WO2010037560A1 - Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation - Google Patents

Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation Download PDF

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Publication number
WO2010037560A1
WO2010037560A1 PCT/EP2009/007088 EP2009007088W WO2010037560A1 WO 2010037560 A1 WO2010037560 A1 WO 2010037560A1 EP 2009007088 W EP2009007088 W EP 2009007088W WO 2010037560 A1 WO2010037560 A1 WO 2010037560A1
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WO
WIPO (PCT)
Prior art keywords
monomer units
detergent additive
vinylpyrrolidone
copolymer
clay mineral
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PCT/EP2009/007088
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German (de)
English (en)
Inventor
Ulrich Sohling
Jovica Zorjanovic
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Süd-Chemie AG
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Application filed by Süd-Chemie AG filed Critical Süd-Chemie AG
Priority to JP2011529483A priority Critical patent/JP2012504666A/ja
Priority to EP09778811.1A priority patent/EP2340298B1/fr
Priority to MX2011003408A priority patent/MX2011003408A/es
Publication of WO2010037560A1 publication Critical patent/WO2010037560A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite

Definitions

  • the invention relates to a detergent additive, in particular for improving the soft feel of textile products, comprising at least one clay mineral and at least one copolymer having cationic monomer units and N-vinylpyrrolidone Monomerein- units. Furthermore, the present invention relates to a process for its preparation, and its use.
  • GB 1 400 898 describes a detergent formulation for the simultaneous cleaning and improvement of the soft handle.
  • anionic, ampholytic and zwitterionic synthetic see surfactants, organic or inorganic "builders" and a smectic three-layer clay mineral used.
  • EP 0 313 146 describes a detergent formulation for improving the soft feel.
  • This contains conventional surfactants, a smectic clay mineral and fountain solution, such as polyols, derived ether and ester alcohols and mono- and oligosaccharides.
  • the detergent formulation contains polymeric flocculants such as polyethylene oxide, polyacrylamide and polyacrylate.
  • Detergent additives to improve the soft feel are also described in US 2005/0170997.
  • silicone oils and optionally ionic polymers and other auxiliaries such as builders, bleaches, flocculants and color transfer inhibitors are used.
  • WO 2008/025505 describes a detergent additive for improving the soft feel of textile products, which contains at least the following components: a) a clay mineral; b) a PVP / VA copolymer.
  • DE 10 2006 016 578 A1 describes a solid, textile softening composition which comprises a water-soluble carrier, a water-soluble polymer, a textile-softening compound and a perfume.
  • the sol-soluble carrier is preferably in particulate form and has an envelope in which the water-soluble polymer, the fabric softening compound and the perfume are contained.
  • the preparation of the compositions is described wherein polyethylene glycol having an average molecular weight of 4000 is first melted. The melt is then mixed with sodium chloride solid carrier, clay textile softening compound and perfume.
  • clay mineral content does not increase the degree of softening to the same extent, so that often and in no small measure other additives have to be used.
  • additives include surfactants,
  • a detergent additive in particular for improving the soft feel of textile products, which contains at least the following components: a) at least one clay mineral; and b) at least one N-vinylpyrrolidone copolymer, wherein the at least one N-vinylpyrrolidone copolymer comprises N-vinylpyrrolidone monomer units and cationic monomer units.
  • the present invention teaches a process for the preparation of such a detergent additive, comprising at least the following steps: a) providing at least one clay mineral, in particular at least one smectite clay mineral; b) providing at least one N-vinylpyrrolidone copolymer, wherein the at least one N-vinylpyrrolidone copolymer comprises N-vinylpyrrolidone monomer units and cationic monomer units, wherein the cationic monomer units preferably comprise monomer units each having at least one quaternized nitrogen atom; preferably, the proportion of quaternized N-vinylimidazole monomer units in the copolymer is between 0 and 45 mol%; and c) mixing the at least one copolymer comprising N-vinylpyrrolidone monomer units and cationic monomer units and the at least one clay mineral.
  • the present invention teaches uses of the detergent additive according to the invention as a component of a washing, cleaning, and / or care formulation and / or for the preparation of a washing, cleaning, and / or care formulation.
  • the present invention provides a detergent additive, in particular for improving the softness of textile products, comprising at least the following components:
  • N-vinylpyrrolidone copolymer comprising N-vinylpyrrolidone monomer units and cationic monomer units.
  • the cationic monomer units comprise or consist of monomer units which each have at least one quaternized nitrogen atom.
  • detergent additive encompasses both detergent additives that can be added to detergent formulations, as well as their aqueous solutions or can be used for their preparation, as well as detergent additives before or after use a detergent formulation on the laundry or in the washing liquid or can be introduced.
  • Detergent additive also includes formulations such as detergent powders, liquid detergents, fabric softeners which may be in the form as provided to consumers or in any preparation precursors thereof.
  • the at least one clay mineral can be both a natural and a synthetically produced clay.
  • clay and clay mineral are used synonymously herein.
  • the construction of particularly advantageous clay minerals will be discussed in detail in the following sections.
  • the influence of clay minerals on the softening of textile fibers, such as cotton can be explained by the fact that the clay mineral, due to its morphological properties (such as platelet-shaped aluminosilicates with a particle size diameter smaller than 2 microns), and its chemical-physical properties (such as the sliding behavior), deposited between and / or on fibers, especially cotton fibers. This allows the fibers to slide better with each other, which leads to the improvement of the soft touch.
  • the clay also supports the washing process by absorbing dirt particles and making them easier to remove when washed.
  • the proportion of N-vinylpyrrolidone monomer units in the copolymer can be less than 60 mol%, according to one embodiment less be as 50 mol%.
  • monomeric units derived from N-vinyl or N-allyl compounds are used as cationic monomer units, which according to one embodiment comprise at least one further nitrogen atom which, according to one embodiment, can be used as a quaternary embroidery unit. substance atom is present.
  • the cationic monomer units are derived from (meth) acrylates which comprise at least one quaternary nitrogen atom.
  • the term "monomer unit 11" describes a component of the copolymer as it is present in a polymer, in particular copolymer, after the polymerization of the respective monomers in polymerized form in the polymer, in particular copolymer, For example, a copolymer comprising 100 monomer units, of which 30 monomer units N-vinylpyrrolidone monomer units have a proportion of N-vinylpyrrolidone monomer units of 30 mol%.
  • the cationic monomer units consist of monomer units or comprise one or more monomer units selected from the group consisting of quaternized N-vinylimidazole monomer units quaternized N, N-dialkylaminoalkyl (meth) acrylate monomer units and monomer units derived from diallyldimethylammonium salts.
  • Quaternized N-vinylimidazole monomer units may have the following Formula I and quaternized N, N-dialkylaminoalkyl (meth) acrylate monomer units may have the following Formula II:
  • the element -Z- can be a straight-chain or branched alkyl or alkenyl chain.
  • the element -Z- may, for example, have from 1 to 30 carbon atoms, preferably from 1 to 8 carbon atoms, preferably from 2 to 6 carbon atoms.
  • the straight-chain or branched alkyl or alkenyl chain can comprise, for example, from 0 to 4, in one embodiment from 1 to 3 double bonds, and depending on the application, it can also be free from double bonds.
  • the alkyl or alkenyl chain may have one or more substituents selected from the group consisting of -OH, -NH 2 , -NHR 1 , -NR 1 R 2 , -NR 1 R 2 R 3 +, and -SH as Substituents, wherein R 1 , R 2 , R 3 are defined below.
  • the alkyl or alkenyl chain has 0 to 3 of these abovementioned substituents, these being identical or different substituents.
  • quaternized N, N-dialkylaminoalkyl methacrylate monomer units may be one or more quaternized monomer units selected from the group consisting of N, N-dimethylamino-methyl methacrylate quaternized with ethyl group, N, N-diethyl quaternized with ethyl group.
  • copolymers lead to particularly satisfactory washing results, in particular a good softness, which at least partially comprise cationic monomer units which have a structural mobility of the cationic, in particular a cationic, at least one quaternized nitrogen atom having monomer unit.
  • structurally determined mobility can be brought about, for example, by the presence of at least one straight-chain or branched alkyl chain which is in particular connected to the quaternized nitrogen atom and can comprise at least one, preferably at least two, preferably at least three carbon atoms.
  • the at least one further comonomer unit is derived from an N-vinyl compound according to one embodiment.
  • the at least one further comonomer unit is derived from a monomer selected from the group of N-vinylimidazole and N-vinylcaprolactam.
  • the N-vinylpyrrolidone copolymer comprising cationic monomer units may comprise N-vinylcaprolactam monomer units, wherein the proportion of N-vinylcaprolactam monomer units in the copolymer is preferably between 0.1 and 75 mol%, preferably between 2 and 55 mol%. %, is. Particularly advantageous washing results can be obtained, for example, if the ratio of N-vinylcaprolactam monomer units to N-vinylpyrrolidone monomer units is preferably from 1: 8 to 8: 1, preferably from 1: 2 to 2: 1, based on the number of monomer units.
  • the ratio of N-vinylcaprolactam monomer units to cationic monomer units having, for example, at least one quaternized nitrogen atom may preferably be from 10: 1 to 1: 1, preferably from 9: 1 to 2: 1, based on the number of monomer units.
  • formula III shows an N-vinylpyrrolidone monomer unit and formula IV shows an N-vinylcaprolactam monomer unit, as may be present, for example, in a copolymer:
  • the detergent additive according to the invention it has surprisingly been found that when using a combination of at least one clay mineral and at least one N-vinylpyrrolidone monomer units and cationic, for example at least one quaternized nitrogen atom-containing monomer units having copolymer a high-quality softness is achieved.
  • the detergent additives of the present invention have resulted in many applications to wash results, particularly softening, washing results using clay mineral based detergent additives and copolymers comprising these monomer units -Combination do not include, are superior.
  • the N-vinylpyrrolidone copolymers can be present both with regular or irregularly alternating structural units (for example -AB-ABA or -AAABBABBB-), and as block copolymers (for example A x -B y ).
  • Possible non-limiting structures for block copolymers include A x B y block copolymers, A x B y A z triblock copolymers, A x B y C z triblock copolymers, A 7 (B x ) z block or block A backbone copolymers and B side chains (comb polymers), as well as mixtures of the foregoing.
  • an N-vinylpyrrolidone copolymer may comprise at least 20, preferably at least 30 monomer units.
  • an N-vinylpyrrolidone copolymer for example, at least 5, preferably at least 15 cationic, in particular in each case at least one quaternized nitrogen atom having monomer units.
  • the detergent additive based on the total weight of the at least one clay mineral, more than 0.001 wt .-%, more preferably more than 0.01 wt .-%, particularly preferably more than 0.1 wt .-% N-vinylpyrrolidone copolymer has.
  • the detergent additive based on the total weight of the at least one clay mineral, more than 0.001 wt .-%, more preferably more than 0.01 wt .-%, particularly preferably more than 0.1 wt .-% N-vinylpyrrolidone copolymer has.
  • With an addition of more than 0.3 wt .-% usually no further improvement is observed, so that a higher proportion of N-vinylpyrrolidone copolymer from an economic point of view is no longer or at most limited useful.
  • an addition of up to 0.06 wt .-% is usually sufficient to obtain the desired washing properties.
  • N-vinylpyrrolidone copolymer of 10 "4 to 5 wt .-%, preferably from 10 " 3 to 1 wt .-%, preferably from 10 ⁇ 3 to 0.3 wt .-%, very particularly preferred from 0.1 to 0.3 wt .-% based on the total weight of the at least one clay mineral.
  • Detergent additives which give a very good softness can, for example, have a total weight of cationic monomer units of the N-vinylpyrollidone copolymer (s), for example up to 0.15% by weight, preferably up to 0.1% by weight, preferably up to 0.09% by weight, more preferably up to 0.05% by weight, even more preferably up to 0.03% by weight, in particular 0.001 to 0.09 wt .-%, based on the total weight of the at least one clay mineral.
  • a total weight of cationic monomer units of the N-vinylpyrollidone copolymer (s) for example up to 0.15% by weight, preferably up to 0.1% by weight, preferably up to 0.09% by weight, more preferably up to 0.05% by weight, even more preferably up to 0.03% by weight, in particular 0.001 to 0.09 wt .-%, based on the total weight of the at least one clay mineral.
  • the detergent additive may further comprise at least one surfactant, which surfactant may be selected based on the general knowledge and teaching of the present invention.
  • Surfactants are charged (ionic surfactant) or uncharged (nonionic surfactant), surface-active organic compounds, wherein at least one hydrophilic molecular segment is soluble in polar solvents and poorly soluble or non-soluble in nonpolar solvents.
  • the surfactant contains at least one further hydrophobic molecular segment which is soluble in non-polar solvents and poorly or not soluble in polar solvents.
  • a general definition of surfactants can also be found, for example, in Römpp Chemie-Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, 1995, p. 4495-4499. Accordingly, surfactants are substances which reduce the interfacial tension and have a characteristic structure of at least one hydrophilic and one hydrophobic group.
  • Clay minerals used may be clay minerals known to the person skilled in the art. Particularly advantageous washing results, especially especially a particularly good softness, could be obtained when the clay minerals are smectite clay minerals. These clays have a structure of layered polysilicate units. Examples of smectic clay minerals are beidellite, hectorite, saponite, stevensite, nontronite and montmorillonite or bentonite.
  • the at least one surfactant comprises at least one nonionic surfactant.
  • nonionic surfactants are hydrophobic hydrocarbon chains and hydrophilic ethylene oxide chains, propylene oxide chains or polyols.
  • Non-limiting examples of nonionic surfactants are fatty alcohol ethoxylates, polyethylene glycol ethers, alkyl glycosides, alkyl polyglycosides, sorbitan fatty acid esters, alkylphenyl ethoxylates, alkyl phosphine oxides, and silicone surfactants.
  • the at least one N-vinylpyrrolidone copolymer comprises only N-vinylpyrrolidone monomer units and cationic monomer units, and optionally N-vinylcaprolactam monomer units.
  • the at least one copolymer contains, in addition to the N-vinylpyrrolidone monomer units and cationic monomer units, one or more other monomer units. These one or more other monomer units may be contained in a proportion of 0.1 to 20 mol% in the N-vinylpyrrolidone copolymer.
  • the N-vinylpyrrolidone copolymer generally has a content of N-vinylpyrrolidone monomer units of about 1 to 99 mol%, preferably 5 to 90 mol%, preferably 35 to 85 mol%.
  • the at least one N-vinylpyrrolidone copolymer has a proportion of cationic, for example at least one quaternized nitrogen atom, monomer units of at least about 5 mol%, preferably at least 10 mol%, more preferably at least 20 mol%. %, more preferably at least 30 mol%, in particular 5 to 40 mol%. It has thus been found that the improvement in the softness surprisingly increases with increasing content or proportion of cationic monomer units in the at least one N-vinylpyrrolidone copolymer.
  • Detergent additives in which an extremely good softening has been achieved may comprise, for example, at least one N-vinylpyrrolidone copolymer in which the total weight cationic monomer units of 9 to 45% by weight ; Preferably from 28 to 38 wt .-%, preferably from 32 to 34 wt .-%, based on the total weight of monomer units of the at least one N-vinylpyrrolidone copolymer, wherein the weight of the counterions of the cationic monomer units is not taken into account.
  • detergent additives in which an extremely good softening has been achieved may comprise, for example, at least one N-vinylpyrrolidone copolymer in which the total weight of N-vinylpyrrolidone monomer units is from 39 to 80% by weight, preferably from 62 to 72% by weight. , preferably from 66 to 68% by weight, based on the total weight of monomer units of the at least one N-vinylpyrrolidone copolymer, wherein the weight of the counterions of the cationic monomer units is not taken into account.
  • detergent additives may comprise at least one N-vinylpyrrolidone copolymer wherein the total weight of N-vinylpyrrolidone monomer units is preferably from 39 to 80% by weight and the total weight of cationic monomer units is preferably from 9 to 45% by weight, each on the total weight of monomer units of the at least one N-vinylpyrrolidone copolymer, wherein the weight of the counterions of the cationic monomer units is not taken into account.
  • the N-vinylpyrrolidone copolymer has a weight ratio of the total weight of N-vinylpyrrolidone monomer units contained in the N-vinylpyrrolidone copolymer to the total weight of cationic, for example at least one, contained in the N-vinylpyrrolidone copolymer quaternized nitrogen atom having monomer units between about 90:10 and 10:90, in particular between about 70:30 and 30:70, wherein the weight of counterions of the cationic monomer units is not taken into account.
  • aqueous fluids in particular aqueous solutions (for example 10 to 30% by weight, preferably 18 to 22% by weight, preferably about 20% by weight, based on the total weight of the aqueous Fluids) of N-vinylpyrrolidone copolymers.
  • the N-vinylpyrrolidone copolymers preferably have a molecular weight in the range of 100,000 to 1,000,000 g / mol. Preferred The molecular weights are 300,000 - 1,000,000 g / mol and 500,000 to 1,000,000 g / mol.
  • ⁇ -carrageenan is a chain molecule composed of the other building blocks, ß-D-galactosido (1, 4) - ⁇ -D-galactose. These dimers are linked 1, 3-glycosidically.
  • the primary alcohol group of ⁇ -D-galactose is esterified with sulfuric acid, and the hydroxy groups on C2 of both galactoses are also approximately 70% esterified with sulfuric acid.
  • ⁇ -carrageenan thus has a sulphate content between 32 and 39%.
  • K and I -Carrageenan are composed of the dimer carrabiose, in which ß-D-galactose is 1, 4-glycosidically bound to ⁇ -D-3,6-anhydrogalactose. These dimers are linked by 1,3-glycosidic bonds to form a chain molecule.
  • the difference between the two carrageenan types lies in the sulfation.
  • the sulfate ester group is located at C-4 of galactose, the sulfate content varies between 25 and 30%.
  • ⁇ -Carrageenan additionally the hydroxy group at the C-2 of the Anhydrogalactose is esterified with sulfuric acid.
  • the sulphate content is between 28 and 35%.
  • the average molecular weight of carrageenan is between 100,000 g / mol and 800,000 g / mol. Because of their approval in food (carrageenan is approved as E407) carrageenans are health and ecologically harmless additives.
  • the detergent additive contains more than 0.0001 wt .-%, preferably more than 0.001 wt .-%, particularly preferably more than 0.01 wt .-% carrageenan, based on the mass of the clay mineral.
  • more than 0.1 wt .-% usually no further improvement is observed, so that a higher proportion of carrageenan from an economic point of view no longer or at best makes limited sense. In most cases an addition of up to 0.06 wt .-% is sufficient to obtain the desired properties.
  • the smectite clay mineral is a bentonite.
  • bentonite consists for the most part of montmorillonite.
  • the aluminosilicate montmorillonite is a three-layer material, composed of two SiO 4 tetrahedral layers, between which there is an octahedral layer of predominantly aluminum ions. Isomorphous replacement of the trivalent aluminum ions by divalent ions, such as calcium or magnesium, produces a negative excess charge, which can be compensated by Mg 2+ , Ca 2+ , Na + , for example.
  • the bentonite By exchanging these cations, the bentonite also acts as an ion exchanger. In addition to the different charges, cations such as Na + and Ca 2+ also significantly influence the swelling behavior of the bentonite. How to store stored calcium ions have a narrower layered structure, while embedded sodium ions allow a more open stratification of the bentonite. In addition, the bentonite is able to store surfactants and thus to change its absorbency of textile fabric.
  • the particle size of the clay mineral can have an influence on the improvement of the softness.
  • the clay mineral is in particulate form, wherein at least 10 wt .-%, preferably at least 14 wt .-%, more preferably between about 10 and 50 wt .-% of the particles, more preferably between about 10 and 30 wt .-% of the particles have a particle size of less than about 600 nm.
  • the particle sizes can be determined by standard methods such as the laser diffraction method using a Fritsch Particle Sizer Analysette 22 Economy (Fritsch, DE) according to the manufacturer's instructions, also with regard to sample pretreatment.
  • the above preferred particle sizes of the clay mineral according to an alternative aspect of the present invention are also independent of the use of the clay mineral in a detergent or detergent additive in combination with the N-vinylpyrrolidone copolymer, the surfactant and / or the carrageenan.
  • the clay mineral in particular the bentonite, is present in activated form, ie divalent or trivalent cations stored between the layers are exchanged for monovalent ions, such as sodium ions or protons.
  • Such activated clay minerals are produced in a manner known per se, for example with soda. By exchanging the ions, the swelling capacity of the bentonite increases, which in turn influences the absorption properties.
  • the clay mineral in particular the bentonite, is characterized in that at least 50%, preferably at least 60% and particularly preferably at least 80% of the cation exchange capacity (CEC) of monovalent cations, such as Na + , K + or NH 4 + , in particular of Na + , is formed.
  • CEC cation exchange capacity
  • the detergent additive in particular a detergent additive which is used as additive to detergent formulations or for the preparation of detergent formulations, preferably contains at least 80% by weight, preferably at least 85% by weight of clay mineral, such as bentonite, based on the total weight of detergent additive.
  • clay mineral such as Bentonite
  • the high proportion of clay mineral, such as Bentonite reduces the cost of the detergent additive compared to the surfactant or other polymeric additives.
  • no chemical classifications of the product are required at low concentrations of surfactant and polymer or copolymer. This results in lower costs for storage, transport and later handling of the detergent additive.
  • the at least one nonionic surfactant of the detergent additive is particularly preferably selected from the group of fatty alcohol ethoxylates and polyethylene glycol ethers. These sub- Divide mainly by the manufacturing process. Both groups have the same basic structure of a linear or branched hydrophobic hydrocarbon chain (C x ) and a hydrophilic ethylene oxide chain (EO y ) with terminal alcohol group (s). These control both the efficiency, ie the required amount of surfactant, and the temperature sensitivity of the surfactant class. Within the hydrophilic ethylene oxide group, moreover, individual ethylene oxide units can be exchanged for propylene oxide units. The resulting changes in the hydrophobic / hydrophilic character can be used specifically in the selection of surfactants.
  • the fatty alcohol ethoxylates in particular can be obtained from natural raw materials and are generally almost completely biodegradable.
  • the detergent additive preferably contains more than 0.001% by weight, more preferably more than 0.01% by weight, particularly preferably more than 0.01% by weight, of fatty alcohol ethoxylate and / or based on the total weight of the at least one clay mineral Polyethylene glycol ether.
  • more than 0.1 wt .-% usually no further improvement is observed, so that a higher proportion of fatty alcohol ethoxylate and / or polyethylene glycol ether from economic point of view is no longer or at best limited makes sense. In most cases an addition of up to 0.06 wt .-% is sufficient to obtain the desired properties.
  • the detergent additive based on the total weight of the at least one clay mineral, more than 0.05 wt .-%, preferably more than 0.5 wt .-%, more preferably more than 1 wt .-% water glass.
  • the weight ratio between N-vinylpyrrolidone monomer units and cationic monomer units comprising N-vinyl pyrrolidone copolymer to water glass can be from 1:10 to 1:40, preferably from 1:15 to 1:25.
  • the detergent additive according to the invention may also be present in liquid form or in the form of powder or shaped articles, such as, for example, tablets or spheres, or in combinations thereof.
  • the use of water glasses ensures that a sufficiently rapid disintegration of the granules or moldings occurs and thus leads in combination with the specified components of the detergent additive to an increased softness.
  • the detergent additive may also include oxidizing substances, complexing substances, for example gallic soap, dyes, in particular UV-active dyes, fragrances, antibacterial substances, antiviral substances, fungicides, bleaching components, in particular sodium perborate tetrahydrate and tetraacetylethylenediamine, sodium alkylbenzenesulfonates, especially with straight-chain alkyl group, ethoxylated fatty alcohols, soaps, zeolites, sodium carbonate, sodium silicate, carboxymethylcellulose, optical brightener, sodium sulfate, enzymes, for example protease, etc.
  • complexing substances for example gallic soap, dyes, in particular UV-active dyes, fragrances, antibacterial substances, antiviral substances, fungicides, bleaching components, in particular sodium perborate tetrahydrate and tetraacetylethylenediamine, sodium alkylbenzenesulfonates, especially with straight-chain alkyl group, ethoxylated
  • Another aspect of the invention relates to a process for the preparation of a detergent additive comprising at least the following steps:
  • the proportion of quaternized N-vinylimidazole monomer units in the copolymer may be between 0 and 45 mol%.
  • the cationic monomer units may preferably comprise cationic monomer units each having at least one quaternized nitrogen atom.
  • Preferred proportions of the N-vinylpyrrolidone monomer units, of the cationic monomer units and of any other comonomer units present as well as further preferred embodiments of the N-vinylpyrrolidone copolymer have already been described above.
  • the process for the preparation of a detergent additive comprises, before, simultaneously with or after step c), at least one surfactant, in particular a nonionic surfactant, being admixed. This may be provided together with the N-vinylpyrollidone copolymer and the clay mineral and mixed therewith in the manner known to those skilled in the art.
  • the surfactant and / or N-vinylpyrollidone copolymer is provided in the form of a common or separate aqueous solution.
  • polar organic solvents such as, for example, methanol, ethanol, formamide, dimethylformamide, pyridine, dimethylsulfoxide-containing solutions are also suitable.
  • the surfactant and the N-vinylpyrollidone copolymer are mixed in a first step.
  • This can be done both from the pure substances, and particularly preferably from aqueous solutions of the surfactant and the N-vinylpyrollidone copolymer.
  • These are then applied to the clay mineral using methods known to those skilled in the art.
  • the application can be done by spraying or by mixing in a mixer with the clay mineral.
  • a mechanical fluidized bed is preferably produced.
  • the intensive mixers known from the prior art can be used in batchwise or continuous processes.
  • the method of making the detergent additive comprises adding carrageenan as described herein. This may be added in a separate aqueous solution or mixed in a common solution with surfactant and N-vinylpyrollidone copolymer with the clay mineral. The addition of carrageenan while the softness is surprisingly further improved.
  • the laundry additive described herein is used to improve the softening.
  • the detergent additive is also suitable as a separate softener both in solid, eg granular rer, as well as in liquid form.
  • the components such as the (nonionic) surfactant or the clay mineral, increase the release of the soil particles and the stabilization of the same in the wash liquor.
  • the detergent additive is used as a component of liquid or solid detergents, cleaners and conditioners, with the foregoing advantages. This reduces the consumption of detergent and reduces the costs for the end user and simplifies the washing process. All conventional washing, cleaning and care agents may be used, such as laundry detergents, dish and dishwashing detergents, stain removers, bleaches, cleaners and conditioners for e.g. Motor vehicles, ships and aircraft, as well as for surface treatment or impregnation.
  • the present invention further teaches the use of a detergent additive to improve the softness of textile products after a washing with the addition of detergent additive, wherein the detergent additive comprises: a) at least one clay mineral; and b) at least one N-vinylpyrrolidone copolymer comprising N-vinylpyrrolidone monomer units and cationic monomer units, wherein the cationic monomer units preferably each have at least one quaternized nitrogen atom.
  • Another aspect of the invention relates to the use of the detergent additive according to the invention for improving the soft feel and / or the color retention of textile products, in particular of fabrics and / or textiles (textile materials), wherein the textile products preferably made of a material selected from the group of Cotton, silk, wool, in particular sheep wool, polyester, polyacrylonitrile, Polyamide, elastane, nylon, viscose, in particular cotton-containing substances, or comprise this.
  • Yet another aspect of the invention relates to the use of at least one carrageenan in a detergent additive and / or a laundry, cleaning or care composition, in particular for improving the soft feel and / or the color retention of textile materials.
  • the percentages by weight of the clay mineral refer to clay mineral, which still has a residual moisture content of 10% by weight, the indication of the residual moisture being based on the weight of the clay mineral dried at 110 ° C. to constant weight.
  • test detergent For the following washing tests, a standard test detergent was used.
  • the composition of this test detergent is shown in Table 1.
  • the components sodium perborate tetrahydrate and tetraacetylethylenediamine were not part of the test detergent and were mixed with the test detergent before dosing. These components were also produced by the Wfk Research Institute for Cleaning nology e. V. related.
  • the data on the mass concentration of these components in the test detergent are also given in Table 1.
  • Table 1 Composition of IEC 60456 (reference basic detergent type A).
  • the bleaching components sodium perborate tetrahydrate and tetraacetylethylenediamine were added.
  • Nessler's reagent (Merck, Art. No. 9028); Boric acid solution, 2%; Caustic soda, 32%; 0.1 N hydrochloric acid; NaCl solution, 0.1%; KCl solution, 0.1%
  • Detection of the ionic freedom of the wash water is carried out on NH 4 + ions with the sensitive Nessler's reagent.
  • the washing rate may vary between 30 minutes and 3 days depending on the type of clay.
  • the washed out NH 4 + clay is removed from the filter, dried at 110 0 C for 2 hours, ground, sieved (63 micron sieve) and dried again at 110 0 C for 2 hours. Thereafter, the NH 4 + content of the clay is determined according to Kjeldahl.
  • Calculation of the CEC The CEC of the clay is the Kjeldahl NH 4 + content of the NH 4 + clay (CEC of some clay minerals, see Appendix). The data are given in meq / 100 g clay.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un additif pour détergent, en particulier pour améliorer le toucher de produits textiles, qui contient au moins les composants suivants : a) au moins un minéral argileux; et b) au moins un copolymère de N-vinylpyrrolidone, le ou les copolymères de N-vinylpyrrolidone comprenant des unités monomères N-vinylpyrrolidone et des unités monomères cationiques. La présente invention concerne également un procédé de préparation de l’additif pour détergent, ainsi que son utilisation.
PCT/EP2009/007088 2008-10-02 2009-10-02 Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation WO2010037560A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2011529483A JP2012504666A (ja) 2008-10-02 2009-10-02 粘土鉱物に基づく洗剤添加剤、その使用、およびその製造方法
EP09778811.1A EP2340298B1 (fr) 2008-10-02 2009-10-02 Additif pour détergent, à base de minéraux argileux, ainsi que son utilisation et des procédés pour sa préparation
MX2011003408A MX2011003408A (es) 2008-10-02 2009-10-02 Aditivo detergente basado en minerales de arcilla, uso del mismo y metodo para la produccion del mismo.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810050360 DE102008050360A1 (de) 2008-10-02 2008-10-02 Waschmitteladditiv auf der Basis von Tonmineralien, sowie dessen Verwendung und Verfahren zu dessen Herstellung
DE102008050360.6 2008-10-02

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WO2010037560A1 true WO2010037560A1 (fr) 2010-04-08

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008058819A1 (fr) * 2006-11-16 2008-05-22 Henkel Ag & Co. Kgaa Composition solide, textile et/ou de soin de la peau

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
ZA734721B (en) 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
DE3887020T2 (de) 1987-07-14 1994-06-09 Procter & Gamble Detergenszusammensetzungen.
EP0313146B2 (fr) 1987-10-19 2001-09-05 The Procter & Gamble Company Compositions détergentes
JP4055544B2 (ja) * 2002-10-11 2008-03-05 ライオン株式会社 液体柔軟剤組成物
JP4589622B2 (ja) * 2003-12-25 2010-12-01 ライオン株式会社 液体柔軟剤組成物
ES2309461T3 (es) 2004-02-03 2008-12-16 THE PROCTER & GAMBLE COMPANY Composicion para usar en el lavado o tratamiento de tejidos.
JP4566828B2 (ja) * 2005-06-09 2010-10-20 花王株式会社 柔軟剤組成物
DE102006016578A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, Textil-weichmachende Zusammensetzung mit einem wasserlöslichen Polymer
DE102006016575A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, textil- und/oder hautpflegende Zusammensetzung
EP1894993A1 (fr) 2006-08-28 2008-03-05 Süd-Chemie Ag Additif détergent au base de minéraux d'argile et des copolymers contenant du PVP

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008058819A1 (fr) * 2006-11-16 2008-05-22 Henkel Ag & Co. Kgaa Composition solide, textile et/ou de soin de la peau

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EP2340298A1 (fr) 2011-07-06
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EP2340298B1 (fr) 2015-12-23
JP2012504666A (ja) 2012-02-23

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