WO2011051646A1 - Treatment of hard surfaces - Google Patents
Treatment of hard surfaces Download PDFInfo
- Publication number
- WO2011051646A1 WO2011051646A1 PCT/GB2010/001859 GB2010001859W WO2011051646A1 WO 2011051646 A1 WO2011051646 A1 WO 2011051646A1 GB 2010001859 W GB2010001859 W GB 2010001859W WO 2011051646 A1 WO2011051646 A1 WO 2011051646A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- quaternised
- amount
- polyamine
- formulation
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
- C08G73/0213—Preparatory process
- C08G73/0226—Quaternisation of polyalkylene(poly)amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
-
- 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
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
Definitions
- the present invention relates to polymeric compounds, formulations containing polymeric compounds useful in the treatment of hard surfaces and to methods of treating hard surfaces in particular to improve their soil resistance.
- soil resistance is imparting improved soil release properties to surfaces to facilitate subsequent cleaning.
- hard surfaces notably hard surfaces in domestic and industrial or institutional cleaning (often abbreviated to ⁇ and I cleaning").
- oily or greasy soils and/or limescale soils including soils made substantially completely of mineral deposits, such as alkali metal, particularly calcium and/or magnesium carbonates, and stains which include such mineral deposits combined with other soil such as water insoluble soap salts, such as calcium and/or magnesium stearates, and greasy or oily soils, can be difficult to remove from hard surfaces.
- hydrophilic soils are usually easier to remove with aqueous wash systems.
- a further benefit from improving the soil resistance of hard surfaces is that it may reduce the tendency to form water tide marks and/or the tendency to leave streaks especially after rinsing.
- the improvement in the soil resistance of substrates, especially hard surfaces, is important in that it reduces the tendency of soil material to adhere to the surfaces, in effect slowing the rate, or reducing the extent, of soiling and/or makes it easier to remove the soil when cleaning the surface, particularly by reducing the mechanical effort required to remove the soil.
- Rhodia have approached this need by suggesting the use of formulations including copolymers of acrylic esters/amides carrying quaternium, particularly diquaternium, substituents for example as described in US 6703358.
- This invention is based on our finding that treatment of hard surfaces with quaternised polyamine polymers which have been block propoxylated and then block ethoxylated can give excellent soil resistance, particularly to oily soils, the deposition of limescale and/or tide marks from insoluble soap salts and/or limescale and to streaking from rinsing water.
- Our experience suggests that propoxylation followed by ethoxylation results in superior performance, at least when quaternised, desirably highly quaternised (see below), polymers are used.
- the combination of a high degree of quaternisation of the polyamine and the polypropoxylation makes the polymer substantive to the surfaces being treated and the subsequent polyethoxylation provides a relatively hydrophilic coating which provides or improves soil repellency.
- quaternised polyalkoxylated polyamine polymers can provide soil repellency when applied from formulations over a wide pH range.
- the present invention accordingly provides, a method of treating hard surfaces to improve soil resistance, particularly resistance to oily soils, the deposition of limescale and water streaks , which comprises applying to the surface a composition comprising a water soluble quaternised, polyamine, polypropoxylate, polyethoxylate.
- the invention includes treatment formulations for hard surfaces comprising, as an agent to improve soil resistance, at least one water soluble quaternised, polyamine, polypropoxylate, polyethoxylate.
- treatment formulations will often be intended to provide cleaning as well as improving soil resistance, and the invention accordingly provides a cleaning formulation comprising at least one detergent surfactant and, as an agent to improve soil resistance, a water soluble quaternised, polyamine, polypropoxylate, polyethoxylate.
- the invention includes a method of treating hard surfaces to improve their soil resistance which comprises applying to the hard surface a water soluble quaternised, polyamine, polypropoxylate, polyethoxylate polymer or a formulations including such a polymer. Most commonly such treatment will be carried out at the same time as cleaning the hard surface, usually with the treatment polymer included in a cleaning formulation and accordingly the invention further includes a method of cleaning hard surfaces which comprises applying to the hard surface an aqueous cleaning composition including at least one detergent surfactant and as an agent to improve the soil resistance of the hard surface, a water soluble quaternised, polyamine, polypropoxylate, polyethoxylate polymer.
- the invention will usually include the following process steps: a) applying to a hard surface an aqueous cleaning composition including at least one detergent surfactant and as an agent to improve the soil resistance of the hard surface, a water soluble quaternised, polyamine, polypropoxylate, polyethoxylate polymer, typically by pouring or spraying the composition on the hard surface or by using an application means;
- hard surface to refer to non-porous solid surfaces such as those of metals, ceramics, glass, wood and plastics, particularly laminated plastics, all including painted, varnished or sealed surfaces, and can be contrasted with other surfaces, particularly soft and absorbent surfaces such as textiles (cleaned in laundry cleaning) and skin (as in cosmetics, more particularly cosmetic removers).
- hard surfaces include: walls, floors, windows, mirrors, doors, tiles and tiled areas, work surfaces, including cutting and chopping boards, domestic fittings e.g. shelves and cupboards, washing and sanitary fixings e.g. sinks, wash basins, baths, showers and WCs, domestic appliances e.g. stoves, ovens, including microwave ovens, washing machines and dryers, dishwashers, refrigerators, freezers and chillers, food preparation machines e.g. mixers, blenders and food processors, in both domestic and institutional and industrial environments, including in hospitals, medical laboratories and medical treatment environments.
- domestic fittings e.g. shelves and cupboards
- washing and sanitary fixings e.g. sinks, wash basins, baths, showers and WCs
- domestic appliances e.g. stoves, ovens, including microwave ovens, washing machines and dryers, dishwashers, refrigerators, freezers and chillers
- food preparation machines e.g. mixers, blenders and food processors
- the water soluble quaternised, polyamine, polypropoxylate, polyethoxylate copolymer of the invention is referred to as a "soil release copolymer".
- the polymers of and used in this invention are described as "water soluble”. By this we mean that the polymers are soluble in water and desirably also in aqueous based formulations e.g. detergent formulations, at a concentration to provide sufficient polymer to satisfactorily treat hard surfaces (bearing in mind that such formulations will usually be diluted before application to hard surfaces). It is further desirable that such formulations remain stable during normal storage before use.
- the polymers will have a water solubility of at least 0.5% and more usually at least 1 % by weight.
- the polymers will desirably not be so hydrophilic or water soluble that they remain in solution and are not substantive to the hard surfaces.
- Polymers which can desirably be used in the invention are also part of the invention which accordingly includes polymers of the general formula (I):
- R 1 represents the molecular framework of a quaternised polyamine apart from p+q+r
- each A 1 is independently a tertiary N atom; a quaternary group N + R2 An s" ⁇
- PO is propyleneoxy
- EO is ethyleneoxy
- n is from 10 to 100;
- n is from 5 to 100;
- p is the number of alkoxylated/quaternised primary amino groups in the polymer
- q is the number of alkoxylated/quaternised secondary amino groups in the polymer
- r is the number of quaternised tertiary amino groups in the polymer
- p+q+r is desirably in the range 200 to 1200, particularly 340 to 700, particularly about 580.
- Compounds of the formula (I) include three types of groups derived from amino groups in the (theoretical) precursor polyamine which can be described:
- polyamine by alkoxylation of the two primary amino hydrogen atoms followed by quaternisation of the amino nitrogen atom;
- N + (PO) n (EO) M R 3 are derived from secondary amino groups in the
- polyamine by alkoxylation of the secondary amino hydrogen atom followed by quaternisation of the amino nitrogen atom;
- N + R2 An s" i/ S , and -N+R ⁇ COO " are derived from tertiary amino groups in the polyamine by oxidation/quaternisation of the amino nitrogen atom;
- formula (I) does not show the plural single bonds between secondary and tertiary amino nitrogen atoms and the framework of the polyamine R 1 .
- the polymer of and used in the invention is based on a polyamine which is polyalkoxylated (see further below) and quaternised.
- a polyamine which is polyalkoxylated (see further below) and quaternised.
- the polyamine will include reactive amino (NH) groups, particularly as secondary amino groups, each providing one reactive "NH” group and/or primary amino groups, each providing two reactive "NH” groups.
- the amino groups may be pendent to the main chain of the polymer or may or form part of the polymeric chain.
- the polyamine desirably has a relatively high molecular weight, typically above 10 kiloDaltons (KDa), and particularly also a relatively high proportion of reactive amino groups (which can be alkoxylated). Both these features can be provided by polyalkyleneimines, particularly polyethyleneimine (PEI), which is especially useful as it is readily available and relatively inexpensive and offers a high proportion of nitrogen atoms (for quaternisation) and reactive amino groups.
- PEI polyethyleneimine
- Polyalkyleneimines, particularly polyethyleneimines, which can be used to make the copolymers of and used in this invention will typically contain:
- the polyamine desirably includes on average at least one reactive NH group per 100 Da, particularly at least one per 75 Da, and especially at least one per 50 Da.
- PEI has a nominal repeat unit of - HCH2CH2- corresponding to one active hydrogen atom per 43 Da.
- each branch in the molecule acts as the root of a fresh chain end, so that typically the number of reactive NH groups (noting that each terminal -IMH2 group corresponds to two reactive NH groups) remains approximately equal to the number of alkyleneimine repeat units in the polymer.
- polyalkyleneimines, particularly polyethylenimines of the molecular weight typically used in this invention it is common that there are approximately equal numbers of primary and tertiary amino groups.
- the polyamine will have a molecular weight of at least 10 k Daltons and commercially polyamines, particularly PEIs, are available with molecular weights up to about 50 kDa. Within this range the molecular weight is desirably from 15 to 30 kDa, particularly about 25 kDa.
- these molecular weight ranges correspond to total numbers of primary secondary and tertiary amino-groups, p+q+r in formula (I), approximately corresponding to numbers of reactive NH groups, of from about 200 to about 1200, desirably about 340 to about 700, particularly about 580.
- p, q and r are approximately equal.
- the group R 1 represents the molecular framework of the polyamine starting material but disregarding the amino groups which are alkoxylated and (at least partially) quaternised. Where the polyamine is has many or most of its nitrogen atoms forming part of the polymer chains as in polyalkylenimines, particularly PEI, the "framework" in R 1 will appears discontinuous.
- the polyamine is polyalkoxylated, specifically by being first block polypropoxylated and then block polyethoxylated.
- the degree of alkoxylation is such that substantially all the primary and secondary amino groups in the polyamine will be (poly)alkoxylated.
- amino groups may be so sterically hindered as to be unreactive and can be regarded as part of the core polyamine framework.
- polypropylenoxy and polyethylenoxy chain segments are block segments, however, in practice it is likely that there will be unreacted propylene oxide in the reaction system at the point that ethylene oxide is introduced and this is likely to give rise to a so-called taper block copolymer chain.
- the length of the polypropyleneoxy chain segments is from 10 to 100, particularly from 20 to 70, especially from 25 to 50, propyleneoxy units.
- the length of the polyethylenoxy chain segments is from 5 to 50, particularly from 5 to 30, especially from 5 to 20, ethyleneoxy units.
- the polypropoxylated and polyethoxylated blocks may contain minor proportions of other alkylenoxy groups.
- the polypropoxylated block may include minor proportions of ethyleneoxy and/or butyleneoxy groups and the polyethoxylated block may include minor proportions of propyleneoxy groups.
- polymers having a molar ratio of PO units to EO units of at least 1 : 1 particularly at least 2:1 and desirably not more than 5:1 , particularly not more than 4:1 , and particularly desirably about 3:1 give better performance in hard surface soil resistance and that accordingly ratios within such ranges are preferred.
- the alkoxylated polyamine polymer is quaternised before use in treating hard surfaces. This increases the water solubility of the polymers and appears to improve the substantivity of the polymer to typical hard surfaces. Generally a minimum of 25%, more usually at least 35%, desirably at least 50%, in particular at least 75%, more usually at least 80% desirably at least 90% e.g. about 95% of the polyamine amino groups are quaternised. In principle even higher percentages of quaternisation may be desirable e.g. up to 100% (or as near as is practical), but may in practice require the use of excess quaternisation reagent (otherwise undesirable as such because typical quaternising reagents are hazardous).
- both the PO:EO ratio is close to the optimum e.g. in the range 2: 1 to 4: 1 particularly about 3: 1 , and that the polymer is at least relatively highly quaternised e.g. at least 35%, particularly at least 70%, especially at least 90% and desirably as near 100% as is practical, of the polyamine amino groups are quaternised.
- the quaternising group [R 2 in formula (I)] is typically a lower alk(en)yl group, more usually a lower alkyl group typically a C-j to Cg, particularly Ci to C4, alkyl, especially methyl or ethyl group.
- the quaternary amino groups will have an associated counter anion [An' in the definitions for formula (I)], which will commonly be a residue of the quaternising agent.
- Common such ions include halide, particularly chloride e.g. as derived from alkyl (commonly methyl) halide (commonly chloride) quaternising agents; and sulphate or alkyl (commonly methyl) sulphate e.g. as derived from alkyl (commonly methyl) sulphate quaternising agents.
- the counter ion is provided by the acidic, usually carboxylate, group of the betaine.
- the polymers of and used in the invention typically have molecular weights of at least 100 kDa, more usually at least 250 kDa, desirably at least 500 kDa, and particularly at least 1 MDa, but typically not more than 3 MDa, more usually not more than 2 MDa, and desirably not more that about 1.75 MDa.
- particularly useful polymers have molecular weights of from 500 kDa to 2 MDa, particularly 750 kDa to 1.75 MDa e.g. from about 1.25 to about 1.6 MDa.
- the polymers of and used in the present invention can be made by generally known synthetic procedures.
- a general reaction scheme in which:
- a polyamine is reacted with propylene oxide (PO) to give an intermediate in which the NH groups are generally mono-propoxylated; followed by ii) further reaction of the intermediate from phase i) with PO to form a polypropoxylated intermediate; followed by
- the initial propoxylation is generally at a molar ratio of PO:available NH of about 1 :1 and typically does not use added catalyst, to give a generally monopropoxylated (based on available NH groups) intermediate.
- the subsequent polypropoxylation and polyethoxylation will typically be catalysed, usually base catalysed, typically using added strong base, generally alkali metal hydroxide such as NaOH or KOH, followed by distilling off water to generate alkoxide ions from the monopropoxylated initial intermediate, or adding alkoxide, usually alkali metal lower alkyl (particularly C-
- the initial monopropoxylation of the reactive NH groups and at least part of the polypropoxylation will be carried out in one stage with possible further polypropoxylation and polyethoxylation carried out in a second and/or subsequent stage.
- the catalyst will typically be neutralised with acid such as acetic acid.
- the generally tertiary amine groups in the fully polyalkoxylated intermediate polymer are subsequently quaternised, typically by treating the polyalkoxylated polyamine copolymer intermediate with an alkylating agent such as an alkyl halide or dialkyl sulphate to form a quaternary amine group; or by reaction with a halo-carboxylic acid, particularly a chloro-carboxylic acid, usually an ⁇ -halo acid, such as a-chloracetic acid to form a betaine.
- this reaction will be carried out using neat reagents, under ambient pressure, at a moderately superambient temperature particularly from 30 to 100°C, e.g. about 60°C, and usually without needing a catalyst.
- the soil release copolymer will typically be used to treat hard surfaces as a solution in an aqueous medium.
- the soil release copolymer will comprise at least 0.1% more usually at least 0.25%, and usually the concentration will not be greater than 2%, more usually not be more than 1.25%, and desirably not be more than 0.75%, all percentages being by weight of the solution.
- the formulation containing the soil release copolymer may be used solely or mainly to provide treatment of the hard surfaces to provide improves soil resistance and this type of formulation will typically be formulated in water and contain the soil release copolymer and may in addition include surfactants such as wetter(s), sequestrant(s) to soften the water used to dilute the concentrate to use concentrations, and fragrance and colour materials.
- wetter (when used) 5 to 60 0.25 to 3
- the treatment When applied separately, the treatment will usually be applied to hard surfaces that are clean or have been separately cleaned.
- the soil release copolymer may also be in formulations used mainly for other purposes such as cleaning formulations, and typical compositions of such formulations are described below.
- other components can include surfactant [though generally not anionic surfactant as these are incompatible with the generally cationic quaternary amine polymers] including detergents, wetters and/or dispersants; soil suspending agents and/or anti-redeposition agents; dye transfer agents and/or dye transfer inhibitors; enzymes; bleaches optionally with bleach activators; hydrotropes; builders; sequestrants (chelating agents); pH adjustment and/or buffering agents; solids such as mild abrasives; corrosion inhibitors; anti-foams; stabilisers; preservatives, particularly biocides such as anti-microbials; radical scavengers; perfume; anti dusting agents; optical brighteners; silicones; dye/pigment; all typically at conventional levels.
- surfactant though generally not anionic surfactant as these are incompatible with the generally cationic
- a typical generic cleaning formulation will typically include the following proportions of materials: Material Concentrate Use
- the formulations of the invention will typically be made up as concentrates and will be diluted, typically with 10 to 400, more usually from 10 to 200 and particularly from 10 to 100 times the formulation weight of water. Dilution will usually occur immediately prior to application of the formulation to the hard surface substrate to be cleaned. It may be applied directly to the surface to be cleaned by pouring and/or spraying or by application e.g. using a mop, cloth or brush.
- the invention accordingly includes a treatment method of the invention which comprises an additional step of diluting the formulation with an appropriate diluent, particularly water, before applying the formulation in diluted form to the hard surface to be treated. More uniform application of the formulation over the hard surface may be effected by wiping the surface with a cloth or mop.
- the copolymer will usually be used as part of a cleaning operation it may be applied separately, desirably suitably diluted, to a surface, particularly a clean surface, in order to treat the surface to improve its subsequent soil resistance.
- some of the diluted formulation will be left to dry on the surface and the surface will not usually be rinsed after treatment.
- part of the formulation will be removed from the hard surface along with soil removed from the surface, but desirably part of the formulation will be left to dry on the surface to enhance treatment of the surface with the quaternised copolymer.
- the surface may be suitably rinsed after cleaning, even though this may remove some of the copolymer form the hard surface.
- the soil release copolymers of and used in this invention have the benefit that they can be used in formulations over a wide pH range, acidic, alkaline or neutral. In this they are superior to currently available materials which are active either in acid or alkali formulations but not both.
- the pH of formulations containing the soil release copolymer of the invention may be from 2 to 12, particularly from 2 to 10 covering from acidic toilet bowl cleaners to alkaline multi-purpose cleaners.
- PEI 1 polyethyleneimine MW ca 25 kDa, Lupasol WF ex BASF
- Polyethyleneimine PEI1 was propoxylated and ethoxylated (in two stages to accommodate the build in the vessels used) and then quaternised as described below.
- PEI 1 [360 g; 18 mmol(PEI); 8.37 mol(NH)] was weighed into a stirred reactor fitted with a vacuum line with liquid and vapour traps, deaerated, heated to 120°C and the PEI 1 vacuum stripped at ca 0.2 bar (20 kPa) for 1 hour.
- Propylene oxide (PO) (490 g; 8.45 mol; ca 1 mol per mol NH) was added over a period of 2 hours; the reaction mixture held at 120°C for a further 2 hours; and then cooled to 90°C.
- the polymers were made by the general method described in Synthesis Example SE1 but varying the nature or amount of the materials used to obtain the polymers SE2 to SE7 as summarised in Table SE1 below.
- alkyl polyglycoside (Glucopon 425N ex Cognis) 5
- EDTA ethylene diamine tetraacetic acid
- Tiles - 15 x 15 cm blue gloss, tilel , and black matt finish, tile2, tiles Before testing the tiles were washed with warm water and detergent and then rinsed with acetone and dried. Metal strips of aluminium (300 x 100mm) divided into 3 segments with adhesive tape, MS1 , and polished steel strip (150 x 75mm) divided into 2 segments with adhesive tape, MS2.
- Solutions of soil release copolymer for testing were prepared in demineralised water and test cleaning formulations described above at 0.1 , 0.5 and 1 %w w active polymer Additive.
- Duplicated test slides were immersed in the aqueous solutions, with similar slides immersed in demineralised water and a formulation blank, for at least one hour. The slides were removed, drained and immediately immersed horizontally in a Petri dish containing 50 ml of fresh (cloudy) 1000 ppm Ca(HC03)2 solution and left overnight. The slides were then removed, rinsed by discharging a pipette of demineralised water (ca 2 ml) across both the front and back of the slide and then left to dry. The % transmission of each slide in was measured in a spectrophotometer (Jenway 6300) at 403nm at 3 points across the surface and the average % transmission reported.
- each tile was divided into two with a thin strip of adhesive tape.
- 1.25 wt% solutions of the active soil release copolymer were made up in the clean3 formulation.
- 1.0 ml of the test solution was applied to and evenly spread over one half of each tile, using a plastic pasteur pipette.
- the other half of the tile was similarly treated using a TBC blank formulation (not including the treatment polymer), or a similar solution of Comp2 comparative material.
- the tile was then allowed to dry horizontally, under ambient conditions for 30 mins; then rinsed by immersion for 5 seconds in a 40 mm deep stainless steel tray filled with ca. 800 ml fresh tap water; and then allowed to dry vertically for 1 hour under ambient conditions.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10768045.6A EP2493959B1 (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces |
AU2010311233A AU2010311233A1 (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces |
BR112012010122A BR112012010122A2 (en) | 2009-10-30 | 2010-10-04 | method for treating hard surfaces to improve resistance to dirt, polymer, and hard surface formulation |
CN201080048114.3A CN102686644B (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces |
MX2012004498A MX2012004498A (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces. |
CA2776245A CA2776245A1 (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces |
US13/504,436 US8709168B2 (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0919097.6A GB0919097D0 (en) | 2009-10-30 | 2009-10-30 | Treatment of hard surfaces |
GB0919097.6 | 2009-10-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011051646A1 true WO2011051646A1 (en) | 2011-05-05 |
Family
ID=41434958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2010/001859 WO2011051646A1 (en) | 2009-10-30 | 2010-10-04 | Treatment of hard surfaces |
Country Status (12)
Country | Link |
---|---|
US (1) | US8709168B2 (en) |
EP (1) | EP2493959B1 (en) |
CN (1) | CN102686644B (en) |
AR (1) | AR078840A1 (en) |
AU (1) | AU2010311233A1 (en) |
BR (1) | BR112012010122A2 (en) |
CA (1) | CA2776245A1 (en) |
CO (1) | CO6541614A2 (en) |
GB (1) | GB0919097D0 (en) |
MX (1) | MX2012004498A (en) |
TW (1) | TW201132673A (en) |
WO (1) | WO2011051646A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013050743A1 (en) | 2011-10-06 | 2013-04-11 | Croda International Plc | Improved treatment of hard surfaces |
EP2662436A1 (en) | 2012-05-11 | 2013-11-13 | The Procter & Gamble Company | Detergent composition |
WO2013167467A1 (en) | 2012-05-11 | 2013-11-14 | Basf Se | Quaternized polyethylenimines with a high quaternization degree |
WO2013167401A1 (en) | 2012-05-11 | 2013-11-14 | Basf Se | Quaternized polyethylenimines with a high ethoxylation degree |
WO2013170002A1 (en) * | 2012-05-11 | 2013-11-14 | The Procter & Gamble Company | Liquid detergent composition for improved shine |
US8754027B2 (en) | 2012-05-11 | 2014-06-17 | Basf Se | Quaternized polyethulenimines with a high ethoxylation degree |
US8759271B2 (en) | 2012-05-11 | 2014-06-24 | The Procter & Gamble Company | Liquid detergent composition for improved shine |
WO2014130257A1 (en) | 2013-02-22 | 2014-08-28 | Croda, Inc. | Treatment of hard surfaces |
US9068147B2 (en) | 2012-05-11 | 2015-06-30 | Basf Se | Quaternized polyethylenimines with a high quaternization degree |
US20220380661A1 (en) * | 2017-12-29 | 2022-12-01 | Arc Products, Inc. | Quaternized alkoxylated polymer surfactant |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US10119101B2 (en) * | 2014-04-28 | 2018-11-06 | Ecolab Usa Inc. | Method of minimizing enzyme based aerosol mist using a pressure spray system |
US9828571B2 (en) | 2015-06-05 | 2017-11-28 | Illinois Tool Works, Inc. | Heavy duty laundry detergent |
CN106833950A (en) * | 2016-12-28 | 2017-06-13 | 于文 | Antibacterial floor cleaner and preparation method thereof |
CN106947619A (en) * | 2017-03-17 | 2017-07-14 | 长沙协浩吉生物工程有限公司 | A kind of compound method of ferment toilet bowl cleaning agent |
CN111996082A (en) * | 2020-08-05 | 2020-11-27 | 名臣健康用品股份有限公司 | Color-changing toilet cleaner composition and preparation method thereof |
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DE2227546A1 (en) | 1972-06-07 | 1974-01-03 | Basf Ag | PROCESS FOR CRACKING CRUDE OIL EMULSIONS |
WO1997042288A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Laundry detergent compositions and methods for providing soil release to cotton fabric |
US6703358B1 (en) | 2000-07-13 | 2004-03-09 | Rhodia Chimie | Cleaning composition for hard surfaces |
WO2005073357A2 (en) | 2004-01-30 | 2005-08-11 | Basf Aktiengesellschaft | Polymer for treating surfaces |
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2009
- 2009-10-30 GB GBGB0919097.6A patent/GB0919097D0/en not_active Ceased
-
2010
- 2010-10-04 MX MX2012004498A patent/MX2012004498A/en not_active Application Discontinuation
- 2010-10-04 CN CN201080048114.3A patent/CN102686644B/en active Active
- 2010-10-04 EP EP10768045.6A patent/EP2493959B1/en not_active Not-in-force
- 2010-10-04 US US13/504,436 patent/US8709168B2/en not_active Expired - Fee Related
- 2010-10-04 WO PCT/GB2010/001859 patent/WO2011051646A1/en active Application Filing
- 2010-10-04 BR BR112012010122A patent/BR112012010122A2/en not_active IP Right Cessation
- 2010-10-04 AU AU2010311233A patent/AU2010311233A1/en not_active Abandoned
- 2010-10-04 CA CA2776245A patent/CA2776245A1/en not_active Abandoned
- 2010-10-15 TW TW099135304A patent/TW201132673A/en unknown
- 2010-10-29 AR ARP100104006A patent/AR078840A1/en not_active Application Discontinuation
-
2012
- 2012-05-29 CO CO12089079A patent/CO6541614A2/en not_active Application Discontinuation
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WO2013050743A1 (en) | 2011-10-06 | 2013-04-11 | Croda International Plc | Improved treatment of hard surfaces |
US9222062B2 (en) | 2011-10-06 | 2015-12-29 | Croda International Plc | Treatment of hard surfaces |
US8754027B2 (en) | 2012-05-11 | 2014-06-17 | Basf Se | Quaternized polyethulenimines with a high ethoxylation degree |
WO2013167401A1 (en) | 2012-05-11 | 2013-11-14 | Basf Se | Quaternized polyethylenimines with a high ethoxylation degree |
WO2013170002A1 (en) * | 2012-05-11 | 2013-11-14 | The Procter & Gamble Company | Liquid detergent composition for improved shine |
US8623806B2 (en) | 2012-05-11 | 2014-01-07 | The Procter & Gamble Company | Liquid detergent composition for improved shine |
WO2013167467A1 (en) | 2012-05-11 | 2013-11-14 | Basf Se | Quaternized polyethylenimines with a high quaternization degree |
US8759271B2 (en) | 2012-05-11 | 2014-06-24 | The Procter & Gamble Company | Liquid detergent composition for improved shine |
US9068147B2 (en) | 2012-05-11 | 2015-06-30 | Basf Se | Quaternized polyethylenimines with a high quaternization degree |
JP2015523425A (en) * | 2012-05-11 | 2015-08-13 | ザ プロクター アンド ギャンブルカンパニー | Liquid detergent composition for improved gloss |
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US20220380661A1 (en) * | 2017-12-29 | 2022-12-01 | Arc Products, Inc. | Quaternized alkoxylated polymer surfactant |
Also Published As
Publication number | Publication date |
---|---|
EP2493959B1 (en) | 2018-05-23 |
TW201132673A (en) | 2011-10-01 |
AR078840A1 (en) | 2011-12-07 |
MX2012004498A (en) | 2012-05-29 |
US20120208736A1 (en) | 2012-08-16 |
BR112012010122A2 (en) | 2016-06-07 |
GB0919097D0 (en) | 2009-12-16 |
CA2776245A1 (en) | 2011-05-05 |
CO6541614A2 (en) | 2012-10-16 |
AU2010311233A1 (en) | 2012-04-26 |
US8709168B2 (en) | 2014-04-29 |
CN102686644A (en) | 2012-09-19 |
CN102686644B (en) | 2014-06-18 |
EP2493959A1 (en) | 2012-09-05 |
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