Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/008—Polymeric surface-active agents
• • 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 the use of certain polymers for strengthening the primary washing power of detergents when washing textiles, in particular against surfactant or enzyme-sensitive soiling.
• detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances whose presence increases the detergent power of surfactants, without generally having to have a pronounced surfactant behavior themselves. Such substances are often referred to as detergency boosters.
• the polymers are alkoxylates based on a low molecular weight alcohol starter, preferably propoxylates, with a weight-average molecular weight M w of 600-10000 g / mol, preferably 1300-6000 g / mol, particularly preferably 1400-4500 g / mol.
• the molecular weight of the low molecular weight alcohol starter is in the range from 60 to 200 g / mol, preferably 70 to 150 g / mol.
• the low molecular weight alcohol starter is selected according to the invention from alcohols with no more than three OH groups.
• the low molecular weight alcohol starter is selected from cyclic diols, cyclic triols and In certain embodiments, the low molecular weight alcohol starter is selected from the list consisting of glycerol, ethylene glycol, 1,2-propanediol, trimethylolpropane (TMP), butanediol, cyclic diols, cyclic triols, 1,1,1-tris (hydroxymethyl) ethane, and mixtures thereof.
• TMP trimethylolpropane
• the low molecular weight alcohol starter is selected from the list consisting of glycerol, ethylene glycol, 1,2-propanediol and trimethylolpropane (TMP). Suitable compounds are also defined by the generic structural formula below.
• the invention thus relates to the use of polymers consisting of alkoxylate based on a low molecular weight alcohol starter with a molecular weight of 60 to 200 g / mol, preferably propoxylate, with a weight average molecular weight M w of 600-10000 g / mol, preferably 1300 6000 g / mol, particularly preferably 1400-4500 g / mol, the low molecular weight alcohol starter being selected from alcohols with no more than three OH groups, for strengthening the primary washing power of detergents when washing textiles, in particular in aqueous and surfactant-containing washing liquid, in particular against surfactant or enzyme-sensitive soiling.
• Another object of the invention is a method for removing, in particular, surfactant- or enzyme-sensitive soiling from textiles, in which a detergent and a polymeric active ingredient are brought into contact with soiled textiles in a washing liquor, in particular aqueous and surfactant-containing.
• This method can be carried out manually or mechanically, for example using a household washing machine. It is possible to use in particular liquid agents and the polymeric active ingredient simultaneously or in succession. The simultaneous use can be carried out particularly advantageously by using a detergent which contains the polymeric active ingredient.
• Soil or enzyme-sensitive soiling is understood to mean those which can usually be at least partially removed from surfactants or with the aid of enzymes, such as soiling of oil, fat, make-up or grass, mousse au chocolat, or egg.
• the polymers used according to the invention also contribute to the removability of such stains in the absence of enzymes or in particular in the absence of bleaching agents.
• the use according to the invention and the method according to the invention are preferably achieved by adding the polymer to an agent free of the corresponding polymer or to a washing liquor which is an agent free from the corresponding polymer contains, the amount of polymer added, based on the total weight of the agent free of the corresponding polymer, preferably in the range from 0.01% by weight to 20% by weight, in particular from 1% by weight to 15% by weight lies.
• the polymer essential to the invention is particularly preferably used together with, in particular, liquid detergents which, based on the total weight of the detergent, have a surfactant concentration of at least 30% by weight, preferably in the range from 30% by weight to 65% by weight and in particular 50% by weight .-% to 58 wt .-% have.
• the washing liquor is produced by adding 7 ml to 100 ml, in particular from 10 ml to 75 ml, preferably from 20 ml to 50 ml of a liquid water-containing detergent to 12 liters to 60 liters, in particular 15 liters to 20 liters of water .
• the polymers essential to the invention can be obtained by processes which are known in principle.
• the starter molecules e.g. B. low molecular weight alcohols with a maximum of three free OH groups, with alkylene oxides, such as. B. ethylene oxide (EO), propylene oxide (PO) and / or butylene oxide (BO), preferably propylene oxide, implemented under alkaline catalysis.
• alkylene oxides such as. B. ethylene oxide (EO), propylene oxide (PO) and / or butylene oxide (BO), preferably propylene oxide, implemented under alkaline catalysis.
• the starting molecule is presented and drained.
• the epoxides are then metered in in the desired sequence and amount using alkaline catalysis, for example using KOH.
• Suitable procedures and reaction conditions for the alkoxylation are generally known to the person skilled in the art and are described, for example, in the standard work M. lonescu, "Chemistry and technology of polyols for polyurethanes", Rapra Technology, Shrewsbury, UK, page 60 ff.
• the starter for producing the polymers can be selected in one embodiment from diols, triplets and a mixture thereof.
• the starter is selected from the group consisting of glycerol, ethylene glycol, 1,2-propanediol, trimethylolpropane (TMP) and mixtures thereof.
• glycerin is the starter.
• the starter is 1,2-propanediol.
• Preferred polymers used according to the invention have a weight-average molecular weight of more than 600 g / mol, particularly preferably the weight-average molecular weight is in the range from 600 to 10,000 g / mol, in particular 1300 to 6000 g / mol, and very particularly preferably 1400 to 4500 g / mol.
• the low molecular weight alcohol starter is reacted with an alkylene oxide, selected from the list consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
• the starter is reacted with an alkylene oxide consisting of propylene oxide or mixtures containing propylene oxide.
• an alkylene oxide consisting of propylene oxide or mixtures containing propylene oxide.
• only propylene oxide is used for the alkoxylation.
• 10 to 18 alkylene oxide units are added per alkylene oxide chain, in particular 12 to 16 alkylene oxide units and particularly preferably 12 to 15 alkylene oxide units.
• the concentration of polymer defined above in the aqueous washing liquor is 0.001 g / l to 5 g / l, in particular 0 .01 g / l to 2 g / l.
• the process is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular in the range from 20 ° C. to 40 ° C.
• the process according to the invention and the use according to the invention are preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
• detergents which can be used in addition to the polymer and which can be present in particular as powdery solids, in post-compacted particle form, as solutions or suspensions, can contain all known ingredients which are customary in such compositions.
• the agents can include, in particular, builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, color transfer inhibitors, graying inhibitors, crease-reducing and shape-maintaining polymeric active ingredients, and further auxiliaries, such as optical brighteners , Foam regulators, colors and fragrances.
• the agents can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants.
• nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear alcohol residues are native Origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical mean values which can correspond to an integer or a fractional number for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• alkyl glycosides of the general formula R 5 O (G) x can also be used as further nonionic surfactants, in which R 5 is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C- Corresponds to atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
• nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
• Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be used.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula in which R stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid or a fatty acid Realkylester or a fatty acid chloride can be obtained.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
• alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Alkyl sulfates of the general formula are also suitable RO-SO 3 M, in which R represents a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14, carbon atoms and M represents a countercation leading to charge neutralization of the sulfuric acid half-ester, in particular a sodium or potassium ion or an ammonium ion of the general formula R 1 R 2 R 3 R 4 N + , in which R 1 , R 2 , R 3 and R 4 independently of one another represent hydrogen, an alkyl group having 1 to 4 C atoms or a hydroxyalkyl group having 2 to 3 C atoms.
• Preferred radicals R are derived from native C 12 -C 18 fatty alcohols, such as, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols or secondary alcohols of this chain length.
• alkyl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 14 alkyl sulfates are particularly preferred.
• the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• cationic and / or amphoteric surfactants can also be used.
• Such surfactants are contained in detergents in amounts of preferably 5% by weight to 65% by weight.
• particularly preferred detergents are liquid and have surfactant contents of at least 30% by weight, preferably in the range from 30% by weight to 60% by weight and in particular from 50% by weight to 56% by weight.
• Such concentrated liquid detergents are advantageous because they require less resources, which is due in particular to a lower transport weight and a smaller consumption size, so compared to lower concentrated detergents, for example, a smaller bottle size and thus less packaging material are required to achieve the same application performance .
• highly concentrated agents are preferred by consumers because they take up little storage space in the household.
• Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "handle” (finish) and reduced electrostatic charging (increased wearing comfort).
• the active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, is unsuitable for biological reasons Degradability is increasingly being replaced by quaternary ammonium compounds, which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
• esters with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se.
• Dimethylolethylene urea is suitable as a finishing agent.
• a detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
• the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid and ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, and ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid, ethylenediaminephosphonic acid
• the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, each based on free acid.
• a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g / mol to 100,000 g / mol.
• Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
• vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
• Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer.
• the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
• the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
• Such polymers generally have a relative molecular mass between 1,000 g / mol and 200,000 g / mol.
• copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
• the organic builder substances in particular for the production of liquid agents, can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
• Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 0.5% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in pasty or liquid, in particular water-containing agents.
• Particularly suitable water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
• crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight. used.
• the detergent grade crystalline sodium aluminosilicates are preferred. Amounts close to the above upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m. Your calcium binding capacity is usually in the range of 100 mg to 200 mg CaO per gram.
• Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
• the alkali silicates that can be used as builders preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
• Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
• Crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 .yH 2 O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
• Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O
• ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O
• the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
• the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
• Builder substances are contained in detergents preferably in amounts of up to 60% by weight, in particular from 0.5% by weight to 40% by weight.
• the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
• component a) in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate, and up to 5% by weight, in particular 0.5% by weight, of Contain 2.5 wt .-% citric acid and / or alkali citrate.
• component a) is 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight of citric acid and / or alkali citrate and up to 5% by weight, in particular 1% by weight .-% to 5 wt .-% alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate. If both alkali carbonate and alkali hydrogen carbonate are present, component a) preferably has alkali carbonate and alkali hydrogen carbonate in a weight ratio of 10: 1 to 1: 1.
• a preferred embodiment contains 1% by weight to 5% by weight alkali silicate with a modulus in the range from 1.8 to 2.5.
• a preferred embodiment contains 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate.
• Phosphonic acids are also understood to mean optionally substituted alkylphosphonic acids which can also have several phosphonic acid groups (so-called polyphosphonic acids).
• hydroxy- and / or aminoalkylphosphonic acids and / or their alkali salts such as, for example, dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane -1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
• dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
• 1-amino-1-phenylmethane diphosphonic acid 1-hydroxyethane -1,1-diphosphonic acid
• amino-tris methylenephosphonic acid
• a preferred embodiment contains 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate.
• Alkali phosphate is the general term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Madrell's salt.
• NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
• Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is easily soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt.
• Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.
• Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
• Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) .
• Substances are colorless crystals that are soluble in water with an alkaline reaction.
• Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
• Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
• Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates.
• pentasodium triphosphate 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
• phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution. dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
• Pentapotassium triphosphate K 5 P 3 O 10 (potassium tripolyphosphate) is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O).
• sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 18 + H 2 O
• the composition contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
• polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
• the homopolymers of acrylic acid and among them in turn those with an average molecular weight in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.
• Enzymes which can be used in the compositions are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®, cellulases such as Celluzyme® and / or Carezyme®.
• amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm
• lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®
• cellulases such as
• Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable.
• the enzymes which may be used can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in detergents preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight.
• the composition contains 5% by weight to 65% by weight, in particular 8 to 55% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 0.5 to 40% by weight.
• % Builder substance and 0.2% by weight to 5% by weight of enzyme selected from the lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.
• the organic solvents which can be used in the detergents include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the compound classes mentioned.
• Such water-miscible solvents are preferably present in the compositions in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
• Polymers derived from nature that can be used as thickeners in aqueous liquid compositions are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, Cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymeric polysaccharide thickeners such as xanthan;
• fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable as thickeners.
• the agents can be system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
• Such pH regulators are preferably not contained in the agents above 20% by weight, in particular from 1.2% by weight to 17% by weight.
• Soil-releasing polymers which are often referred to as "soil release” active ingredients or because of their ability to make the treated surface, for example the fiber, dirt-repellent, "soil repellents", are, for example, nonionic or cationic cellulose derivatives.
• the particularly polyester-active dirt-releasing polymers include copolyesters from dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
• the preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR 11 -) a OH, which is also used as a polymer Diol H- (O- (CHR 11 -) a ) b OH may be present.
• Ph represents an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
• R 11 is hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures, a a number from 2 to 6 and b a number from 1 to 300.
• the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
• the degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140.
• the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred dirt-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000
• the acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among them, the sodium and potassium salts are particularly preferred.
• small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester.
• these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
• the preferred diols HO- (CHR 11 ) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in where a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms.
• R 11 is hydrogen and a is a number from 2 to 6
• R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms.
• those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
• diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
• Polyethylene glycol with an average molecular weight in the range from 1000 to 6000 is particularly preferred among the polymeric diols.
• these polyesters can also be end group-closed, alkyl groups having 1 to 22 C atoms and esters of monocarboxylic acids being suitable as end groups.
• the end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 C atoms, in particular 5 to 18 C atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, oleic acid, oleic acid, l
• the end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid.
• the hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group.
• the number of hydroxymonocarboxylic acid units per end group is preferably in the range from 1 to 50, in particular from 1 to 10.
• Color transfer inhibitors that are suitable for use in detergents for washing textiles include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
• the agents can contain anti-crease agents, since textile fabrics, in particular made from rayon, wool, cotton and their mixtures, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing and squeezing across the fiber direction.
• anti-crease agents include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
• Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular from the textile fiber suspended in the liquor.
• Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose.
• Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
• Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used.
• the agents can contain optical brighteners, including in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned optical brighteners can also be used.
• Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes.
• the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
• the peroxygen compounds optionally present in the agents, in particular the agents in solid form are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, such as perborate, percarbonate and / or persilicate.
• Hydrogen peroxide can also be generated using an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are used , they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
• Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or, in particular in liquid agents, hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide is particularly preferably used.
• Peroxygen compounds are preferably present in detergents in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight.
• customary bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and / or customary transition metal complexes activating the bleach can be used.
• the optional component of the bleach activators in particular in amounts of 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds commonly used, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N.
• -acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenol sulfonate, and acylated sugar derivatives, especially pentaacetylgluconitrile, and cationic trimethyl nitrilonate, as well as cationic trimetonitrile nitrate, as well as cationic trimethyl nitrilonate, as well as cationic trimetonitrile nitrate.
• the bleach activators can be coated or granulated with coating substances in a known manner during storage, with tetraacetylethylenediamine granulated with carboxymethylcellulose with average grain sizes of 0.01 mm to 0.8 mm, granulated 1.5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile made up in particulate form is particularly preferred.
• Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.
• the preparation of solid agents presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation.
• a method having an extrusion step is preferred for producing the agents with increased bulk density, in particular in the range from 650 g / l to 950 g / l.
• Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
• the agents are present, in particular in concentrated liquid form, as a portion in a completely or partially water-soluble envelope. The portioning makes it easier for the consumer to measure it.
• the agents can be packaged in foil bags, for example.
• Pouch packaging made of water-soluble film makes it unnecessary for the consumer to tear open the packaging. In this way it is easy to dose a single portion measured for one wash cycle by inserting the bag directly into the washing machine or by inserting it the bag in a certain amount of water, for example in a bucket, a bowl or in the hand wash basin.
• the foil pouch surrounding the washing portion dissolves without residue when a certain temperature is reached.
• water-soluble detergent portions There are numerous processes in the prior art for producing water-soluble detergent portions which are in principle also suitable for producing agents which can be used in the context of the present invention.
• the best known processes are the tubular film processes with horizontal and vertical sealing seams.
• the thermoforming process deep-drawing process
• the water-soluble casings do not necessarily have to consist of a film material, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.
• the filling material is injected into the capsule that forms, the injection pressure of the filling liquid pressing the polymer tapes into the spherical half-shell cavities.
• a process for the production of water-soluble capsules, in which the filling and then the sealing is carried out, is based on the so-called Bottle-Pack® process.
• a tube-like preform is guided into a two-part cavity. The cavity is closed, the lower tube section being sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
• the shell material used for the production of the water-soluble portion is preferably a water-soluble polymer thermoplastic, particularly preferably selected from the group (optionally partially acetalized) of polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and its derivatives, blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethyl cellulose and / or polyvinyl alcohol blends.
• Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant).
• Polyvinyl alcohols which are particularly suitable in the context of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and Clariant L648.
• the water-soluble thermoplastic used to prepare the portion can optionally also contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
• the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol% and in particular 82 mol% % to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 g / mol to 100,000 g / mol, preferably from 11,000 g / mol to 90,000 g / mol, particularly preferably from 12,000 g / mol to 80,000 g / mol and in particular from 13,000 g / mol to 70,000 g / mol. It is further preferred if the thermoplastics in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight of the water-soluble polymeric thermoplastic.
• the hydroxyl number was determined titrimetrically based on ASTM E 1899-97.
• the amine number was determined by titration with trifluoromethanesulfonic acid.
• P1: 47.0 g (0.51 mol) glycerol and 5.00 g 50% (wt.%) KOH solution were mixed and then dewatered in an autoclave at 100 ° C. and ⁇ 10 mbar for two hours.
• the autoclave was rendered inert by flushing three times with nitrogen, then a pre-pressure of 2 bar was set.
• the reactor was heated to 120-130 ° C and 1068 g (18.4 mol) of propylene oxide were metered in to produce three 12 PO / OH chains (a total of 36 PO / glycerol). After the end of the metering, the reaction was allowed to react until the pressure was constant.
• Table 1 Detergent composition (% by weight) Ingredient / agent V1 W1 W2 Linear C 10-13 alkyl benzene sulfonate 20th 20th 20th C 13/15 oxo alcohol with 8 EO 25th 25th 25th C 12-18 fatty acid 8th 8th 8th Polymer P1 - 5 Polymer P2 - - 5 Propylene glycol 10 10 10 glycerin 5 5 5 Monoethanolamine 6 6 6 DTPMPA 7Na 1 1 1 Ethanol 3 3 3 3 Soil Release Polymer Texcare® SRN 170 1.5 1.5 1.5 Perfume & Others * 5.5 5.5 5.5 water To 100 * Other: Other additives, for example dyes, enzymes, bitter substances, stabilizers, optical brighteners, color transfer inhibitors, etc.

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• 2018
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