EP3625320A1 - Composition - Google Patents

Composition

Info

Publication number
EP3625320A1
EP3625320A1 EP18723009.9A EP18723009A EP3625320A1 EP 3625320 A1 EP3625320 A1 EP 3625320A1 EP 18723009 A EP18723009 A EP 18723009A EP 3625320 A1 EP3625320 A1 EP 3625320A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
monomer
composition according
nhc
copolymer
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.)
Pending
Application number
EP18723009.9A
Other languages
German (de)
English (en)
Inventor
Adam Peter Jarvis
Susanne Henning Rogers
Matthew Rhys THOMAS
Peter William WILLS
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 Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP3625320A1 publication Critical patent/EP3625320A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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 aqueous detergent compositions including a rheology modifying polymer useful for home care applications, including hand dish wash and laundry.
  • a trend in detergent formulating is to reduce the amount of surfactant and to replace these petrochemical derived ingredients with highly weight efficient ingredients selected from cleaning and soil release polymers, sequestrants and enzyme cocktails.
  • Typically some surfactant is retained in the composition and the work horse surfactant linear alkyl benzene sulphonate (LAS) is frequently a key part of the surfactant blend.
  • LAS work horse surfactant linear alkyl benzene sulphonate
  • the polymer ethoxylated polyethylene imine may be used as one of the weight efficient ingredients. Suitable compositions are taught, for example, in WO09153184.
  • Hydrophobically modified alkali swellable emulsion (HASE) copolymers are a type of synthetic associative rheology modifier.
  • This rheology modifier typically contains a backbone consisting of randomly distributed methacrylic acid (MAA) and ethylacrylate (EA) monomers, amongst other possible monomer components.
  • MAA methacrylic acid
  • EA ethylacrylate
  • hydrophobically modified groups Inserted into this backbone are a small proportion of hydrophobically modified groups, usually less than 3 mol%.
  • the monomers to form these hydrophobic groups are sometimes referred to as surfmers or associative monomers. Due to its structure, the copolymer, when dissolved in an alkaline aqueous liquid, induces a variety of interacting forces such as hydrophobic, hydrogen bonding, electrostatic, etc and this modifies the rheology of the liquid.
  • HASE copolymers are usually synthesized via the emulsion polymerization technique.
  • US 5 015 71 1 (Coatex) discloses a thickening terpolymer of the MAA EA surfmer type.
  • US 5 015 71 1 makes the following disclosure: "The first type of monomer, which is a carboxylic acid with an ethylenic unsaturation site, is a C3-C20, preferably C3-C12, compound having an ethylenic bond and at least one carboxylic group or a carboxylic acid anhydride group.
  • the carboxylated ethylenic monomer can be selected from among monoacids, such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, cinnamic acid, diacids, such as itaconic acid, fumaric acid, maleic acid, and citraconic acid, carboxylic acid anhydrides, such as maleic anhydride and diacid hemiesters, such as the C1-4 monoesters of maleic or itaconic acids.
  • the carboxyl ethylene monomer is preferably selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid".
  • US 4 384 096 discloses a copolymer having 42% MAA, 6% IA, 42% EA and 10% surfmer (where IA is itaconic acid).
  • the surfmer used was Nonylphenoxy poly(ethyleneoxy)g ethyl Methacrylate.
  • US 4 384 096 contains a general disclosure relating to the use of Itaconic acid as follows: "Acrylic or methacrylic acid or a mixture thereof with itaconic or fumaric acid are preferred, but crotonic and aconitic acid and half esters of these and other polycarboxylic acids such as maleic acid with Ci - C 4 alkanols are also suitable, particularly if used in minor amount in combination with acrylic or methacrylic acid".
  • Low dosage compositions formulated this way are suitable for laundry and hard surface cleaning applications. Both the removal of the surfactant and the use of cleaning polymers like ethoxylated polyethylene imine and polyester soil release polymers cause a drop in viscosity of the liquid.
  • the pour viscosity of a concentrated liquid should be at least as high as a conventional dilute liquid and possibly even higher so that they have a reason to believe that the liquid contains the same cleaning power as a higher dosage detergent liquid with higher surfactant levels and possibly without such high levels of viscosity reducing polymer additives. It is also desirable to be able to include particulate materials into such liquid detergent compositions, for example encapsulated perfume or visual cues.
  • the liquid should have rheology that provides a yield stress (also known as critical stress) so that the particles remain stably suspended and dispersed and yet the composition may be poured from a bottle or dispensed by a suitable spray or pump mechanism.
  • Crosslinked hydrophobically modified copolymers are exemplified in US2004 063855 (Rohm and Haas) and where such a polymer was used at 1.5 wt% with a specified clay and 22.3 wt% mixed surfactant. It is stated that the composition synergistically increases the low shear (e. g., suspending or stabilizing) viscosity significantly while having little effect on the mid-shear (pouring) viscosity.
  • WO 2013/045377 and WO 2014/082955 describe HASE rheology modifying copolymers.
  • WO 2013/045377 describes copolymers in slightly acidic or neutral pH compositions which exhibit high viscosity at low shear.
  • WO 2013/045377 further makes no mention of including viscosity reducing polymers.
  • WO 2014/082955 describes copolymers in alkaline compositions. The suspending viscosity (shear rate of 1 s "1 ) is high for these polymers in simple test solution (shown in Figures 3 and 4) and the pour viscosity is suitable in a surfactant-containing composition including EPEI (shown in Tables 2 and 3).
  • the copolymers may be utilised in compositions comprising linear alkyl benzene sulphonate anionic surfactant which is the workhorse surfactant found in most laundry and dish wash compositions.
  • an aqueous detergent liquid composition according to claim 1 .
  • the polymer (ii) is a polymer formed from the polymerisation of surfactant monomer (also known as a surfmer), monomer (A1 ). In this way, polymer (ii) is either a homopolymer of monomer (A1 ) or a copolymer of monomer (A1 ) and
  • monomer (A2) constitutes at least 50%, more preferably at least 80%, especially preferably at least 90% and most preferably at least 95% of the total weight of the polymer.
  • R 1 and R 2 are each independently selected from H and C1-3 alkyl, and R 3 has the formula (VII)
  • R 22 is C2-C4 and mixtures thereof, preferably C2;
  • the average number of alkoxy units R 22 0, is from 6 to 40;
  • R 23 is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.
  • R 1 and R 2 are each independently selected from H and C1-3 alkyl, and R 3 has the formula (VIII)
  • R 4 , R 5 and R 10 are each independently H or methyl.
  • the molar ratio of monomer (A1 ) to monomer (A2) may be in the range of 10:90 to 90:10. In some embodiments, the molar ratio of monomer (A1 ) to monomer (A2) may be in the range of 30:70 to 70:30. In some embodiments, the polymer (ii) is formed from 50 % or more by mole of
  • the aqueous detergent liquid further includes:
  • R 11 and R 12 are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine;
  • R 15 is a C1-C30 alkyl
  • z is 0 or 1 ;
  • f is an integer in the range of 0 to 30; and g is 0 or 1 ; with the proviso that when f is 0, g is 0, and when f is in the range of 1 to 30; g is 1 ;
  • R 16 0)h is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2-C4-oxyalkylene units, wherein R 16 is C2H4, C3H6, C4H8, or a mixture thereof, and h is an integer in the range of 5 to 250;
  • R 17 is substituted or unsubstituted alkyl selected from the group consisting of
  • R17 alkyl group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy, and halogen.
  • the cross linking monomer comprising polyfunctional units carrying multiple reactive functionalisation groups selected from the group consisting of vinyl, allyl and functional mixtures thereof.
  • monomer (Surfmer) D has the formula (V)
  • R 18 and R 19 are each independently selected from H, and C1-3 alkyl
  • R 20 is C2-C4 and mixtures thereof, preferably C2;
  • n the average number of alkoxy units R 20 O, is from 6 to 40;
  • R 21 is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.
  • the liquid detergent composition may optionally include (iv) at least 0.01 wt% suspended particles. Additionally or alternatively, the liquid detergent composition may optionally include (v) at least 2 wt% of a viscosity reducing polymer.
  • (meth)acrylic acid includes both acrylic acid and methacrylic acid and the term (meth)acrylate includes both acrylate and methacrylate.
  • the viscosity of the liquid at 20 s "1 and 25°C is preferably at least 0.3 Pa.s, most preferably at least 0.4 Pa.s. This viscosity is also known as the pour viscosity of the composition.
  • the compositions preferably have a yield stress of at least 0.1 Pa to facilitate the preferred suspending properties.
  • compositions exhibit suitable pour viscosities while also having a useful rheology for suspending or spraying, despite the inclusion of polymers that have the effect of reducing the pour viscosity of the composition.
  • the suspended particles may comprise microcapsules and a preferred type of microcapsules is perfume encapsulates.
  • the suspended particles may comprise visual cues.
  • the visual cues may be beads or may comprise lamellar particles formed from sheets of polymer film.
  • viscosity reducing polymers are ethoxylated polyethylene imine and/or polyester soil release polymer.
  • polymer (v) comprises at least 3 wt% of ethoxylated polyethylene imine.
  • copolymer (iii) is formed by addition polymerisation in the presence of: 0.1 to 5 wt% of monomer A; 15 to 60 wt% of monomer B; 30 to 70 wt% of monomer C; 1 to 25 wt% of monomer D and 0.005 to 5 wt.% of cross-linking agent E.
  • Copolymer (iii) preferably has a molecular weight Mw of at least 500 000, more preferably 1 million Daltons.
  • maleic anhydride as the first monomer (A) in the copolymerisation of copolymer (iii). In some embodiments 1 wt.% or less, 0.6 wt.% or less, 0.5 wt.% or less of the first monomer (A) is present in the copolymerisation of copolymer (iii). In further embodiments
  • first monomer (A) is present in the copolymerisation of copolymer (iii) in an amount in the range of 0.1 to 1 wt.%, in the range 0.25 to 0.75 wt.%, or in the range of 0.4 to 0.6 wt.%.
  • copolymers (iii) are crosslinked alkali swellable hydrophobically modified acrylic copolymers, C-HASE. These polymers require alkaline conditions to swell and so should be added to the composition such that they are exposed to appropriate alkaline
  • the surfactant system (i) comprises at least 5 wt% total surfactant. In some embodiments, the surfactant system (i) comprises 15 wt.% or more total surfactant.
  • the surfactant system (i) comprises at least 3 wt% of anionic surfactant, most preferably the anionic surfactant comprises linear alkyl benzene sulphonate, which is the workhorse surfactant found in most laundry and hand dish wash compositions.
  • the detergent composition comprises an effective amount of at least one enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase. More advantageously it comprises at least 2 of this group of
  • the fourth monomer D is more preferably a surfmer of formula (VI):
  • each R 18 and R 19 are independently selected from H, Ci to C3 alkyl, preferably R 18 is a methyl group and R 19 is H; d ranges from 6 to 40 and e ranges from 6 to 40, preferably d ranges from 10 to 30 and e ranges 15 to 35 most preferably d ranges from 12 to 22 and e ranges from 20 to 30. It is preferable that e is greater or equal to d.
  • the amount of monomer D in copolymer (iv) is in the range of 2 to 15 wt.%, more preferably 3 to 12 wt.% and more preferably 5 to 10 wt. %.
  • the level of copolymer (iii) in the detergent composition is from 0.05 to 2 wt% of the total composition; more preferably from 0.1 to 1 wt%.
  • the polymer is also referred to herein as a "Polysurfmer”.
  • R 1 and R 2 are each independently selected from H and C1-3 alkyl, and R 3 has the formula (VII)
  • R 22 is C2-C4 and mixtures thereof, preferably C2;
  • the average number of alkoxy units R 22 0, is from 6 to 40;
  • R 23 is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.
  • R 1 and R 2 are each independently selected from H and C1-3 alkyl, and R 3 has the formula (VIII)
  • R 1 is H and R 2 is a methyl group.
  • t ranges from 6 to 40 and s ranges from 6 to 40, preferably t ranges from 10 to 30 and s ranges 15 to 35, most preferably t ranges from 12 to 22 and s ranges from 20 to 30. It is preferable that s is greater or equal to t.
  • R 4 , R 5 and R 10 are each independently H or methyl. In some embodiments, R 4 and R 10 are H and R 5 is methyl.
  • the molar ratio of monomer (A1 ) to monomer (A2) may be in the range of 10:90 to 90:10. In some embodiments, the molar ratio of monomer (A1 ) to monomer (A2) is in the range of 30:70 to 70:30, 40:60 to 40:60 or 45:65 to 65:45.
  • Polymer (ii) has an average degree of polymerisation of 30 or more. In other words, the polymer has on average 30 or more units of total monomer (A1 ) (and monomer (A2) when present).
  • the average degree of polymerisation is in the range of 40 to 200.
  • the method of poylmerisation of polymer (ii) is not particularly limited.
  • the polymerisation may be single-electron transfer (SET) polymerisation or free radical polymerisation (FRP).
  • SET single-electron transfer
  • FRP free radical polymerisation
  • the optional copolymers (iii) described herein are crosslinked addition polymers formed by copolymerisation and crosslinking in the presence of three or four different ethylenically unsaturated monomers and a cross-linker.
  • monomer ratios are wt% and are based on the amounts of the monomers used. The monomers will lose their unsaturation as they are polymerised and may become salts when neutralised or swollen.
  • Monomer nomenclature and ratios are all made with reference to the unsaturated, and where appropriate unneutralised, starting monomer materials.
  • the copolymer may be formed in the presence of a monomer A which may ring open to form a diacidic unit in the polymer.
  • Diacidic unit means that carboxylate groups are attached to adjacent carbon atoms in the carbon backbone of the copolymer.
  • this unit is formed from a cyclic ethylenically unsaturated anhydride monomer of formula (II). It is preferred that monomer A is such an anhydride.
  • R 11 and R 12 are individually selected from H, C1-C3 alkyl, phenyl, chlorine and bromine.
  • Use of a cyclic anhydride monomer with ethylenic unsaturation gives a cis diacid if the ring opens.
  • Such a diacid has both carboxylate groups arranged on the same side of the polymer - but on different carbon atoms.
  • R 11 is hydrogen and R 12 is selected from the group comprising hydrogen, methyl, bromine and phenyl. More preferably R 11 is hydrogen and R 12 is selected from hydrogen and methyl. Most preferably R 11 and R 12 are hydrogen so that the anhydride is maleic anhydride. This is the precursor for maleic acid. It is thought that because maleic acid produces carboxylate groups on adjacent carbon atoms in the polymer backbone this increases the localised charge density and causes the difference in performance compared with copolymers not containing this diacid. Itaconic acid which is outside the scope of this invention provides a polymer element where one carbon carries two carboxylate groups and the other carries none. Fumaric acid is the trans isomer of maleic acid it cannot be formed from maleic anhydride monomer by hydrolysis during the emulsion polymerization.
  • Amounts of Monomer A present in the copolymerisation may range from 0.1 to 5 wt%, preferably from 0.2 to 4 wt%, and more preferably from 0.3 to 1 wt%, and optimally from 0.4 to 0.6 wt% of the total copolymer.
  • the second monomer B is a monoacidic vinyl monomer. Suitable monomers are acrylic acid, methacrylic acid, and combinations thereof. In the compositions, the acid groups may be neutralized to form salts. Typical salt counterions to the acid groups are sodium, potassium, ammonium and
  • Amounts of the monoacidic vinyl monomer in the copolymerisation may range from 15 to 60 wt%, preferably from 20 to 55 wt%, more preferably from 25 to 50 wt% of the total monomers.
  • the third monomer, C includes one or more C-i-Cs esters of acrylic or methacrylic acid.
  • Illustrative ester monomers are ethylacrylate, methylacrylate, ethylmethacrylate, methylmethacrylate, butylacrylate, butylmethacrylate and mixtures thereof. Ethyl acrylate is preferred.
  • the amount of acrylate ester monomers in the copolymerisation may range from 30 to 70 wt%, preferably from 25 to 60 wt%, and more preferably from 40 to 65 wt% of the total monomers.
  • the fourth ethylenically unsaturated monomer consists of a surfmer of formula (III):
  • Ar is divalent aryl; G is H or methyl;
  • z is 0 or 1 ;
  • f is an integer in the range of 0 to 30; and g is 0 or 1 ; with the proviso that when f is 0, g is 0, and when f is in the range of 1 to 30; g is 1 ;
  • R 16 0) n is polyoxyalkylene, which is a homopolymer, a random copolymer, or a block copolymer of C2-C 4 -oxyalkylene units, wherein R 16 is C2H 4 , C3H6, CUHs, or a mixture thereof, and n is an integer in the range of 5 to 250;
  • R 17 is substituted or unsubstituted alkyl selected from the group consisting of Cs-C 4 o linear alkyl, Cs-C 4 o branched alkyl, Cs-C 4 o carbocyclic alkyl, C2-C 4 o alkyl-substituted, phenyl, aryl-substituted C2-C 40 alkyl, and Cs-Cso complex ester; wherein the R 17 group optionally comprises one or more substituents selected from the group consisting of hydroxy, alkoxy, and halogen.
  • Surfmer D has the formula (IV)
  • R 18 and R 19 are each independently selected from H, and C1-3 alkyl
  • R 20 is C2-C 4 and mixtures thereof, preferably C2;
  • n the average number of alkoxy units R 20 O, is from 6 to 40;
  • R 21 is alkyl or alkylaryl where the alkyl part is linear or branched; and the total number of carbons is from 8 to 40.
  • the fourth monomer D is more preferably a surfmer of formula (V).
  • each R 18 and R 19 are independently selected from H, Ci to Cs alkyl.
  • R 18 is a methyl group and R 19 is H.
  • d ranges from 6 to 40 and e ranges from 6 to 40, preferably d ranges from 10 to 30 and e ranges 15 to 35 most preferably d ranges from 12 to 22 and e ranges from 20 to 30. It is preferable that d is greater or equal to e.
  • the amount of surfmer D in the copolymer may range from 1 to 25 wt%, preferably from 3 to 20 wt%, and more preferably from 2 to a 12 wt% of the total copolymer.
  • a crosslinking agent such as a monomer having two or more ethylenic unsaturated groups, is included with the copolymer components during polymerization.
  • Illustrative examples are divinyl benzene, divinyl naphthalene, trivinyl benzene, triallyl
  • pentaerythritol diallyl pentaerythritol, diallyl sucrose, octaallyl sucrose, trimethylol propane diallyl ether, 1 ,6-hexanediol di(meth) acrylate, tetramethylene tri(meth) acrylate, trimethylol propane tri(meth)acrylate, polyethoxylated glycol di(meth) acrylate, alkylene bisacrylamides, bisphenol A polyethyoxylated dimethacrylate, trimethylolpropane polyethoxylated trimethacrylate, ethylene glycol dimethacrylate and butylene glycol dimethacrylate, diallyl phthalate, allyl methacrylate, diacrylobutylene and similar materials.
  • Preferred for the present invention is bisphenol A polyethoxylated glycol diacrylate, diallyl pentaerythritol and trimethylolpropane triacrylate.
  • Amounts of the cross linking agent used in the copolymerisation may range from 0.005 to 5 wt%, preferably from 0.05 to 3 wt%, more preferably from 1 to 2 wt%, optimally from 0.2 to 1 wt% of the total monomers.
  • the molecular weight of the copolymer is typically over 1 million.
  • the copolymer may be prepared in the presence of a chain transfer agent when a crosslinking agent is used.
  • chain transfer agents are carbon tetrachloride, bromoform, bromotrichloromethane, and compounds having a mercapto group, e.g., long chain alkyl mercaptans and thioesters such as dodecyl-, octyl-, tetradecyl- or hexadecyl-mercaptans or butyl-, isooctyl- or dodecyl-thioglycolates.
  • the amount of chain transfer agent is typically from 0.01 % to 5%, preferably from 0.1 % to 1 %, based on weight of the copolymer components. If the crosslinking agent is used in conjunction with a chain transfer agent, which are conflicting operations for polymerization purposes, not only is exceptional efficiency observed but also very high compatibility with hydrophilic surfactants.
  • Total amount of polymer (ii) and copolymer (iii) when present in the composition is from 0.05 to 3 wt% of the total composition; more preferably from 0.08 to 2 wt%, even 0.1 to 1 wt%.
  • copolymer (iii) is present in the composition.
  • the percentage weight of polymer (ii) may be greater than the weight of monomer D as provided in copolymer (iii) in the composition.
  • polymer (ii) may represent 5 weight percent and monomer D may represent 3 weight percent based on the total weight of polymer (ii) and copolymer (iii) (in other words, copolymer (iii) represents 95 percent by weight of the total weight of polymer (ii) and copolymer (iii)).
  • the compositions includes polymer (ii) and copolymer (iii) and the weight ratio of polymer (ii) to monomer D in copolymer (iii) in the composition is in the range of 2:1 to 10:1 , 3:1 to 8:1 , or 3.5:1 to 6:1 .
  • the polymer (and copolymer when present) may be used with other rheology modifiers or thickeners to make up the rheology modified system.
  • Preferred thickeners are thickening polymers and thickening clays.
  • the polymer (ii) and/or copolymer (iii), in aqueous dispersion or in the dry form, may be blended into an aqueous system to be thickened followed, in the case of a pH-responsive thickener, by a suitable addition of acidic or basic material if required.
  • the pH of the system to be thickened is at, or is adjusted to, at least 5, preferably at least 6, more preferably at least 7; preferably the pH is adjusted to no more than 13.
  • the neutralizing agent is preferably a base such as an amine base or an alkali metal or ammonium hydroxide, most preferably sodium hydroxide, ammonium hydroxide or triethanolamine (TEA).
  • the polymer (ii) and/or copolymer (iii) may first be neutralized in aqueous dispersion and then blended.
  • the surfactant preferably is blended into the aqueous composition separately from the copolymer prior to neutralization. Suspended particles
  • compositions have a shear thinning rheology that makes it suitable for suspending particles.
  • preferred compositions comprise suspended particles. These particles are preferably solid; that is to say they are neither liquid nor gas. However, within the term solid we include particles with either rigid or deformable solid shells which may then contain fluids.
  • the solid particles may be microcapsules such as perfume encapsulates, or care additives or other benefit agents in encapsulated form.
  • the particles may be enzymes or other cleaning actives that are insoluble or are encapsulated to prevent or reduce interaction with other composition ingredients.
  • the particles may take the form of insoluble ingredients such as silicones, quaternary ammonium materials, insoluble polymers, insoluble optical brighteners and other known benefit agents as described, for example, in EP1328616.
  • the amount of suspended particles may be from 0.001 to up to 10 or even 20 wt%.
  • One type of solid particle to be suspended is a visual cue, for example the type of flat film cue described in EP131 19706.
  • the cue may itself contain a segregated component of the detergent composition. Because the cue must be water-soluble, yet insoluble in the composition, it is conveniently made from a modified polyvinyl alcohol that is insoluble in the presence of the mixed surfactant system. In that case, the detergent composition preferably comprises at least 5 wt% anionic surfactant.
  • the suspended particles can be any type. This includes perfume encapsulates, care encapsulates and/ or visual cues or suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials. The closer the match of the density of the suspended particles to that of the liquid. Typically, up to 5 wt% of suspended particles may be suspended stably; however, amounts up to 20 wt% are possible.
  • the benefit agents that may be delivered via suspended particles include any compatible benefit agent which can provide a benefit to a substrate which is treated with a preferably surfactant-containing composition can be used.
  • Advantages of the particles of the invention in the presence of surfactant are a good retention of the benefit agent on storage of a formulation and controllable release of the benefit agent during and after product usage.
  • Preferred benefit agents are fragrances, profragrance, clays, enzymes, antifoams, fluorescers, bleaching agents and precursors thereof (including photo-bleach), dyes and/or pigments, conditioning agents (for example cationic surfactants including water- insoluble quaternary ammonium materials, fatty alcohols and/or silicones), lubricants (e.g. sugar polyesters), colour and photo-protective agents (including sunscreens),
  • conditioning agents for example cationic surfactants including water- insoluble quaternary ammonium materials, fatty alcohols and/or silicones
  • lubricants e.g. sugar polyesters
  • colour and photo-protective agents including sunscreens
  • antioxidants include ceramides, reducing agents, sequestrants, colour care additives (including dye fixing agents), unsaturated oil, emollients, moisturisers, insect repellents and/or pheromones, drape modifiers (e.g. polymer latex particles such as PVAc) and antimicrobial and microbe control agents. Mixtures of two or more of these may be employed. Particular benefit agents are described in further detail below.
  • Benefits include, for laundry applications, benefits of softening, conditioning, lubricating, crease reducing, ease of ironing, moisturising, colour preserving and/or anti-pilling, quick drying, UV protecting, shape retaining, soil releasing, texturising, insect repelling, fungicidal, dyeing and/or fluorescent benefit to the fabric.
  • a highly preferred benefit is the delivery of fragrance (whether free and/or encapsulated), or pro-fragrance or other volatile benefit agent.
  • Preferred sunscreens are vitamin B3 compounds. Suitable vitamin B3 compounds are selected from niacin, niacinamide, nicotinyl alcohol, or derivatives or salts thereof. Preferred anti-oxidants include vitamin E, retinol, antioxidants based on hydroxytoluene such as IrganoxTM or commercially available antioxidants such as the TrolloxTM series.
  • Perfume is one example of a volatile benefit agent.
  • Typical volatile benefit agents have a molecular weight of from 50 to 500. Where pro-fragrances are used the molecular weight will generally be higher.
  • Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavour Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavour Chemicals by S. Arctander 1969, Montclair, N.J.
  • perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
  • the perfume component could also be in the form of a pro- fragrance.
  • WO 2002/038120 P&G
  • Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well-known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15 to 25 wt% of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20 wt% would be present within the encapsulate.
  • Typical perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100 to 250 Celsius. It is also advantageous to encapsulate perfume components which have a low LogP (i.e. those which will be partitioned into water), preferably with a LogP of less than 3.0.
  • perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus,
  • Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian By means of the present invention these materials can be transferred to textile articles that will be worn or otherwise come into contact with the human body (such as handkerchiefs and bed-linen).
  • the volatile benefit agents also include insect repellent materials (where insect should be read broadly to include other pests which are arthropods but not strictly hexapods - for example ticks). Many of these materials overlap with the class of perfume components and some are odourless to humans or have a non-perfume odour.
  • repellents include: DEET (N,N-diethyl-m-toluamide), essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p-menthane-3,8-diol (PMD), lcaridin, also known as Picaridin, D-Limonene, Bayrepel, and KBR 3023, Nepetalactone, also known as "catnip oil”, Citronella oil, Permethrin, Neem oil and Bog Myrtle.
  • Known insect repellents derived from natural sources include: Achillea alpina, alpha-terpinene, Basil oil (Ocimum basilicum), Callicarpa americana (Beautyberry), Camphor, Carvacrol, Castor oil (Ricinus communis), Catnip oil (Nepeta species), Cedar oil (Cedrus atlantica), Celery extract (Apium graveolens), Cinnamon (Cinnamomum Zeylanicum, leaf oil), Citronella oil (Cymbopogon fleusus), Clove oil (Eugenic caryophyllata), Eucalyptus oil (70%+ eucalyptol, also known as cineol), Fennel oil (Foeniculum vulgare), Garlic Oil (Allium sativum), Geranium oil (also known as Pelargonium graveolens), Lavender oil (Lavandula officinalis), Lemon eucalyptus (Corymbia citri
  • the benefit agent may be encapsulated alone or co-encapsulated with carrier materials, further deposition aids and/or fixatives.
  • Preferred materials to be co-encapsulated in carrier particles with the benefit agent include waxes, paraffins, stabilizers and fixatives.
  • PVP polyvinyl pyrrolidone
  • PVA polyvinyl alcohol
  • cellulose ethers polystyrene
  • the yield stress needs to be larger than the stress imposed on the network by the microcapsules or cues otherwise the network is disrupted and the particles can sink or float depending on whether or not they are denser than the base liquid.
  • Perfume microcapsules are almost neutrally buoyant and small, so the required yield stress is low. Air bubbles are bigger and have the biggest density difference and so require a high yield stress (>0.5 Pa, depending on bubble size). If the yield stress is not too high the air bubbles can escape by floating and disengaging from the surface.
  • Microcapsules preferably comprise a solid shell. Microcapsules carrying an anionic charge should be well dispersed to avoid agglomeration issues. Microcapsules with a cationic charge may also be used. The microcapsule may have a melamine
  • suitable shell material may be selected from (poly)urea, (poly)urethane, starch/ polysaccharide, xyloglucan and aminoplasts.
  • Delivery aids may be present at the surface of the particle (microcapsule). These can advantageously be selected from non-ionic materials, preferably cellulose derivatives and polyesters, so give better substantivity to a plurality of substrates. Particularly preferred polysaccharide additional deposition aids include dextran, hydroxy-propyl methyl cellulose, hydroxy-ethyl methyl cellulose, hydroxy-propyl guar, hydroxy-ethyl ethyl cellulose, methyl cellulose, locust bean gum, xyloglucan, guar gum.
  • polyester additional deposition aids include polymers having one or more nonionic hydrophilic components comprising oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene segments, and, one or more hydrophobic components comprising terephthalate segments.
  • the average particle diameter of the microcapsules lies in the range from 1 to 100 micrometer and at least 90 wt% of the microcapsules preferably has a diameter in this range. More preferably, 90 wt% of the microcapsules have a diameter in the range 2 to 50 micrometers, even more preferably 5 to 50 micrometers. Most preferred are microcapsules with diameters less than 30 micrometers.
  • microcapsules in the range 8 to 1 1 microns it is advantageous to have a very narrow particle size distribution, for instance 90 wt% of microcapsules in the range 8 to 1 1 microns. Microcapsules in the range 2 to 5 microns cannot be dispersed so effectively due to the high surface area of the smaller particles.
  • the composition comprises at least 0.01 wt% of microcapsules, preferably with an anionic charge.
  • microcapsules may deliver a variety of benefit agents by deposition onto substrates such as laundry fabric. To obtain maximum benefit they should be well dispersed through the liquid detergent composition and the vast majority of the microcapsules must not be significantly agglomerated. Any microcapsules that become agglomerated during manufacture of the liquid remain so in the container and will thus be dispensed unevenly during use of the composition. This is highly undesirable.
  • the contents of the microcapsules are normally liquid. For example, fragrances, oils, fabric softening additives and fabric care additives are possible contents.
  • Preferred microcapsules are particles termed core-in-shell microcapsules.
  • core-in-shell microcapsules refers to encapsulates whereby a shell which is substantially or totally water-insoluble at 40°C surrounds a core which comprises or consists of a benefit agent (which is either liquid or dispersed in a liquid carrier).
  • Suitable microcapsules are those described in US-A-5 066 419 which have a friable coating, preferably an aminoplast polymer.
  • the coating is the reaction product of an amine selected from urea and melamine, or mixtures thereof, and an aldehyde selected from formaldehyde, acetaldehyde, glutaraldehyde or mixtures thereof.
  • the coating is from 1 to 30 wt% of the particles.
  • Core-in-shell microcapsules of other kinds are also suitable for use in the present invention.
  • Ways of making such other microcapsules of benefit agents such as perfume include precipitation and deposition of polymers at the interface such as in coacervates, as disclosed in GB-A-751 600, US-A-3 341 466 and EP-A-385 534, as well as other polymerisation routes such as interfacial condensation, as described in US-A-3 577 515, US-A-2003/0125222, US-A-6 020 066 and WO-A-03/101606.
  • Microcapsules having polyurea walls are disclosed in US-A-6 797 670 and US-A-6 586 107.
  • a preferred class of core-in-shell perfume microcapsule comprises those disclosed in WO 2006/066654 A1 . These comprise a core having from about 5% to about 50 wt% of perfume dispersed in from about 95% to about 50 wt% of a carrier material.
  • This carrier material preferably is a non-polymeric solid fatty alcohol or fatty ester carrier material, or mixtures thereof.
  • the esters or alcohols have a molecular weight of from about 100 to about 500 and a melting point from about 37°C to about 80°C, and are substantially water-insoluble.
  • the core comprising the perfume and the carrier material are coated in a substantially water-insoluble coating on their outer surfaces. Similar microcapsules are disclosed in US 5,154,842 and these are also suitable.
  • microcapsules may attach to suitable substrates, e.g. to provide persistent fragrance that is desirably released after the cleaning process is complete.
  • the detergent compositions may have a yield stress, also called critical stress, of at least 0.08 Pa, preferably at least 0.09 Pa, more preferably at least 0.1 Pa, even at least 0.15 Pa measured at 25°C. These increasing levels of yield stress are capable of suspending particles of increasingly different density from the bulk liquid. A yield stress of 0.09 Pa has been found sufficient to suspend most types of perfume encapsulates.
  • the detergent liquid may be formulated as a concentrated detergent liquid for direct application to a substrate, or for application to a substrate following dilution, such as dilution before or during use of the liquid composition by the consumer or in washing apparatus.
  • Cleaning may be carried out by simply leaving the substrate in contact for a sufficient period of time with a liquid medium constituted by or prepared from the liquid cleaning composition.
  • a liquid medium constituted by or prepared from the liquid cleaning composition.
  • the cleaning medium on or containing the substrate is agitated.
  • liquid detergent compositions are preferably concentrated liquid cleaning
  • the liquid compositions are pourable liquids. Throughout this specification, all stated viscosities are those measured at a shear rate of 20 s "1 and at a temperature of 25°C unless stated to be otherwise. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle.
  • the liquid detergent compositions according to the invention are shear-thinning liquids.
  • Optional ingredients are shear-thinning liquids.
  • the polymer (ii) used in the present invention (as well as the cross linked hydrophobically modified copolymer (iii)) has been found to be compatible with usual ingredients that may be found in detergent liquids.
  • detergent liquids for example: clays; enzymes, particularly: lipase, cellulase, protease, mannanase, amylase and pectate lyase; cleaning polymers, including ethoxylated polyethylene imines (EPEI) and polyester soil release polymers; chelating agents or sequestrants, including HEDP (1 - Hydroxyethylidene -1 ,1 ,-diphosphonic acid) which is available, for example, as Dequest® 2010 from Thermphos; detergency builders; hydrotropes; neutralising and pH adjusting agents; optical brighteners; antioxidants and other preservatives, including Proxel®; other active ingredients, processing aids, dyes or pigments, carriers, fragrances, sud
  • compositions may be packaged in any form of container. Their shear thinning properties means that they may be dispensed from a squez bottle, from a pump dispenser, from a trigger spray dispenser or by being simply poured from a bottle.
  • the most advantageous form of packing is the type where the product is poured from a bottle, possibly into a measuring cup.
  • the controlled high pour viscosity of the compositions as claimed makes the compositions ideally suited to this mode of dispensing.
  • the bottle may be rigid or deformable.
  • a deformable bottle allows the bottle to be squeezed to aid dispensing.
  • If clear bottles are used they may be formed from PET. Polyethylene or clarified polypropylene may be used.
  • the container is clear enough that the liquid, with any visual cues therein, is visible from the outside.
  • the bottle may be provided with one or more labels, or with a shrink wrap sleeve which is desirably at least partially transparent, for example 50% of the area of the sleeve is transparent.
  • the adhesive used for any transparent label should not adversely affect the transparency.
  • Figure 1 shows a rheology curve for surfactant-containing detergent compositions, some of the compositions including a polysurfmer polymer (ii) of the as described herein.
  • the monomer stock solution was used either as above, or freeze dried to remove water and methacrylic acid to produce solutions with either 0 wt.% or 6.3wt.% methacrylic acid.
  • Monomer stock solution B (75g) and a-azo-iso-butyronitrile (0.675g) were dissolved in propan-2-ol (243ml_) and water (19.5ml_) in a 3-necked round bottomed flask fitted with a condenser and large stirrer bar. The solution was sparged with nitrogen for 60 minutes before being heated to 75°C for 20 hours. The resulting polysurfmer was purified by removal of solvent in vacuo and analysed using NMR and GPC. Table 1 - Synthesised polysurfmer polymers
  • a 3-armed round bottom flask was charged with ethyl acrylate (46.7g), methacrylic acid (27.9g), maleic anhydride (0.39g), Surfmer A (2.55g of stock solution - C12 surfmer (61w%)), polysurfmer 1 (6.04g), methacrylic acid (22w% ) and water (12w%)) and trimethylolpropane triacrylate (0.42g).
  • the mixture was sealed and sparged with nitrogen for 60 minutes before adding and sodium dodecyl sulfonate (SDS) (0.78g) and deoxygenated water (23.75g) and stirring into a pre-emulsion.
  • SDS sodium dodecyl sulfonate
  • a multineck round bottom flask was fitted with a nitrogen sparge and overhead stirrer.
  • Deoxygenated water (137g) and SDS (0.23g) were added, stirred at 200 rpm and heated to 90°C.
  • Ammonium persulfate (0.0552g) in water (1 ml) was added via syringe.
  • the pre-emulsion was fed into the reaction solution via peristaltic pump over 120 minutes.
  • the a second aliquot of ammonium persulfate (0.0246g) in water (1 ml) was added and the reaction stirred for a further 4hrs.
  • the resulting emulsion was left to cool before being bottled and solids content measured (28.25w%).
  • the amount of surfmer in the total polymer/copolymer mixture is 1 .93 wt. % and the amount of polysurfmer in the total polymer/copolymer mixture is 7.71 wt.%. This provides a surfmer to polysurfmer ratio of 1 :4.
  • Example 3 The synthesis of Example 3 was repeated with a surfmer to polysurfmer ratio of 4:1 .
  • a round bottom flask was charged with ethyl acrylate (EA) (66.19 g), methacrylic acid (MAA)(40.41 g), maleic anhydride (MA) (0.552 g) trimethylolpropane triacrylate (X-linker) (0.576g) and Surfmer A (7.36 g).
  • EA ethyl acrylate
  • MAA methacrylic acid
  • MA maleic anhydride
  • X-linker 0.576g
  • Surfmer A 7.36 g
  • the mixture was sealed and purged with nitrogen for 60 minutes before sodium dodecyl sulfonate (1 .03 g) and deoxygenated water (26.5 g) was added and stirred forming a pre-emulsion.
  • a multineck round bottom flask was fitted with a nitrogen sparge and overhead stirrer.
  • the polysurfmer/copolymer mixture resulting from Examples 3 and 4, and copolymer 4 of Example 5 were added at a level of 1 wt.% to a detergent base, M10, as specified in Table X and the viscosity measured using the following method.
  • Rheology flow curves are generated using the following three step protocol:- Instrument - Paar Physica - MCR300 with Automatic Sample Changer (ASC)
  • Step 1 Controlled stress steps from 0.01 to 400 Pa; 40 steps logarithmically spaced in stress with 40 s being spent at each point to measure the shear rate (and hence viscosity); Step 1 is terminated once a shear rate of 0.1 s "1 is reached.
  • Step 2 Controlled shear rate steps from 0.1 to 1200 s "1 ; 40 steps logarithmically spaced in shear rate with 6 seconds being spent at each point to determine the stress required to maintain the shear rate and hence the viscosity.
  • Step 3 Controlled shear rate steps from 1200 to 0.1 s "1 ; 40 steps logarithmically spaced in shear rate with 6 seconds being spent at each point to determine the stress required to maintain the shear rate and hence the viscosity.
  • the yield stress in Pa is taken to be the value of the stress at a shear rate of 0.1 s "1 . I.e. the equivalent of the y-axis intercept in a Herschel-Buckley plot of shear stress vs. shear rate.
  • Figure 1 shows the rheology curves of liquid detergent compositions including the polysurfmer/copolymer mixture resulting from Examples 3 and 4, and copolymer 4 of Example 5. The figure shows that only the detergent composition including the polysurfmer/copolymer mixture of Example 3 exhibits an increase in viscosity at a shear stress of 0.1 Pa.
  • LAS is linear alkyl benzene sulphonate
  • SLES is sodium lauryl ether sulphate 3EO
  • EPEI is ethoxylated polyethylene imine PEI(600) 20EO
  • MPG is mono propylene glycol
  • opolymer thickener is polymer(ii) and copolymer mixture of Example 3

Abstract

La présente invention concerne une composition de liquide détergente aqueuse comprenant : (i) un système tensioactif comprenant un tensioactif anionique, et (ii) au moins 0,05 % en pds d'un polymère formé à partir de la polymérisation de monomères constitués du monomère (A1) : R1C=CR2R3 (A1) et éventuellement du monomère (A2) : R4C=CR5R6 (A2) R1 et R2 étant chacun indépendamment sélectionnés parmi un atome H, un groupe méthyle, -C(=O)OH, ou -C(=O)OR7, où R7 est un groupe alkyle en C1 à C30 ; R3 est un groupe T1-[CH2]k-[O]p-[R8O]q-Y1-R9 T1 est un groupe -CH2C(=O)O-, -C(=O)O-, -O-, -CH2O-, -NHC(=O)NH-, -C(=O)NH-, -Ar-(CE2)x-NHC(=O)O-, -Ar-(CE2)x-NHC(=O)NH-, ou -CH2CH2NHC(=O)-; Ar est un groupe aryle divalent; E est un atome H ou un groupe méthyle; x a la valeur de 0 ou 1; k est un nombre entier situé dans la plage de 0 à 30; et p a la valeur de 0 ou 1; éventuellement à condition que lorsque k a la valeur de 0, p a la valeur de 0, et lorsque k se trouve dans la plage de 1 à 30; p a la valeur de 1; (R8O)q est un groupe polyoxyalcylène, qui est un homopolymère, un copolymère aléatoire, ou un copolymère séquencé de motifs oxyalcylène en C2 à C4, où R8 est un groupe C2H4, C3H6, C4H8, ou un mélange de ceux-ci, et n est un nombre entier d'une valeur située dans la plage de 5 à 250; Y1 est un groupe -R8O-, -R8H-, -C(=O)-, -C(=O)NH-, =R8NHC(=O)NH-, ou - C(=O)NHC(=O)-; et R9 est un groupe alkyle substitué ou non substitué sélectionné dans le groupe constitué d'un groupe alkyle linéaire en C8 à C40, d'un groupe alkyle ramifié en C8 à C40, d'un groupe alkyle carbocyclique en C8 à C40, d'un groupe alkyle substitué en C2 à C40, d'un groupe phényle, alkyle en C2 à C40 substitué par un groupe aryle, et d'un ester complexe en C8 à C80 ; où le groupe alkyle R11 comprend éventuellement un ou plusieurs substituants sélectionnés dans le groupe constitué du groupe hydroxyle, alcoxy, et halogéno; R4 et R5 sont indépendamment un atome H ou un groupe alkyle en C1-4, préférablement un atome H ou un groupe méthyle; R6 est un groupe -C(O)-OR10, où R10 est un atome H ou un groupe alkyle en C1-4, préférablement un groupe H ou un groupe méthyle, plus préférablement un groupe H; et où le degré de polymérisation du polymère (ii) est de 30 ou plus.
EP18723009.9A 2017-05-15 2018-05-11 Composition Pending EP3625320A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17171132 2017-05-15
PCT/EP2018/062260 WO2018210700A1 (fr) 2017-05-15 2018-05-11 Composition

Publications (1)

Publication Number Publication Date
EP3625320A1 true EP3625320A1 (fr) 2020-03-25

Family

ID=58709852

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18723009.9A Pending EP3625320A1 (fr) 2017-05-15 2018-05-11 Composition

Country Status (2)

Country Link
EP (1) EP3625320A1 (fr)
WO (1) WO2018210700A1 (fr)

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL95044C (fr) 1953-06-30
US3577515A (en) 1963-12-13 1971-05-04 Pennwalt Corp Encapsulation by interfacial polycondensation
US3341466A (en) 1966-10-31 1967-09-12 Brynko Carl Process for making capsules
US4384096A (en) 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
FR2633930B1 (fr) 1988-07-07 1991-04-19 Coatex Sa Agent epaississant modificateur des caracteristiques rheologiques de compositions aqueuses chargees et/ou pigmentees, blanches ou colorees
US4946624A (en) 1989-02-27 1990-08-07 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
US5062995A (en) * 1990-02-06 1991-11-05 Lever Brothers Company, Division Of Conopco, Inc. Polymeric carbamate detergent builders
US5066419A (en) 1990-02-20 1991-11-19 The Procter & Gamble Company Coated perfume particles
US5154842A (en) 1990-02-20 1992-10-13 The Procter & Gamble Company Coated perfume particles
DE19646110A1 (de) 1996-11-08 1998-05-14 Bayer Ag Mikrokapseln unter Verwendung von Iminooxadiazindion-Polyisocyanaten
ZA9711582B (en) 1996-12-23 1999-06-23 Allied Colloids Ltd Particles having surface properties and methods of making them
DE10000223A1 (de) 2000-01-05 2001-07-12 Basf Ag Mikrokapselzubereitungen und Mikrokapseln enthaltende Wasch- und Reinigungsmittel
DE10051194A1 (de) 2000-10-16 2002-04-25 Bayer Ag Mikrokapseln mit Wänden aus Polyharnstoff
DE10051190A1 (de) 2000-10-16 2002-04-25 Bayer Ag Mikrokapseln mit Wänden aus Polyharnstoff
ES2475948T3 (es) 2000-10-27 2014-07-11 The Procter & Gamble Company Composiciones líquidas estabilizadas
US20020094938A1 (en) 2000-11-08 2002-07-18 The Procter & Gamble Company Photo-labile pro-fragrance conjugates
GB0106560D0 (en) 2001-03-16 2001-05-02 Quest Int Perfume encapsulates
GB0129983D0 (en) 2001-12-14 2002-02-06 Unilever Plc Unit dose products
JP2005528200A (ja) 2002-05-31 2005-09-22 マクマスター・ユニバーシテイ ポリウレアカプセル中に疎水性有機分子をカプセル化する方法
DE60303752T2 (de) 2002-09-30 2006-09-21 Rohm And Haas Co. Verdickungsmittel für wässerige Systeme mit einem hohen Gehalt an grenzflächenaktiven Mitteln
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
US20040142868A1 (en) 2003-01-21 2004-07-22 Sleeman Mark W. Method of treating liver steatosis in a mammal
DE602005014815D1 (de) 2004-12-23 2009-07-16 Unilever Nv Flüssigwaschmittel und ihre verwendung
PL2300586T3 (pl) 2008-06-16 2015-08-31 Unilever Nv Ulepszenia dotyczące czyszczenia tkanin
ES2534766T3 (es) * 2010-02-12 2015-04-28 Basf Se Uso de un copolímero como espesante en agentes de lavado líquidos con menor tendencia al agrisado
GB201116660D0 (en) 2011-09-28 2011-11-09 Unilever Plc Thickening vinyl copolymers
WO2014082874A1 (fr) * 2012-11-29 2014-06-05 Unilever Plc Compositions détergentes aqueuses structurées par un polymère
CN104797697B (zh) 2012-11-29 2018-10-23 荷兰联合利华有限公司 增稠水性洗涤液
BR112017016279B1 (pt) * 2015-01-29 2022-04-26 Unilever Ip Holdings B.V. Composição líquida de detergente aquoso espessado

Also Published As

Publication number Publication date
WO2018210700A1 (fr) 2018-11-22

Similar Documents

Publication Publication Date Title
AU2013351426B2 (en) Polymer structured aqueous detergent compositions
CA2275792C (fr) Compositions contenant du parfum
CN101868528B (zh) 关于织物处理组合物的改进
EP2841551B1 (fr) Compositions détergentes liquides isotropes aqueuses structurées de façon externe
EP2748297B1 (fr) Perfectionnements apportés aux polymères, auxiliaires de dépôt, agents traitants ciblés et compositions de traitement de substrats
CN103987830B (zh) 关于织物处理组合物的改进
WO2018210524A1 (fr) Composition
EP3625320A1 (fr) Composition
WO2018210523A1 (fr) Composition
EP2753681B1 (fr) Perfectionnements apportés aux agents traitants ciblés et compositions de traitement de substrats
WO2018210522A1 (fr) Composition
AU2020247336B2 (en) Laundry detergent compositions
CN104870320B (zh) 容纳织物处理流体的销售包装
EP3158047B1 (fr) Compositions détergentes, liquides, isotropes, aqueuses, structurées de façon externe
WO2019086273A1 (fr) Composition

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191111

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER GLOBAL IP LIMITED

Owner name: UNILEVER IP HOLDINGS B.V.

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER GLOBAL IP LIMITED

Owner name: UNILEVER IP HOLDINGS B.V.

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20220901