Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
  • C11D3/3742—Nitrogen containing silicones
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/662—Carbohydrates or derivatives
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention relates to a hard surface treatment composition.
• the composition comprises non-ionic surfactant and non-volatile cationic silicone, wherein the amount of non-volatile cationic silicone is no greater than 20% by weight of the composition, and the composition has a pH value of no greater than 1 1.8.
• This invention also relates to a process for preparing the composition and a method for forming a hydrophobic coating.
• Droughts, poor irrigation and insufficient plumbing systems are just some of the reasons that cause water shortages in certain regions. Shortages of water can create serious social problems, such as health issues, that are a direct result of inadequate cleaning applications in the absence of sufficient amounts of water.
• the commercial hard surface treatment product may be acidic, neutral, or alkali.
• the present inventers have recognized that there is a need to develop a composition with relatively high concentration of water, which can produce hydrophobic coatings on hard surface not only when it has a pH value of no greater than 8, but also when it has a pH value of greater than 8.
• This invention is therefore directed to a hard surface treatment composition comprising non-ionic surfactant and non-volatile cationic silicone, wherein the amount of non-volatile cationic silicone is no greater than 20% by weight of the composition, and the composition has a pH value of no greater than 1 1 .8. It was surprisingly found that, such a composition can generate hydrophobic coatings on hard surface even when it has a pH value of 11 .
• Such hydrophobic coating has the benefits of anti-water mark, oil repellence, and/or easy cleaning of aged soil.
• the present invention provides a hard surface treatment composition comprising non-ionic surfactant and non-volatile cationic silicone, wherein the amount of non-volatile cationic silicone is no greater than 20% by weight of the composition, and the composition has a pH value of no greater than 1 1 .8.
• the present invention provides a process for preparing the composition of the present invention, the process comprising steps of emulsifying the cationic silicone, and combining the emulsified cationic silicone with the non-ionic surfactant.
• the present invention provides a method for forming a hydrophobic coating on a surface, the method comprising applying the composition of the present invention to the surface and drying the composition to yield the hydrophobic coating.
• Hard surface of present invention generally refers to any surface in household including the window, kitchen, bathroom, toilet, furniture, or floor including windows, mirrors, sinks, basins, toilet bowls, baths/shower trays, wall tiles, floor tiles, cooker tops, oven interiors, cookware, washing machine drums, cooker hoods, extractor fans.
• These surfaces may be made of glass, glazed ceramics, metal, stone, plastics, lacquer, wood, or combination thereof.
• Hydrophobic/hydrophobicity for the purposes of the present invention is used to describe a molecule or portion of a molecule that is attracted to, and tends to be dissolved by oil (in preference to water), or a surface that has a contact angle against water of greater than 80°. Such an angle may be measured with a goniometer or other water droplet shape analysis systems, for example by Drop shape analysis system 100 (DSA 100, Kruss) using water droplet of 10 ⁇ at 25 °C.
• Particle size refers to particle diameter unless otherwise stated.
• diameter means the z-average particle size measured, for example, using dynamic light scattering (see international standard ISO 13321 ) with an instrument such as a Zetasizer NanoTM (Malvern Instruments Ltd, UK).
• diameter means the apparent volume median diameter (D50, also known as x50 or sometimes d(0.5)) of the particles measurable for example, by laser diffraction using a system (such as a MastersizerTM 2000 available from Malvern Instruments Ltd) meeting the requirements set out in ISO 13320.
• pH values referred to herein are measured at a temperature of 25°C.
• Non-volatile as used herein means having vapor pressure from 0 to 0.1 mm Hg (13.3 Pa), preferably from 0 to 0.05 mm Hg, more preferably from 0 to 0.01 mm Hg at 25 °C.
• Non-ionic surfactants suitable for the present invention may comprise:
• R 1 R 2 R 3 N-0 • tertiary amine oxides of structure R 1 R 2 R 3 N-0, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, e.g. dimethyldodecylamine oxide;
• R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide;
• dialkyl sulphoxides of structure R 1 R 2 S 0, where R 1 is an alkyl group of from 10 to 18 carbon atoms and R 2 is methyl or ethyl, for instance methyl-tetradecyl sulphoxide;
• fatty acid alkylolamides such as the ethanol amides
• alkyl mercaptans • alkyl polyglucosides (APG), for example Cs-Ci6 alkyl polyglycoside;
• the non-ionic surfactant comprises compounds produced by the condensation of simple alkylene oxides with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom; alkyl polyglucosides; or a mixture thereof.
• the non-ionic surfactant comprises
• polyoxyethylene sorbitan fatty acid esters for example polyoxyethylene sorbitan Ce-24 fatty acid esters
• the non-ionic surfactant comprises ethoxylated alkyl alcohols, alkyl polyglucosides, or a mixture thereof; and still even more preferably ethoxylated Ce ⁇ de alkyl alcohols, C5-C20 alkyl polyglucosides, or a mixture thereof.
• Ethoxylated alkyl alcohols are preferably ethoxylated C8-C12 alkyl alcohols, whereby yet more preferably the average degree of ethoxylation is between 5 and 8.
• An example of particularly effective (and therefore preferred) surfactants are ethoxylated C9-C11 alkyl alcohols with an average degree of ethoxylation of 8, including for instance the commercially surfactant Neodol 91 -8.
• Preferred alkyl polyglucosides are represented by formula of RO - (G) n , wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated, G is a saccharide group, and the degree of polymerisation, n, may have a value of from 1 to 10;
• R has a mean alkyl chain length of from C5 to C20, G is selected from C5 or Ce monosaccharide residues and n has a value of from 1 to 6; more preferably R has a mean alkyl chain length of from C6 to Ci6, G is glucose and n has a value of from 1 to 2.
• Suitable alkyl polyglucosides include those from the Glucopon ® range, e.g. Glucopon ® 425 N from BASF.
• the non-ionic surfactant preferably comprises at least 10%, more preferably at least 25% and even more preferably from 40 to 100% of ethoxylated alkyl alcohols by weight of the total non-ionic surfactant.
• the hard surface treatment composition preferably comprises non-ionic surfactant in amount of from 0.01 to 15%, more preferably from 0.1 to 10%, even more preferably from 0.3 to 8% and still even more preferably from 0.8 to 6% and most preferably from 1 .2 to 4.8% by weight of the total composition.
• Cationic silicone refers to silicone which is positively charged on either branch chain or main chain of the silicone, but preferably on branch chain of the silicone. Whilst not being bound by any particular theory or explanation, the present inventors believe that the positive charge of cationic silicone helps the deposition of silicones onto a hard surface, forming a hydrophobic layer attached strongly to the hard surface even in an alkali composition. The layer can enhance resistance to deposition of soil and/or stains or at least make such substances easier to remove.
• the non-volatile cationic silicone preferably comprises a quaternary ammonium modified silicone. More preferably, the non-volatile cationic silicone is a quaternary ammonium silicone. Preferably, the quaternary ammonium group is carried by side or pendant group carried by the polymeric backbone.
• the quaternary ammonium silicone may be represented by the formula of:
• each R is independently hydrogen, phenyl, OH or a C1-C10 alkyl group, preferably R is OH or a C1-C6 alkyl group and more preferably a C1-C6 alkyl group, and most preferably a CH3 group;
• each a is independently an integer from 0 to 3, preferably each a is 0;
• each b is an integer from 0 to 1 , b may be 2 when a is not 0, preferably b is 0 or
• n and n are integers whereby the sum of n+m ranges from 1 to 3,500, preferably from 10 to 2000 and more preferably from 100 to 1200;
• each R 1 is independently a monovalent radical of formula -(CR 2 2) X L,
• each R 2 is independently H, OH, OCH3 or C1-4 alkyl or C1-4 hydroxylalkyl, preferably each R 2 is independently H, C1-4 alkyl, or C1-4 hydroxylalkyl; x is integer from 1 to 10, preferably from 2 to 6;
• L is a quaternized amine, preferably represented by one of the following groups:
• each R 2 is independently H, OH, OCH 3 , C1-4 alkyl, or C1-4 hydroxylalkyl; each R 3 is independently hydrogen, phenyl, benzyl, a Cns alkyl or a Ci- 18 hydroxylalkyl;
• each y is independently an integer from 1 to 4.
• each z is independently an integer from 1 to 5;
• each A " is independently anion, preferably fluoride, chloride, bromide or iodide anion.
• each R is independently OH, or C1-C4 alkyl group; each a is 0; b is 1 or 2; m and n are integers wherein the sum of n+m ranges from 10 to 2,000; each R 1 is independently a monovalent radical of formula -(CR 2 2 ) X L, where each R 2 is independently H, or Ci-4 alkyl, x is integer from 1 to 4, and L is a quaternized amine represented by one of groups selected from (1 ) to (5) where each R 2 is independently H, Ci-4 alkyl or Ci-4 hydroxylalkyl; each R 3 is independently hydrogen, a Ci to Cie alkyl or a Ci to Cie hydroxylalkyl; each y is independently an integer from 1 to 4; each z is independently an integer from 1 to 5; and each A " is independently an anion.
• each R is methyl; each a is 0; b is 1 ; m and n are integers wherein the sum of n+m ranges from 50 to 1 ,500; each R 1 is independently a monovalent radical of formula -(CH2)xL, wherein x is integer from 1 to 4, and L is a quaternized amine represented by one of groups selected from (1 ) to (5) where each R 3 is independently hydrogen, a Ci to Cis alkyl or a Ci to Cis hydroxylalkyl; each y is independently an integer from 1 to 4; each z is independently an integer from 1 to 5; and each A " is independently an anion.
• the mole % amine functionality of the aminosilicone is preferably in the range of from 0.1 to 8%, more preferably from 0.3 to 6% and most preferably from 0.5 to 4%,
• the weight-average molecular weight of the non-volatile cationic silicone is preferably from 800 to 2,000,000, more preferably from 1500 to 200,000, even more preferably from 3200 to 50,000, and most preferably from 5000 to 15000 Daltons.
• the weight-average molecular weight may be measured by following the standard of ASTM D4001-2013.
• the non-volatile cationic silicone is emulsified droplets of silicone.
• the emulsified non-volatile silicone suitable for use in the compositions of the invention preferably has a D3,2 average particle diameter (Sauter mean diameter) in the composition of from 10 nm to 20 micron, preferably from 20 nm to 5 micron, more preferably from 30 to 2 micron, even more preferably from 40 nm to 800 nm, and most preferably from 50 to 200 nm.
• the non-volatile cationic silicone is emulsified by emulsifier selected from cationic emulsifier, non-ionic emulsifier, anionic emulsifier, or a mixture thereof.
• the emulsifier comprises cationic emulsifier, non-ionic emulsifier, or a mixture thereof. Even more preferably the emulsifier comprises non-ionic emulsifier. Preferably, the emulsifier is different from the non-ionic surfactant of the present invention.
• Non-ionic emulsifier is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylglucosides, polyoxyethylen, fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, poly(oxyethylene)- poly(oxypropylene)-poly(oxyethylene) tri-block copolymer (also referred to as poloxamers), poly(oxyethylene)-poly(oxypropylene) block copolymer derived from the sequential addition of propylene oxide and ethylene oxide to ethylene diamine (also referred to as poloxamines), or mixtures thereof.
• non-ionic emulsifier is selected from polyoxyethylene alkyl ethers, alkylglucosides, fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, or mixtures thereof.
• Cationic emulsifier is preferably a quaternary ammonium salt. More preferably, the cationic surfactants have the formula N + R 4 R 5 R 6 R 7 X " , wherein R 4 , R 5 , R 6 , and R 7 are independently (Ci to C30) alkyl or benzyl and X is hydroxide or halogen. Preferably, one, two or three of R 4 , R 5 , R6, and R 7 are independently (C 4 to C30) alkyl and the other R 4 , R 5 , R6, and R 7 group or groups are (C1-C6) alkyl or benzyl and X is hydroxide, chlorine or bromine.
• the cationic surfactants has the formula of N + (CH 3 )2R 8 R 9 X " , where R 8 , and R 9 are independently (C12 to C30) alkyl and X is hydroxide, chlorine or bromine, and most preferably the cationic is C12-C30 alkyltrimethylammonium chloride.
• the viscosity of the non-volatile cationic silicone itself (not the emulsion or the final hard surface composition) is typically from 20 to 2,000,000 cSt (centi-Stokes) at 25 °C, more preferably from 500 cSt to 800,000 cSt, even more preferably from 2,400 to 80,000 cSt, still even more preferably from 4,000 to 15,000 cSt, and most preferably from 8,000 to 15,000 cSt.
• the non-volatile cationic silicone is present in the composition in amount from 0.01 to 20% by weight of the composition, more preferably from 0.1 to 15%, even more preferably from 0.2 to 9%, still even more preferably from 0.4 to 6%, most preferably from 0.8 to 4% by weight of the total composition.
• the non-volatile cationic silicone accounts for at least 25% by weight of the total non-volatile silicone in the composition, more preferably from 40% to 100%, even more preferably from 75% to 100% by weight of the total non-volatile silicone in the composition.
• the weight ratio of the nonionic surfactant to the non-volatile cationic silicone is preferably from 1 :100 to 100:1 , more preferably from 0.07:1 to 15:1 , even more preferably from 1 :5 to 6:1 , and most preferably from 0.4:1 to 3:1.
• the hard surface treatment composition of the present invention preferably comprises at least 30% of water by weight of the composition. More preferably, the composition comprises at least 50%, even more preferably from 70 to 99%, still even more preferably from 77 to 97% and most preferably from 84 and 93% of water by weight of the composition.
• the composition preferably comprises organic solvents selected from Ci-8 alcohol, ether having 2 to 16 carbon atoms, ester of C2-24 organic acid, Ce-18 cyclic terpene, and a mixture thereof. More preferably the composition comprises organic solvents selected from C2-8 alcohol, ether having total 2 to 16 carbon atoms, ester having total 2 to 16 carbon atoms, Ce-16 cyclic terpene, and a mixture thereof. Even more preferably the composition comprises organic solvents selected from C2-8 alcohol, ether having total 2 to 12 carbon atoms, ester having total 2 to 12 carbon atoms, C6-12 cyclic terpene, and a mixture thereof.
• the composition comprises ethanol, isopropyl alcohol, n-butanol, iso-butanol, n-butoxypropanol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl ester of caprylic acid, methyl ester of heptylic acid, dimethyl- 2-methyl glutarate, esters of polyglycerol, soybean oil methyl ester, limonene or a mixture thereof.
• the composition comprises ethanol, isopropyl alcohol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl ester of caprylic acid, methyl ester of heptylic acid, dimethyl-2-methyl glutarate, esters of polyglycerol and C2-8 acid, soybean oil methyl ester, limonene or a mixture thereof.
• the composition comprises ethanol, isopropyl alcohol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl ester of caprylic acid, methyl ester of heptylic acid, dimethyl-2-methyl glutarate, limonene or a mixture thereof.
• the composition comprises isopropyl alcohol, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, or a mixture thereof.
• the organic solvent may be present in the composition in a concentration of 0 to 20%, preferably 0.5-15% by weight of the composition.
• the composition preferably comprises abrasive particle, more preferably in amount of 2 to 40%, even more preferably from 5 to 15% by weight of the composition.
• the abrasive particles can be of any suitable material, both organic and inorganic but preferably comprises inorganic abrasive particles. More preferably the abrasive comprises particles made of zeolites, calcites, dolomites, feldspar, silicas, silicates, other carbonates, aluminas, bicarbonates, borates and sulphates. Even more preferably the composition comprises calcite, silica particles, olive stone fragments, or a mixture thereof.
• the abrasive particles preferably have a volume average median diameter d(0.5) of 150 ⁇ or below, more preferably of between 1 to 100 ⁇ , more preferably from 5 to 80 ⁇ and still even more preferably between 10 and 70 ⁇ .
• the abrasive particles have sharp edges and an average a particle has at least one edge or surface having concave curvature. More preferably, the particles herein have a multitude of sharp edges and each particle has at least one edge or surface having concave curvature.
• the sharp edges of the particles are defined by edges having a tip radius below 20 pm, preferably below 8 pm, most preferably below 5 pm.
• the tip radius is defined by the diameter of an imaginary circle fitting the 15 curvature of the edge extremity.
• the composition may comprise from 0.2 to 1.2% of thickener by weight of the composition. This provides the optimum rheological properties of the composition. Suitable thickeners include the modified celluloses for example hydroxyethyl cellulose.
• the hard surface cleaning composition according to the invention may further comprise dyes, perfume, and/or preservatives. If present, the amount may be from 0.001 to 5% by weight of the composition.
• the composition preferably has a pH value of 1 to 1 1 , preferably from 3 to 1 1 .
• the hard surface treatment composition of the invention may have any appearance, ranging from opaque to fully transparent.
• the composition is preferably at least partially transparent or translucent, more preferably transparent.
• at least partially transparent or translucent is meant that a 1 cm thick sample of the composition transmits at least 20%, preferably at least 50%, of light having wavelength of 460 nm.
• transparent is meant that a 1 cm thick sample of the composition transmits at least 70%, preferably at least 90%, of light having wavelength of 460 nm.
• the composition may be packed in any form, but preferably is packaged as a conventional hard surface treatment or cleaning product.
• the preferred packaging is a spray applicator. Pump dispersers (whether spray or non-spray pumps) and pouring applications (bottles etc) are also possible. It is also possible to impregnate a wipe with the composition.
• composition of the present invention may be produced by any convenient way. However it is preferred that the process for preparing the composition comprises the steps in sequence of:
• the emulsion comprises at least 10% of non-volatile cationic silicone by weight of the emulsion, more preferably from 15 to 90%, even more preferably from 20% to 80% by weight of the emulsion.
• step (a) is carried out at least half an hour before step (b), more preferably at least 1 day, even more preferably from 1 week to 5 years before step (b).
• any general way for treating a hard surface is acceptable.
• the way for treating a hard surface by the composition is spraying the composition onto the hard surface, or wiping the hard surface by wipe impregnated with the composition, or pouring the composition onto the hard surface, or combination thereof.
• the way for treating a hard surface is spraying the composition onto a hard surface, and/or wiping a hard surface by wipe impregnated with the composition.
• spraying is employed for treating a hard surface, there is no limitation how the composition is sprayed.
• a spraying bottle for hard surface cleaning product is favourable.
• wipe including woven or nonwoven cloth, natural or synthetic sponges or spongy sheets, "squeegee” materials, paper towel, or the like is suitable.
• the wipe may be impregnated dry, or more preferably in wet form.
• the method for treating a hard surface may optionally further comprises the steps of allowing soil and/or stains to deposit.
• the soil or stains will be easily removed when the hard surface is subsequently cleaned according to the method of this invention.
• the composition of the invention is also preferably applied to the hard surface during the subsequent cleaning.
• treating of a hard surface with the composition may be followed by a rinsing step, preferably with water. Therefore a most preferred method for treating a hard surface comprises:
• the soils and stains of present invention may comprise all kinds of soils and stains generally encountered in the household, either of organic or inorganic origin, whether visible or invisible to the naked eye, including soiling solid debris and/or with bacteria or other pathogens.
• the method and compositions according to the invention may be used to treat surface susceptible to fatty or greasy soil and stains.
• This example demonstrates the effect of types of silicones on the surface wettability of hard surface treated by the samples.
• Neodel 91 -8 from
• Drop shape analysis system 100 (DSA 100, Kruss) was used to measure the contact angles at 25°C. 5 ⁇ of water droplets were employed and the average values and standard derivations of contact angles were obtained from at least 3 droplets.
• the pH value of the samples and the contact angle of the generated coatings were listed in the last two rows in Table 1 .
• the generated coatings were all hydrophobic.
• an aminosilicone which is not cationic silicone was incorporated into a composition having pH value of 1 1 , it did not produce a hydrophobic coating.
• This example demonstrates the effect of types of surfactants on the surface wettability of hard surface treated by the samples.
• composition containing non-ionic surfactant and cationic silicone can yield a hydrophobic coating on hard surface.
• the composition containing anionic surfactant and cationic silicone did not yield hydrophobic coating. It was unexpectedly found that the composition containing non-ionic surfactant can yield more hydrophobic coating than other surfactants, for example anionic surfactant.

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• Engineering & Computer Science (AREA)
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• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Materials Engineering (AREA)
• Detergent Compositions (AREA)

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• 2015
  • 2015-06-25 WO PCT/EP2015/064346 patent/WO2016020107A1/en active Application Filing
  • 2015-06-25 EP EP15730519.4A patent/EP3177688A1/de not_active Withdrawn

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