WO2020160996A1 - Improvements relating to fabric cleaning - Google Patents

Improvements relating to fabric cleaning Download PDF

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Publication number
WO2020160996A1
WO2020160996A1 PCT/EP2020/052274 EP2020052274W WO2020160996A1 WO 2020160996 A1 WO2020160996 A1 WO 2020160996A1 EP 2020052274 W EP2020052274 W EP 2020052274W WO 2020160996 A1 WO2020160996 A1 WO 2020160996A1
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WIPO (PCT)
Prior art keywords
composition
weight
weight based
total weight
anionic surfactants
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PCT/EP2020/052274
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French (fr)
Inventor
Nathan Robert BELL
Gary Alan Robert GRANT
David Rankin KENNEDY
Emily Grace SMITH
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
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Application filed by Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to EP20701792.2A priority Critical patent/EP3921402A1/en
Publication of WO2020160996A1 publication Critical patent/WO2020160996A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates or phosphonites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/364Organic compounds containing phosphorus containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters or polycarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D1/721End blocked ethers

Definitions

  • the present invention is concerned with improvements relating to fabric cleaning, and with an improved process for removing microorganisms from fabrics using a liquid laundry detergent.
  • US2015/0322387A1 describes an anti-microbial cleaning composition, comprising by weight of the composition, from 0.001% to 3% of a nonionic anti-microbial agent, and from 0.1% to 3% of a soil dispersant.
  • US2017/0191005A1 describes an aqueous liquid laundry formulation comprising an ester based laundry ingredient; an effective cleaning amount of protease enzyme; an effective cleaning amount of lipase enzyme; and from 5 to 60wt% surfactant; wherein at least 70wt% of the effective cleaning amount of lipase enzyme is encapsulated and separated from the ester based laundry ingredient and the liquid by a coating which is insoluble in the formulation but which dissolves on dilution with the wash; and wherein the laundry formulation comprises at least 20wt% water.
  • WO2009153184 describes such an approach, where the preferred formulations have high amounts of soil release polymer and antiredeposition polymer relative to the total detersive surfactants level.
  • the present invention addresses this problem.
  • the present invention provides a liquid laundry detergent composition for improved removal of microorganisms from fabrics, the composition comprising: a) from 5 to 11.5% (by weight based on the total weight of the composition) of
  • d) from 0.25 to 2% of transition metal ion sequestrants; in which the total amount of anionic surfactants (a) + nonionic surfactants (b) ranges from 8 to 15% (by weight based on the total weight of the composition); and in which the weight ratio of anionic surfactants (a) to nonionic surfactants (b) ranges from 3:1 to 12:1.
  • the invention further provides use of a liquid laundry composition according to the present invention for removal of microorganisms from fabrics.
  • laundry detergent in the context of this invention denotes formulated compositions intended for and capable of wetting and cleaning fabrics such as clothing, linens and other household textiles.
  • the term“linen” is often used to describe certain types of laundry items including bed sheets, pillow cases, towels, tablecloths, table napkins and uniforms.
  • Textiles can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.
  • liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.
  • liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.
  • liquid in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid, and that the composition is flowable at 15°C and above. Accordingly, the term“liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes.
  • the viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec 1 . This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle.
  • Pourable liquid detergent compositions generally have a viscosity of from 200 to 2,500 mPa.s, preferably from 200 to 1500 mPa.s.
  • polyethylene glycols having a weight average molecular weight (M w ) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates). Mixtures of any of the above described materials may also be used.
  • M w weight average molecular weight
  • Non-aqueous carriers when included, may be present in an amount ranging from 0.1 to 20%, preferably from 1 to 15%, and more preferably from 3 to 12% (by weight based on the total weight of the composition).
  • the composition of the invention preferably has a pH in the range of 5 to 9, more preferably 7 to 8, when measured on dilution of the composition to 1 % using
  • composition of the invention comprises from 5 to 11.5% (by weight based on the total weight of the composition) of anionic surfactants (a) selected from linear
  • Linear alkylbenzene sulfonates for use in the invention generally contain from about 10 to about 18 carbon atoms in the linear alkyl chain.
  • Commercial LAS is a mixture of closely related isomers and alkyl chain homologues, each containing an aromatic ring sulfonated at the“para" position and attached to a linear alkyl chain at any position except the terminal carbons.
  • the linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of from 12 to 14 carbon atoms.
  • Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers. except for the 1 -phenyl isomer.
  • LAS is produced as a salt by neutralizing it with a suitable counterion, which is typically selected from alkali metals such as sodium and potassium (preferably sodium); or ammoniacal counterions such as ammonium, monoethanolamine (MEA) and triethanolamine (TEA). Mixtures of such counterions may also be employed.
  • LAS may be formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.
  • Alkyl ether sulfates (AES) for use in the invention generally contain a straight or branched chain alkyl group having 10 to 16 carbon atoms.
  • Preferred types of AES have a structure corresponding to general formula (I):
  • M is preferably sodium, potassium, ammonium or ethanolamine
  • R is preferably a linear alkyl group having from 12 to 14 carbon atoms, and the average degree of ethoxylation n preferably ranges from 2.5 to 3.5.
  • AES generally contain a mixture of homologues and the degree of ethoxylation is a statistical average value which may be an integer or a fraction.
  • the value of n in general formula (I) is governed by the starting molar ratio of ethylene oxide to aliphatic alcohol in the ethoxylation reaction and the temperature, time and catalytic conditions under which the ethoxylation reaction takes place.
  • a commercially produced AES having general formula (I) will usually comprise a mixture of homologues in which from 55 to 80 mol% of the total mixture is made up of homologues with ethoxy chains of 5EO or less (down to OEO, i.e. unethoxylated alkyl sulfate), with the remainder of the mixture made up of homologues with ethoxy chains of 6EO or more (up to about 10EO).
  • Higher homologues e.g. up to about 15EO
  • a preferred mixture of anionic surfactants (a) for use in the invention contains:
  • the weight ratio of (ai):(aii) in the mixture preferably ranges from 8:1 to 1 :1 , more preferably from 4:1 to 2:1.
  • the total amount of anionic surfactants (a) in a composition of the invention preferably ranges from 8 to 11.5% (by weight based on the total weight of the composition).
  • composition of the invention comprises from 1 to 5% (by weight based on the total weight of the composition) of nonionic surfactants (b) selected from aliphatic alcohol ethoxylates.
  • Aliphatic alcohol ethoxylates for use in the invention may suitably be selected from Cs to Ci 8 primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
  • Preferred aliphatic alcohol ethoxylates for use in the invention may be selected from C12 to Ci5 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10, most preferably 7 to 9 moles of ethylene oxide per mole of alcohol.
  • the total amount of nonionic surfactants (b) in a composition of the invention preferably ranges from 1 to 3% (by weight based on the total weight of the composition).
  • the weight ratio of anionic surfactants (a) to nonionic surfactants (b) in a composition of the invention preferably ranges rom 3:1 to 10:1 , more preferably from 3.5:1 to 9.5:1.
  • the total amount of anionic surfactants (a) + nonionic surfactants (b) in a composition of the invention preferably ranges from 9 to 14%, more preferably from 10 to 13% (by weight based on the total weight of the composition).
  • a particularly preferred composition of the invention comprises, as the anionic surfactants (a) and nonionic surfactants (b):
  • composition of the invention comprises from 2.75 to 15% (by weight based on the total weight of the composition) of polymeric cleaning boosters (c) selected from soil release polymers and mixtures thereof with antiredeposition polymers.
  • polymeric cleaning boosters can aid the removal of microorganisms from fabrics.
  • SRPs help to improve the detachment of soils from fabric by modifying the fabric surface during washing.
  • the adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.
  • SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped.
  • the SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity.
  • the weight average molecular weight (M w ) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
  • SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid) with diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol).
  • the copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units.
  • oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
  • DMT dimethyl terephthalate
  • PG propylene
  • cellulosic derivatives such as hydroxyether cellulosic polymers, Ci-C 4 alkylcelluloses and C 4 hydroxyalkyl celluloses
  • Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (I):
  • R 1 and R 2 independently of one another are X-(OC 2 H 4 ) n -(OC 3 H 6 ) m ;
  • X is C1 -4 alkyl and preferably methyl
  • n is a number from 12 to 120, preferably from 40 to 50;
  • n is a number from 1 to 10, preferably from 1 to 7;
  • a is a number from 4 to 9.
  • n, n and a are not necessarily whole numbers for the polymer in bulk.
  • the total amount of SRP in a composition of the invention preferably ranges from 0.2 to 2%, more preferably from 0.4 to 1% (by weight based on the total weight of the composition) of one or more SRPs
  • Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil.
  • Suitable anti-redeposition polymers for use in the invention include alkoxylated polyethyleneimines.
  • Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • Preferred alkoxylated polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • polyethylenimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M w ).
  • the polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer.
  • the alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification.
  • a preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
  • Another type of suitable anti-redeposition polymer for use in the invention includes cellulose esters and ethers, for example sodium
  • the total amount of anti-redeposition polymer in a composition of the invention preferably ranges from 2.1 to 5%, more preferably from 2.2 to 3% (by weight based on the total weight of the composition).
  • a composition of the invention preferably comprises, as the polymeric cleaning boosters (c), a mixture of SRP (as further described above) and antiredeposition polymer (as further described above).
  • a particularly preferred composition of the invention comprises, as the polymeric cleaning boosters (c):
  • polyethyleneimines with a polyethyleneimine backbone of 300 to 10000 weight average molecular weight (M w ).and an average degree of ethoxylation of from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
  • the total amount of polymeric cleaning boosters (c) in a composition of the invention preferably ranges from 2.9 to 5%, more preferably from 3 to 4% and most preferably from greater than 3% to 3.5% (by weight based on the total weight of the composition).
  • the composition of the invention comprises from 0.25 to 2% of transition metal ion sequestrants (d).
  • the sequestrants (d) may help to improve the stability or cleaning performance of the composition, primarily by coordinating (i.e. binding) those transition metal ions which might otherwise interfere with these aspects.
  • transition metal ions which are commonly found in wash water include divalent and trivalent transition metal ions such as ferrous, ferric, manganese and copper ions.
  • Suitable sequestrants (d) include phosphonates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotris(methylene phosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta(methylene phosphonic acid (DTPMP) and their respective sodium or potassium salts. HEDP and DTPMP are preferred. Mixtures of any of the above described materials may also be used.
  • the total amount of sequestrants (d) in a composition of the invention preferably ranges from 0.3 to 0.9%, more preferably from 0.5 to 0.7% (by weight based on the total weight of the composition).
  • composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability, as follows:
  • a composition of the invention may contain one or more builders. Builders enhance or maintain the cleaning efficiency of the composition, primarily by controlling water hardness (calcium and magnesium) ions.
  • Builders for use in the invention can be of the organic or inorganic type, or a mixture thereof.
  • Suitable organic builders include polycarboxylates, in acid and/or salt form.
  • alkali metal e.g. sodium and potassium
  • alkanolammonium salts are preferred.
  • Specific examples of such materials include sodium and potassium citrates, sodium and potassium tartrates, the sodium and potassium salts of tartaric acid monosuccinate, the sodium and potassium salts of tartaric acid disuccinate, sodium and potassium ethylenediaminetetraacetates, sodium and potassium N(2-hydroxyethyl)- ethylenediamine triacetates, sodium and potassium nitrilotriacetates and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetates.
  • Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g. acrylic, methacrylic, vinylacetic, and crotonic acids) and/or unsaturated dicarboxylic acids (e.g. maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides).
  • unsaturated monocarboxylic acids e.g. acrylic, methacrylic, vinylacetic, and crotonic acids
  • unsaturated dicarboxylic acids e.g. maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides
  • Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic and maleic acid.
  • the polymers may be in acid, salt or partially neutralised form and may suitably have a molecular weight (Mw) ranging from about 1 ,000 to 100,000, preferably from about 2,000 to about 85,000,
  • Preferred builders for use in the invention may be selected from polycarboxylates (e.g. citrates) in acid and/or salt form (preferably in sodium salt form) and mixtures thereof.
  • Builder when included, may be present in an amount ranging from about 0.1 to about 1 %, (by weight based on the total weight of the composition).
  • a composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the anionic surfactants (a) and nonionic surfactants (b) described above.
  • cosurfactants such as amphoteric (zwitterionic) and/or cationic surfactants
  • Specific cationic surfactants include Csto Cis alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof.
  • Cationic surfactant when included, may be present in an amount ranging from about 0.1 to about 5% (by weight based on the total weight of the composition).
  • amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term“alkyl” being used to include the alkyl portion of higher acyl radicals.
  • Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from about 0.1 to about 5% (by weight based on the total weight of the composition).
  • Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond.
  • saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid
  • fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids.
  • Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).
  • the fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • Fatty acids and/or their salts when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).
  • a composition of the invention may comprise one or more rheology modifiers.
  • examples of such materials include polymeric thickeners and/or structurants such as
  • HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer.
  • acidic vinyl monomer such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer.
  • associative monomer in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section.
  • a preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section.
  • Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from linear or branched C8-C40 alkyl (preferably linear C12- C22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one further monomer selected from C1 -C4 alkyl (meth) acrylates, polyacidic vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof.
  • the polyethoxylated portion of the associative monomer (i) generally comprises about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.
  • a composition of the invention will preferably comprise from 0.1 to 5% (by weight based on the total weight of the composition) of one or more polymeric thickeners such as, for example, the HASE copolymers which are described above.
  • compositions of the invention may also have their rheology modified by use of one or more external structurants which form a structuring network within the composition.
  • external structurants include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre.
  • the presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid. Enzymes
  • a composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof.
  • the enzymes are preferably present with
  • a composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability.
  • additional optional ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye.
  • foam boosting agents e.g. bactericides
  • preservatives e.g. bactericides
  • polyelectrolytes e.g. bactericides
  • anti-shrinking agents e.g. bactericides
  • anti-wrinkle agents e.g. bactericides
  • anti-oxidants e.g. s, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye.
  • a composition of the invention generally contains no more than 0.2%, preferably no more than 0.1 %, more preferably no more than 0.01 % and most preferably 0% (by weight based on the total weight of the composition) of oxidising agents selected from halogen- based bleaches (e.g. alkali metal hypochlorites and alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids), oxygen-based bleaches (e.g. sodium perborate (tetra-or monohydrate), sodium percarbonate and hydrogen peroxide) and mixtures thereof.
  • halogen- based bleaches e.g. alkali metal hypochlorites and alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids
  • oxygen-based bleaches e.g. sodium perborate (tetra-or monohydrate), sodium percarbonate and hydrogen peroxide
  • a composition of the invention generally contains no more than 0.2% and preferably no more than 0.1% (by weight based on the total weight of the composition of biocides selected from quaternary ammonium salts (such as benzalkonium chloride,
  • imidazolium derivatives such as 1 ,10-di(3-decyl-2-methylimidazolium)decane dichloride, 1 ,10-di(3-decyl-2- methylimidazolium)decane dibromide, 1 ,12-di(3-decyl-2-methylimidazolium)dodecane dichloride, 1 ,12-di(3-octyl-2-methylimidazolium)dodecane dichloride, or 1 ,10-di(3-decyl-2- methylimidazolium)decane dichloride); biguanide compounds (such as polyaminopropyl biguanide (PHMB); guanidine compounds such as ethyl biguanide (PHMB); guanidine compounds such as ethyl biguanide (PHMB); guanidine compounds such as ethyl biguanide (PHMB); guan
  • a composition of the invention may also contain less than 0.001 % and preferably 0% (by weight based on the total weight of the composition) of a nonionic biocide.
  • Said biocide is preferably a diphenyl ether, more preferably a hydroxyl diphenyl ether.
  • the method of removing microorganisms from fabric according to the invention comprises the steps of: i) providing a dose of the liquid laundry detergent composition described above, ii) diluting the dose in water to obtain a wash liquor which comprises from 0.035 to 0.8g/l of the anionic surfactants (a),
  • microorganisms are Staphylococcus species (such as S. aureus, S.
  • the dose of liquid laundry detergent composition may be provided by packaging the composition as unit doses in polymeric film soluble in the wash water.
  • the composition may be supplied in multidose plastics packs with a top or bottom closure.
  • a dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
  • the method may suitably be carried out in a top-loading or front-loading automatic washing machine or can be carried out by hand.
  • automatic washing machines the dose of composition is typically put into a dispenser and from there it is flushed into the machine by the water flowing into the machine, thereby forming the wash liquor.
  • Dosages for a typical front-loading washing machine may range from about 10 ml to about 60 ml, preferably about 15 to 40 ml. Dosages for a typical top-loading washing machine (using from 40 to 60 litres of water to form the wash liquor) may be higher, e.g. up to about 100 ml. Lower dosages of composition (e.g. 50 ml or less) may be used for hand washing methods (using about 1 to 10 litres of water to form the wash liquor).
  • the wash liquor comprises from 0.25 to 0.55 g/l of the anionic surfactants (a).
  • a subsequent aqueous rinse step and drying the laundry is preferred. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor.
  • the laundry drying step can take place either in an automatic dryer or in the open air.
  • Examples according to the invention are indicated by a number; and comparative examples (not according to the invention) are indicated by a letter.
  • Liquid laundry detergent formulations were prepared by sequential mixing of the ingredients as shown in Table 1. Table 1
  • the detergents were assessed for their efficacy at removing typical human skin bacteria from inoculated textiles.
  • a 4 log reduction of the bacterial population compared to a water control is considered a pass.

Abstract

The invention provides a liquid laundry detergent composition for improved removal of microorganisms (e.g. Staphylococcus species) from fabrics, the composition comprising: a) from 5 to 11.5% (by weight based on the total weight of the composition) of anionic surfactants selected from linear alkylbenzene sulfonates and mixtures thereof with alkyl ether sulfate; b) from 1 to 5% (by weight based on the total weight of the composition) of nonionic surfactants selected from aliphatic alcohol ethoxylates; c) from 2.75 to 15% (by weight based on the total weight of the composition) of polymeric cleaning boosters selected from soil release polymers and mixtures thereof with antiredeposition polymers; d) from 0.25 to 2% of transition metal ion sequestrants; in which the total amount of anionic surfactants (a) + nonionic surfactants (b) ranges from 8 to 15% (by weight based on the total weight of the composition); and in which the weight ratio of anionic surfactants (a) to nonionic surfactants (b) ranges from 3:1 to 12:1.

Description

IMPROVEMENTS RELATING TO FABRIC CLEANING
Field of the Invention
The present invention is concerned with improvements relating to fabric cleaning, and with an improved process for removing microorganisms from fabrics using a liquid laundry detergent.
Background and Prior Art
During wear, fabrics are prone to contamination with microorganisms from the human skin together with sebaceous lipids, sweat and dead skin cells serving as microbial substrates. An unpleasant odor generated from laundry hung to dry, or even laundry that is already dry, is thought to arise as a consequence of microorganisms surviving the laundering process (for example Staphylococcus species such as S. aureus, S.
epidermis, S. intermedius, S. saprophyticus and S. hyicus ).
Traditional approaches to combat microbial contamination have involved laundering at elevated temperatures and in a highly alkaline medium along with the use of oxidizing bleaches or quaternary ammonium biocides.
However, environmental awareness and rising energy costs are driving the trend towards milder and lower temperature (40°C or less) fabric washing conditions. Washing at cooler temperatures is also advisable for care of coloured and/or delicate fabrics.
At the same time, environmental regulations are becoming more stringent in many countries, making it necessary for formulators to produce detergents that reduce potential negative impacts on wastewater and waterways, and reduce greenhouse gas emissions.
One route to improving the environmental profile of liquid laundry detergents is the addition of highly weight efficient or multi-functional materials to replace traditional materials such as surfactants, resulting in a lower overall chemicals usage. US2015/0322387A1 describes an anti-microbial cleaning composition, comprising by weight of the composition, from 0.001% to 3% of a nonionic anti-microbial agent, and from 0.1% to 3% of a soil dispersant.
US2017/0191005A1 describes an aqueous liquid laundry formulation comprising an ester based laundry ingredient; an effective cleaning amount of protease enzyme; an effective cleaning amount of lipase enzyme; and from 5 to 60wt% surfactant; wherein at least 70wt% of the effective cleaning amount of lipase enzyme is encapsulated and separated from the ester based laundry ingredient and the liquid by a coating which is insoluble in the formulation but which dissolves on dilution with the wash; and wherein the laundry formulation comprises at least 20wt% water.
WO2009153184 describes such an approach, where the preferred formulations have high amounts of soil release polymer and antiredeposition polymer relative to the total detersive surfactants level.
Whilst liquid laundry detergents of the type described in WO2009153184 have proven to be successful, the satisfactory removal of microorganisms presents a continuing challenge, especially in view of the shift towards milder and lower temperature fabric washing conditions.
The present invention addresses this problem.
Summary of the Invention
The present invention provides a liquid laundry detergent composition for improved removal of microorganisms from fabrics, the composition comprising: a) from 5 to 11.5% (by weight based on the total weight of the composition) of
anionic surfactants selected from linear alkylbenzene sulfonates and mixtures thereof with alkyl ether sulfate;
b) from 1 to 5% (by weight based on the total weight of the composition) of nonionic surfactants selected from aliphatic alcohol ethoxylates; c) from 2.75 to 15% (by weight based on the total weight of the composition) of polymeric cleaning boosters selected from, soil release polymers and mixtures thereof with antiredeposition polymers;
d) from 0.25 to 2% of transition metal ion sequestrants; in which the total amount of anionic surfactants (a) + nonionic surfactants (b) ranges from 8 to 15% (by weight based on the total weight of the composition); and in which the weight ratio of anionic surfactants (a) to nonionic surfactants (b) ranges from 3:1 to 12:1.
The invention also provides a method of removing microorganisms from fabric which comprises the steps of: i) providing a dose of the liquid laundry detergent composition described above, ii) diluting the dose in water to obtain a wash liquor which comprises from 0.035 to 0.8g/l of the anionic surfactants (a),
and
iii) washing the fabrics with the wash liquor so formed.
The invention further provides use of a liquid laundry composition according to the present invention for removal of microorganisms from fabrics.
Detailed Description and Preferred Embodiments
Liquid laundry detergents
The term“laundry detergent” in the context of this invention denotes formulated compositions intended for and capable of wetting and cleaning fabrics such as clothing, linens and other household textiles. The term“linen” is often used to describe certain types of laundry items including bed sheets, pillow cases, towels, tablecloths, table napkins and uniforms. Textiles can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.
Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.
The term“liquid” in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid, and that the composition is flowable at 15°C and above. Accordingly, the term“liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes. The viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec1. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. Pourable liquid detergent compositions generally have a viscosity of from 200 to 2,500 mPa.s, preferably from 200 to 1500 mPa.s.
Liquid detergent compositions which are pourable gels generally have a viscosity of from 1 ,500 mPa.s to 6,000 mPa.s, preferably from 1 ,500 mPa.s to 2,000 mPa.s.
A composition of the invention may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% water (by weight based on the total weight of the composition). The composition may also incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol);
polyethylene glycols having a weight average molecular weight (Mw) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates). Mixtures of any of the above described materials may also be used.
Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 20%, preferably from 1 to 15%, and more preferably from 3 to 12% (by weight based on the total weight of the composition).
The composition of the invention preferably has a pH in the range of 5 to 9, more preferably 7 to 8, when measured on dilution of the composition to 1 % using
demineralised water.
The composition of the invention comprises from 5 to 11.5% (by weight based on the total weight of the composition) of anionic surfactants (a) selected from linear
alkylbenzene sulfonates and mixtures thereof with alkyl ether sulfate
Linear alkylbenzene sulfonates (LAS) for use in the invention generally contain from about 10 to about 18 carbon atoms in the linear alkyl chain. Commercial LAS is a mixture of closely related isomers and alkyl chain homologues, each containing an aromatic ring sulfonated at the“para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of from 12 to 14 carbon atoms. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers. except for the 1 -phenyl isomer. LAS is produced as a salt by neutralizing it with a suitable counterion, which is typically selected from alkali metals such as sodium and potassium (preferably sodium); or ammoniacal counterions such as ammonium, monoethanolamine (MEA) and triethanolamine (TEA). Mixtures of such counterions may also be employed. LAS may be formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.
Alkyl ether sulfates (AES) for use in the invention generally contain a straight or branched chain alkyl group having 10 to 16 carbon atoms. Preferred types of AES have a structure corresponding to general formula (I):
R-0-(CH2CH2-0)n-S03-M (I) in which R is a straight or branched chain alkyl group having 10 to 16 carbon atoms, n is a number that represents the degree of ethoxylation and ranges from 2 to 4, and M is an alkali metal, ammonium or alkanolammonium cation;
In general formula (I), M is preferably sodium, potassium, ammonium or ethanolamine, R is preferably a linear alkyl group having from 12 to 14 carbon atoms, and the average degree of ethoxylation n preferably ranges from 2.5 to 3.5.
Commercially produced AES generally contain a mixture of homologues and the degree of ethoxylation is a statistical average value which may be an integer or a fraction. The value of n in general formula (I) is governed by the starting molar ratio of ethylene oxide to aliphatic alcohol in the ethoxylation reaction and the temperature, time and catalytic conditions under which the ethoxylation reaction takes place.
A commercially produced AES having general formula (I) will usually comprise a mixture of homologues in which from 55 to 80 mol% of the total mixture is made up of homologues with ethoxy chains of 5EO or less (down to OEO, i.e. unethoxylated alkyl sulfate), with the remainder of the mixture made up of homologues with ethoxy chains of 6EO or more (up to about 10EO). Higher homologues (e.g. up to about 15EO) may also be present in small amounts (typically no more than 1 to 2 mol% of the total mixture per individual homologue).
Mixtures of any of the above described materials may also be used.
A preferred mixture of anionic surfactants (a) for use in the invention contains:
(ai) On to Ci5 LAS, and
(aii) Ci2 to CM linear AES with an average degree of ethoxylation ranging from 2.5 to 3.5.
The weight ratio of (ai):(aii) in the mixture preferably ranges from 8:1 to 1 :1 , more preferably from 4:1 to 2:1. The total amount of anionic surfactants (a) in a composition of the invention preferably ranges from 8 to 11.5% (by weight based on the total weight of the composition).
The composition of the invention comprises from 1 to 5% (by weight based on the total weight of the composition) of nonionic surfactants (b) selected from aliphatic alcohol ethoxylates.
Aliphatic alcohol ethoxylates for use in the invention may suitably be selected from Cs to Ci8 primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.
Preferred aliphatic alcohol ethoxylates for use in the invention may be selected from C12 to Ci5 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10, most preferably 7 to 9 moles of ethylene oxide per mole of alcohol.
Mixtures of any of the above described materials may also be used.
The total amount of nonionic surfactants (b) in a composition of the invention preferably ranges from 1 to 3% (by weight based on the total weight of the composition).
The weight ratio of anionic surfactants (a) to nonionic surfactants (b) in a composition of the invention preferably ranges rom 3:1 to 10:1 , more preferably from 3.5:1 to 9.5:1.
The total amount of anionic surfactants (a) + nonionic surfactants (b) in a composition of the invention preferably ranges from 9 to 14%, more preferably from 10 to 13% (by weight based on the total weight of the composition).
A particularly preferred composition of the invention comprises, as the anionic surfactants (a) and nonionic surfactants (b):
(ai) from 6 to 10% (by weight based on the total weight of the composition) of Cn to C15 LAS; (aii) from 1 to 3% (by weight based on the total weight of the composition) of C12 to CM linear AES with an average degree of ethoxylation ranging from 2.5 to 3.5, and
(b) from 1 to 3% (by weight based on the total weight of the composition) of C12 to C15 primary linear alcohol ethoxylate with an average of from 5 to 10 moles of ethylene oxide per mole of alcohol.
The composition of the invention comprises from 2.75 to 15% (by weight based on the total weight of the composition) of polymeric cleaning boosters (c) selected from soil release polymers and mixtures thereof with antiredeposition polymers. Without wishing to be bound by theory, it is believed that polymeric cleaning boosters can aid the removal of microorganisms from fabrics.
SRPs help to improve the detachment of soils from fabric by modifying the fabric surface during washing. The adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.
SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped. The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (Mw) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.
SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid) with diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.
Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, Ci-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example C1-C6 vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.
Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (I):
Figure imgf000010_0001
in which R1 and R2 independently of one another are X-(OC2H4)n-(OC3H6)m ;
in which X is C1 -4 alkyl and preferably methyl;
n is a number from 12 to 120, preferably from 40 to 50;
m is a number from 1 to 10, preferably from 1 to 7; and
a is a number from 4 to 9.
Because they are averages, m, n and a are not necessarily whole numbers for the polymer in bulk.
Mixtures of any of the above described materials may also be used. The total amount of SRP in a composition of the invention (such as, for example, the copolyesters of general formula (I) as are described above) preferably ranges from 0.2 to 2%, more preferably from 0.4 to 1% (by weight based on the total weight of the composition) of one or more SRPs
Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil. Suitable anti-redeposition polymers for use in the invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. Preferred alkoxylated
polyethylenimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (Mw). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone. Another type of suitable anti-redeposition polymer for use in the invention includes cellulose esters and ethers, for example sodium
carboxymethyl cellulose.
Mixtures of any of the above described materials may also be used.
The total amount of anti-redeposition polymer in a composition of the invention preferably ranges from 2.1 to 5%, more preferably from 2.2 to 3% (by weight based on the total weight of the composition).
A composition of the invention preferably comprises, as the polymeric cleaning boosters (c), a mixture of SRP (as further described above) and antiredeposition polymer (as further described above). A particularly preferred composition of the invention comprises, as the polymeric cleaning boosters (c):
(ci) from 0.2 to 2%, more preferably from 0.4 to 1% (by weight based on the total weight of the composition) of SRP selected from copolyesters of dicarboxylic acids with diols and polydiols, and
(cii) from 2.1 to 5%, more preferably from 2.2 to 3% (by weight based on the total weight of the composition) of anti-redeposition polymer selected from ethoxylated
polyethyleneimines with a polyethyleneimine backbone of 300 to 10000 weight average molecular weight (Mw).and an average degree of ethoxylation of from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
The total amount of polymeric cleaning boosters (c) in a composition of the invention preferably ranges from 2.9 to 5%, more preferably from 3 to 4% and most preferably from greater than 3% to 3.5% (by weight based on the total weight of the composition).
The composition of the invention comprises from 0.25 to 2% of transition metal ion sequestrants (d). The sequestrants (d) may help to improve the stability or cleaning performance of the composition, primarily by coordinating (i.e. binding) those transition metal ions which might otherwise interfere with these aspects. Examples of such transition metal ions which are commonly found in wash water include divalent and trivalent transition metal ions such as ferrous, ferric, manganese and copper ions.
Suitable sequestrants (d) include phosphonates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotris(methylene phosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta(methylene phosphonic acid (DTPMP) and their respective sodium or potassium salts. HEDP and DTPMP are preferred. Mixtures of any of the above described materials may also be used. The total amount of sequestrants (d) in a composition of the invention preferably ranges from 0.3 to 0.9%, more preferably from 0.5 to 0.7% (by weight based on the total weight of the composition).
Optional ingredients
A composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability, as follows:
Builders
A composition of the invention may contain one or more builders. Builders enhance or maintain the cleaning efficiency of the composition, primarily by controlling water hardness (calcium and magnesium) ions.
Builders for use in the invention can be of the organic or inorganic type, or a mixture thereof.
Suitable inorganic builders include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites, and mixtures thereof. Specific examples of such materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.
Suitable organic builders include polycarboxylates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrates, sodium and potassium tartrates, the sodium and potassium salts of tartaric acid monosuccinate, the sodium and potassium salts of tartaric acid disuccinate, sodium and potassium ethylenediaminetetraacetates, sodium and potassium N(2-hydroxyethyl)- ethylenediamine triacetates, sodium and potassium nitrilotriacetates and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetates. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g. acrylic, methacrylic, vinylacetic, and crotonic acids) and/or unsaturated dicarboxylic acids (e.g. maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic and maleic acid. The polymers may be in acid, salt or partially neutralised form and may suitably have a molecular weight (Mw) ranging from about 1 ,000 to 100,000, preferably from about 2,000 to about 85,000, and more preferably from about 2,500 to about 75,000
Mixtures of any of the above described materials may also be used. Preferred builders for use in the invention may be selected from polycarboxylates (e.g. citrates) in acid and/or salt form (preferably in sodium salt form) and mixtures thereof.
Builder, when included, may be present in an amount ranging from about 0.1 to about 1 %, (by weight based on the total weight of the composition).
Cosurfactants
A composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the anionic surfactants (a) and nonionic surfactants (b) described above.
Specific cationic surfactants include Csto Cis alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof. Cationic surfactant, when included, may be present in an amount ranging from about 0.1 to about 5% (by weight based on the total weight of the composition).
Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term“alkyl” being used to include the alkyl portion of higher acyl radicals. Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from about 0.1 to about 5% (by weight based on the total weight of the composition).
Mixtures of any of the above described materials may also be used.
Fatty Acid
A composition of the invention may in some cases contain one or more fatty acids and/or salts thereof.
Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).
The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.
Mixtures of any of the above described materials may also be used.
Fatty acids and/or their salts, when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).
Rheology modifiers
A composition of the invention may comprise one or more rheology modifiers. Examples of such materials include polymeric thickeners and/or structurants such as
hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer. The term“associative monomer” in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section. A preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section. Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from linear or branched C8-C40 alkyl (preferably linear C12- C22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one further monomer selected from C1 -C4 alkyl (meth) acrylates, polyacidic vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.
Mixtures of any of the above described materials may also be used.
When included, a composition of the invention will preferably comprise from 0.1 to 5% (by weight based on the total weight of the composition) of one or more polymeric thickeners such as, for example, the HASE copolymers which are described above.
Compositions of the invention may also have their rheology modified by use of one or more external structurants which form a structuring network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre. The presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid. Enzymes
A composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present with
corresponding enzyme stabilizers.
Further Optional Ingredients
A composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the composition).
A composition of the invention generally contains no more than 0.2%, preferably no more than 0.1 %, more preferably no more than 0.01 % and most preferably 0% (by weight based on the total weight of the composition) of oxidising agents selected from halogen- based bleaches (e.g. alkali metal hypochlorites and alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids), oxygen-based bleaches (e.g. sodium perborate (tetra-or monohydrate), sodium percarbonate and hydrogen peroxide) and mixtures thereof.
A composition of the invention generally contains no more than 0.2% and preferably no more than 0.1% (by weight based on the total weight of the composition of biocides selected from quaternary ammonium salts (such as benzalkonium chloride,
didecyldimethylammonium chloride, didecylmethylpolyoxyethyleneammonium propionate, didecylmethylammonium carbonate, or benzethonium chloride); imidazolium derivatives (such as 1 ,10-di(3-decyl-2-methylimidazolium)decane dichloride, 1 ,10-di(3-decyl-2- methylimidazolium)decane dibromide, 1 ,12-di(3-decyl-2-methylimidazolium)dodecane dichloride, 1 ,12-di(3-octyl-2-methylimidazolium)dodecane dichloride, or 1 ,10-di(3-decyl-2- methylimidazolium)decane dichloride); biguanide compounds (such as polyaminopropyl biguanide (PHMB); guanidine compounds such as ethoxyethylguanidine chloride and polyaminopropyl guanidine hydrochloride(PHMG)); and bis(aminoalkyl)alkylamine compounds (such as bis(aminopropyl)dodecylamine) and mixtures thereof.
A composition of the invention may also contain less than 0.001 % and preferably 0% (by weight based on the total weight of the composition) of a nonionic biocide. Said biocide is preferably a diphenyl ether, more preferably a hydroxyl diphenyl ether.
Packaging, dosing and use
The method of removing microorganisms from fabric according to the invention comprises the steps of: i) providing a dose of the liquid laundry detergent composition described above, ii) diluting the dose in water to obtain a wash liquor which comprises from 0.035 to 0.8g/l of the anionic surfactants (a),
and
iii) washing the fabrics with the wash liquor so formed.
Preferably the microorganisms are Staphylococcus species (such as S. aureus, S.
epidermis, S. intermedius, S. saprophyticus and S. hyicus; and especially S. aureus).
The dose of liquid laundry detergent composition may be provided by packaging the composition as unit doses in polymeric film soluble in the wash water. Alternatively the composition may be supplied in multidose plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.
The method may suitably be carried out in a top-loading or front-loading automatic washing machine or can be carried out by hand. In automatic washing machines, the dose of composition is typically put into a dispenser and from there it is flushed into the machine by the water flowing into the machine, thereby forming the wash liquor.
Dosages for a typical front-loading washing machine (using 10 to 15 litres of water to form the wash liquor) may range from about 10 ml to about 60 ml, preferably about 15 to 40 ml. Dosages for a typical top-loading washing machine (using from 40 to 60 litres of water to form the wash liquor) may be higher, e.g. up to about 100 ml. Lower dosages of composition (e.g. 50 ml or less) may be used for hand washing methods (using about 1 to 10 litres of water to form the wash liquor).
Preferably, the wash liquor comprises from 0.25 to 0.55 g/l of the anionic surfactants (a).
A subsequent aqueous rinse step and drying the laundry is preferred. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor. The laundry drying step can take place either in an automatic dryer or in the open air.
The invention will now be further described with reference to the following non-limiting Examples.
EXAMPLES
All weight percentages are by weight based on total weight unless otherwise specified.
Examples according to the invention are indicated by a number; and comparative examples (not according to the invention) are indicated by a letter.
Liquid laundry detergent formulations were prepared by sequential mixing of the ingredients as shown in Table 1. Table 1
Figure imgf000020_0001
The detergents were assessed for their efficacy at removing typical human skin bacteria from inoculated textiles.
Method Knitted cotton and polyester test fabrics were hygiene washed twice on a cotton 60°C cycle using an ECE reference powder, dried and cut into 1 cm2 pieces (test carriers). The sterilised, dried test carriers were inoculated with Staphyloccous aureus ATCC 6538, (a typical example of a skin colonising bacterial species). Bovine serum albumin (BSA) was used as a model interfering substance and was added to the bacterial inoculum at 0.3%.
Polycotton (50:50) ballast fabric was cut into pieces of approx.6 x 8 cm2, sterilised and dried. The formulations of Table 1 were used to wash the inoculated test carriers in a model wash system according to typical front loader washing conditions (5.5g/L test formulation in 9L of 25° French Hard water at 30°C for 66 minutes followed by 2 rinses). Sufficient ballast fabric was used to provide a representative main wash load (5L test wash liquor to 1 kg fabric).
Following the wash the bacteria were recovered into quench by vortexing the test carriers with glass beads. Survivors were enumerated by serial dilution and viable counting. The data was then used to calculate the log reduction of the bacterial population achieved, compared with that of a water control.
Results
The results are shown in Table 2.
Table 2
Figure imgf000021_0001
A 4 log reduction of the bacterial population compared to a water control is considered a pass.
It can be seen from the results that Examples 1 to 3 according to the invention pass the test whereas the comparative Example A does not.

Claims

1. A liquid laundry detergent composition for improved removal of microorganisms from fabrics, the composition comprising: a) from 5 to 11.5% (by weight based on the total weight of the composition) of
anionic surfactants selected from linear alkylbenzene sulfonates and mixtures thereof with alkyl ether sulfate;
b) from 1 to 5% (by weight based on the total weight of the composition) of nonionic surfactants selected from aliphatic alcohol ethoxylates;
c) from 2.75 to 15% (by weight based on the total weight of the composition) of polymeric cleaning boosters selected from soil release polymers and mixtures thereof with antiredeposition polymers;
d) from 0.25 to 2% of transition metal ion sequestrants; in which the total amount of anionic surfactants (a) + nonionic surfactants (b) ranges from 8 to 15% (by weight based on the total weight of the composition); and in which the weight ratio of anionic surfactants (a) to nonionic surfactants (b) ranges from 3:1 to 12:1.
2. A composition according to claim 1 , in which the anionic surfactants (a) are
(ai) On to Ci5 LAS, and
(aii) Ci2 to CM linear AES with an average degree of ethoxylation ranging from 2.5 to 3.5.
3. A composition according to claim 1 or claim 2, in which the total amount of anionic surfactants (a) ranges from 8 to 11.5% (by weight based on the total weight ofthe composition).
4. A composition according to any one of claims 1 to 3, in which the nonionic
surfactants (b) are selected from C12 to C15 primary linear alcohol ethoxylates with an average of from 5 to 10 moles of ethylene oxide per mole of alcohol.
5. A composition according to any one of claims 1 to 4, in which the total amount of nonionic surfactants (b) ranges from 1 to 3% (by weight based on the total weight of the composition).
6. A composition according to any one of claims 1 to 5, which comprises:
(ai) from 6 to 10% (by weight based on the total weight of the composition) of Cn to Ci5 LAS;
(aii) from 1 to 3% (by weight based on the total weight of the composition) of C12 to CM linear AES with an average degree of ethoxylation ranging from 2.5 to 3.5, and
(b) from 1 to 3% (by weight based on the total weight of the composition) of C12 to Ci5 primary linear alcohol ethoxylate with an average of from 5 to 10 moles of ethylene oxide per mole of alcohol.
7. A composition according to any preceding claim which comprises, as the
polymeric cleaning boosters (c):
(ci) from 0.2 to 2%, more preferably from 0.4 to 1% (by weight based on the total weight of the composition) of SRP selected from copolyesters of dicarboxylic acids with diols and polydiols, and
(cii) from 2.1 to 5%, more preferably from 2.2 to 3% (by weight based on the total weight of the composition) of anti-redeposition polymer selected from ethoxylated polyethyleneimines with a polyethyleneimine backbone of 300 to 10000 weight average molecular weight (Mw).and an average degree of ethoxylation of from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.
8. A composition according to any preceding claim in which the sequestrants (d) are selected from HEDP and DTPMP and mixtures thereof; and in which the total amount of sequestrants (d) ranges from 0.3 to 0.9% (by weight based on the total weight of the composition).
9. A method of removing microorganisms from fabric which comprises the steps of: i) providing a dose of the liquid laundry detergent composition according to any one of claims 1 to 8,
ii) diluting the dose in water to obtain a wash liquor which comprises from 0.035 to 0.8g/l of the anionic surfactants (a),
and
iii) washing the fabrics with the wash liquor so formed.
10. A method according to claim 9, in which the microorganisms are Staphylococcus species.
11. Use of a liquid laundry detergent composition according to any one of claims 1 to 8 for removal of microorganisms from fabrics.
12. Use according to claim 11 , wherein a dose of the liquid laundry detergent
composition is provided and diluted in water to obtain a wash liquor which comprises from 0.035 to 0.8g/L of the anionic surfactants (a), and the fabrics are washed with the wash liquor so formed.
13. Use according to claim 11 or claim 12, wherein the microorganisms are
Staphylococcus species.
PCT/EP2020/052274 2019-02-04 2020-01-30 Improvements relating to fabric cleaning WO2020160996A1 (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2009153184A1 (en) 2008-06-16 2009-12-23 Unilever Plc Improvements relating to fabric cleaning
US20150322387A1 (en) 2014-05-12 2015-11-12 The Procter & Gamble Company Anti-microbial cleaning composition
US20170191005A1 (en) 2014-05-22 2017-07-06 Conopco, Inc., D/B/A Unilever Aqueous liquid detergent formulation comprising enzyme particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009153184A1 (en) 2008-06-16 2009-12-23 Unilever Plc Improvements relating to fabric cleaning
US20150322387A1 (en) 2014-05-12 2015-11-12 The Procter & Gamble Company Anti-microbial cleaning composition
US20170191005A1 (en) 2014-05-22 2017-07-06 Conopco, Inc., D/B/A Unilever Aqueous liquid detergent formulation comprising enzyme particles

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