WO2018118824A1 - Composition de détergent textile - Google Patents
Composition de détergent textile Download PDFInfo
- Publication number
- WO2018118824A1 WO2018118824A1 PCT/US2017/067156 US2017067156W WO2018118824A1 WO 2018118824 A1 WO2018118824 A1 WO 2018118824A1 US 2017067156 W US2017067156 W US 2017067156W WO 2018118824 A1 WO2018118824 A1 WO 2018118824A1
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- WO
- WIPO (PCT)
- Prior art keywords
- detersive surfactant
- coated
- detergent particle
- acid
- detersive
- 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.)
- Ceased
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- 0 CC(c1ccccc1)c(cc1C(C)c2ccccc2)cc(C(C)c2ccccc2)c1O*(C)(*)N Chemical compound CC(c1ccccc1)c(cc1C(C)c2ccccc2)cc(C(C)c2ccccc2)c1O*(C)(*)N 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
Definitions
- the present invention relates to a laundry detergent composition having a lenticular size and shape, and to a process for making such lenticular detergent compositions.
- compositions that are in the form of lenticles.
- These solid particles are of a shape and size that exhibit improved physical performance characteristics compared to the conventional particulate detergent products. For example, dosing from the container, especially a bottle, can be improved compared to conventional laundry detergent powders.
- the larger size of such lenticular particles means that the surface area to volume ratio is much less than for conventional detergent particles. Hence dissolution behaviour can be much worse unless mitigating steps are taken.
- the lenticular particles often have the form of a surfactant-rich core surrounded by a coating layer. Hence there is an interest in processes that can change the properties of the surfactant-rich cores through process conditions such as shear rate and temperature so as to increase dissolution behaviours.
- the present invention seeks to provide a lenticular laundry detergent product having an improved dissolution profile and a process of making such a lenticular laundry detergent product.
- the present invention provides a coated detergent particle having perpendicular dimensions x, y and z, wherein x is from 1 to 2 mm, y is from 2 to 8mm, and z is from 2 to 8 mm, wherein the particle comprises:
- detersive surfactant selected from anionic detersive surfactant and/or non-ionic detersive surfactant
- (c) optionally, from 10wt% to 40wt% citric acid and/or salts thereof; wherein the detersive surfactant comprises from 51wt% to 100wt% alkyl benzene sulphonate,
- the coating comprises the inorganic salt (b), and wherein the core comprises the detersive surfactant (a),
- alkyl benzene sulphonate has a degree of orientation of at least 92%, preferably at least 95%.
- the coated detergent particle has perpendicular dimensions x, y and z, wherein x is from 1 to 2 mm, y is from 2 to 8mm, and z is from 2 to 8 mm, wherein the particle comprises:
- detersive surfactant selected from anionic detersive surfactant and/or non-ionic detersive surfactant
- (c) optionally, from 10wt% to 40wt% citric acid and/or salts thereof; wherein the detersive surfactant comprises from 51wt% to 100wt% alkyl benzene sulphonate,
- the coating comprises the inorganic salt (b), and wherein the core comprises the detersive surfactant (a),
- alkyl benzene sulphonate has a degree of orientation of at least 92%, preferably at least 95%.
- the coated detergent particle is also referred to herein as the composition.
- the composition has a pH in the range of from 7.6 to 10.0.
- the composition has a reserve alkalinity to pH 7.5 of greater than 3.0.
- the composition is in the form of a coated laundry detergent particle that is curved.
- the coating comprises the inorganic salt (b), and wherein the core comprises the detersive surfactant (a).
- the coated laundry detergent particle may be shaped as a disc.
- the coated laundry detergent particle does not have hole; that is to say, the coated laundry detergent particle does not have a conduit that passes through the core: i.e. the coated detergent particle has a topologic genus of zero.
- the composition may comprise from 0.05 wt% to 4.0wt% soil release polymer.
- the composition may comprise from 0.1wt% to 3.0wt% carboxymethylcellulose (CMC).
- the composition may comprise from 0.1wt% to 5.0wt% calcite.
- the composition may comprise from lwt% to 10wt% carboxylate polymer.
- the composition may comprise less than 10wt% total level of silicates and aluminosilicates.
- the composition may comprise from 0.00 lwt% to 0.5 wt% hueing dye.
- composition may comprise from 0.001wt% to 0.5wt% organic pigment and/or inorganic pigment.
- the composition may comprise from 0.2 wt% to 10wt% chelant, preferably phosphonate chelant.
- composition preferably comprises from 10wt% to 40wt% sodium carbonate.
- the process comprises the following steps:
- step (ii) extruding the detersive mixture of step (i) to form an extruded material
- Step (iv) removing water from the wet coated extruded material to form the coated detergent particle, wherein, in step (ii) the material in the orifice of the extruder is subjected to a shear rate of at least 0.033ms 1 , preferably least 0.33ms 1 .
- the anionic detersive surfactant is selected from alkyl benzene sulphonate, alkyl ether sulphate and/or alkyl sulphate.
- the detersive mixture has a hardness of from IMPa to lOOMPa during the roller compaction step (ii).
- a suitable detersive surfactant comprises from 80wt% to 95wt% alkyl benzene sulphonate, and from 6wt% to 10wt% 8% alkyl ethoxylated alcohol having an average degree of ethoxylation of from 5 to 9.
- Such a detersive surfactant can be prepared by blending the nonionic detersive surfactant into HLAS and rapidly neutralizing the mix with aqueous caustic solution followed by drying in an oven, preferably a vacuum oven until the eRH of the surfactant is less than 10%. This surfactant can then be milled in any suitable device, such as a coffee grinder or mill.
- a suitable detersive surfactant comprises at least 51wt% alkyl benzenesulphonate.
- a suitable detersive surfactant comprises no more than 20wt% non-ionic detersive surfactant.
- the detersive surfactant is dried prior to step (ii).
- a suitable drying means include an evaporator or drier.
- a suitable drying means include a wiped film evaporator, fluid bed drier and/or a tube drier.
- the detersive mixture introduced into step (ii) comprises less than 1.5 wt% water.
- the detersive mixture is cooled prior to step (ii).
- a suitable cooling means indues a chill roll.
- the detersive surfactant may be transferred to a mill and milled to particles of less than 1.5 mm, preferably less than 1 mm, before it is fed to the extrusion step (ii).
- a powdered flow aid with a particle diameter of from ⁇ . ⁇ to ⁇ is added to the mill in an amount of 0.5wt% to 5 wt% (wt% based on the detersive misture), and blended into the surfactant particles during milling.
- Step (ii) The detersive mixture of step (i) is extruded to form an extruded material.
- the extruder has a void commensurate with the size of the particle before coating.
- the detersive mixture is fed into a twin-screw co-rotating extruder equipped with a die-plate and cutting mechanism.
- the extruder is typically cooled during operation.
- a suitable extruder is an APV 24.
- Another suitable extruder includes a roller compactor.
- Extrusion rates of from 2 to 8 kg/hr are suitable, and a die-plate with orifices of from 3 to 7 mm can be used.
- the die-plate can be equipped with a rotary cutter so as to give an extrudate thickness of from 1mm to 2mm.
- the temperature of the detersive mixture does not exceed 45°C, and preferably does not exceed 40°C, during the extrusion step (ii).
- the extruded material produced by step (ii) is an oblate spheroid.
- the diameter of the extruded material produced by step (ii) is greater than 4mm
- the coating material is selected from powdered inorganic material and mixtures of such material and nonionic material with a melting point in the range 40°C to 90°C.
- step (iv) is carried out in a fluidized bed and/or a drum.
- the coated detergent particle comprises from lwt% to 5wt% water.
- the coated detergent particle is curved.
- a suitable detersive surfactant system typically comprises at least
- a suitable detersive surfactant system typically comprises at least 5% alcohol ethoxylate having an average degree of ethoxylation in the range of from 10 to 50 as a percentage of the total detersive surfactant system.
- the detersive surfactant comprises C8-C24 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 20 to 50, and preferably the compositon comprises from lwt% to 10wt% C8-C24 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 20 to 50.
- a suitable highly ethoxylated alcohol is Lutensol® AO30 from BASF and/or
- Anionic detersive surfactant Suitable anionic detersive surfactants include sulphonate and sulphate detersive surfactants.
- Suitable sulphonate detersive surfactants include methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates, preferably Cio-13 alkyl benzene sulphonate.
- Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
- Suitable sulphate detersive surfactants include alkyl sulphate, preferably C 8-18 alkyl sulphate, or predominantly C12 alkyl sulphate.
- a preferred sulphate detersive surfactant is alkyl alkoxylated sulphate, preferably alkyl ethoxylated sulphate, preferably a C 8-18 alkyl alkoxylated sulphate, preferably a C 8-18 alkyl ethoxylated sulphate, preferably the alkyl alkoxylated sulphate has an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulphate is a C 8-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 and most preferably from 0.5 to 1.5.
- alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted, and may be derived from petrochemical material or biomaterial.
- anionic detersive surfactants include alkyl ether carboxylates.
- Suitable anionic detersive surfactants may be in salt form, suitable counter-ions include sodium, calcium, magnesium, amino alcohols, and any combination thereof.
- suitable counter- ion is sodium.
- Alkyl ether carboxylic acid A suitable alkyl ether carboxylic acid has the following structure:
- R is selected from saturated and mono-unsaturated C10 to C26 linear or branched alkyl chains, preferably C12 to C24 linear or branched alkyl chains, most preferably a C16 to C20 linear alkyl chain; n is selected from 5 to 20, preferably 7 to 13, more preferably 8 to 12, most preferably 9.5 to 10.5; and
- the alkyl ether carboxylic acid may be present from 0.5 to 20 wt%, preferably from 2 to 14 wt%, most preferably from 2.5 to 5 wt%. It may be present in acid or salt form, most preferably as its sodium salt. Suitable materials are sold under the AKYPO ® (Kao) and Empicol ® C (Huntsman) brand names.
- Non-ionic detersive surfactant Suitable non-ionic detersive surfactants are selected from the group consisting of: Cs-Cis alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C6-C12 alkyl phenol alkoxylates wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; alkylpolysaccharides, preferably alkylpolyglycosides; methyl ester ethoxylates; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
- Cs-Cis alkyl ethoxylates such as, NEODOL® non-ionic surfactants from Shell
- Suitable non-ionic detersive surfactants are alkylpolyglucoside and/or an alkyl alkoxylated alcohol.
- Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, preferably C 8-18 alkyl alkoxylated alcohol, preferably a C 8-18 alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is a C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5 and most preferably from 3 to 7.
- the alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
- Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants.
- a suitable amino acid derivative complexing agent is selected from one or more of the following, in any stereoisomer or mixture of stereoisomer form:
- the composition comprises from 0.1wt% to 10wt% methylglycinediacetic acid and salts thereof (MGDA)
- amino acid derivative complexing agent it may be preferred to formulate the amino acid derivative complexing agent in acid form.
- amino acid derivative complexing agent in salt form, especially preferred is the sodium salt form.
- Suitable MGDA salts are produced by BASF.
- Suitable GLDA salts are produced by Akzo Nobel and Showa Denko.
- Suitable ASDA salts are produced by Mitsubishi Rayon.
- Alkoxylated polyaryl/polyalkyl phenol A suitable alkoxylated polyaryl/polyalkyl phenol has the following structure:
- Ri is selected from linear of branched C3-C15 alkyl groups and aryl groups
- X is selected from ethoxy or propoxy groups
- n is from 2 to 70
- T is selected from H, SO 3 -, COO- and PO3 2"
- the alkoxylated polyaryl or alkoxylated polyalkyl phenol is preferably selected from groups (i) to (iv):
- R is selected from SO 3 -, COO- and PO3 2" , preferably selected from SO 3 - and COO-, wherein n is selected from 2 to 54.
- R is selected from SO 3 -, COO- and PO 3 2- , preferably selected from SO 3 - and COO-, wherein n is selected from 6 to 50.
- Such compounds are available from industrial suppliers, for example Solvay under the Soprophor trade name, from Clariant under the Emulsogen trade name, Aoki Oil Industrial Co. under the Blaunon trade name, from Stepan under the Makon trade name, and from TOTO Chemical Industry Co. under the Sorpol trade name.
- suitable compounds are Emulsogen® TS160, Hostapal® BV conc., Sapogenat® T110 or Sapogenat® T139, all from Clariant.
- the alkoxylated polyaryl/polyalkyl phenol may be present at levels of 0.5-20wt%, preferably l-15wt%, most preferably 3-10wt%.
- Amylase variant comprises: (a) a deletion and/or a substitution at two or more positions corresponding to positions R181 , G182, H183 and G184 of the mature polypeptide of SEQ ID NO: 1 , and
- substitutions selected from the group consisting of: I206Y;F;Q;P;R;V;C;G;A;C;D;E;H;K;L;M;N;S;T, particularly I206Y;F;C;L;H;S, N195F;Y;H;K;L,
- E190P;R;V;F;C;G;A;C;D;Q;H;I;K;L;M;N;S;T;Y particularly E190P, A204Q;P;R;V;F;C;G;C;D;E;H;I;K;L;M;N;S;T;Y, particularly A204T, H210M;D;C;A;Q;S;F;N;E;T, P21 lQ;R;V;F;C;G;A;C;D;E;H;l;K;L;M;N;S;T;Y,particularly P211L;M;S;Q;G;V;W;A;H;T;R; E212T;R;S;V;L;Y;R;T;G;
- V213Q;P;R;F;C;G;A;C;D;E;H;I;K;L;M;N;S;T;Y particularly V213T;A;G;S;C;L;P, V214Q;P;R;F;C;G;A;C;D;E;H;I;K;L;M;N;S;T;Y, particularly V214T;I, L217M;Q;V;I;H, particularly L217V,
- One preferred amylase variant comprises a sequence corresponding to SEQ ID NO: 1 with the following mutations: H183*+G184*+I405L+A421H+A422P+A428T.
- a suitable amylase is commercially available from Novozymes under the Amplify® brand name, for example as a liquid raw material as Amplify® 12L.
- a suitable lipase is a variant of SEQ ID NO:2 comprising:
- One preferred lipase is a variant of SEQ ID NO: 2 comprising the following substitutions: T231R, N233R, D27R, G38A, D96E, Di l l A, G163K, D254S and P256T
- One preferred lipase is a variant of SEQ ID NO: 2 comprising the following substitutions T231R, N233R, N33Q, G91Q, E210Q, I255A.
- Suitable lipases are commercially available from Novozymes, for example as Lipex Evity 100L (a liquid raw material) and Lipex Evity 105T (a granulate). These lipases have different structures to the products Lipex 100L, Lipex 100T and Lipex Evity 100T which are outside the scope of this particular lipase definition.
- Metalloproteases can be derived from animals, plants, bacteria or fungi.
- Suitable metalloprotease can be selected from the group of neutral metalloproteases and Myxobacter metalloproteases.
- Suitable metalloproteases can include collagenases, hemorrhagic toxins from snake venoms and thermolysin from bacteria.
- thermolysin enzyme variants include an M4 peptidase, more preferably the thermolysin enzyme variant is a member of the PepSY ⁇ Peptidase_M4 ⁇ Peptidase_M4_C family.
- thermolysin enzyme variant can have at least 50% identity to the thermolysin set forth in SEQ ID NO: 3.
- the thermolysin enzyme variant is from a genus selected from the group consisting of Bacillus, Geobacillus, Alicyclobacillus, Lactobacillus, Exiguobacterium, Brevibacillus, Paenibacillus, Herpeto siphon, Oceanobacillus, Shewanella, Clostridium, Staphylococcus, Flavobacterium, Stigmatella, Myxococcus, Vibrio, Methanosarcina, Chryseobacterium, Streptomyces,Kribbella, Janibacter, Nocardioides, Xanthamonas, Micromonospora, Burkholderia, Dehalococcoides,Croceibacter, Kordia, Microscilla, Thermoactinomyces, Chloroflexus, Listeria, Plesiocystis,Hali
- thermolysin enzyme variant is from a genus selected from the group consisting of Bacillus, Geobacillus, Alicyclobacillus, Lactobacillus, Exiguobacterium, Brevibacillus, Paenibacillus, Herpeto siphon, Oceanobacillus, Shewanella, Clostridium, Staphylococcus, Flavobacterium, Stigmatella, Myxococcus, Vibrio, Methanosarcina, Chryseobacterium, and Pseudoalteromonas.
- thermolysin enzyme is from the genus Bacillus.
- Preferred metalloproteases include thermolysin, matrix metalloproteinases and those metalloproteases derived from Bacillus subtilis, Bacillus thermoproteolyticus, Geobacillus stearothermophilus or Geobacillus sp. , or Bacillus amyloliquefaciens, as described in US PA 2008/0293610A1.
- a specially preferred metalloprotease belongs to the family EC3.4.24.27.
- thermolysin variants described in WO2014/71410.
- the metalloprotease is a variant of a parent protease, said parent protease having at least 60%, or 80%, or 85% or 90% or 95% or 96% or 97% or 98% or 99% or even 100% identity to SEQ ID NO:3 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO:3:
- the metalloprotease protease is a variant of a parent protease, said parent protease having at least 60%, or 80%, or 85% or 90% or 95% or 96% or 97% or 98% or 99% or even 100% identity to SEQ ID NO:3 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO:3:
- metalloproteases are the NprE variants described in WO2007/044993, WO2009/058661 and US 2014/0315775.
- the protease is a variant of a parent protease, said parent protease having at least 45%, or 60%, or 80%, or 85% or 90% or 95% or 96% or 97% or 98% or 99% or even 100% identity to SEQ ID NO:4 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO:4:
- Another suitable metalloprotease is a variant of a parent protease, said parent protease having at least 60%, or 80%, or 85% or 90% or 95% or 96% or 97% or 98% or 99% or even 100% identity to SEQ ID NO:4 including those with substitutions at one or more of the following sets of positions versus SEQ ID NO:4:
- M138L/V190I/D220P S129I/V190I, S129V/V190I, S129V/D220P, S129I/F130L/D220P, T004V/S023N, T059K S66Q/S129I, T059R S66N/S129I, S129I/F130L/M138L/V190I/D220P and T059K S66Q/S 129V.
- Especially preferred metalloproteases for use herein belong belong to EC classes EC 3.4.22 or EC3.4.24, more preferably they belong to EC classes EC3.4.22.2, EC3.4.24.28 or
- Suitable commercially available metalloprotease enzymes include those sold under the trade names Neutrase® by Novozymes A/S (Denmark), the Corolase® range including
- a preferred metalloprotease is selected from the M4 Metalloprotease Family.
- a suitable water-soluble builder system comprising one or more aminocarboxylates, selected from: methylglycine diacetic acid (MGDA) and/or alkali metal or ammonium salts thereof; N,N-dicarboxymethyl glutamic acid (GLDA) and/or alkali metal or ammonium salts thereof; Aspartic acid ⁇ , ⁇ -diacetic acid (ASDA) and/or alkali metal or ammonium salts thereof; Ethylene diamine-N,N'-disuccunic acid (EDDS) and/or alkali metal or ammonium salt thereof; 2-hydroxy propylene diamine-N,N'-disuccunic acid (HPDDS), and/or alkali metal or ammonium salt thereof; ethylenediamine-N,N'-diglutaric acid (EDDG and/or alkali metal or ammonium salt thereof; ethylenediamine-N,N'-bis-(orthohydroxyphenyl)acetic acid (EDDHA)
- a suitable phosphonate chelant is selected from: 1- hydroxy ethane- 1,1-diphosphonic acid (HEDP); Diethylene triamine pentamethylene phosphonic acid (DTPMP, CW-Base); 2-phosphonobutane-l,2,4-tricarboxylic acid (PBTC); Amino trimethylene phosphonic acid (ATMP); Ethylenediamine tetramethylene phosphonic acid (EDTMP); Diethylenetriamine pentamethylene phosphonic acid (DTPMP); Aminotrimethylene phosphonic acid (ATMP); salts of the aforementioned materials; and any combination thereof.
- HEDP 1- hydroxy ethane- 1,1-diphosphonic acid
- DTPMP Diethylene triamine pentamethylene phosphonic acid
- CW-Base 2-phosphonobutane-l,2,4-tricarboxylic acid
- PBTC 2-phosphonobutane-l,2,4-tricarboxylic acid
- ATMP Amino trim
- Carboxylate polymer The composition may comprise a carboxylate polymer, such as a maleate/acrylate random copolymer, maleic-olefin copolymers or polyacrylate homopolymer.
- Suitable carboxylate polymers include: polyacrylate homopolymers having a molecular weight of from 4,000 Da to 9,000 Da; maleate/acrylate random copolymers having a molecular weight of from 50,000 Da to 100,000 Da, or from 60,000 Da to 80,000 Da.
- Acusol 410N, Acusol 445N polyacrylic acid, Na salt
- Acusol 450N and Acusol 480N modified polyacrylic acid, Na salt
- Acusol 460N maleic acid/olefin, Na salt
- Sokolan CP5 and Sokolan CP12S maleic acid/acrylic acid, Na salt
- Sokolan CP 9 maleic acid/olefin, Na salt.
- the Acusol series are available from Rohm & Haas, Philadelphia, PA and the Sokolan series are available from BASF (Germany and New Jersey).
- Suitable carboxylate polymers can contain other monomers including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, modified maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
- Suitable carboxylate polymers can also containing 2-acrylamido-2-methyl-l- propanesulfonic acid, 2-methacrylamido-2-methyl-l-propanesulfonic acid, 3-methacrylamido-2- hydroxy-propanesulfonic acid, allysulfonic acid, methallysulfonic acid, 2-hydroxy-3-(2- propenyloxy)propanesulfonic acid, 2-methyl-2-propenen-l-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropylmethacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and water soluble salts thereof.
- Another suitable carboxylate polymer is a co-polymer that comprises: (i) from 50 to less than 98 wt% structural units derived from one or more monomers comprising carboxyl groups; (ii) from 1 to less than 49 wt% structural units derived from one or more monomers comprising sulfonate moieties; and (iii) from 1 to 49 wt% structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II): formula (I):
- Ro represents a hydrogen atom or CH3 group
- R represents a CH2 group, CH2CH2 group or single bond
- X represents a number 0-5 provided X represents a number 1-5 when R is a single bond
- Ri is a hydrogen atom or Ci to C20 organic group
- Ro represents a hydrogen atom or CH3 group
- R represents a CH2 group, CH2CH2 group or single bond
- X represents a number 0-5
- Ri is a hydrogen atom or Ci to C20 organic group.
- the composition may comprise a soil release polymer.
- a suitable soil release polymer has a structure as defined by one of the following structures (I), (II) or (III):
- a, b and c are from 1 to 200;
- d, e and f are from 1 to 50;
- Ar is a 1,4-substituted phenylene
- sAr is 1,3-substituted phenylene substituted in position 5 with SCbMe;
- Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are Ci-Cis alkyl or C2-C10 hydroxyalkyl, or mixtures thereof;
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H or Ci-Cis n- or iso-alkyl; and R 7 is a linear or branched Ci-Cis alkyl, or a linear or branched C2-C30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group.
- Suitable soil release polymers are sold by Clariant under the TexCare® series of polymers, e.g. TexCare® SRN240 and TexCare® SRA300.
- Other suitable soil release polymers are sold by Solvay under the Repel-o-Tex® series of polymers, e.g. Repel-o-Tex® SF2 and Repel-o-Tex® Crystal.
- Anti-redeposition polymer examples include polyethylene glycol polymers and/or polyethyleneimine polymers.
- Suitable polyethylene glycol polymers include random graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol; and (ii) hydrophobic side chain(s) selected from the group consisting of: C4-C25 alkyl group, polypropylene, polybutylene, vinyl ester of a saturated Ci-C 6 mono-carboxylic acid, Ci-C 6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof.
- Suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone can be in the range of from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da.
- the molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can be in the range of from 1:1 to 1:5, or from 1: 1.2 to 1:2.
- the average number of graft sites per ethylene oxide units can be less than 1, or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can be in the range of from 0.1 to 0.5, or from 0.2 to 0.4.
- a suitable polyethylene glycol polymer is Sokalan HP22. Suitable
- polyethylene glycol polymers are described in WO08/007320.
- Cellulosic polymer Suitable cellulosic polymers are selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl cellulose, sulphoalkyl cellulose, more preferably selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixures thereof.
- Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da.
- Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, e.g. as described in WO09/154933.
- Suitable care polymers include cellulosic polymers that are cationically modified and/or hydrophobically modified. Such modified cellulosic polymers can provide anti- abrasion benefits and dye lock benefits to fabric during the laundering cycle.
- Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.
- Suitable care polymers also include guar polymers that are cationically and/or hydrophobically modified.
- Other suitable care polymers include dye lock polymers, for example the condensation oligomer produced by the condensation of imidazole and epichlorhydrin, preferably in ratio of 1:4:1.
- Suitable care polymers include amino-silicone, which can provide fabric feel benefits and fabric shape retention benefits.
- the composition may comprise an alkoxylated polyalkyleneimine, wherein said alkoxylated polyalkyleneimine has a polyalkyleneimine core with one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein said alkoxylated polyalkyleneimine has an empirical formula (I) of (PEI) a -(EO)t > -Ri, wherein a is the average number- average molecular weight (MWPEI) of the polyalkyleneimine core of the alkoxylated polyalkyleneimine and is in the range of from 100 to 100,000 Daltons, wherein b is the average degree of ethoxylation in said one or more side chains of the alkoxylated polyalkyleneimine and is in the range of from 5 to 40, and wherein Ri is independently selected from the group consisting of hydrogen, C1-C4 alkyls, and combinations thereof.
- MWPEI average number- average molecular weight
- the composition may comprise an alkoxylated polyalkyleneimine, wherein said alkoxylated polyalkyleneimine has a polyalkyleneimine core with one or more side chains bonded to at least one nitrogen atom in the polyalkyleneimine core, wherein the alkoxylated polyalkyleneimine has an empirical formula (II) of (PEI) 0 -(EO)m(PO) n -R2 or (PEI) 0 -(PO)n(EO) m - R2, wherein o is the average number-average molecular weight (MWPEI) of the
- polyalkyleneimine core of the alkoxylated polyalkyleneimine is in the range of from 100 to 100,000 Daltons, wherein m is the average degree of ethoxylation in said one or more side chains of the alkoxylated polyalkyleneimine which ranges from 10 to 50, wherein n is the average degree of propoxylation in said one or more side chains of the alkoxylated polyalkyleneimine which ranges from 1 to 50, and wherein R2 is independently selected from the group consisting of hydrogen, C1-C4 alkyls, and combinations thereof.
- Suitable bleach includes sources of hydrogen peroxide, bleach activators, bleach catalysts, pre-formed peracids and any combination thereof.
- a particularly suitable bleach includes a combination of a source of hydrogen peroxide with a bleach activator and/or a bleach catalyst.
- Source of hydrogen peroxide include sodium perborate and/or sodium percarbonate.
- Suitable bleach activators include tetra acetyl ethylene diamine and/or alkyl oxybenzene sulphonate.
- Bleach catalyst The composition may comprise a bleach catalyst.
- Suitable bleach catalysts include oxaziridinium bleach catalysts, transistion metal bleach catalysts, especially manganese and iron bleach catalysts.
- a suitable bleach catalyst has a structure corresponding to general formula below:
- R 13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso- decyl, iso-tridecyl and iso-pentadecyl.
- Pre-formed peracid Suitable pre-form peracids include phthalimido-peroxycaproic acid. However, it is preferred that the composition is substantially free of pre-formed peracid. By: “substantially free” it is meant: “no deliberately added”.
- Suitable enzymes include lipases, proteases, cellulases, amylases and any combination thereof.
- Protease Suitable proteases include metalloproteases and/or serine proteases. Examples of suitable neutral or alkaline proteases include: subtilisins (EC 3.4.21.62); trypsin-type or chymotrypsin-type proteases; and metalloproteases.
- the suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.
- Suitable commercially available protease enzymes include those sold under the trade names
- Alcalase® Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxacal®, Maxapem®, Preferenz P® series of proteases including Preferenz® P280, Preferenz® P281, Preferenz® P2018-C,
- BLAP BLAP
- BLAP R BLAP with S3T + V4I + V199M + V205I + L217D
- BLAP X BLAP with S3T + V4I + V205I
- BLAP F49 BLAP with S3T + V4I + A194P + V199M + V205I + L217D
- a suitable protease is described in WO11/140316 and WOl 1/072117.
- Amylase Suitable amylases are derived from AA560 alpha amylase endogenous to
- Bacillus sp. DSM 12649 preferably having the following mutations: R118K, D183*, G184*, N195F, R320K, and/or R458K.
- Suitable commercially available amylases include Stainzyme®, Stainzyme® Plus, Natalase, Termamyl®, Termamyl® Ultra, Liquezyme® SZ, Duramyl®, Everest® (all Novozymes) and Spezyme® AA, Preferenz S® series of amylases, Purastar® and Purastar® Ox Am, Optisize® HT Plus (all Du Pont).
- a suitable amylase is described in WO06/002643.
- Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum.
- cellulases include Celluzyme®, Carezyme®, and Carezyme® Premium, Celluclean® and Whitezyme® (Novozymes A/S), Revitalenz® series of enzymes (Du Pont), and Biotouch® series of enzymes (AB Enzymes).
- Suitable commercially available cellulases include Carezyme® Premium, Celluclean® Classic. Suitable cellulases are described in WO07/144857 and WO10/056652.
- Suitable lipases include those of bacterial, fungal or synthetic origin, and variants thereof. Chemically modified or protein engineered mutants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces), e.g., from H.
- T. lanuginosa T. lanuginosus
- the lipase may be a "first cycle lipase", e.g. such as those described in WO06/090335 and WO 13/ 116261.
- the lipase is a first-wash lipase, preferably a variant of the wild- type lipase from Thermomyces lanuginosus comprising T231R and/or N233R mutations.
- Preferred lipases include those sold under the tradenames Lipex®, Lipolex® and Lipoclean® by Novozymes, Bagsvaerd, Denmark.
- Liprl 139 e.g. as described in WO2013/171241
- TfuLip2 e.g. as described in WO2011/084412 and WO2013/033318.
- bleaching enzymes such as
- peroxidases/oxidases which include those of plant, bacterial or fungal origin and variants thereof.
- Commercially available peroxidases include Guardzyme® (Novozymes A/S).
- Other suitable enzymes include choline oxidases and perhydrolases such as those used in Gentle Power BleachTM.
- Suitable enzymes include pectate lyases sold under the tradenames X-Pect®, Pectaway® (from Novozymes A/S, Bagsvaerd, Denmark) and PrimaGreen® (DuPont) and mannanases sold under the tradenames Mannaway® (Novozymes A/S, Bagsvaerd, Denmark), and Mannastar® (Du Pont).
- identity refers to the relatedness between two amino acid sequences.
- the degree of sequence identity between two amino acid sequences is determined using the Needleman-Wunsch algorithm (Needleman and Wunsch, 1970, /. Mol. Biol. 48: 443-453) as implemented in the Needle program of the EMBOSS package (EMBOSS: The European Molecular Biology Open Software Suite, Rice et al, 2000, Trends Genet. 16: 276-277), preferably version 3.0.0 or later.
- the optional parameters used are gap open penalty of 10, gap extension penalty of 0.5, and the EBLOSUM62 (EMBOSS version of
- Brightener Suitable fluorescent brighteners include: di-styryl biphenyl compounds, e.g. Tinopal® CBS-X, di-amino stilbene di-sulfonic acid compounds, e.g. Tinopal® DMS pure Xtra and Blankophor® HRH, and Pyrazoline compounds, e.g. Blankophor® SN, and coumarin compounds, e.g. Tinopal® SWN.
- di-styryl biphenyl compounds e.g. Tinopal® CBS-X
- di-amino stilbene di-sulfonic acid compounds e.g. Tinopal® DMS pure Xtra and Blankophor® HRH
- Pyrazoline compounds e.g. Blankophor® SN
- coumarin compounds e.g. Tinopal® SWN.
- Preferred brighteners are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[l,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl)amino 1 ,3,5- triazin-2-yl)]amino ⁇ stilbene-2- 2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-l,3,5-triazin-2-yl)]amino ⁇ stilbene-2- 2' disulfonate, and disodium 4,4'- bis(2-sulfostyryl)biphenyl.
- a suitable fluorescent brightener is C.I. Fluorescent Brightener 260, which may be used in its beta or alpha crystalline forms, or a mixture of these forms.
- Hueing agent Suitable hueing agents include small molecule dyes, typically falling into the Colour Index (C.I.) classifications of Acid, Direct, Basic, Reactive (including hydrolysed forms thereof) or Solvent or Disperse dyes, for example classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination.
- C.I. Colour Index
- Solvent or Disperse dyes for example classified as Blue, Violet, Red, Green or Black, and provide the desired shade either alone or in combination.
- Preferred such hueing agents include Acid Violet 50, Direct Violet 9, 66 and 99, Solvent Violet 13 and any combination thereof.
- hueing agents are known and described in the art which may be suitable for the present invention, such as hueing agents described in WO2014/089386.
- Suitable hueing agents include phthalocyanine and azo dye conjugates, such as described in WO2009/069077.
- Suitable hueing agents may be alkoxylated. Such alkoxylated compounds may be produced by organic synthesis that may produce a mixture of molecules having different degrees of alkoxylation. Such mixtures may be used directly to provide the hueing agent, or may undergo a purification step to increase the proportion of the target molecule.
- Suitable hueing agents include alkoxylated bis-azo dyes, such as described in WO2012/054835, and/or alkoxylated thiophene azo dyes, such as described in WO2008/087497 and WO2012/166768.
- the hueing agent may be incorporated into the detergent composition as part of a reaction mixture which is the result of the organic synthesis for a dye molecule, with optional purification step(s).
- reaction mixtures generally comprise the dye molecule itself and in addition may comprise un-reacted starting materials and/or by-products of the organic synthesis route.
- Suitable hueing agents can be incorporated into hueing dye particles, such as described in WO
- the composition at lwt% dilution in deionized water at 20°C has a reserve alkalinity to pH 7.5 of less than 3.0gNaOH/100g, preferably less than 2.5gNaOH/100g, or even less than 2.0gNaOH/100g.
- the term "reserve alkalinity” is a measure of the buffering capacity of the detergent composition (g/NaOH/lOOg detergent composition) determined by titrating a 1% (w/v) solution of detergent composition with hydrochloric acid to pH 7.5 i.e. in order to calculate Reserve Alkalinity as defined herein:
- lOg sample accurately weighed to two decimal places, of fully formulated detergent composition.
- the sample should be obtained using a Pascall sampler in a dust cabinet.
- the degree of surfactant lamellar alignment can be determined and quantified by the use of
- SAXS Small Angle X-Ray Scattering techniques
- SAXS analysis was caried out on the extrudates as follows: A Xenocs Xeusss 2.0 machine was used equipped with a Pilatus 200k detector and a Cu Genix source. The sample to detector distance was 363mm as per manfacturers recommendations for surfactant type materials.
- the data was recorded using a 2D detector so as to allow measurement of the degree of orientation of the lamellar phase.
- extruded material from each shear rate was cut using a very sharp knife edge to form extrudate discs or "salami slices" of approx 1mm thickness.
- Each extrudate being tested was mounted in a grooved sample holder and measured in two perpindicular orientations as shown below. All measurements were carried out at ambient ( ⁇ 20 °C).
- the tengant of the minima at ⁇ /2 and 3 ⁇ /2 is defined as the constant baseline. Integration of the full curve is then carried out.
- Surfactant powder was prepared as follows lOOOg of C12-14 linear alkylbenzene sulphonic acid (HLAS) (sourced from Tensachem SA) was placed in the bowl of a kitchen Kenwood K-Blade mixer. 245g of a 50% active sodium hydroxide solution were gradually added to the HLAS over a 5 minute period with vigorous stirring so as to avoid excessive generation of heat. After the sodium hydroxide solution had been added, the stirring was continued at a medium speed for a further 20 minutes to allow the reaction to complete. The stirring was then stopped and the paste allowed to cool to ambient.
- HLAS C12-14 linear alkylbenzene sulphonic acid
- the composition of the surfactant powder was calculated (based on measurement of weight loss) to be 88.4% LAS, 8.6% AE7, 1.8% PEG 4000 with the balance being water and miscellaneous. This powder was then divided into three batches and used to make surfactant extrudates at different shear rates as follows. All tests were done at ambient temperature ( ⁇ 20 °C) with no sources of external heating or cooling on the die or piston. ⁇ 30g of surfactant powder was loaded into a die consisting of a circular steel cylinder of length 100mm and internal diameter 26mm. One end of the die was open to allow entry of a suitable piston or punch and in the other end there was a 5mm diameter circular orifice located axisymmetrically.
- the length of the orifice through the steel of the die was 3mm.
- the loaded die was suitably mounted on an Instron 3369 Compression Tester and a suitable punch placed in the die such that it closely fitted the internal diameter but could still be moved without excessive force.
- the punch loosely compressed the surfactant powder.
- the crosshead of the Instron was moved such that the load cell of the Instron (model 2525) forced the punch down at a controlled speed. This first compressed the surfactant powder and then forced the surfactant powder to be extruded through the orifice at a controlled constant speed. This was continued until all the surfactant powder had been extruded.
- the test was carried out at three different crosshead speeds (0.1 mm/minute, 0.5mm/minute and 5mm/minute) using ⁇ 30g portions of the powder made above. This gave three separate examples of extrudates made at different crosshead speeds and thus different shear rates in the orifice.
- Shear Rate ⁇ 4 x Velocity ⁇ /Radius
- Velocity average velocity of material passing through the orifice in metres/second
- the samples were then coated with inorganic coating agent and tested for solubility.
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Abstract
La présente invention concerne une particule de détergent revêtue ayant des dimensions perpendiculaires x, y et z, x étant de 1 à 2 mm, y étant de 2 à 8 mm, et z étant de 2 à 8 mm, la particule comprenant : (g) de 20 % en poids à 39 % en poids de tensioactif détersif choisi parmi un tensioactif détersif anionique et/ou un tensioactif détersif non ionique ; (h) de 10 % en poids à 40 % en poids de sels inorganiques choisis parmi du carbonate de sodium, du sesquicarbonate de sodium, du bicarbonate de sodium et des mélanges quelconques de ceux-ci ; (i) éventuellement, de 10 % en poids à 40 % en poids d'acide citrique et/ou de sels de celui-ci ; le tensioactif détersif comprenant de 51 % en poids à 100 % en poids de benzènesulfonate d'alkyle, le revêtement comprenant le sel inorganique (b), et le cœur comprenant le tensioactif détersif (a), le benzènesulfonate d'alkyle présentant un degré d'orientation d'au moins 92 %, de préférence d'au moins 95 %.
Applications Claiming Priority (34)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16206498 | 2016-12-22 | ||
| EP16206451.3 | 2016-12-22 | ||
| EP16206480.2 | 2016-12-22 | ||
| EP16206490.1 | 2016-12-22 | ||
| EP16206477.8 | 2016-12-22 | ||
| EP16206461.2 | 2016-12-22 | ||
| EP16206477 | 2016-12-22 | ||
| EP16206451 | 2016-12-22 | ||
| EP16206498.4 | 2016-12-22 | ||
| EP16206487.7 | 2016-12-22 | ||
| EP16206487 | 2016-12-22 | ||
| EP16206480 | 2016-12-22 | ||
| EP16206490 | 2016-12-22 | ||
| EP16206461 | 2016-12-22 | ||
| EP16206503.1 | 2016-12-22 | ||
| EP16206503 | 2016-12-22 | ||
| EP17173000.5 | 2017-05-26 | ||
| EP17173005.4A EP3339417A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17172999.9A EP3339413A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173005.4 | 2017-05-26 | ||
| EP17173006.2 | 2017-05-26 | ||
| EP17172999.9 | 2017-05-26 | ||
| EP17173001.3 | 2017-05-26 | ||
| EP17173007.0 | 2017-05-26 | ||
| EP17173004.7A EP3339416A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173007.0A EP3339419A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173085.6 | 2017-05-26 | ||
| EP17173001.3A EP3339407A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173006.2A EP3339418A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173002.1A EP3339415A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173085.6A EP3339421A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
| EP17173004.7 | 2017-05-26 | ||
| EP17173002.1 | 2017-05-26 | ||
| EP17173000.5A EP3339414A1 (fr) | 2016-12-22 | 2017-05-26 | Composition de détergent pour lessive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018118824A1 true WO2018118824A1 (fr) | 2018-06-28 |
Family
ID=58778973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2017/067156 Ceased WO2018118824A1 (fr) | 2016-12-22 | 2017-12-19 | Composition de détergent textile |
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| Country | Link |
|---|---|
| EP (2) | EP3339421A1 (fr) |
| WO (1) | WO2018118824A1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019130146A1 (fr) * | 2017-12-29 | 2019-07-04 | Zobele Holding S.P.A. | Additif de blanchisserie pour éliminer les taches |
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- 2017-05-26 EP EP17173085.6A patent/EP3339421A1/fr not_active Withdrawn
- 2017-05-26 EP EP17173083.1A patent/EP3339420A1/fr not_active Withdrawn
- 2017-12-19 WO PCT/US2017/067156 patent/WO2018118824A1/fr not_active Ceased
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3339421A1 (fr) | 2018-06-27 |
| EP3339420A1 (fr) | 2018-06-27 |
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