EP0636687A2 - Perfectionnements apportés aux hydrotropes - Google Patents

Perfectionnements apportés aux hydrotropes Download PDF

Info

Publication number
EP0636687A2
EP0636687A2 EP94305448A EP94305448A EP0636687A2 EP 0636687 A2 EP0636687 A2 EP 0636687A2 EP 94305448 A EP94305448 A EP 94305448A EP 94305448 A EP94305448 A EP 94305448A EP 0636687 A2 EP0636687 A2 EP 0636687A2
Authority
EP
European Patent Office
Prior art keywords
composition according
alkyl
polymer
styrene
surfactant
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Withdrawn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
EP94305448A
Other languages
German (de)
English (en)
Other versions
EP0636687A3 (fr
Inventor
Paul Terrance Kimpton
Philip Ashley Lagar
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
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 National Starch and Chemical Ltd, National Starch and Chemical Corp filed Critical National Starch and Chemical Ltd
Publication of EP0636687A2 publication Critical patent/EP0636687A2/fr
Publication of EP0636687A3 publication Critical patent/EP0636687A3/fr
Withdrawn legal-status Critical Current

Links

Images

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
    • 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

Definitions

  • This invention concerns hydrotropes (or hydrotropic agents), ie substances which will solubilise a surfactant in an aqueous solution of an electrolyte without significantly altering the surface active properties of the surfactant, and relates to a novel class of hydrotropes and their use in aqueous compositions, particularly cleaning compositions.
  • liquid cleaning products contain electrolytes (such as phosphates, silicates, hypochlorites etc), and also surfactants, which are typically included for their detergency and wetting properties.
  • electrolytes such as phosphates, silicates, hypochlorites etc
  • surfactants which are typically included for their detergency and wetting properties.
  • Many surfactants are insoluble in the electrolytes at the concentrations used, and hydrotropes are employed to assist in the formulation and stabilisation of many liquid cleaning products.
  • hydrotropes are currently used in products such as liquid detergents, multi-surface cleaners, automatic and manual dishwashing detergents, and all-purpose cleaning products.
  • Hydrotropes are generally low molecular weight compounds, often with an amphiphilic character, having both hydrophilic and hydrophobic functional groups.
  • Examples of materials currently used as hydrotropes include sodium xylene sulphonate (SXS or NXS), phosphate esters and alkyl polyglycosides.
  • the present invention is based on the discovery that certain polymers can function as hydrotropes.
  • an aqueous composition comprising electrolyte, surfactant and polymeric hydrotrope.
  • the polymer may be a homopolymer or a copolymer, and preferably comprises hydrophilic and hydrophobic monomers.
  • the hydrophilic monomer is preferably selected from 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 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.
  • 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
  • hydrophobic moieties may also be introduced into the polymer by chain transfer agents and initiators, eg. mercaptans, eg dodecyl mercaptans, and peroxides and azo initiators, eg. dilauryl peroxide, AZBN (azoiso butyronitrile). Mixtures hydrophobic monomers may also be used.
  • chain transfer agents and initiators eg. mercaptans, eg dodecyl mercaptans, and peroxides and azo initiators, eg. dilauryl peroxide, AZBN (azoiso butyronitrile).
  • a single monomer with both hydrophilic and hydrophobic properties may also be used.
  • the polymer preferably has the following formula: where E is a hydrophilic functional group; R is H or a lower (C1-C10) alkyl group or is a hydrophilic functional group; R1 is H a lower alkyl group or an aromatic group; R2 is H or a cyclic, alkyl or aromatic group.
  • One preferred polymer comprises acrylic acid and styrene, possibly with minor amounts of dodecylmercaptan (DDM).
  • Acrylic acid is preferably present in an amount in the range 50-80% by wt
  • the styrene is preferably present in an amount in the range 20-50% by weight
  • DDM is preferably present in an amount up to about 1% by weight, eg 0.1 - 1% by weight.
  • a particularly preferred polymer comprises 50.81 wt% acrylic acid, 48.93 wt% styrene, 0.26 wt% DDM, with a molecular weight of about 1,000 and substantially no cross-linking. This polymer is found to be very versatile and to have a wide range of uses and applications.
  • Another 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.
  • the polymer is preferably substantially non cross-linked, although a degree of cross-linking can be tolerated.
  • the polymer typically has a molecular weight of between about 1000 and 1,000,000.
  • polymers with molecular weights at the bottom end of the range are preferred, as these generally make better hydrotropes.
  • a polymer with a molecular weight of about 1000 is found to be very versatile and useful in a wide range of applications.
  • Polymers with higher molecular weights, eg about 100,000, also function well as hydrotropes and may additionally perform a thickening function which may be desirable in certain applications, eg production of thickened bleach compositions.
  • Suitable polymers can be readily made in conventional manner, eg by emulsion or solution polymerisation, and are preferably in the form of low viscosity aqueous solutions or powders.
  • Suitable polymers are also commercially available, eg acrylic acid/styrene copolymers such as those sold under the Trade Name Joncryl, ethylene/acrylic acid copolymers such as those sold under the Trade Name Primacore, polystyrene sulphonate homopolymers such as those sold under the Trade Name Versa, eg Versa TL502, methacrylic acid/ethyl acrylate copolymers such as those sold under the Trade Name Alcogum, eg Alcogum L11, and various predominantly acrylic acid/ester copolymers such as those sold under the Trade Names Acrysol ICS1, Rheovis CRX and Viscalex HV30.
  • acrylic acid/styrene copolymers such as those sold under the Trade Name Joncryl
  • ethylene/acrylic acid copolymers such as those sold under the Trade Name Primacore
  • polystyrene sulphonate homopolymers such as those sold under the Trade Name Versa, eg Vers
  • the polymer is present in an appropriate amount to achieve desired results, such as particular desired composition properties, and suitable amounts can be readily determined by experiment. Typically amounts in the range 0.1 to 15% by wt as active material are suitable, preferably 0.5 to 10% by wt.
  • Formulations to which the hydrotrope may be added may contain 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, 4EO), 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 ether sulph
  • alkyl diphenyloxide sulphonate eg. that sold under the Trade Name Dowfax 3B2
  • 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 al
  • Suitable mixtures of surfactants are generally found to give good results.
  • Surfactant is conveniently present in an amount in the range 0.5 to 80% by wt active matter, typically about 3% by wt active matter.
  • the electrolyte may comprise one or more of a wide range of materials, including salts of complex phosphates, silicates, hypochlorites, carbonates, hydroxides, organic and mineral acids, and sequestrants such as ethylenediaminetetracetic acid and sodium nitrilotriacetate.
  • Electrolyte is typically present in an amount in the range 1 to 30% by wt as active material.
  • composition may include optional ingredients such as, buffer, fragrance, colouring agents, whiteners, solvents and builders, to improve the physical properties of the product of its performance during use or for aesthetic reasons.
  • optional ingredients such as, buffer, fragrance, colouring agents, whiteners, solvents and builders, to improve the physical properties of the product of its performance during use or for aesthetic reasons.
  • Suitable proportions of all ingredients may be readily determined by experiment for any particular formulation.
  • the invention can provide substantially clear, stable, homogenous, isotropic, solutions, that are desirably stable over a range of temperatures, eg -5 to 50°C.
  • hydrophobic groups of the polymer are, according to their hydrophobicity, incorporated into either the region between the surfactant headgroups in a micelle (commonly called the palisade layer), or into the lipophilic interior of the micelles. Replusions between anionic groups in the highly charged polymer backbone decrease the extent to which surfactant molecules can pack into energetically favourable conformations to give liquid crystalline phases. Polymeric hydrotropes therefore act as efficient solubilizers for such surfactants.
  • polymeric hydrotropes in preferred embodiments of the invention at least, can have certain advantages compared with use of conventional hydroptropes, including the following:
  • polyacrylic acid copolymers are known to be good dispersants, scale inhibitors and crystal modifiers and show favourable toxicology.
  • polymeric hydrotrope may act to increase the rate of dissolution of surfactant in water: this is a useful property in detergents.
  • the hydrotrope can also act as a dispersant and an emulsifier, and can reduce soil redeposition, a useful property in laundry products (liquids and powders).
  • compositions in accordance with the invention can be embodied as a wide range of household, institutional and industrial cleaning products, particularly fabric and hard surface cleaning products, such as heavy and light duty liquid detergents, fabric washing detergents, automatic and manual dishwashing detergents, caustic oven cleaners (where the hydrotrope acts to solubilise surfactant and thicken), thickened bleach compositions (with the hydrotrope performing a thickening function), toilet cleaners, multi-surface cleaners etc.
  • fabric and hard surface cleaning products such as heavy and light duty liquid detergents, fabric washing detergents, automatic and manual dishwashing detergents, caustic oven cleaners (where the hydrotrope acts to solubilise surfactant and thicken), thickened bleach compositions (with the hydrotrope performing a thickening function), toilet cleaners, multi-surface cleaners etc.
  • a substantially non cross-linked polymer (referred to as polymer 1) of acrylic acid (50.81% wt), styrene (48.93% wt) and DDM (0.26% wt) with a molecular weight of about 1,000 (characterised by GPC compared with polyacrylate standards) was made on a pilot scale by convention solution polymerisation techniques.
  • the materials used are as follows:
  • the initial charge of deionised water and isopropyl alcohol was 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 reactor contents were heated to reflux (approximately 86°C).
  • the alcohol cosolvent was removed from the polymer solution by azeotropic distillation under vacuum. During the distillation deionised water was added to the reactor to maintain reasonable polymer viscosity.
  • the polymer solution was cooled to less than 60°C and a solution of a base, such as sodium hydroxide solution, was added maintaining the reactor temperature below 60°C to yield a polymer solution having a final pH of approximately 7.
  • a base such as sodium hydroxide solution
  • the resulting product was an aqueous solution of acrylic acid/styrene/DDM co-polymer with the following typical properties:
  • hydrotrope There are several tests described in the prior art to determine the efficiency of a hydrotrope.
  • One such test that indicates if a chemical can peform as hydrotrope is to establish whether the material will raise the "inverse cloud point" of an aqueous solution of a nonionic surfactant such as an alcohol ethoxylate.
  • Figure 1 illustrates the effects of some common hydrotropes and other materials on the inverse cloud point of Ethylan CD916. This figure includes data for various controls (shown in solid bars), various known hydrotropes (shown in dotted bars) and also polymer 1 (shown in a hatched bar).
  • Figure 2 includes results for controls (shown in solid bars), commercially available hydrotropes (hatched bars) and polymer 1 (dotted bar).
  • Figure 2 shows that the performance of polymer 1 is comparable to that of certain selected commerically available hydrotropes and that it assists in solubilising the surfactant at lower temperatures. Hydrotropes tend to decrease the cloud point of this class of surfactants.
  • Dobanol 91-6 is an alcohol ethoxylate (C9 ⁇ 11/6EO) which is chemically very similar to Ethylan CD916.
  • a 100g aliquot of the caustic mixture under test was weighed into a 250ml sample bottle and placed under stir on a magnetic stirrer plate. The mass of the bottle and aliquot was also recorded. The hydrotrope mixture was then placed in a burette and the caustic mixture titrated against the hydrotrope mixture until the solution became clear; this point was deemed the end point. The mass of the sample bottle and contents was then recorded and thus the amount of hydrotrope and final caustic level calculated. A plot of percent NaOH on the ordinate against percent hydrotrope on the abscissa was produced in order to determine the hydrotropic performance of the test sample.
  • polymer 1 exhibits improved efficiencies at solubilizing an alcohol ethoxylate in caustic soda solutions of 1 - 12% w/w caustic compared with the phosphate ester hydrotrope.
  • the polymer shows improved efficiency (ie lower dose level of hydroptrope) up to and above 15% w/w active caustic soda.
  • Polymer 1 thus functions effectively as a hydrotrope, and of the three materials tested in the Example, it is the best performer at NaOH concentrations below about 12%.
  • Polymer 1 is thus an effective hydrotope and can be used in a range of cleaning formulations.
  • Examples of typical formulations are as follows:
  • a substantially non-cross linked polymer (referred to as polymer 2) of methacrylic acid (54% wt) and styrene (46% wt) with a molecular weight of about 100,000 (characterised by GPC compared with polyacrylic standards) was made by conventional emulsion polymerisation techniques.
  • This polymer also functions as a hydrotrope and is also found to be hypochlorite-stable and so to be useful in thickening hypochlorite bleach compositions.
  • Example 5 Behavour of polymer 2 in 5% Sodium Hypochlorite
  • Example 6 Thickened bleach composition using polymer 2
  • a thickened 5% hypochlorite formulation was made by mixing the following ingredients: Component Use Level (%) Empicol MD (30% active) 2 Empicol ESB3 (27.5% active) 1 Polymer 2 (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.
  • the surfactant Synperonic A7 forms two types of liquid crystal phase on dilution with water. Between about 70 and about 50% w/w surfactant in water, a lamellar liquid crystalline system is formed. However, between 50 and 40% w/w in water, the surfactant forms an immobile gel, called the hexagonal phase. It is the formation of the latter around droplets of neat surfactant in water which retards the dissolution. Commercially available hydrotropes are able to break up or prevent the liquid crystalline phases from forming.
  • the surfactant A3 forms only lamellar liquid crystalline structures and is not truly soluble in water. Again, commercial surfactant-based hydrotropes are particularly efficient at disrupting the molecular packing in lamellar phases.
  • the detergent had the following composition: 25% Zeolite 4A (ex Degussa) 4% Na silicate 2.4:1 10% Soda ash 9% Na LABS 1% Neodol 25-9 q.s. Sodium sulphate Polymer 1 as indicated
  • Neodol 25-9 is a C12-C15 synthetic alcohol ethoxylated with 9 moles of ethylene oxide, available from Shell Chemicals and also known under the Trade Name Dobanol.
  • Polymer 1 thus shows some activity as an antiredeposition agent against a polar clay soil, although no such effect was observed in similar tests using non-polar soils.
  • a red iron oxide pigment with a high dispersant demand was used to illustrate the dispersant action of polymer 1 compared to sodium xylene sulphonate.
  • 350g of pigment were slurried into 300g of deionized water at pH6.
  • An aliquot of polymer 1 or sodium xylene sulphonate was added to the slurry and the slurry high-shear mixed at 2000rpm for 15 minutes. After a two minute period, the viscosity of the slurry was measured on a Brookfield RVT viscometer using spindle 4 at 100rpm.
  • a further aliquot of polymer solution or sodium xylene sulphonate was then added and the slurry mixed at high shear for a further 10 minutes. The viscosity of the slurry was measured and the addition of polymer or sodium xylene sulphonate followed by mixing was repeated until the viscosity of the slurry started to rise.
  • Results are shown in Figure 5.
  • the excellent dispersant action of polymer 1 is evident from the dispersant demand curve.
  • the minimum in the curve for the slurry dispersed with polymer 1 occurs at a low dose and at a low viscosity.
  • the sodium xylene sulphonate did not disperse the iron oxide and a highly viscous paste was formed.
  • the performance of polymer 1 is comparable to that of commercially used dispersants such as homopolymers of acrylic acid, eg Narlex LD31.
  • polymer 1 The ability of polymer 1 to emulsify oils of various hydrophobicity was determined by conducting experiments using two water-insoluble fragrances, a general all-pupose household product fragrance and a skin-care fragrance.
  • a 1g portion of one fragrance was dispersed into deionized water using high shear mixing such that the level of fragrance dispersed was 0.5% by weight.
  • the dispersion was stabilized with either 1,2,3 or 4% by weight of active polymer 1.
  • Polymer 1 was made by an alternative route to the aqueous synthesis of Example 1, involving instead synthesis in non-ionic surfactant.
  • the resulting polymer can be used in non-aqueous systems, where its effect on dissolution rate of surfactants may be useful.
  • the surfactant is charged to the reactor and is heated to the reaction temperature, 80-90°C. At this temperature the surfactant should be liquid.
  • the reaction temperature concurrent feeds of monomer and initiator are added over 3 and 3.5 hours respectively.
  • the batch is held at the reaction temperature for 1 hour to finish polymerising any unreacted monomer.
  • the batch is cooled to less than 30°C and transferred to storage.

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)
EP94305448A 1993-07-30 1994-07-22 Perfectionnements apportés aux hydrotropes. Withdrawn EP0636687A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB939315854A GB9315854D0 (en) 1993-07-30 1993-07-30 Improvements in or relating to hydrotropes
GB9315854 1993-07-30

Publications (2)

Publication Number Publication Date
EP0636687A2 true EP0636687A2 (fr) 1995-02-01
EP0636687A3 EP0636687A3 (fr) 1996-05-01

Family

ID=10739739

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94305448A Withdrawn EP0636687A3 (fr) 1993-07-30 1994-07-22 Perfectionnements apportés aux hydrotropes.

Country Status (2)

Country Link
EP (1) EP0636687A3 (fr)
GB (1) GB9315854D0 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0697422A1 (fr) 1994-07-22 1996-02-21 National Starch and Chemical Investment Holding Corporation Améliorations dans ou en relation à des polymères
EP0967266A1 (fr) * 1998-06-26 1999-12-29 National Starch and Chemical Investment Holding Corporation Détergent liquide isotrope
US6281178B1 (en) 1996-02-14 2001-08-28 Stepan Company Reduced residue hard surface cleaner comprising hydrotrope
WO2003060054A3 (fr) * 2002-01-15 2004-01-08 Nat Starch Chem Invest Liant pour substrats a faible teneur en formaldehyde et hydroresitance elevee
EP0797656B2 (fr) † 1994-12-13 2004-03-17 Unilever N.V. Composition detergente
WO2005044967A3 (fr) * 2003-10-30 2005-08-11 Procter & Gamble Compositions servant a nettoyer et a renforcer la brillance des sols
EP1659168A1 (fr) * 2004-11-23 2006-05-24 National Starch and Chemical Investment Holding Corporation Composition de tensio-actif contenant un copolymère amphiphilique
US7183250B2 (en) 2003-06-17 2007-02-27 National Starch And Chemical Investment Holding Corporation Surfactant composition containing hydrophobically modified polymer
WO2007042450A1 (fr) * 2005-10-14 2007-04-19 Basf Se Procede pour stabiliser des compositions liquides d'agents lavants et compositions liquides d'agents lavants
CN109661555A (zh) * 2016-07-28 2019-04-19 霍尼韦尔国际公司 推进剂和自我保护组合物
US11603508B2 (en) 2018-10-26 2023-03-14 Ecolab Usa Inc. Synergistic surfactant package for cleaning of food and oily soils
WO2024088520A1 (fr) 2022-10-25 2024-05-02 Symrise Ag Détergents liquides et compositions de nettoyage à pouvoir hydrotrope amélioré

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA722623A (en) * 1963-10-21 1965-11-30 General Aniline And Film Corporation Stabilized liquid heavy duty detergent composition
PH25826A (en) * 1986-03-14 1991-11-05 Johnson & Son Inc S C Prespotter laundry detergent
DE3838093A1 (de) * 1988-11-10 1990-05-17 Basf Ag Verwendung von copolymerisaten als zusatz zu fluessigwaschmitteln
GB2237813A (en) * 1989-10-31 1991-05-15 Unilever Plc Liquid detergent
ES2107047T3 (es) * 1992-07-29 1997-11-16 Unilever Nv Composicion detergente.

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0697422A1 (fr) 1994-07-22 1996-02-21 National Starch and Chemical Investment Holding Corporation Améliorations dans ou en relation à des polymères
US5650473A (en) * 1994-07-22 1997-07-22 National Starch And Chemical Investment Holding Corporation Methods for making styrene copolymers and uses thereof
US5789511A (en) * 1994-07-22 1998-08-04 National Starch And Chemical Investment Holding Corporation Methods for making styrene copolymers and uses thereof
US5886076A (en) * 1994-07-22 1999-03-23 National Starch And Chemical Investment Holding Coporation Methods for making styrene copolymers and uses thereof
EP0697422B1 (fr) * 1994-07-22 1999-08-18 National Starch and Chemical Investment Holding Corporation Méthode de préparation d'un polymère par polymérisation en solution
EP0797656B2 (fr) † 1994-12-13 2004-03-17 Unilever N.V. Composition detergente
US6281178B1 (en) 1996-02-14 2001-08-28 Stepan Company Reduced residue hard surface cleaner comprising hydrotrope
EP0967266A1 (fr) * 1998-06-26 1999-12-29 National Starch and Chemical Investment Holding Corporation Détergent liquide isotrope
WO2003060054A3 (fr) * 2002-01-15 2004-01-08 Nat Starch Chem Invest Liant pour substrats a faible teneur en formaldehyde et hydroresitance elevee
US7183250B2 (en) 2003-06-17 2007-02-27 National Starch And Chemical Investment Holding Corporation Surfactant composition containing hydrophobically modified polymer
WO2005044967A3 (fr) * 2003-10-30 2005-08-11 Procter & Gamble Compositions servant a nettoyer et a renforcer la brillance des sols
EP1659168A1 (fr) * 2004-11-23 2006-05-24 National Starch and Chemical Investment Holding Corporation Composition de tensio-actif contenant un copolymère amphiphilique
WO2007042450A1 (fr) * 2005-10-14 2007-04-19 Basf Se Procede pour stabiliser des compositions liquides d'agents lavants et compositions liquides d'agents lavants
CN109661555A (zh) * 2016-07-28 2019-04-19 霍尼韦尔国际公司 推进剂和自我保护组合物
CN115479503A (zh) * 2016-07-28 2022-12-16 霍尼韦尔国际公司 推进剂和自我保护组合物
US11603508B2 (en) 2018-10-26 2023-03-14 Ecolab Usa Inc. Synergistic surfactant package for cleaning of food and oily soils
US12084629B2 (en) 2018-10-26 2024-09-10 Ecolab Usa Inc. Synergistic surfactant package for cleaning of food and oily soils
WO2024088520A1 (fr) 2022-10-25 2024-05-02 Symrise Ag Détergents liquides et compositions de nettoyage à pouvoir hydrotrope amélioré

Also Published As

Publication number Publication date
GB9315854D0 (en) 1993-09-15
EP0636687A3 (fr) 1996-05-01

Similar Documents

Publication Publication Date Title
JP2514239B2 (ja) 洗剤組成物
US5789511A (en) Methods for making styrene copolymers and uses thereof
JPS59161407A (ja) 共重合物及びその用途
EP0446761A1 (fr) Compositions détergentes liquides aqueuses à visco-élasticité linéaire, notamment pour lave-vaisselle automatique, ou à stabilité améliorée à température élevée
CA2156173A1 (fr) Peroxyacides
EP0636687A2 (fr) Perfectionnements apportés aux hydrotropes
JP2000505132A (ja) 特定のアルキルベンゼンスルホネート界面活性剤を含有する非水性洗剤組成物
AU650130B2 (en) Linear viscoelastic aqueous liquid automatic dishwasher detergent composition having improved chlorine stability
US20030162679A1 (en) Hydrophobically modified polymer formulations
JPH0684520B2 (ja) 液体洗剤組成物
US6462013B1 (en) Isotropic liquid detergent comprising ethylenically unsaturated acid monomer-C1 to C24 chain transfer agent polymerization product
JPS60152600A (ja) 石灰石けん分散組成物及びその使用方法
WO1996037597A1 (fr) Formulations de detergents
US6511952B1 (en) Use of 2-methyl-1, 3-propanediol and polycarboxylate builders in laundry detergents
WO1996018716A1 (fr) Composition detergente
CA2066623C (fr) Detersifs liquides des polymeres deflocucants
JPS6286098A (ja) 洗剤用ビルダー
JPS5927794B2 (ja) 洗剤用ビルダ−及び該洗剤用ビルダ−を含有する洗剤組成物
EP0301884B1 (fr) Compositions détergentes liquides
EP0636691A2 (fr) Compositions de blanchiment
EP0636689A2 (fr) Compositions de blanchiment
EP0510945A2 (fr) Compositions détergentes liquides aqueuses à visco-élasticité linéaire, notamment pour lave-vaisselle automatique
EP0517309A1 (fr) Composition détergente aqueuse liquide, visco-élastique linéaire, spécialement pour le lavage de la vaisselle en machine avec stabilité améliorée à haute température
EP0517313A1 (fr) Composition détergente aqueuse liquide visco-élastique linéaire, spécialement pour le lavage de la vaisselle en machine avec stabilité amélioré à haute température
EP0523826A1 (fr) Composition détergente liquide aqueuse visco-élastique, notamment pour lave-vaisselle automatique, de distribution améliorée

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19960920

17Q First examination report despatched

Effective date: 19980717

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19981128