973-09-24 1978-07-25 Betz Laboratories, Inc. Removal of microbiological deposits
GB1528592A (en) * 1974-12-10 1978-10-11 Procter & Gamble Floor care and cleaning composition
DE3671645D1 (de) * 1985-03-06 1990-07-05 Procter & Gamble Fluessiges reinigungsmittel.

Also Published As

Publication number Publication date
CA2019642C (en) 1994-12-27
ZA904890B (en) 1992-02-26
JPH04504278A (ja) 1992-07-30
JPH0689360B2 (ja) 1994-11-09
DE69024957D1 (de) 1996-02-29
EP0479826A1 (en) 1992-04-15
WO1991000332A1 (en) 1991-01-10
AU630470B2 (en) 1992-10-29
BR9007469A (pt) 1992-06-16
AU5840390A (en) 1991-01-17
GB8914462D0 (en) 1989-08-09
ES2082859T3 (es) 1996-04-01
CA2019642A1 (en) 1990-12-23
DE69024957T2 (de) 1996-05-30

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