EP0636691A2 - Bleichmittelzusammensetzungen - Google Patents

Bleichmittelzusammensetzungen Download PDF

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Publication number
EP0636691A2
EP0636691A2 EP94305449A EP94305449A EP0636691A2 EP 0636691 A2 EP0636691 A2 EP 0636691A2 EP 94305449 A EP94305449 A EP 94305449A EP 94305449 A EP94305449 A EP 94305449A EP 0636691 A2 EP0636691 A2 EP 0636691A2
Authority
EP
European Patent Office
Prior art keywords
composition according
surfactant
hypochlorite
sodium
styrene
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.)
Withdrawn
Application number
EP94305449A
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English (en)
French (fr)
Other versions
EP0636691A3 (de
Inventor
Paul Terrance Kimpton
Robert William Hodgetts
David Paul Salter
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.)
Akzo Nobel NASH Ltd
Ingredion Inc
Original Assignee
National Starch and Chemical Ltd
National Starch and Chemical Corp
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Filing date
Publication date
Application filed by National Starch and Chemical Ltd, National Starch and Chemical Corp filed Critical National Starch and Chemical Ltd
Publication of EP0636691A2 publication Critical patent/EP0636691A2/de
Publication of EP0636691A3 publication Critical patent/EP0636691A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • This invention concerns bleach compositions, particularly thickened aqueous bleach compositions.
  • a bleach composition comprising an active halogen or a peroxy bleach material; surfactant; and polymeric thickener comprising charged, hydrophilic monomer and uncharged, hydrophobic monomer.
  • the charged, hydrophilic monomer is preferably selected from the group: acrylic acid and substituted acrylic acids, eg. methacrylic acid, maleic acid and half-esters thereof, crotonic and itaconic acids and other alkene carboxylic acids and their derivatives, carboxylated styrene, sulphonated styrene, ethylene sulphonic acid, and certain nitrogen-based monomers eg acrylamide, vinyl pyrollidone, and mixtures of such hydrophilic monomers.
  • acrylic acid and substituted acrylic acids eg. methacrylic acid, maleic acid and half-esters thereof, crotonic and itaconic acids and other alkene carboxylic acids and their derivatives, carboxylated styrene, sulphonated styrene, ethylene sulphonic acid, and certain nitrogen-based monomers eg acrylamide, vinyl pyrollidone, and mixtures of such hydrophilic monomers.
  • the uncharged hydrophobic monomer is preferably selected from the group: styrene and substituted styrenes eg. alpha-methyl styrene, alpha-olefins, eg. C12-alpha-olefin, vinyl ethers, eg. butyl vinyl ether; allyl ethers, eg. butyl allyl ether; unsaturated hydrocarbons, eg ethylene, propylene, cyclohexene and dienes, eg. 1,6 hexadiene, divinyl benzene, cyclohexadiene.
  • Such hydrophobic moieties may also be introduced into the polymer by chain transfer agents and initiators, eg.
  • mercaptans eg. dodecyl mercaptans
  • peroxides and azo initiators eg. dilauryl peroxide, AZBN (azoiso butyronitrile).
  • AZBN azoiso butyronitrile
  • a single monomer with both hydrophilic and hydrophobic properties may also be used.
  • the preferred polymer comprises a copolymer of methacrylic acid and styrene, conveniently having proportions (wt %) of methacrylic acid and styrene ranging from 80:20 to 20:80.
  • Additional monomers such as acrylic esters, acrylates, olefins and substituted styrenes, may optionally be included, eg in place of up to about half of the amount of styrene.
  • the polymer is preferably substantially non cross-linked, for reasons that will be explained below, although a degree of cross-linking can be tolerated.
  • the polymer preferably has a molecular weight of about 100,000, although this is not critical and indeed it can be difficult to produce a polymer having an accurately specified molecular weight. Molecular weights in the range 80,000 to 120,000 are thus regarded as about 100,000. If the molecular weight is substantially lower, then this has a deleterious effect on thickening properties of the polymer. Further, if the molecular weight of the polymer is too high, then clarity and stability of the composition can be adversely affected.
  • One particularly preferred polymer comprises 54 wt% methacrylic acid and 46% styrene, with a molecular weight of about 100,000 and substantially no cross-linking. Such a polymer is found to be hypochlorite-stable and to be an effective thickener in hypochlorite bleach.
  • Such polymers can be readily made in conventional manner, eg by emulsion polymerisation.
  • the polymer is present in an appropriate amount to achieve thickening to a desired degree, and is typically present in an amount from 0.1 to 7.5% by wt as active material, preferably 0.5 to 3% by wt as active material.
  • Suitable amounts for any particular composition can be readily determined by experiment, depending on bleach concentration, target viscosity and other considerations. In general, the greater the concentration of bleach material, the greater the amount of polymer (and also surfactant) required to achieve a given viscosity.
  • the bleach material may comprise one or more peroxy compounds, as are well known in the art, including peracids and salts thereof, and hydrogen peroxide and derivatives thereof.
  • the bleach material comprises one or more halogen compounds, as are also well known in the art, including alkali metal and alkaline earth salts of hypohalite, haloamines, haloimines, haloimides and haloamides.
  • Hypochlorite and compounds producing hypochlorite in aqueous solution are preferred. Particuarly preferred is sodium hypochlorite, NaOCl, typically in an amount ranging from 0.2 to 15% by weight, more preferably 0.2 to 10% by weight, and typically providing an amount of available of chlorine in the range 1 to 5% by wt.
  • the surfactant has a cleaning function, and it is possible to use a single surfactant or a mixture of surfactants selected from a wide range, including the following: alkyl ether sulphates, eg. lauryl ether sulphate, such as those sold under the Trade Names Empicol ESB3 (Na salt with 2 ethylene oxide (EO) units), Empicol MD, (Na salt, 4E0), Empimin KSN and Perlankrol ESD (both Na salt, 3 EO), alcohol sulphates, eg lauryl alcohol sulphate, such as those sold under the Trade Names Empicol LZV and Empicol LX28, tallow alcohol sulphates, such as those sold under the Trade Name Empicol TAS30, alkyl benzene sulphonates, eg that sold under the Trade Name Nansa SL30, paraffin sulphonates, eg that sold under the Trade Name Lutensit A-PS, alkyl phenol
  • Olin CS1 alkyl polyglucosides, eg. those sold under the Trade Name Plantaren, EP/PO block copolymers, eg those sold under the Trade Plurafac, Triton, and Monolan PC, alkyl diphenyloxide sulphonates eg.
  • fatty acid amides eg those sold under the Trade Names Empilan CME/CDE, acyl sarcosinates, alkyl taurides, sulphosuccinates, eg that sold under the Trade Name Empimin OT, alpha-olefin sulphonates, phosphate esters (alkyl and/or aryl), eg those sold under the Trade Name Phospholan, ethoxyated fatty acids, triethanolamine lauryl sulphate, eg that sold under the Trade Name Empicol TL40, triethanolamine alkyl benzene sulphonate, eg that sold under the Trade Name Nansa TS50, sodium alpha olefin sulphonate, eg that sold under the Trade Name Nansa LSS38.
  • fatty acid amides eg those sold under the Trade Names Empilan CME/CDE
  • acyl sarcosinates alkyl taurides
  • Suitable mixtures of surfactants are generally found to give good results.
  • composition is preferably substantially free of nonionic surfactant and nitrogen-based surfactant.
  • lauryl ether sulphates eg those sold under the Trade Names Empicol ESB3 (lauryl ether sulphate, Na salt, with 2 ethylene oxide units (2EO)), and Empicol MD (lauryl ether sulphate, Na salt, with 4 EO).
  • Empicol ESB3 lauryl ether sulphate, Na salt, with 2 ethylene oxide units (2EO)
  • Empicol MD lauryl ether sulphate, Na salt, with 4 EO.
  • a mixture of these two surfactants eg in wt proportions of active matter of MD: ESB3 of 2:1, is found to give particularly good results in a hypochlorite bleach composition.
  • Surfactant is conveniently present in an amount in the range 0.5 to 5% by wt active matter, typically about 2% to 3% by wt active matter.
  • compositions in accordance with the invention including polymeric thickener, thickening of hypochlorite bleach can be obtained with less surfactant (typically 2-3% by wt active matter) than is possible in the absence of polymer. It is thought the polymer acts as a hydrotrope, and thickening arises due to the interaction of the polymer with surfactant rod micelles and not solely from the swelling of the polymer. As a result of these interactions, marked increases in viscosity can be obtained. Compositions in accordance with the invention can thus be more cost-effective than conventional compositions.
  • a high bleach composition typically containing about 3-6% by wt active hypochlorite
  • active hypochlorite such as a toilet or drain cleaner
  • one or more relatively soluble surfactants i.e. a surfactant for which a 10% solution in water has a cloud point below about 0°C, preferably below -3°C. If a surfactant of lower solubility is used, the surfactant will generally salt out and so not be appropriate.
  • Suitable relatively soluble surfactants include sodium lauryl ether sulphate (SLES) eg Empimin KSN or Perlankrol ESD, triethanolamine lauryl sulphate, eg Empicol TL40, and triethanolamine alkyl benzene sulphonate, e.g. Nansa TS50.
  • SLES sodium lauryl ether sulphate
  • triethanolamine lauryl sulphate eg Empicol TL40
  • triethanolamine alkyl benzene sulphonate e.g. Nansa TS50.
  • a low bleach composition typically containing up to 3% by wt active hypochlorite
  • a mixture of relatively soluble surfactant as defined above
  • relatively insoluble surfactant i.e. a surfactant for which a 10% solution in water has a cloud point above 0°C.
  • Such relatively insoluble surfactants do not have a tendency to form hexagonal liquid crystal structures: instead these surfactants form lamellar liquid crystal structures at higher concentrations in water or hydrated crystalline structures.
  • Suitable relatively insoluble surfactants include sodium alkylbenzene sulphonate (LABS), e.g. Nansa SL30, sodium lauryl sulphate, e.g. Empicol LX28 and sodium alpha olefin sulphonate, e.g. Nansa LSS38.
  • LABS sodium alkylbenzene sulphonate
  • Nansa SL30 sodium lauryl sulphate
  • Empicol LX28 e.g. Empicol LX28
  • sodium alpha olefin sulphonate e.g. Nansa LSS38.
  • the viscosity of such low bleach compositions can be controlled by varying the proportions and/or amount of relatively soluble surfactant and relatively insoluble surfactant.
  • Bleach products containing less than 3.0% active sodium hypochlorite have hitherto been particularly difficult to thicken with surfactants and mixtures of surfactants. This is due to insufficient electrolyte being present to bring about the necessary reductions in surfactant solubility. As surfactant solubility decreases rod micelles form and through tangling increase the solution viscosity. Increases in electrolyte level through additions of sodium chloride merely catalyze the decomposition of the sodium hypochlorite, and hence cannot be made. The present invention can thus overcome such difficulties.
  • the polymer thus acts to enhance thickening and enables use of surfactants (and mixtures thereof) not previously possible.
  • a wider range of surfactants is thus available for use in compositions in accordance with the invention so surfactants can be selected for cleaning properties and cost effectiveness.
  • the composition may optionally include electrolyte.
  • electrolyte Low levels of electrolytes such as sodium chloride function to provide ions in aqueous solution and have been shown to improve solution viscosity.
  • Sodium chloride is generally present in sodium hypochlorite as available commercially, or may be added to the composition in appropriate amounts such that the stability of the sodium hypochlorite will not be adversely affected.
  • composition may also optionally include buffer, to maintain pH.
  • buffer typically between 11 and 14, eg about 13, are generally appropriate to achieve desired viscosity and stability.
  • Some reagents function both as electrolyte and buffer.
  • ingredients such as fragrance, colouring agents, whiteners, solvents and builders may be included for aesthetic reason or to improve properties.
  • compositions in accordance with the invention comprise hypochlorite bleach, the preferred methacrylic acid/styrene polymer discussed above (having 54% methacrylic acid and 46% styrene, a molecular weight of about 100,000 and being substantially non-cross linked), and surfactant.
  • the surfactant comprises sodium lauryl ether sulphate (SLES) .
  • the surfactant comprises a mixture of sodium alkylbenzene sulphonate (LABS) and sodium lauryl ether sulphate (SLES).
  • Non cross-linked polymers are found to give compositions with better clarity than those using cross-linked polymer, particularly if perfume (which is generally an oil) is present in the composition.
  • hypochlorite bleach containing both polymer and surfactant is found to have substantially improved characteristics of viscosity and clarity as compared with hypochlorite containing only polymer or only surfactant.
  • This effect is not fully understood, but is much more marked with substantially non cross-linked polymer, and it is thought that the polymer interacts with the surfactant micelles in some way, as discussed above.
  • compositions in accordance with the invention in preferred embodiments at least, have certain advantages over similar prior art compositions, including the following:
  • compositions of the invention find particular, but not exclusive, application in hard surface cleaning, eg of bathroom and kitchen surfaces.
  • Polymer A A substantially non-cross linked polymer (referred to as Polymer A) of methacrylic acid (54% wt) and styrene (46% wt) with a molecular weight of about 100,000 (characterised by GPC compared with polyacrylate standards) was made on a pilot scale by conventional emulsion polymerisation techniques.
  • the materials used were as follows:
  • the initial charge of deionised water and surfactants were added to a 15 litre stainless steel reactor fitted with a lid which has inlet ports for an agitator, water condenser and for the addition of monomer and initiator solutions.
  • the contents of the reactor were heated to 80°C under nitrogen.
  • the resulting product was an aqueous dispersion of methacrylic acid/styrene copolymer, with the following typical properties.
  • Example 2 Behaviour of Polymer A in 5% Sodium Hypochlorite
  • polymer B a crosslinked version of polymer A (known as polymer B) was prepared by a similar process to that used to prepare polymer A.
  • Example 4 Thickened bleach composition using polymer A
  • a thickened 5% hypochlorite formulation was made by mixing the following ingredients: Component Use Level (%) (% w/w active matter) Empicol MD (30% active) 2 Empicol ESB3 (27.5% active) 1 Polymer A (31% active) 1.74 Sodium hypochlorite (14% active) 5 Fragrance 0.3% Water 100% pH was adjusted to 13 with 4% caustic.
  • the resulting composition had a clear aspect and a viscosity (Brookfield) 3/20 rpm of 275 mPas. and is suitable for use eg as a domestic multi-surface cleaning product.
  • compositions comprising polymer A, sodium hypochlorite and various surfactants, and from the information obtained suitable formulations for a hard surface cleaner and a lavatory cleaner with bleach were obtained.
  • Formulations containing polymer A were made using the following addition order of ingredients. The polymer was first dispersed in deionised water before caustic solution was added. When fully neutralised to pH13, the relatively soluble surfactants were added with gentle stirring followed by addition of the cosurfactant, fragrance and dye. Lastly, sodium hypochlorite solution was added dropwise and the formulation stirred for a further 10 to 15 minutes before a measurement of initial viscosity was made on a Haake viscometer.
  • Table 1 Hypochlorite Formulations containing mixtures of soluble surfactants INGREDIENTS %W/W ACTIVE Polymer A 0.5 0.5 Sodium Laurylether Sulphate (Perlankrol ESD) 2.0 1.3 Amine Oxide 0.5 1.3 Sodium Hypochlorite 2.0 2.0 Sodium Hydroxide 0.7 0.7 Viscosity AT 106s ⁇ 1 460 mPas 220 mPas
  • FIG. 4 is a plot of viscosity versus total surfactant for this system.
  • FORMULATION A Hard Surface Cleaner INGREDIENT % W/W ACTIVE Polymer A 0.5% LABS 0.5% Sodium Lauryl Ether Sulphate 2.0% Sodium Hydroxide 0.7% Fragrance qs Dye qs Sodium Hypochlorite 2.0%
  • Formulation A has an initial viscosity of 800 mPas, at a shear rate of 106s ⁇ 1.
  • the formulation has good long term storage stability and resistance to phase separation over three freeze/thaw cycles. Results of viscosity measurements with time on various samples made without fragrance or dye are shown in Figure 5, providing an indication of stability with time.
  • a model soil comprising of 100g olive oil, 10g instant coffee and 10g of carbon black was applied in thin films to 3 clean, dry ceramic tiles and the soiled tiles conditioned in an incubator for 2 days at 40°C.
  • a 1g aliquot of one of the formulations or a commercial product was pipetted onto the centre of a tile and after 2 minutes, an estimte of the area over which the liquid had spread was made. The wetted area was then rubbed with a small brush with light pressure. The amount of soil removed was assessed visually by estimating the area of tile exposed by rubbing.
  • FORMULATION B Lavatory Cleaner with Bleach INGREDIENT %W/W ACTIVE Polyer A 0.5% LABS 0.4% Sodium Lauryl Ether Sulphate 1.7% Sodium Hydroxide 0.7% Fragrance qs Dye qs Sodium Hypochlorite 2.0%
  • Formulation B has an initial viscosity of 300 mPas at a shear rate of 106s ⁇ 1!
  • a thickened formulation containing 5.0% active sodium hypochlorite can be made as follows: FORMULATION C: Premium thickened Bleach Product INGREDIENT %W/W ACTIVE Polymer A 1.0% Sodium Laurylether Sulphate 3.0% Sodium Hydroxide 0.7% Fragrance qs Dye qs Sodium Hypochlorite 5.0% Viscosity 130 mPas at shear rate of 106s ⁇ 1
  • the viscosity of the formulation depends to a large extent on the dissolved electrolyte and is less dependent on the amount of polymer A.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP94305449A 1993-07-30 1994-07-22 Bleichmittelzusammensetzungen. Withdrawn EP0636691A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9315760 1993-07-30
GB939315760A GB9315760D0 (en) 1993-07-30 1993-07-30 Bleach compositions

Publications (2)

Publication Number Publication Date
EP0636691A2 true EP0636691A2 (de) 1995-02-01
EP0636691A3 EP0636691A3 (de) 1996-05-01

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997045520A1 (de) * 1996-05-24 1997-12-04 Henkel Kommanditgesellschaft Auf Aktien Wässrige bleich- und desinfektionsmittel
GB2346891A (en) * 1999-02-03 2000-08-23 Mcbride Robert Ltd Cleaning composition
US6187221B1 (en) 1999-05-12 2001-02-13 National Starch And Chemical Investment Holding Corporation Controlled release bleach thickening composition having enhanced viscosity stability at elevated temperatures
US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0244006A1 (de) * 1986-04-22 1987-11-04 Unilever N.V. Allzweck-Reinigerzusammensetzung
EP0256638A1 (de) * 1986-08-07 1988-02-24 The Clorox Company Verdickte Hypochlorit-Zusammensetzung und ihre Verwendung
EP0329419A2 (de) * 1988-02-17 1989-08-23 Unilever Plc Reinigungsmittel enthaltende vernetzte, polymere Verdickungsmittel und Hypochloritbleiche
EP0346995A2 (de) * 1988-06-13 1989-12-20 Unilever N.V. Flüssige Reinigungsmittel
EP0385522A2 (de) * 1989-02-27 1990-09-05 Unilever N.V. Flüssiges Reinigungsmittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0244006A1 (de) * 1986-04-22 1987-11-04 Unilever N.V. Allzweck-Reinigerzusammensetzung
EP0256638A1 (de) * 1986-08-07 1988-02-24 The Clorox Company Verdickte Hypochlorit-Zusammensetzung und ihre Verwendung
EP0329419A2 (de) * 1988-02-17 1989-08-23 Unilever Plc Reinigungsmittel enthaltende vernetzte, polymere Verdickungsmittel und Hypochloritbleiche
EP0346995A2 (de) * 1988-06-13 1989-12-20 Unilever N.V. Flüssige Reinigungsmittel
EP0385522A2 (de) * 1989-02-27 1990-09-05 Unilever N.V. Flüssiges Reinigungsmittel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997045520A1 (de) * 1996-05-24 1997-12-04 Henkel Kommanditgesellschaft Auf Aktien Wässrige bleich- und desinfektionsmittel
GB2346891A (en) * 1999-02-03 2000-08-23 Mcbride Robert Ltd Cleaning composition
US6187221B1 (en) 1999-05-12 2001-02-13 National Starch And Chemical Investment Holding Corporation Controlled release bleach thickening composition having enhanced viscosity stability at elevated temperatures
US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system

Also Published As

Publication number Publication date
GB9315760D0 (en) 1993-09-15
EP0636691A3 (de) 1996-05-01

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