EP1326953A1 - Use of water-soluble or water-dispersible polyether blocks containing graft polymers as coating material and packaging for washing, cleaning and for the treatment of laundry - Google Patents
Use of water-soluble or water-dispersible polyether blocks containing graft polymers as coating material and packaging for washing, cleaning and for the treatment of laundryInfo
- Publication number
- EP1326953A1 EP1326953A1 EP01976301A EP01976301A EP1326953A1 EP 1326953 A1 EP1326953 A1 EP 1326953A1 EP 01976301 A EP01976301 A EP 01976301A EP 01976301 A EP01976301 A EP 01976301A EP 1326953 A1 EP1326953 A1 EP 1326953A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- graft polymers
- water
- polymerization
- washing
- use according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/044—Solid compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0082—Coated tablets
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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
- C11D3/3788—Graft polymers
Definitions
- graft polymers containing water-soluble or water-dispersible polyether blocks as coating and packaging means for washing, cleaning and laundry treatment agents
- the invention relates to the use of graft polymers containing water-soluble or water-dispersible polyether blocks as coating agents for particulate detergents and cleaning agents and as packaging material for detergents, cleaning agents and post-treatment agents for the production of individual portions for metering the agents in the washing process together with the Packing material.
- films made of water-soluble polymers such as polyvinyl alcohol or mixtures of polyvinyl alcohol, which can be obtained by 85 to 90% hydrolysis of polyvinyl acetate and acrylic acid, have been used, cf. JP-A-61-057 700 and DE-A-31 48 931.
- detergents are packaged in foil bags made from the polymers mentioned and added to the washing machine in the form of individual sealed packs. If they come into contact with water, the foil bags disintegrate and release the detergent contained in them.
- films made from polyvinyl alcohol have the disadvantage that they stick to one another in a moist environment, in particular when several bags of polyvinyl alcohol containing a detergent lie one above the other.
- EP-A-0 479 404 In order to reduce the stickiness of water-soluble films made of polyvinyl alcohol for the packaging of detergents and cleaning agents, it is known from EP-A-0 479 404 to combine a base film made of polyvinyl alcohol on at least one surface with a second plastic material, the less is water-soluble as polyvinyl alcohol and is present in the form of a discontinuous, at least partially non-particulate layer on at least the outer surface of the film.
- polyvinyl alcohol as packaging film has the disadvantage that the polyvinyl alcohol does not always completely dissolve in the washing liquor, tends to gel and is deposited on the laundry.
- polyvinyl alcohol has a slow dissolution rate and tends to become brittle and the flexibility decreases dramatically in low ambient humidity. That is why polyvinyl alcohol is usually added to plasticizers in the form of low molecular weight compounds. This required Chen plasticizers often pass from the casing into the contents and lead to changes there. The shell becomes poor in plasticizers and becomes brittle and unstable during storage.
- DE-B-1 077 430 discloses a process for the preparation of graft polymers of vinyl esters, in which polyalkylene glycols and / or their derivatives are dissolved in at least one vinyl ester, if appropriate in the presence of further solvents, and the solution is polymerized by free radicals.
- the graft polymers are used in the textile industry, as adhesives and adhesives, in the leather industry, as raw materials for the coatings industry, in the photo industry and as hair care products.
- DE-B-1 081 229 discloses a process for the preparation of water-soluble modified polyvinyl alcohols which consist of at least 50% by weight of polyvinyl alcohol units. They are prepared by completely or partially saponifying graft polymers of at least one vinyl ester on polyalkylene glycols in the acidic or alkaline pH range. The proportion of polyalkylene glycol in the graft polymer is 0.1 to 50% by weight.
- the modified polyvinyl alcohols are colorless to slightly colored loose powders that easily dissolve in water. They are used, for example, for the production of water-soluble packaging films, as sizing and finishing agents and for cosmetic articles.
- DE-B-1 094 457 discloses modified polyvinyl alcohols which consist of a graft polymer of at least one vinyl ester and optionally other monomers which can be copolymerized therewith on polyalkylene glycols, the graft polymer having been saponified to such an extent that the modified polyvinyl alcohol formed is already cold Water is soluble, but contains less than 50 wt .-% of polyvinyl alcohol units.
- the modified polymers are suitable as protective colloids for the production of polymer dispersions and as starting materials for the production of foams. They are also used as a material for the production of softer, slightly water-soluble, clear transparent films, used as sizing and finishing agents and in cosmetics.
- graft polymers which are prepared by grafting polyalkylene oxides with vinyl acetate and whose vinyl acetate units are optionally saponified up to 15%, as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.
- WO-A-00/18375 discloses the use of graft polymers of vinyl esters on the polyethers defined in more detail therein, such as polyalkylene glycols as coating agents, binders and / or film-forming auxiliaries in pharmaceutical dosage forms.
- the present invention is based on the object of avoiding skin contact of the user with the agents when dispensing detergents, cleaning agents and laundry post-treatment agents and to provide packaging material for portionwise metering of the agents, which is in the washing machine in contact with water the agent releases and is soluble or dispersible in water.
- R 1 hydroxy, amino, -CC 24 alkyl, R 9 -COO-, R 9 -NH-COO-, polyalcohol residue;
- R 8 is hydrogen, amino-Ci-Cg-alkyl, -CC 24 alkoxy, R 9 -C0-, R 9 -NH-C0-;
- R 10 is hydrogen, C 1 -C 24 alkyl, R 9 -CO-;
- n 1 or, if R 1 is a polyalcohol radical, 1 to 8;
- Such graft polymers are known from WO-A-00/18375 cited in the prior art.
- polyethers of the general formula I selected from the group consisting of polyalkylene oxides based on ethylene oxide, propylene oxide and butylene oxide, polytetrahydrofuran and poly- lyglycerin used.
- polymers with the following structural units result.
- copolymers can be both homopolymers and copolymers, the copolymers being randomly distributed or being in the form of so-called block polymers.
- the polymers used according to the invention include both pure graft polymers and mixtures of the above.
- terminal primary hydroxyl groups of the polyethers produced on the basis of alkylene oxides or glycerol and the secondary OH groups of polyglycerol can either be present freely or etherified on one or both sides with C 1 -C 4 alcohols or with C 1 -C 2 carboxylic acids be esterified. However, they can also be replaced by primary amino groups by reductive amination with hydrogen-ammonia mixtures under pressure or converted to aminopropylene end groups by cyanoethylation with acrylonitrile and hydrogenation.
- alkyl radicals for R 1 and R 8 to R 10 are branched or unbranched C 1 -C 2 -alkyl radicals, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1 -Dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1 -dirnethylpropyl, 1, 2 -dimethylpropyl, 1-methylpentyl, 2 -Methyl - pentyl, 3 -Methylpentyl, 4 -Methylpentyl, 1, 1 -Dimethylbutyl, 1, 2 -Dimethylbutyl, 1, 3 -Dimethylbutyl, 2, 2 -Dimethylbut
- branched or unbranched C] _- C 12 -, particularly preferably Ci-Cg-alkyl radicals may be mentioned.
- the average molecular weight (number average) of the polyethers (b) is at least 300 and is generally ⁇ 500,000. It is preferably 500 to 100,000, particularly preferably 500 to 50,000, very particularly preferably 800 to 15,000 and especially 1000 to 10 000th
- Homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40 to 99% by weight are advantageously used.
- the proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference.
- Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers.
- copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and / or isobutylene oxide and copolymers of ethylene oxide, propylene oxide and butylene oxide or isobutylene oxide are suitable.
- the copolymers preferably contain 40 to 99 mol% of ethylene oxide and 1 to 60 mol% of propylene oxide or 1 to 30 mol% of butylene oxide or 1 to 60 mol% of propylene oxide and (iso) butylene oxide.
- branched homopolymers or copolymers can also be used as the graft base.
- R 1 in general formula I low molecular weight polyalcohols
- Polymers can be formed in which at least one, preferably one to eight, particularly preferably one to five of the hydroxyl groups present in the polyalcohol molecule in the form of an ether bond with the following polyether radical according to formula I.
- the alkylene oxide units can be randomly distributed in the polymer or in the form of blocks.
- polyesters of polyalkylene oxides and aliphatic C 1 -C 4, preferably C 1 -C 4 diisocyanates or aromatic dicarboxylic acids for example oxalic acid, succinic acid, adipic acid or terephthalic acid, with average molecular weights of 1500 to 25,000, described in ⁇ P-A- 0 743 962, to be used as a graft base.
- polycarbonates of polyalkylene oxides and aliphatic C 1 -C 2 prepared by phosgenation before - added Ci-Cg diisocyanates or aromatic diisocyanates, for example hexamethylene diisocyanate or phenylene diisocyanate, as the graft base.
- Polyesters, polycarbonates or polyurethanes can contain up to 500, preferably up to 100, polyalkylene oxide units, it being possible for the polyalkylene oxide units to consist both of homopolymers and of copolymers of different alkylene oxides.
- Polymers which can be obtained by polymerizing are preferably used
- R 8 is hydrogen, amino-Cx-Cg-alkyl, C 1 -C 24 alkyl, R 9 -CO-, R 9 -NH-CO;
- R 9 is C 1 -C 24 alkyl
- R 10 is hydrogen, C 1 -C 24 alkyl, R 9 -CO-;
- n 1 or, if R 1 is a polyalcohol radical, 1 to 8, -
- Polymers which are obtainable by polymerizing are particularly preferably used
- R 1 is hydroxy, Cx-Cia-alkoxy, polyalcohol radical
- R 8 is hydrogen, -CC 2 -alkyl
- R 10 is hydrogen, C 1 -C 12 alkyl
- n 1 or, if R 1 is a polyalcohol radical, 1 to 5;
- Polymers are especially preferably used, which are he ⁇ biblich by polymerization of
- R 1 is hydroxy, Ci-Cg-alkoxy, especially hydroxy
- R 8 is hydrogen, Ci-Cg-alkyl, especially hydrogen
- R 10 is hydrogen, -CC 6 alkyl
- component (a) for the polymerization in the presence of the polyethers of the formula I:
- Vinyl esters of aliphatic, saturated or unsaturated c ⁇ ⁇ c 24 -carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, ündecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, palmitoleic acid Oleic acid, arachidic acid, behenic acid, lignoceric acid, cerotinic acid and melissa acid.
- carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, ündecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, palmitoleic acid Oleic
- Vinyl esters of the above-mentioned C 1 -C 2 -carboxylic acids, in particular of the C 1 -C 6 -carboxylic acids, especially acetic acid, are preferably used.
- Mixtures of the respective monomers from group (a) can of course also be graft-polymerized.
- the vinyl esters (a) can also be used in a mixture with one or more comonomers (c).
- the comonomers (c) can be hydrophobic or hydrophilic, and the compounds usually used as crosslinkers are also suitable.
- the proportion of these additional monomers (c) in the mixture of (a) + (c) should be limited to 0.1 to 30% by weight. Fractions of 1 to 20% by weight of the comonomers (c) in the mixture are preferred.
- Suitable hydrophobic comonomers (c) can be selected from the following groups; mixtures of the monomers can of course also be used here:
- alkyl radicals reference is made to the C 1 -C 24 -alkyl radicals already mentioned and their hydroxylation products.
- branched or unbranched C 1 -C 4 alkyl radicals in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl and their hydroxylation products to call.
- Monomers of groups (ci) to (c 3 ) are particularly preferred.
- Methyl (meth) acrylate, ethyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methyl vinyl ether and ethyl vinyl ether are very particularly preferred.
- Suitable hydrophilic comonomers (c) are, for example, monoethylenically unsaturated C 3 -Cs carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and aconitic acid, and also N-vinyl lactams, such as N-vinyl pyrrolidone, N-vinyl imidazole or N-Vi - nylcaprolactam.
- Preferred hydrophilic comonomers (c) are acrylic acid, methacrylic acid and N-vinylpyrrolidone.
- Suitable comonomers (c) usually used as crosslinkers are compounds which contain at least two ethylenically unsaturated non-conjugated double bonds in the molecule.
- alkylenebisacrylamides such as methylenebisacrylamide and N, N'-acryloylethylenediamine
- vinylalkyleneureas such as N, N'-divinylethyleneurea and N, N'-divinylpropyleneurea, ethylidene-bis-3- (N-vinylpyrrolidone), N, ' -Divinylimidazolyl (2,2 ') butane, 1,1'-bis (3,3'-vinylbenzimidazolid-2-one) -1, -butane
- alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate
- aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and also vinyl acrylate, allyl (meth) acrylate, divinyld
- Graft polymers whose graft base is a polyglycerol can be obtained by polymerizing
- R 8 and Rio are hydrogen, C 1 -C 24 alkyl, R 9 -CO-;
- R 9 is C 1 -C 24 alkyl
- R x is a polyalcohol radical, 1 to 8;
- Particularly preferred graft polymers on polyglycerols can be obtained by polymerizing
- branched and / or cyclic polyglycerols can also be used as the graft base.
- the graft polymers based on polyglycerol may optionally contain, in addition to the vinyl esters (a), at least one further of the comonomers (c) mentioned above in copolymerized form.
- Preferred comonomers (c) are C-Cg-alkyl esters of monoalkyl-unsaturated C 3 -C 8 -carboxylic acids, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam and (meth) acrylic acid.
- the K values of the graft polymers are, for example, in the range from 10 to 200, preferably in the range from 15 to 150, particularly preferably in the range from 15 to 100, very particularly preferably in the range from 20 to 80.
- the K value desired in each case can be adjusted in a manner known per se through the composition of the starting materials.
- the K values are determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 and 71 to 74 (1932) in N-methylpyrrolidone at 25 ° C. and polymer concentrations, which depend on the K value range are 0.1% by weight to 5% by weight.
- the vinyl esters (a) and, if desired, the comonomers (c) in the presence of the polyethers (b) can be used as the graft base both with the aid of initiators which form free radicals and by the action of high-energy radiation, which also includes the action of high-energy electrons should be polymerized.
- the polymerization can be, for example, solution polymerization, bulk polymerization, emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization, without the methods which can be used being restricted thereto.
- the preferred bulk polymerization can be carried out by dissolving the polyether (b), in particular the polyalkylene oxide (b), in at least one vinyl ester (a) and, if desired, one or more comonomers (c), and the mixture after adding a Polymerization initiator polymerized.
- the graft polymerization can also be carried out semi-continuously by first introducing a portion, for example 10% by weight, of this mixture and heating it to the polymerization temperature and adding the rest of the mixture to be polymerized after the polymerization has started and the progress of the polymerization.
- the graft polymers can also be obtained by placing the polyether (b) in a reactor, heating to the polymerization temperature and at least one vinyl ester (a) and, if desired, comonomer (c) (separately or as a mixture) and polymerization initiator either in one batch or preferably continuously added and polymerized.
- the quantitative ratio of the polyethers (b) used as the graft base to the vinyl esters (a) or the mixture of the vinyl esters (a) and the comonomers (c) is in the range from 1: 0.5 to 1:50, preferably in the range from 1: 1.5 to 1:35 and particularly preferably in the range from 1: 2 to 1:30.
- Organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide and di-tert are particularly suitable as polymerization initiators.
- the amounts of initiator or initiator mixtures used, based on monomer (a) and optionally (c) used, are from 0.01 to 10% by weight, preferably from 0.3 to 5% by weight.
- the graft polymerization takes place in the temperature range from 40 to 200 ° C., preferably in the range from 50 to 140 ° C., particularly preferably in the range from 60 to 110 ° C. It is usually carried out under atmospheric pressure, but can also take place under reduced or elevated pressure, preferably between 1 and 5 bar. If desired, the graft polymerization described above can also be carried out in a solvent or solvent mixture. Suitable solvents are, for example, aliphatic and cycloaliphatic monohydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec. -Butanol, ter.
- polyhydric alcohols for example glycols, such as ethylene glycol, propylene glycol and butylene glycol, and glycerin.
- Alkyl ethers of polyhydric alcohols for example methyl or ethyl ethers of the dihydric alcohols, ether alcohols, such as diethylene glycol and triethylene glycol, and cyclic ethers, such as dioxane.
- the graft polymerization can also be carried out in water as a solvent. If water-insoluble products formed during the polymerization are to be obtained directly in dissolved form, water-miscible organic solvents can be added during the polymerization, e.g. monohydric alcohols with 1 to 3 carbon atoms, acetone or dimethylformamide.
- graft polymerization in water can also be carried out by adding the water-insoluble graft polymers by adding customary emulsifiers or protective colloids, e.g. Polyvinyl alcohol, converted into a fine dispersion.
- the emulsifiers used are, for example, ionic or nonionic surfactants whose HLB value is in the range from 3 to 13.
- HLB value For the definition of the HLB value, reference is made to the publication by W.C. Griffin, J. Soc. Cosmetic Che., Volume 5, 249 (1954). If surfactants are used in the graft polymerization, their amount, based on the graft copolymer, is e.g. 0.1 to 5% by weight.
- the ester groups can be completely or partially saponified (hydrolyzed) after the polymerization.
- the saponification is carried out in a manner known per se by adding a base, preferably an alcoholic alkali metal hydroxide solution, in particular a methanolic sodium or potassium hydroxide solution, at temperatures in the range from 10 to 70 ° C., preferably in the range from 15 to 30 ° C. ,
- the degree of saponification depends on the amount of base used, on the saponification temperature and on the saponification time and can accordingly be in the range from 0 to 100 mol%.
- the solids content of the aqueous polymer dispersions or solutions obtained after the alcohol has been replaced by water is generally 10 to 70% by weight, preferably 15 to 65% by weight, particularly preferably 20 to 60 % By weight. 0
- aqueous dispersions or solutions of the graft polymers used according to the invention are obtained with a viscosity of less than 1000 mPas.
- the viscosity is preferably from 5 to 400 mPas, particularly preferably from 10 to 250 mPas.
- the graft polymer dispersions or solutions can be prepared by various drying processes, e.g. Spray drying, Fluidized 0 Spray Drying, drum drying or freeze drying, can be transferred into powder form. Because of the low viscosity of the solutions or dispersions, spray drying is preferably used as the drying process. From the graft polymer dry powder thus obtained, an aqueous dispersion or solution can be prepared again by adding it to water. Powdery graft polymers have the advantage over dispersions and solutions, in particular aqueous dispersions and solutions, of better storage stability, easier transport and a lower tendency to infest germs. 0
- the graft polymers can be in pure form or together with the usual auxiliaries on a core containing active ingredients, e.g. applied to tablets from a washing or cleaning agent.
- auxiliaries are e.g. Color pigments for coloring, white pigments such as titanium dioxide to increase opacity, talc and silicon dioxide as an anti-adhesive, polyethylene glycols, glycerin, propylene glycol, triacetin and triethyl citrate as plasticizers and various surface-active substances such as sodium lauryl sulfate to improve the wetting behavior - tens.
- graft polymers to be used according to the invention with other film formers or polymers, for example in a ratio of 1: 9 to 9: 1.
- the following polymers can be used for this, c -: Polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, water-soluble cellulose derivatives, such as hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose and hydroxyethyl cellulose, acrylate and methacrylate copolymers, polyvinyl alcohols, poly 5 ethylene glycols and polyethylene oxide-polypropylene oxide block polyols. Melts from such polymer mixtures can be processed, for example, to give films, granules or powders. The films can be used directly for the packaging of detergents and cleaning agents. 0
- the coating of particulate detergents and cleaning agents is desirable because this prevents contact of constituents of the detergents or cleaning agents with the skin of the user in the usual dosage of these agents in the household. This advantage applies particularly to such washing and
- Detergents containing ingredients that may cause skin irritation or allergic reactions e.g. Alkali carbonates, oxidizing agents such as perborates, or enzymes.
- the coating of particulate detergents and cleaning agents also has the advantage that the breaking strength and the abrasion of the coated particles are improved compared to the uncoated particles of the same composition.
- Particulate detergents and cleaning agents are to be understood to mean all customary commercial forms of these products, e.g. Granules, pellets, scales, strands, balls, tablets and powder.
- Some examples of the composition of washing and cleaning agents (including bleaching agents) are given in Tables 1 and 2.
- the detergents can be customary powder detergents or compact detergents with a bulk density of, for example, 550 to 1000 g / l.
- the usual methods can be used for coating particulate detergents and cleaning agents, e.g. Coating in the fluidized bed or in the horizontal drum coater, immersion sword process or boiler coating process.
- Detergent tablets, detergent tablets and spheres, granules and such forms of detergent and cleaner formulations are preferably coated, of which 1 to 5 moldings, such as tablets or spheres, are required for a wash cycle.
- the coating compositions are applied, for example, to the particulate detergents and cleaners in a thickness of 5 to 1000 ⁇ m, preferably 30 to 500 ⁇ m and in particular in a thickness of 40 to 100 ⁇ m.
- the invention also relates to the use of the graft polymers described above as packaging material for washing, cleaning and laundry aftertreatment compositions for the production of individual portions for metering the compositions in the washing process together with the packaging material.
- the amount of washing, cleaning or laundry aftertreatment agent individually portioned and packaged for a washing cycle is described in the literature e.g. referred to as "single packaging", “unit packaging detergent” or “sachets for packaging measured portions of detergents".
- films can be produced from the graft polymers to be used according to the invention, for example by extrusion or by casting.
- the thickness of the films is, for example, 10 to 1000 ⁇ m, preferably 30 to 500 ⁇ m and is usually in the range from 40 to 100 ⁇ m.
- Bags or sacks for the packaging of powder detergents, liquid detergents, cleaning agents and laundry aftertreatment agents, for example, are produced from the water-soluble films of graft polymers. After filling with one of the agents mentioned, the bags or sacks are closed, for example welded, sealed or glued with the aid of an adhesive.
- the amount of active agent which is packaged in the bags is preferably such that, for example, 1 to 5, in particular 1 bag is sufficient for a single wash cycle.
- the foil pouch disintegrates, releasing the agent packed in it.
- the packaging material is very easily soluble or easily dispersible in water or in the wash liquor. With the help of the washing, cleaning and laundry care packaged in individual portions it is possible to achieve an optimal dosage of the agents without the risk of the user coming into contact with, for example, alkaline components of a detergent formulation.
- Graft polymers preferably used are by polymerization of
- polyethylene glycols with a number average molecular weight of 500 to 100,000, preferably 1000 to 50,000 and
- the vinyl acetate units of the preferred graft polymers are mostly hydrolyzed to 80 to 100 mol%.
- the K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71 to 74 (1932) in N-methylpyrrolidone at a temperature of 25 ° C. and a polymer concentration of 1% by weight.
- Grip feeling reduced surface roughness, more pleasant grip feeling compared to uncoated tablets
- Abrasion no abrasion when rubbed with the finger, after shaking for 10 minutes in a rotary mixer (from Gerhardt) with 1 tablet each in a screw-cap glass (500 ml) with a tablet coated with 50 mg according to Example 1 and with one uncoated tablet 960 mg.
- the release time for the film bag made of a film with a thickness of 40 ⁇ was 20 seconds, for the film bag made of a film with a thickness of 100 ⁇ the residue-free dissolution took 60 seconds.
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- Detergent Compositions (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the use of water-soluble or water-dispersible, film-forming graft polymers, which are obtainable by radical polymerisation of (a) vinyl esters of aliphatic C1-C24 carboxylic acids in the presence of, (b) polyethers with an average molecular weight (average number) of at least 300, as coating material for particle shaped washing and cleaning agents, and as packaging for washing, cleaning and laundry treating agents for producing individual portions for dosing said agents in the cleaning process together with the packaging.
Description
Verwendung von wasserlöslichen oder wasserdispergierbaren Poly- etherblöcken enthaltenden Pfropfpolymerisaten als Beschichtungsund Verpackungsmittel für Wasch-, Reinigungs- und Wäschebehand- lungsmittelUse of graft polymers containing water-soluble or water-dispersible polyether blocks as coating and packaging means for washing, cleaning and laundry treatment agents
Beschreibungdescription
Die Erfindung betrifft die Verwendung von wasserlöslichen oder wasserdispergierbaren Polyetherblöcken enthaltenden Pfropfpolyme- risaten als Beschichtungsmittel für teilchenförmige Wasch- und Reinigungsmittel und als Verpackungsmaterial für Wasch-, Reinigungs- und Wäschenachbehandlungsmittel zur Herstellung von einzelnen Portionen für die Dosierung der Mittel im Waschprozeß zu- sammen mit dem Verpackungsmaterial.The invention relates to the use of graft polymers containing water-soluble or water-dispersible polyether blocks as coating agents for particulate detergents and cleaning agents and as packaging material for detergents, cleaning agents and post-treatment agents for the production of individual portions for metering the agents in the washing process together with the Packing material.
Zum portionierten Verpacken von Wasch- und Reinigungsmitteln hat man beispielsweise Folien aus wasserlöslichen Polymeren wie Poly- vinylalkohol oder Mischungen aus Polyvinylalkohol , der durch 85 bis 90%ige Hydrolyse von Polyvinylacetat erhältlich ist, und Acrylsäure, verwendet, vgl. JP-A-61-057 700 und DE-A-31 48 931. So werden beispielsweise Waschmittel in Folienbeuteln aus den genannten Polymeren verpackt und in Form von einzelnen versiegelten Packungen in die Waschmaschine gegeben. Bei einem Kontakt mit Wasser zerfallen die Folienbeutel und setzen das darin enthaltene Waschmittel frei. Filme aus Polyvinylalkohol haben jedoch den Nachteil, daß sie in feuchter Umgebung miteinander verkleben, insbesondere dann, wenn mehrere ein Waschmittel enthaltende Beutel aus Polyvinylalkohol übereinander liegen.For portioned packaging of detergents and cleaning agents, for example, films made of water-soluble polymers such as polyvinyl alcohol or mixtures of polyvinyl alcohol, which can be obtained by 85 to 90% hydrolysis of polyvinyl acetate and acrylic acid, have been used, cf. JP-A-61-057 700 and DE-A-31 48 931. For example, detergents are packaged in foil bags made from the polymers mentioned and added to the washing machine in the form of individual sealed packs. If they come into contact with water, the foil bags disintegrate and release the detergent contained in them. However, films made from polyvinyl alcohol have the disadvantage that they stick to one another in a moist environment, in particular when several bags of polyvinyl alcohol containing a detergent lie one above the other.
Um die Klebrigkeit von wasserlöslichen Filmen aus Polyvinylalkohol für die Verpackung von Wasch- und Reinigungsmitteln zu reduzieren, ist aus der EP-A-0 479 404 bekannt, eine Grundfolie aus Polyvinylalkohol auf mindestens einer Oberfläche mit einem zwei- ten Kunststoffmaterial zu kombinieren, das weniger wasserlöslich ist als Polyvinylalkohol und in Form einer diskontinuierlichen, mindestens teilweise nicht teilchenförmigen Schicht auf mindestens der Außenfläche der Folie vorliegt.In order to reduce the stickiness of water-soluble films made of polyvinyl alcohol for the packaging of detergents and cleaning agents, it is known from EP-A-0 479 404 to combine a base film made of polyvinyl alcohol on at least one surface with a second plastic material, the less is water-soluble as polyvinyl alcohol and is present in the form of a discontinuous, at least partially non-particulate layer on at least the outer surface of the film.
Die Verwendung von Polyvinylalkohol als Verpackungsfolie hat den Nachteil, daß sich der Polyvinylalkohol nicht immer vollständig in der Waschflotte löst, zur Gelbildung neigt und sich auf dem Waschgut ablagert. Zudem weist Polyvinylalkohol eine langsame Lösungsgeschwindigkeit auf und neigt bei niedriger Umgebungsfeuchte zur Versprödung und einer dramatischen Abnahme der Flexibilität. Deshalb werden Polyvinylalkohol üblicherweise Weichmacher in Form von niedermolekularen Verbindungen zugesetzt. Diese erforderli-
chen Weichmacher treten häufig von der Hülle in das Füllgut über und führen dort zu Veränderungen. Die Hülle verarmt an Weichmachern und wird im Laufe der Lagerung spröde und instabil.The use of polyvinyl alcohol as packaging film has the disadvantage that the polyvinyl alcohol does not always completely dissolve in the washing liquor, tends to gel and is deposited on the laundry. In addition, polyvinyl alcohol has a slow dissolution rate and tends to become brittle and the flexibility decreases dramatically in low ambient humidity. That is why polyvinyl alcohol is usually added to plasticizers in the form of low molecular weight compounds. This required Chen plasticizers often pass from the casing into the contents and lead to changes there. The shell becomes poor in plasticizers and becomes brittle and unstable during storage.
Aus der EP-A-0 253 566 sind für die portionsweise Dosierung von Waschmitteln Folienbeutel bekannt, die ein Waschmittel enthalten und deren Wandmaterial aus einem Verbund aus Polyethylenoxiden und einem wasserunlöslichen, aber wasserdurchlässigen Material, z.B. einem Vlies, besteht. Diese Art der Waschmitteldosierung hat den Nachteil, daß der wasserunlösliche Bestandteil des Verpak- kungsmaterials nach jeder Wasche aus dem Waschgut entfernt werden muß.From EP-A-0 253 566 foil bags are known for the portioned dosage of detergents which contain a detergent and whose wall material is made of a composite of polyethylene oxides and a water-insoluble but water-permeable material, e.g. a fleece. This type of detergent dosing has the disadvantage that the water-insoluble component of the packaging material has to be removed from the laundry after each wash.
Aus der DE-B-1 077 430 ist ein Verfahren zur Herstellung von Pfropf olymerisaten von Vinylestern bekannt, wobei man Polyalky- lenglykole und/oder deren Derivate in mindestens einem Vinylester gegebenenfalls in Gegenwart von weiteren Lösemitteln löst und die Lösung radikalisch polymerisier . Die Pfropfpolymerisate werden in der Textilindustrie, als Haft- und Klebemittel, in der Leder- industrie, als Grundstoff für die Lackindustrie, in der Photoin- dustrie und als Haarpflegemittel verwendet.DE-B-1 077 430 discloses a process for the preparation of graft polymers of vinyl esters, in which polyalkylene glycols and / or their derivatives are dissolved in at least one vinyl ester, if appropriate in the presence of further solvents, and the solution is polymerized by free radicals. The graft polymers are used in the textile industry, as adhesives and adhesives, in the leather industry, as raw materials for the coatings industry, in the photo industry and as hair care products.
Aus der DE-B-1 081 229 ist ein Verfahren zur Herstellung wasserlöslicher modifizierter Polyvinylalkohole bekannt, die zu minde- stens 50 Gew.-% aus Polyvinylalkoholeinheiten bestehen. Sie werden dadurch hergestellt, daß man Pfropfpolymerisate mindestens eines Vinylesters auf Polyalkylenglykolen im sauren oder alkalischen pH-Bereich vollständig oder teilweise verseift. Der Polyal- kylenglykolanteil im Pfropfpolymerisat beträgt 0,1 bis 50 Gew.-%. Die modifizierten Polyvinylalkohole sind farblose bis wenig gefärbte lockere Pulver, die sich leicht in Wasser lösen. Sie werden beispielsweise zur Herstellung von wasserlöslichen Verpak- kungsfolien, als Schlichte- und Appreturmittel und für kosmetische Artikel verwendet.DE-B-1 081 229 discloses a process for the preparation of water-soluble modified polyvinyl alcohols which consist of at least 50% by weight of polyvinyl alcohol units. They are prepared by completely or partially saponifying graft polymers of at least one vinyl ester on polyalkylene glycols in the acidic or alkaline pH range. The proportion of polyalkylene glycol in the graft polymer is 0.1 to 50% by weight. The modified polyvinyl alcohols are colorless to slightly colored loose powders that easily dissolve in water. They are used, for example, for the production of water-soluble packaging films, as sizing and finishing agents and for cosmetic articles.
Aus der DE-B-1 094 457 sind modifizierte Polyvinylalkohole bekannt, die aus einem Pfropfpolymerisat mindestens eines Vinylesters und gegebenenfalls anderen, damit copolymerisierbaren Monomeren auf Polyalkylenglykolen bestehen, wobei das Pfropfpolyme- risat so weit verseift ist, daß der entstandene modifizierte Polyvinylalkohol bereits in kaltem Wasser löslich ist, jedoch weniger als 50 Gew.-% an Polyvinylalkoholeinheiten enthält. Die modifizierten Polymerisate eignen sich als Schutzkolloid für die Herstellung von Polymerdispersionen und als Ausgangsstoff für die Herstellung von Schaumstoffen. Sie werden außerdem als Material für die Herstellung weicher, leicht wasserlöslicher, klar durch-
sichtiger Folien, als Schlichte- und Appreturmittel und in der Kosmetik verwendet.DE-B-1 094 457 discloses modified polyvinyl alcohols which consist of a graft polymer of at least one vinyl ester and optionally other monomers which can be copolymerized therewith on polyalkylene glycols, the graft polymer having been saponified to such an extent that the modified polyvinyl alcohol formed is already cold Water is soluble, but contains less than 50 wt .-% of polyvinyl alcohol units. The modified polymers are suitable as protective colloids for the production of polymer dispersions and as starting materials for the production of foams. They are also used as a material for the production of softer, slightly water-soluble, clear transparent films, used as sizing and finishing agents and in cosmetics.
Aus der US-A-4 746 456 ist die Verwendung von Pfropf olymerisa - ten, die durch Pfropfen von Polyalkylenoxiden mit Vinylacetat hergestellt werden und deren Vinylacetateinheiten gegebenenfalls bis zu 15 % verseift sind, als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von Synthesefasern enthaltendem Textilgut bekannt .US Pat. No. 4,746,456 discloses the use of graft polymers, which are prepared by grafting polyalkylene oxides with vinyl acetate and whose vinyl acetate units are optionally saponified up to 15%, as graying inhibitors in the washing and aftertreatment of textile goods containing synthetic fibers.
Aus der WO-A-00/18375 ist die Verwendung von Pfropfpolymerisaten von Vinylestern auf den darin näher definierten Polyethern wie Polyalkylenglykolen als Überzugsmittel, Bindemittel und/oder filmbildender Hilfsstoff in pharmazeutischen Darreichungsformen bekannt.WO-A-00/18375 discloses the use of graft polymers of vinyl esters on the polyethers defined in more detail therein, such as polyalkylene glycols as coating agents, binders and / or film-forming auxiliaries in pharmaceutical dosage forms.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, bei der Dosierung von Wasch-, Reinigungs- und Wäschenachbehandlungsmitteln einen Hautkontakt des Anwenders mit den Mitteln zu vermeiden und für eine portionsweise Dosierung der Mittel ein Verpackungsmaterial zur Verfügung zu stellen, das in der Waschmaschine bei Kontakt mit Wasser das Mittel freigibt und in Wasser löslich oder dispergierbar ist.The present invention is based on the object of avoiding skin contact of the user with the agents when dispensing detergents, cleaning agents and laundry post-treatment agents and to provide packaging material for portionwise metering of the agents, which is in the washing machine in contact with water the agent releases and is soluble or dispersible in water.
Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von wasserlöslichen oder wasserdispergierbaren, filmbildenden Pfropf - Polymerisaten, die erhältlich sind durch radikalische Polymerisation vonThe object is achieved according to the invention with the use of water-soluble or water-dispersible, film-forming graft polymers which can be obtained by radical polymerization of
(a) Vinylestern von aliphatischen Cι-C2 -Carbonsäuren in Gegenwart von(a) Vinyl esters of aliphatic C 2 -C 2 carboxylic acids in the presence of
(b) Polyethern eines mittleren Molekulargewichts (Zahlenmittel) von mindestens 300 der allgemeinen Formel I(b) polyethers with a number average molecular weight of at least 300 of the general formula I.
^o rfR3-o 7fR4-o^A- R5-o-y-Rε-o-^-R7-o^ -Ru ^ o rfR 3 -o 7 fR 4 -o ^ A- R 5 -oyR ε -o - ^ - R 7 -o ^ -R u
in der die Variablen unabhängig voneinander folgende Bedeutung haben:in which the variables have the following meaning independently of one another:
R1 Hydroxy, Amino, Cι-C24-Alkyl, R9-COO-, R9-NH-COO-, Polyalko- holrest;
R8 Wasserstoff, Amino-Ci-Cg-alkyl, Cι-C24-Alkoxy, R9-C0-, R9-NH-C0-;R 1 hydroxy, amino, -CC 24 alkyl, R 9 -COO-, R 9 -NH-COO-, polyalcohol residue; R 8 is hydrogen, amino-Ci-Cg-alkyl, -CC 24 alkoxy, R 9 -C0-, R 9 -NH-C0-;
R2 bis R7 R 2 to R 7
- (CR2 ) 2- , -(CH2.3-. -(CH2)4-, -CH2-CH(CH3)-, -CH2-CH (CH2-CH3 ) - , -CH2-CHOR10-CH2- ;- (CR 2 ) 2 -, - (CH2.3-. - (CH 2 ) 4 -, -CH 2 -CH (CH 3 ) -, -CH 2 -CH (CH 2 -CH 3 ) -, -CH 2- CHOR 10 -CH 2 -;
R9 Cχ-C24-Alkyl;R 9 Cχ-C 24 alkyl;
R10 Wasserstoff, C1-C24-Alkyl, R9-CO-;R 10 is hydrogen, C 1 -C 24 alkyl, R 9 -CO-;
A -CO-O-, -CO-B-CO-O-, -CO-NH-B-NH-CO-O;A -CO-O-, -CO-B-CO-O-, -CO-NH-B-NH-CO-O;
B -(CH2)t-/ gegebenenfalls substituiertes Arylen;B - (CH 2 ) t- / optionally substituted arylene;
n 1 oder, wenn R1 einen Polyalkoholrest bedeutet, 1 bis 8;n 1 or, if R 1 is a polyalcohol radical, 1 to 8;
s 0 bis 500;s 0 to 500;
t 1 bis 12;t 1 to 12;
u 1 bis 5000;u 1 to 5000;
v 0 bis 5000;v 0 to 5000;
w 0 bis 5000;w 0 to 5000;
x 1 bis 5000;x 1 to 5000;
y 0 bis 5000;y 0 to 5000;
z 0 bis 5000z 0 to 5000
als Beschichtungsmittel für teilchenförmige Wasch- und Reinigungsmittel und als Verpackungsmaterial für Wasch-, Reinigungsund Wäschenachbehandlungsmittel zur Herstellung von einzelnen Portionen für die Dosierung der Mittel im Waschprozeß zusammen mit dem Verpackungsmaterial.as a coating agent for particulate washing and cleaning agents and as packaging material for washing, cleaning and laundry aftertreatment agents for the production of individual portions for dosing the agents in the washing process together with the packaging material.
Solche Pfropf olymerisate sind aus der zum Stand der Technik genannten WO-A-00/18375 bekannt. Als Pfropfgrundlage (b) werden generell Polyether der allgemeinen Formel I, ausgewählt aus der Gruppe, bestehend aus Polyalkylenoxiden auf Basis von Ethylen- oxid, Propylenoxid und Butylenoxid, Polytetrahydrofuran sowie Po-
lyglycerin verwendet. Je nach Art der Monomerbausteine ergeben sich Polymere mit folgenden Struktureinheiten.Such graft polymers are known from WO-A-00/18375 cited in the prior art. Generally, polyethers of the general formula I selected from the group consisting of polyalkylene oxides based on ethylene oxide, propylene oxide and butylene oxide, polytetrahydrofuran and poly- lyglycerin used. Depending on the type of monomer building blocks, polymers with the following structural units result.
-(CH2)2-0-, -(CH2)3-0-, -(CH2)4-0-, -CH2-CH(CH3)-0-, -CH2-CH(CH2-CH3) -0-, -CH2-CHOR10-CH2-O- ;- (CH 2 ) 2 -0-, - (CH 2 ) 3 -0-, - (CH 2 ) 4 -0-, -CH 2 -CH (CH 3 ) -0-, -CH 2 -CH (CH 2 -CH 3 ) -0-, -CH 2 -CHOR 10 -CH 2 -O-;
Dabei kann es sich sowohl um Ho opolymere als auch um Copolymere handeln, wobei die Copolymere statistisch verteilt sein oder als sogenannte Blockpolymere vorliegen können.These can be both homopolymers and copolymers, the copolymers being randomly distributed or being in the form of so-called block polymers.
Je nach Pfropfungsgrad sind unter den erfindungsgemäß verwendeten Polymerisaten sowohl reine Pfropfpolymerisate als auch Mischungen der o.g. Pfropf olymerisate mit ungepfropf ten Polyethern der Formel I und Homo- oder Copolymerisaten der Vinylester (a) und gegebenenfalls weiteren Comonomeren (c) zu verstehen.Depending on the degree of grafting, the polymers used according to the invention include both pure graft polymers and mixtures of the above. To understand graft polymers with ungrafted polyethers of the formula I and homo- or copolymers of the vinyl esters (a) and, if appropriate, further comonomers (c).
Die endständigen primären Hydroxylgruppen der auf Basis von Alky- lenoxiden oder Glycerin hergestellten Polyether sowie die sekundären OH-Gruppen von Polyglycerin können sowohl frei vorliegen als auch ein- oder beidseitig mit Cι-C4-Alkoholen verethert bzw. mit Cι-C2 -Carbonsäuren verestert sein. Sie können jedoch auch durch reduktive Aminierung mit Wasserstoff -Ammoniak-Gemischen unter Druck gegen primäre Aminogruppen ausgetauscht oder durch Cyanethylierung mit Acrylinitril und Hydrieren in Aminopropylend- gruppen umgewandelt sein.The terminal primary hydroxyl groups of the polyethers produced on the basis of alkylene oxides or glycerol and the secondary OH groups of polyglycerol can either be present freely or etherified on one or both sides with C 1 -C 4 alcohols or with C 1 -C 2 carboxylic acids be esterified. However, they can also be replaced by primary amino groups by reductive amination with hydrogen-ammonia mixtures under pressure or converted to aminopropylene end groups by cyanoethylation with acrylonitrile and hydrogenation.
Als Alkylreste für R1 und R8 bis R10 seien verzweigte oder unverzweigte Cι-C2 -Alkylreste, bevorzugt Methyl, Ethyl, n-Propyl, 1-Methylethyl, n-Butyl, 1 -Methylpropyl, 2 -Methylpropyl, 1, 1-Dimethylethyl, n-Pentyl, 1-Methylbutyl, 2 -Methylbutyl, 3-Methylbutyl, 2, 2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 1, 1 -Dirnethylpropyl, 1, 2 -Dimethylpropyl, 1 -Methylpentyl, 2 -Methyl - pentyl, 3 -Methylpentyl, 4 -Methylpentyl, 1 , 1 -Dimethylbutyl, 1, 2 -Dimethylbutyl, 1, 3 -Dimethylbutyl, 2 , 2 -Dimethylbutyl , 2, 3 -Dimethylbutyl, 3 , 3 -Dimethylbutyl, 1-Ethylbutyl , 2 -Ethylbutyl , 1, 1,2-Trimethylpropyl, 1, 2, 2-Trimethylpropyl, 1 -Ethyl -1-methyl - propyl, 1- Ethyl -2 -methylpropyl, n-Heptyl, 2-Ethylhexyl, n-Octyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl, n-Octadecyl, n-Nonadecyl oder n-Eicosyl, genannt.As alkyl radicals for R 1 and R 8 to R 10 are branched or unbranched C 1 -C 2 -alkyl radicals, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1 -Dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1 -dirnethylpropyl, 1, 2 -dimethylpropyl, 1-methylpentyl, 2 -Methyl - pentyl, 3 -Methylpentyl, 4 -Methylpentyl, 1, 1 -Dimethylbutyl, 1, 2 -Dimethylbutyl, 1, 3 -Dimethylbutyl, 2, 2 -Dimethylbutyl, 2, 3 -Dimethylbutyl, 3, 3 -Dimethylbutyl, 1 -Ethylbutyl, 2 -Ethylbutyl, 1, 1,2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1 -Ethyl -1-methyl-propyl, 1-ethyl -2-methylpropyl, n-heptyl, 2-ethylhexyl, n -Octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl , called.
Als bevorzugte Vertreter der oben genannten Alkylreste seien verzweigte oder unverzweigte C]_-C12- , besonders bevorzugt Ci-Cg-Alkylreste genannt .
Das mittlere Molekulargewicht (Zahlenmittel) der Polyether (b) beträgt mindestens 300 und ist in der Regel < 500 000. Es beträgt bevorzugt 500 bis 100 000, besonders bevorzugt 500 bis 50000, ganz besonders bevorzugt 800 bis 15 000 und vor allem 1000 bis 10 000.As preferred representatives of the alkyl radicals mentioned above, branched or unbranched C] _- C 12 -, particularly preferably Ci-Cg-alkyl radicals may be mentioned. The average molecular weight (number average) of the polyethers (b) is at least 300 and is generally <500,000. It is preferably 500 to 100,000, particularly preferably 500 to 50,000, very particularly preferably 800 to 15,000 and especially 1000 to 10 000th
Vorteilhafterweise verwendet man Homopolymerisate des Ethylen- oxids oder Copolymerisate mit einem Ethylenoxidanteil von 40 bis 99 Gew.-%. Für die bevorzugt einzusetzenden Ethylenoxidpoly- merisate beträgt somit der Anteil an einpolymerisiertem Ethylen- oxid 40 bis 100 mol-%. Als Comonomer für diese Copolymerisate kommen Propylenoxid, Butylenoxid und/oder Isobutylenoxid in Betracht. Geeignet sind beispielsweise Copolymerisate aus Ethylenoxid und Propylenoxid, Copolymerisate aus Ethylenoxid und Butylenoxid und/oder Isobutylenoxid sowie Copolymerisate aus Ethylenoxid, Propylenoxid und Butylenoxid oder Isobutylenoxid. Die Copolymerisate enthalten vorzugsweise 40 bis 99 mol-% Ethylenoxid und 1 bis 60 mol-% Propylenoxid oder 1 bis 30 mol-% Butylenoxid bzw. 1 bis 60 mol-% Propylenoxid und (Iso) Butylenoxid.Homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40 to 99% by weight are advantageously used. The proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference. Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers. For example, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and / or isobutylene oxide and copolymers of ethylene oxide, propylene oxide and butylene oxide or isobutylene oxide are suitable. The copolymers preferably contain 40 to 99 mol% of ethylene oxide and 1 to 60 mol% of propylene oxide or 1 to 30 mol% of butylene oxide or 1 to 60 mol% of propylene oxide and (iso) butylene oxide.
Neben geradkettigen können auch verzweigte Homo- oder Copolymerisate als Pfropfgrundlage verwendet werden.In addition to straight-chain, branched homopolymers or copolymers can also be used as the graft base.
Verzweigte Polymerisate können hergestellt werden, indem man beispielsweise an niedrigmolekulare Polyalkohole (= R1 in der allgemeinen Formel I), z.B. Pentaerythrit, Glycerin und Zucker bzw. Zuckeralkohole wie Saccharose, D-Sorbit und D-Mannit, Disaccha- ride, Ethylenoxid und gegebenenfalls noch Propylenoxid und/oder Butylenoxide oder Polyglycerin anlagert.Branched polymers can be prepared by, for example, low molecular weight polyalcohols (= R 1 in general formula I), for example pentaerythritol, glycerol and sugar or sugar alcohols such as sucrose, D-sorbitol and D-mannitol, disaccharide, ethylene oxide and optionally nor propylene oxide and / or butylene oxides or polyglycerol.
Dabei können Polymerisate gebildet werden, bei denen mindestens eine, bevorzugt eine bis acht, besonders bevorzugt eine bis fünf der in dem Polyalkoholmolekül vorhandenen Hydroxylgruppen in Form einer Etherbindung mit dem folgenden Polyetherrest gemäß Formel IPolymers can be formed in which at least one, preferably one to eight, particularly preferably one to five of the hydroxyl groups present in the polyalcohol molecule in the form of an ether bond with the following polyether radical according to formula I.
-f^O^^-O^Rio-^A-t-R^O-H-R^O^R^O^R8 -f ^ O ^^ - O ^ R i o- ^ AtR ^ OHR ^ O ^ R ^ O ^ R 8
verknüpft sein können.can be linked.
Die Alkylenoxid-Einheiten können im Polymerisat statistisch verteilt sein oder in Form von Blöcken vorliegen.
Es ist aber auch möglich, Polyester von Polyalkylenoxiden und aliphatischen Cι-Cι -, bevorzugt Ci-Cg-Diisocyanaten oder aromatischen Dicarbonsäuren, z.B. Oxalsäure, Bernsteinsäure, Adipinsäure oder Terephthalsäure, mit mittleren Molekulargewichten von 1500 bis 25 000, beschrieben in ΞP-A-0 743 962, als Pfrop grundlage zu verwenden.The alkylene oxide units can be randomly distributed in the polymer or in the form of blocks. However, it is also possible to use polyesters of polyalkylene oxides and aliphatic C 1 -C 4, preferably C 1 -C 4 diisocyanates or aromatic dicarboxylic acids, for example oxalic acid, succinic acid, adipic acid or terephthalic acid, with average molecular weights of 1500 to 25,000, described in ΞP-A- 0 743 962, to be used as a graft base.
Es ist weiterhin möglich, durch Phosgenierung hergestellte Poly- carbonate von Polyalkylenoxiden und aliphatischen Cι-Cι2-, bevor - zugt Ci-Cg- Diisocyanaten oder aromatischen Diisocyanaten, z.B. Hexamethylendiisocyanat oder Phenylendiisocyanat, als Pfropf - grundlage zu verwenden.It is also possible to use polycarbonates of polyalkylene oxides and aliphatic C 1 -C 2 prepared by phosgenation, before - added Ci-Cg diisocyanates or aromatic diisocyanates, for example hexamethylene diisocyanate or phenylene diisocyanate, as the graft base.
Die o.g. Polyester, Polycarbonate oder Polyurethane können bis zu 500, bevorzugt bis zu 100 Polyalkylenoxideinheiten enthalten, wobei die Polyalkylenoxideinheiten sowohl aus Homopolymeren als auch aus Copolymeren unterschiedlicher Alkylenoxide bestehen können.The above Polyesters, polycarbonates or polyurethanes can contain up to 500, preferably up to 100, polyalkylene oxide units, it being possible for the polyalkylene oxide units to consist both of homopolymers and of copolymers of different alkylene oxides.
Bevorzugt werden Polymerisate verwendet, die erhältlich sind durch Polymerisation vonPolymers which can be obtained by polymerizing are preferably used
(a) mindestens einem Vinylester von aliphatischen Cι-C2 -Carbon- säuren in Gegenwart von(a) at least one vinyl ester of aliphatic C 2 -C 2 carboxylic acids in the presence of
(b) Polyethern eines mittleren Molekulargewichts (Zahlenmittel) von 500 bis 100 000 der allgemeinen Formel Ia,(b) polyethers with an average molecular weight (number average) of 500 to 100,000 of the general formula Ia,
Hf ^-o-h-H^-h-H-o-^ )a - in der die Variablen unabhängig voneinander folgende Bedeu¬ tung haben:Hf ^ - ^ o -hh -HH- o - ^) a - in which the variables have the following independent significance ¬ tone:
R1 Hydroxy, Amino, C1-C24-Alkoxy, R9-COO-, R9-NH-COO, -Polyalkoholrest;R 1 hydroxy, amino, C 1 -C 24 alkoxy, R 9 -COO-, R 9 -NH-COO, -polyalcohol radical;
R8 Wasserstoff, Amino-Cx-Cg-alkyl, C1-C24-Alkyl, R9-CO-, R9-NH-CO;R 8 is hydrogen, amino-Cx-Cg-alkyl, C 1 -C 24 alkyl, R 9 -CO-, R 9 -NH-CO;
R2 bis R4 R 2 to R 4
-(CH2)2-# -(CH2.3-. -(CH2 ) 4-, -CH2-CH(CH3 ) -, -CH2-CH(CH2-CH3)-, -CH2-CHOR10-CH2- ;
R9 C1-C24-Alkyl ;- (CH 2 ) 2 - # - ( CH2.3-. - (CH 2 ) 4 -, -CH 2 -CH (CH 3 ) -, -CH 2 -CH (CH 2 -CH 3 ) -, -CH 2- CHOR 10 -CH 2 -; R 9 is C 1 -C 24 alkyl;
R10 Wasserstoff, C1-C24-Alkyl, R9-CO-;R 10 is hydrogen, C 1 -C 24 alkyl, R 9 -CO-;
n 1 oder, wenn R1 einen Polyalkoholrest bedeutet, 1 bis 8 ,-n 1 or, if R 1 is a polyalcohol radical, 1 to 8, -
u 1 bis 5000;u 1 to 5000;
v 0 bis 5000;v 0 to 5000;
w 0 bis 5000.w 0 to 5000.
Besonders bevorzugt werden Polymerisate verwendet, die erhältlich sind durch Polymerisation vonPolymers which are obtainable by polymerizing are particularly preferably used
(a) mindestens einem Vinylester von aliphatischen Cι-Ci2~Carbo - säuren, in Gegenwart von(a) at least one vinyl ester of aliphatic C 1 -C 2 ~ carboxylic acids, in the presence of
(b) Polyethern eines mittleren Molekulargewichts (Zahlenmittel) von 500 bis 50 000 der allgemeinen Formel Ia, in der die Variablen unabhängig voneinander folgende Bedeutung haben:(b) polyethers with an average molecular weight (number average) of 500 to 50,000 of the general formula Ia, in which the variables have the following meaning independently of one another:
R1 Hydroxy, Cx-Cia-Alkoxy, Polyalkoholrest;R 1 is hydroxy, Cx-Cia-alkoxy, polyalcohol radical;
R8 Wasserstoff, Cι-Cι2-Alkyl;R 8 is hydrogen, -CC 2 -alkyl;
R2 bis R4 R 2 to R 4
-{CH2 ) 2-. -(CH2.3-. -(CH2.4-. -CH2-CH(CH3)-, -CH2-CH(CH2-CH3) -, -CH2-CHOR10-CH2- ;- {CH 2 ) 2 -. - (CH2.3-. - (CH2.4-. -CH 2 -CH ( CH 3 ) -, -CH 2 -CH (CH 2 -CH 3 ) -, -CH 2 -CHOR 10 -CH 2 -;
R10 Wasserstoff, C1-C12-Alkyl;R 10 is hydrogen, C 1 -C 12 alkyl;
n 1 oder, wenn R1 einen Polyalkoholrest bedeutet, 1 bis 5;n 1 or, if R 1 is a polyalcohol radical, 1 to 5;
u 2 bis 2000;u 2 to 2000;
v 0 bis 2000;v 0 to 2000;
w 0 bis 2000.w 0 to 2000.
Ganz besonders bevorzugt werden Polymerisate verwendet, die er¬ hältlich sind durch Polymerisation vonPolymers are especially preferably used, which are he ¬ hältlich by polymerization of
(a) mindestens einem Vinylester von aliphatischen Ci-Cg-Carbonsäu- ren, insbesondere Vinylacetat, in Gegenwart von
(b) Polyethern eines mittleren Molekulargewichts (Zahlenmittel) von 1000 bis 10 000 der allgemeinen Formel Ia, in der die Variablen unabhängig voneinander folgende Bedeutung haben:(a) at least one vinyl ester of aliphatic Ci-Cg carboxylic acids, in particular vinyl acetate, in the presence of (b) polyethers with an average molecular weight (number average) of 1000 to 10,000 of the general formula Ia, in which the variables have the following meaning independently of one another:
R1 Hydroxy, Ci-Cg-Alkoxy, insbesondere Hydroxy;R 1 is hydroxy, Ci-Cg-alkoxy, especially hydroxy;
R8 Wasserstoff, Ci-Cg-Alkyl, insbesondere Wasserstoff;R 8 is hydrogen, Ci-Cg-alkyl, especially hydrogen;
R2 bis R4 R 2 to R 4
-(CH2)2-, -{CH2)3-, -CH2-CH(CH3)-, -CH2-CHOR10-CH2- , insbesondere -(CH2)2;- (CH 2 ) 2 -, - {CH 2 ) 3 -, -CH 2 -CH (CH 3 ) -, -CH 2 -CHOR 10 -CH 2 -, especially - (CH 2 ) 2 ;
R10 Wasserstoff, Cι-C6-Alkyl;R 10 is hydrogen, -CC 6 alkyl;
n 1;n 1;
u 5 bis 500;u 5 to 500;
v 0 bis 500, insbesondere 0;v 0 to 500, in particular 0;
w 0 bis 500, insbesondere 0.w 0 to 500, in particular 0.
Für die Polymerisation in Gegenwart der Polyether der Formel I seien als Komponente (a) folgende copolymerisierbare Monomere ge- nannt :The following copolymerizable monomers may be mentioned as component (a) for the polymerization in the presence of the polyethers of the formula I:
Vinylester von aliphatischen, gesättigten oder ungesättigten cι~c 24-Carbonsäuren, wie Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Valeriansäure, Isovaleriansäure, Capronsäure, Ca- prylsäure, Caprinsäure, ündecylensäure, Laurinsäure, Myristin- säure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Ölsäure, Arachinsäure, Behensäure, Lignocerinsäure, Cerotinsäure und Melissensäure.Vinyl esters of aliphatic, saturated or unsaturated c ι ~ c 24 -carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, ündecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, palmitoleic acid Oleic acid, arachidic acid, behenic acid, lignoceric acid, cerotinic acid and melissa acid.
Bevorzugt werden Vinylester der oben genannten Cι-Ci2-Carbonsäu- ren, insbesondere der Ci-Cg-Carbons uren, vor allem von Essigsäure , verwendet .Vinyl esters of the above-mentioned C 1 -C 2 -carboxylic acids, in particular of the C 1 -C 6 -carboxylic acids, especially acetic acid, are preferably used.
Selbstverständlich können auch Mischungen der jeweiligen Monome - ren aus der Gruppe (a) pfropfpolymerisiert werden.Mixtures of the respective monomers from group (a) can of course also be graft-polymerized.
Die Vinylester (a) können daneben auch in Mischung mit einem oder mehreren Comonomeren (c) eingesetzt werden. Die Comonomere (c) können hydrophob oder hydrophil sein, geeignet sind auch die üblicherweise als Vernetzer verwendeten Verbindungen. Der Anteil dieser zusätzlichen Monomeren (c) in der Mischung aus (a)+(c)
sollte dabei auf 0,1 bis 30 Gew. -% beschränkt sein. Bevorzugt sind Anteile von 1 bis 20 Gew. -% der Comonomeren (c) in der Mischung .The vinyl esters (a) can also be used in a mixture with one or more comonomers (c). The comonomers (c) can be hydrophobic or hydrophilic, and the compounds usually used as crosslinkers are also suitable. The proportion of these additional monomers (c) in the mixture of (a) + (c) should be limited to 0.1 to 30% by weight. Fractions of 1 to 20% by weight of the comonomers (c) in the mixture are preferred.
Geeignete hydrophobe Comonomere (c) können aus folgenden Gruppen ausgewählt werden, dabei können selbstverständlich auch Mischungen der Monomere eingesetzt werden:Suitable hydrophobic comonomers (c) can be selected from the following groups; mixtures of the monomers can of course also be used here:
(ci) Cι-C24-Alkylester von monoethylenisch ungesättigten C3-C8-Carbonsäuren;(Ci) -C-C 24 alkyl esters of monoethylenically unsaturated C 3 -C 8 carboxylic acids;
(c2) Cι-C24-Hydroxyalkylester von monoethylenisch ungesättigten C3-C8-Carbonsäuren;(C 2 ) -C-C 24 hydroxyalkyl esters of monoethylenically unsaturated C 3 -C 8 carboxylic acids;
(c3) Cι-C2 -Alkyl-Vinylether(c 3 ) -C 2 alkyl vinyl ether
(c4) N-Vinyllactame;(c 4 ) N-vinyl lactams;
(05) monoethylenisch ungesättigte C3-C8-Carbonsäuren.(0 5 ) monoethylenically unsaturated C 3 -C 8 carboxylic acids.
Als monoethylenisch ungesättigte C3 -Ca-Carbonsäure kommen z.B. Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure und Aconitsäure in Frage.Suitable monoethylenically unsaturated C 3 -Ca-carboxylic acid as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and aconitic acid, come into question.
Als Beispiele für die Alkylreste sei auf die bereits genannten Cι-C24-Alkylreste und deren Hydroxylierungsprodukte verwiesen. Bevorzugt sind dabei verzweigte oder unverzweigte C1-C4-Alkylreste, insbesondere Methyl, Ethyl, n-Propyl, 1-Methylethyl, n-Bu- tyl, 1 -Methylpropyl- , 2 -Methylpropyl, 1, 1-Dimethylethyl und deren Hydroxylierungsprodukte zu nennen.As examples of the alkyl radicals, reference is made to the C 1 -C 24 -alkyl radicals already mentioned and their hydroxylation products. Preferred are branched or unbranched C 1 -C 4 alkyl radicals, in particular methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl and their hydroxylation products to call.
Besonders bevorzugt sind Monomere der Gruppen (ci) bis (c3). Ganz besonders bevorzugt sind Methyl (meth) acrylat, Ethyl (meth) acrylat, Hydroxymethyl (meth) acrylat, 2 -Hydroxyethyl (meth) acrylat, Methyl - vinylether und Ethylvinylether .Monomers of groups (ci) to (c 3 ) are particularly preferred. Methyl (meth) acrylate, ethyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methyl vinyl ether and ethyl vinyl ether are very particularly preferred.
Geeignete hydrophile Comonomere (c) sind z.B. monoethylenisch ungesättigte C3-Cs-Carbonsäuren wie Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure und Aconitsäure, sowie auch N-Vinyllactame, wie N-Vinylpyrrolidon, N-Vinylimidazol oder N-Vi - nylcaprolactam.Suitable hydrophilic comonomers (c) are, for example, monoethylenically unsaturated C 3 -Cs carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and aconitic acid, and also N-vinyl lactams, such as N-vinyl pyrrolidone, N-vinyl imidazole or N-Vi - nylcaprolactam.
Bevorzugte hydrophile Comonomere (c) sind Acrylsäure, Methacrylsäure und N-Vinylpyrrolidon.
Geeignete üblicherweise als Vernetzer eingesetzte Comonomere (c) sind Verbindungen, die mindestens zwei ethylenisch ungesättigte nichtkonjugierte Doppelbindungen im Molekül enthalten. Bevorzugte Beispiele sind Alkylenbisacrylamide, wie Methylenbisacrylamid und N,N' -Acryloylethylendiamin, Vinylalkylenharnstoffe, wie N,N'- Divinylethylenharnstoff und N, N' -Divinylpropylenharnstof f , Ethy- liden-bis-3- (N-Vinylpyrrolidon) , N, ' -Divinylimidazo- lyl (2,2' )butan, 1,1' -Bis- (3,3' -vinylbenzimidazolid- 2-on) -1 , -butan, Alkylenglycoldi (meth) acrylate, wie Ethylen- glykoldi (meth) acrylat, Tetraethylenglykoldi (meth) acrylat und Die- thylenglykoldi (meth) acrylat , aromatische Divinylverbindungen, wie Divinylbenzol und Divinyltoluol, sowie Vinylacrylat, Allyl (meth) acrylat, Divinyldioxan, Pentaerythrittriallylether und Triallylamine.Preferred hydrophilic comonomers (c) are acrylic acid, methacrylic acid and N-vinylpyrrolidone. Suitable comonomers (c) usually used as crosslinkers are compounds which contain at least two ethylenically unsaturated non-conjugated double bonds in the molecule. Preferred examples are alkylenebisacrylamides, such as methylenebisacrylamide and N, N'-acryloylethylenediamine, vinylalkyleneureas, such as N, N'-divinylethyleneurea and N, N'-divinylpropyleneurea, ethylidene-bis-3- (N-vinylpyrrolidone), N, ' -Divinylimidazolyl (2,2 ') butane, 1,1'-bis (3,3'-vinylbenzimidazolid-2-one) -1, -butane, alkylene glycol di (meth) acrylates, such as ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and also vinyl acrylate, allyl (meth) acrylate, divinyldioxane, pentaerythritol triallyl ether and triallylamines.
Pfropfpolymerisate, deren Pfropfgrundlage ein Polyglycerin ist, sind erhältlich durch Polymerisation vonGraft polymers whose graft base is a polyglycerol can be obtained by polymerizing
(a) mindestens einem Vinylester von aliphatischen Cι-C24-Carbon- säuren in Gegenwart von(a) at least one vinyl ester of aliphatic C 24 -C 24 carboxylic acids in the presence of
(b) Polyglycerin der allgemeinen Formel Ib(b) polyglycerol of the general formula Ib
in der die Variablen unabhängig voneinander folgende Bedeutung haben:in which the variables have the following meaning independently of one another:
R1 Hydroxy, C1-C2 ~Alkoxy, R9-COO-, Polyalkoholrest;R 1 hydroxy, C 1 -C 2 ~ alkoxy, R 9 -COO-, polyalcohol radical;
R8 und Rio Wasserstoff, C1-C24-Alkyl, R9-CO-;R 8 and Rio are hydrogen, C 1 -C 24 alkyl, R 9 -CO-;
R9 C1-C24-Alkyl;R 9 is C 1 -C 24 alkyl;
n 1 oder, wenn Rx einen Polyalkoholrest bedeutet, 1 bis 8;n 1 or, if R x is a polyalcohol radical, 1 to 8;
u 1 bis 2000.u 1 to 2000.
Besonders bevorzugte Pfropfpolymerisate auf Polyglycerinen sind erhältlich durch Polymerisation vonParticularly preferred graft polymers on polyglycerols can be obtained by polymerizing
(a) mindestens einem Vinylester von aliphatischen Ci-Cg-Carbon- säuren in Gegenwart von
(b) Polyglycerin der allgemeinen Formel Ib, in der die Variablen unabhängig voneinander folgende Bedeutung haben:(a) at least one vinyl ester of aliphatic Ci-Cg-carboxylic acids in the presence of (b) polyglycerol of the general formula Ib, in which the variables have the following meaning independently of one another:
Rl Hydroxy, Cι-C3-Alkoxy;R l hydroxy, -CC 3 alkoxy;
R8 und Ri° Wasserstoff, Cι-C6-Alkyl;R 8 and Ri ° hydrogen, -CC 6 alkyl;
n 1;n 1;
u 1 bis 100.u 1 to 100.
Neben linearen Polyglycerinen können auch verzweigte und/oder cy- clische Polyglycerine als Pfropfgrundlage verwendet werden.In addition to linear polyglycerols, branched and / or cyclic polyglycerols can also be used as the graft base.
Die Pfropfpolymerisate auf Basis von Polyglycerin können gegebenenfalls zusätzlich zu den Vinylestern (a) mindestens ein weiteres der bereits oben genannten Comonomere (c) einpolymerisiert enthalten.The graft polymers based on polyglycerol may optionally contain, in addition to the vinyl esters (a), at least one further of the comonomers (c) mentioned above in copolymerized form.
Bevorzugte Comonomere (c) sind C-Cg-Alkylester von monoalkyle- nisch ungesättigten C3-C8-Carbonsäuren, N-Vinylpyrrolidon, N-Vi- nylimidazol, N-Vinylcaprolactam und (Meth) Acrylsäure.Preferred comonomers (c) are C-Cg-alkyl esters of monoalkyl-unsaturated C 3 -C 8 -carboxylic acids, N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam and (meth) acrylic acid.
Die K-Werte der Pfropfpolymerisate liegen beispielsweise im Be- reich von 10 bis 200, bevorzugt im Bereich um 15 bis 150, besonders bevorzugt im Bereich von 15 bis 100, ganz besonders bevorzugt im Bereich von 20 bis 80. Der jeweils gewünschte K-Wert läßt sich in an sich bekannter Weise durch die Zusammensetzung der Einsatzstoffe einstellen. Die K-Werte werden bestimmt nach H. Fikentscher, Cellulose-Chemie, Bd. 13, S. 58 bis 64 und 71 bis 74 (1932) in N-Methylpyrrolidon bei 25°C und Polymerkonzentrationen, die je nach K-Wert-Bereich bei 0,1 Gew.-% bis 5 Gew. -% liegen.The K values of the graft polymers are, for example, in the range from 10 to 200, preferably in the range from 15 to 150, particularly preferably in the range from 15 to 100, very particularly preferably in the range from 20 to 80. The K value desired in each case can be adjusted in a manner known per se through the composition of the starting materials. The K values are determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58 to 64 and 71 to 74 (1932) in N-methylpyrrolidone at 25 ° C. and polymer concentrations, which depend on the K value range are 0.1% by weight to 5% by weight.
Zur Herstellung der Propfpolymerisate können die Vinylester (a) und gewünschtenfalls die Comonomere (c) in Gegenwart der Poly- ether (b) als Pfropfgrundlage sowohl mit Hilfe von Radikale bildenden Initiatoren als auch durch Einwirkung energiereicher Strahlung, worunter auch die Einwirkung energiereicher Elektronen verstanden werden soll, polymerisiert werden.To prepare the graft polymers, the vinyl esters (a) and, if desired, the comonomers (c) in the presence of the polyethers (b) can be used as the graft base both with the aid of initiators which form free radicals and by the action of high-energy radiation, which also includes the action of high-energy electrons should be polymerized.
Die Polymerisation kann beispielsweise eine Lösungspolymerisation, Polymerisation in Substanz, Emulsionspolymerisation, umgekehrte Emulsionspolymerisation, Suspensionspolymerisation, umgekehrte Suspensionspolymerisation oder Fällungspolymerisation sein, ohne daß die verwendbaren Methoden darauf beschränkt sind.
Bei der bevorzugt durchgeführten Polymerisation in Substanz kann man so vorgehen, daß man den Polyether (b) , insbesondere das Polyalkylenoxid (b) , in mindestens einem Vinylester (a) und gewünschtenfalls einem oder mehreren Comonomeren (c) löst und die Mischung nach Zugabe eines Polymerisationsinitiators polymeri- siert. Die PfropfPolymerisation kann auch halbkontinuierlich durchgeführt werden, indem man zunächst einen Teil, z.B. 10 Gew.-%, dieser Mischung vorlegt und auf Polymerisationstemperatur erhitzt und nach dem Anspringen der Polymerisation den Rest der zu polymerisierenden Mischung nach Fortschritt der Polymerisation zugibt. Die Pfropfpolymerisate können auch dadurch erhalten werden, daß man den Polyether (b) in einem Reaktor vorlegt, auf die Polymerisationstemperatur erwärmt und mindestens einen Vinylester (a) und gewünschtenfalls Comonomer (c) (getrennt oder als Mischung) und Polymerisationsinitiator entweder auf einmal, absatzweise oder vorzugsweise kontinuierlich zufügt und polymerisiert .The polymerization can be, for example, solution polymerization, bulk polymerization, emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization, without the methods which can be used being restricted thereto. The preferred bulk polymerization can be carried out by dissolving the polyether (b), in particular the polyalkylene oxide (b), in at least one vinyl ester (a) and, if desired, one or more comonomers (c), and the mixture after adding a Polymerization initiator polymerized. The graft polymerization can also be carried out semi-continuously by first introducing a portion, for example 10% by weight, of this mixture and heating it to the polymerization temperature and adding the rest of the mixture to be polymerized after the polymerization has started and the progress of the polymerization. The graft polymers can also be obtained by placing the polyether (b) in a reactor, heating to the polymerization temperature and at least one vinyl ester (a) and, if desired, comonomer (c) (separately or as a mixture) and polymerization initiator either in one batch or preferably continuously added and polymerized.
Das Mengenverhältnis der als Pfropfgrundlage verwendeten Poly- ether (b) zu den Vinylestern (a) bzw. der Mischung der Vinylester (a) und der Comonomere (c) liegt im Bereich von 1 : 0,5 bis 1 : 50, bevorzugt im Bereich von 1 : 1,5 bis 1 : 35 und besonders bevorzugt im Bereich von 1 : 2 bis 1 : 30.The quantitative ratio of the polyethers (b) used as the graft base to the vinyl esters (a) or the mixture of the vinyl esters (a) and the comonomers (c) is in the range from 1: 0.5 to 1:50, preferably in the range from 1: 1.5 to 1:35 and particularly preferably in the range from 1: 2 to 1:30.
Als Polymerisationsinitiatoren eignen sich vor allem organische Peroxide, wie Diacetylperoxid, Dibenzoylperoxid, Succinylperoxid, Di-tert . -butylperoxid, tert . -Butylperbenzoat, tert . -Butylperpiva - lat, tert . -Butylpermaleinat , Cumolhydroperoxid, Diisopropylpero- xidicarbonat, Bis- (o-toluyl) -peroxid, Didecanoylperoxid, Dioctanoylperoxid, Dilauroylperoxid, tert . -Butylperisobutyrat, tert. -Butylperacetat, Di-tert. -Amylperoxid, tert. -Butylhydropero- xid sowie Mischungen der genannten Initiatoren, Redoxinitiatoren und Azostarter.Organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide and di-tert are particularly suitable as polymerization initiators. -butyl peroxide, tert. Butyl perbenzoate, tert. -Butylperpiva - lat, tert. -Butyl permaleinate, cumene hydroperoxide, diisopropyl peroxydicarbonate, bis (o-toluyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert. Butyl perisobutyrate, tert. -Butyl peracetate, di-tert. -Amyl peroxide, tert. -Butyl hydroperoxide and mixtures of the initiators, redox initiators and azo starters mentioned.
Die verwendeten Mengen an Initiator bzw. Initiatorgemischen, bezogen auf eingesetztes Monomer (a) und gegebenenfalls (c) , liegen bei 0,01 bis 10 Gew.-%, vorzugsweise bei 0,3 bis 5 Gew.-%.The amounts of initiator or initiator mixtures used, based on monomer (a) and optionally (c) used, are from 0.01 to 10% by weight, preferably from 0.3 to 5% by weight.
Die PfropfPolymerisation erfolgt im Temperaturbereich von 40 bis 200°C, bevorzugt im Bereich von 50 bis 140°C, besonders bevorzugt im Bereich von 60 bis 110°C. Sie wird üblicherweise unter atmosphärischem Druck durchgeführt, kann jedoch auch unter vermindertem oder erhöhtem Druck, vorzugsweise zwischen 1 und 5 bar, ablaufen.
Falls gewünscht, kann die oben beschriebene PfropfPolymerisation auch in einem Lösemittel bzw. Lösemittelgemisch durchgeführt werden. Geeignete Lösemittel sind beispielsweise aliphatische und cycloaliphatische einwertige Alkohole, wie Methanol, Ethanol, n- Propanol, Isopropanol, n-Butanol, sek. -Butanol, ter . -Butanol, n- Hexanol und Cyclohexanol, mehrwertige Alkohole, z.B. Glykole, wie Ethylenglykol, Propylenglykol und Butylenglykol , und Glycerin. Alkylether mehrwertiger Alkohole, z.B. Methyl- oder Ethylether der zweiwertigen Alkohole, Etheralkohole, wie Diethylenglykol und Triethylenglykol, sowie cyclische Ether, wie Dioxan.The graft polymerization takes place in the temperature range from 40 to 200 ° C., preferably in the range from 50 to 140 ° C., particularly preferably in the range from 60 to 110 ° C. It is usually carried out under atmospheric pressure, but can also take place under reduced or elevated pressure, preferably between 1 and 5 bar. If desired, the graft polymerization described above can also be carried out in a solvent or solvent mixture. Suitable solvents are, for example, aliphatic and cycloaliphatic monohydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec. -Butanol, ter. -Butanol, n-hexanol and cyclohexanol, polyhydric alcohols, for example glycols, such as ethylene glycol, propylene glycol and butylene glycol, and glycerin. Alkyl ethers of polyhydric alcohols, for example methyl or ethyl ethers of the dihydric alcohols, ether alcohols, such as diethylene glycol and triethylene glycol, and cyclic ethers, such as dioxane.
Die PfropfPolymerisation kann auch in Wasser als Lösemittel durchgeführt werden. Sollen bei der Polymerisation gebildete wasserunlösliche Produkte direkt in gelöster Form anfallen, kön- nen mit Wasser mischbare organische Lösemittel bei der Polymerisation zugesetzt werden, z.B. einwertige Alkohole mit 1 bis 3 Kohlenstoffatomen, Aceton oder Dimethylformamid.The graft polymerization can also be carried out in water as a solvent. If water-insoluble products formed during the polymerization are to be obtained directly in dissolved form, water-miscible organic solvents can be added during the polymerization, e.g. monohydric alcohols with 1 to 3 carbon atoms, acetone or dimethylformamide.
Man kann jedoch auch bei der Pfropf olymerisation in Wasser so verfahren, daß man die wasserunlöslichen Pfropfpolymerisate durch Zugabe üblicher Emulgatoren oder Schutzkolloide, z.B. Polyvinylalkohol, in eine feinteilige Dispersion überführt. Als Emulgatoren verwendet man beispielsweise ionische oder nichtionische Ten- side, deren HLB-Wert im Bereich von 3 bis 13 liegt. Zur Definition des HLB-Werts wird auf die Veröffentlichung von W.C. Griffin, J. Soc. Cosmetic Che ., Band 5, 249 (1954) hingewiesen. Falls bei der Propfpolymerisation Tenside eingesetzt werden, beträgt deren Menge, bezogen auf das Pfropfcopolymerisat, z.B. 0, 1 bis 5 Gew.-%.However, graft polymerization in water can also be carried out by adding the water-insoluble graft polymers by adding customary emulsifiers or protective colloids, e.g. Polyvinyl alcohol, converted into a fine dispersion. The emulsifiers used are, for example, ionic or nonionic surfactants whose HLB value is in the range from 3 to 13. For the definition of the HLB value, reference is made to the publication by W.C. Griffin, J. Soc. Cosmetic Che., Volume 5, 249 (1954). If surfactants are used in the graft polymerization, their amount, based on the graft copolymer, is e.g. 0.1 to 5% by weight.
Üblicherweise verwendet man 5 bis 200 Gew.-%, vorzugsweise 10 bis 100 Gew.-%, organisches Lösemittel, Wasser oder Gemisch aus Wasser und organischem Lösemittel, bezogen auf das Pfropf - Polymerisat.5 to 200% by weight, preferably 10 to 100% by weight, of organic solvent, water or a mixture of water and organic solvent, based on the graft polymer, is usually used.
Zur Erhöhung der Hydrophilie der erfindungsgemäß verwendeten Pfropfpolymerisate können die Estergruppen nach der Polymerisation vollständig oder teilweise verseift (hydrolysiert) werden. Die Verseifung erfolgt in an sich bekannter Weise durch Zugabe einer Base, bevorzugt einer alkoholischen Alkalimetallhydroxidlö- sung, insbesondere einer methanolischen Natrium- oder Kalium- hydroxidlösung, bei Temperaturen im Bereich von 10 bis 70°C, bevorzugt im Bereich von 15 bis 30°C.To increase the hydrophilicity of the graft polymers used according to the invention, the ester groups can be completely or partially saponified (hydrolyzed) after the polymerization. The saponification is carried out in a manner known per se by adding a base, preferably an alcoholic alkali metal hydroxide solution, in particular a methanolic sodium or potassium hydroxide solution, at temperatures in the range from 10 to 70 ° C., preferably in the range from 15 to 30 ° C. ,
Der Verseifungsgrad hängt ab von der Menge der eingesetzten Base, von der Verseifungste peratur und der Verseifungszeit und kann entsprechend im Bereich von 0 bis 100 mol-% liegen. Bevorzugt
liegt er im Bereich von 20 bis 100 mol-%, besonders bevorzugt im Bereich von 40 bis 100 %, insbesondere von 65 bis 100 mol-% und ganz besonders bevorzugt im Bereich von 80 bis 100 mol-%.The degree of saponification depends on the amount of base used, on the saponification temperature and on the saponification time and can accordingly be in the range from 0 to 100 mol%. Prefers it is in the range from 20 to 100 mol%, particularly preferably in the range from 40 to 100%, in particular from 65 to 100 mol% and very particularly preferably in the range from 80 to 100 mol%.
5 Der Feststoffgehalt der nach Austausch des Alkohols durch Wasser (z.B. durch Wasserdampfdestillation) erhaltenen wäßrigen Polymerisat-Dispersionen bzw. -Lösungen beträgt in der Regel 10 bis 70 Gew.-%, bevorzugt 15 bis 65 Gew.-%, besonders bevorzugt 20 bis 60 Gew. -% . 05 The solids content of the aqueous polymer dispersions or solutions obtained after the alcohol has been replaced by water (for example by steam distillation) is generally 10 to 70% by weight, preferably 15 to 65% by weight, particularly preferably 20 to 60 % By weight. 0
Je nach Verseifungsgrad und Konzentration erhält man wäßrige Dispersionen oder Lösungen der erfindungsgemäß verwendeten Pfropfpolymerisate mit einer Viskosität kleiner 1000 mPas . Bei einer Polymerisatkonzentration von 20 Gew. -% beträgt die Viskosi- 5 tat bevorzugt von 5 bis 400 mPas, besonders bevorzugt von 10 bis 250 mPas.Depending on the degree of saponification and concentration, aqueous dispersions or solutions of the graft polymers used according to the invention are obtained with a viscosity of less than 1000 mPas. With a polymer concentration of 20% by weight, the viscosity is preferably from 5 to 400 mPas, particularly preferably from 10 to 250 mPas.
Die Propfpolymerisat-Dispersionen oder -Lösungen können durch verschiedene Trocknungsverfahren, z.B. Sprühtrocknung, Fluidized 0 Spray Drying, Walzentrocknung oder Gefriertrocknung, in Pulverform überführt werden. Wegen der geringen Viskosität der Lösungen bzw. Dispersionen wird als Trocknungsverfahren bevorzugt die Sprühtrocknung eingesetzt. Aus dem so erhaltenen PfropfPolymerisat -Trockenpulver läßt sich durch Eintragen in Wasser erneut eine 5 wäßrige Dispersion bzw. Lösung herstellen. Pulverförmige Pfropfpolymerisate haben gegenüber Dispersionen und Lösungen, insbesondere wäßrigen Dispersionen und Lösungen, den Vorteil einer besseren Lagerfähigkeit, einer einfacheren Transportmöglichkeit sowie einer geringeren Neigung für Keimbefall. 0The graft polymer dispersions or solutions can be prepared by various drying processes, e.g. Spray drying, Fluidized 0 Spray Drying, drum drying or freeze drying, can be transferred into powder form. Because of the low viscosity of the solutions or dispersions, spray drying is preferably used as the drying process. From the graft polymer dry powder thus obtained, an aqueous dispersion or solution can be prepared again by adding it to water. Powdery graft polymers have the advantage over dispersions and solutions, in particular aqueous dispersions and solutions, of better storage stability, easier transport and a lower tendency to infest germs. 0
Die Pfropfpolymerisate können in reiner Form oder aber zusammen mit den üblichen Hilfsstoffen auf einen wirkstoffhaltigen Kern, z.B. auf Tabletten aus einem Wasch- oder Reinigungsmittel, appli- ziert werden. Übliche Hilfsstoffe sind z.B. Farbpigmente zur Ein- 5 färbung, Weißpigmente, wie Titandioxid, zur Erhöhung der Deckkraft, Talkum und Siliciumdioxid als Antiklebemittel, Poly- ethylenglykole, Glycerin, Propylenglykol, Triacetin und Triethyl- citrat als Weichmacher und verschiedene oberflächenaktive Stoffe, wie Natriumlaurylsulfat, zur Verbesserung des Benetzungsverhal- tens .The graft polymers can be in pure form or together with the usual auxiliaries on a core containing active ingredients, e.g. applied to tablets from a washing or cleaning agent. Common auxiliaries are e.g. Color pigments for coloring, white pigments such as titanium dioxide to increase opacity, talc and silicon dioxide as an anti-adhesive, polyethylene glycols, glycerin, propylene glycol, triacetin and triethyl citrate as plasticizers and various surface-active substances such as sodium lauryl sulfate to improve the wetting behavior - tens.
Es ist ferner möglich, die erfindungsgemäß zu verwendenden Pfropfpolymerisate mit anderen Filmbildnern bzw. Polymeren beispielsweise im Verhältnis 1:9 bis 9:1 zu kombinieren. Hierzu , c- können beispielsweise folgende Polymere eingesetzt werden:
Polyvinylpyrrolidon, Polyvinylpyrrolidon-Copolymere, wasserlösli - ehe Cellulosederivate, wie Hydroxypropylcellulose, Hydroxypropyl - methylcellulose, Methylcellulose und Hydroxyethylcellulose, Acrylat- und Methacrylat-Copolymere, Polyvinylalkohole, Poly- 5 ethylenglykole und Polyethylenoxid-Polypropylenoxid-Blockpoly- mere. Schmelzen aus solchen Polymermischungen können z.B. zu Folien, Granulaten oder Pulvern verarbeitet werden. Die Folien können direkt zur Verpackung von Wasch- und Reinigungsmitteln eingesetzt werden. 0It is also possible to combine the graft polymers to be used according to the invention with other film formers or polymers, for example in a ratio of 1: 9 to 9: 1. The following polymers can be used for this, c -: Polyvinylpyrrolidone, polyvinylpyrrolidone copolymers, water-soluble cellulose derivatives, such as hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose and hydroxyethyl cellulose, acrylate and methacrylate copolymers, polyvinyl alcohols, poly 5 ethylene glycols and polyethylene oxide-polypropylene oxide block polyols. Melts from such polymer mixtures can be processed, for example, to give films, granules or powders. The films can be used directly for the packaging of detergents and cleaning agents. 0
Die Beschichtung von teilchenförmigen Wasch- und Reinigungsmitteln ist wünschenswert, weil dadurch bei der üblichen Dosierung dieser Mittel im Haushalt ein Kontakt von Bestandteilen der Wasch- oder Reinigungsmittel mit der Haut des Anwenders vermieden 5 wird. Dieser Vorteil gilt besonders für solche Wasch- undThe coating of particulate detergents and cleaning agents is desirable because this prevents contact of constituents of the detergents or cleaning agents with the skin of the user in the usual dosage of these agents in the household. This advantage applies particularly to such washing and
Reinigungsmittel, die Bestandteile enthalten, die zu einer Hautreizung oder allergischen Reaktionen der Haut führen können, z.B. Alkalicarbonate, Oxidationsmittel, wie Perborate, oder Enzyme. Die Beschichtung von teilchenförmigen Wasch- und Reini- o gungsmitteln hat darüber hinaus noch den Vorteil, daß die Bruchfestigkeit und der Abrieb der beschichteten Teilchen gegenüber den unbeschichteten Teilchen gleicher Zusammensetzung verbessert ist.Detergents containing ingredients that may cause skin irritation or allergic reactions, e.g. Alkali carbonates, oxidizing agents such as perborates, or enzymes. The coating of particulate detergents and cleaning agents also has the advantage that the breaking strength and the abrasion of the coated particles are improved compared to the uncoated particles of the same composition.
5 Unter teilchenförmigen Wasch- und Reinigungsmitteln sollen alle üblichen Handelsformen dieser Produkte verstanden werden, z.B. Granulate, Pellets, Schuppen, Stränge, Kugeln, Tabletten und Pulver. Einige Beispiele für die Zusammensetzung von Wasch- und Reinigungsmitteln (einschließlich von Bleichmitteln) werden in 0 den Tabellen 1 und 2 gegeben. Bei den Waschmitteln kann es sich um übliche pulverförmige Waschmittel oder um Kompaktwaschmittel mit einer Schüttdichte von beispielsweise 550 bis 1000 g/l handeln.5 Particulate detergents and cleaning agents are to be understood to mean all customary commercial forms of these products, e.g. Granules, pellets, scales, strands, balls, tablets and powder. Some examples of the composition of washing and cleaning agents (including bleaching agents) are given in Tables 1 and 2. The detergents can be customary powder detergents or compact detergents with a bulk density of, for example, 550 to 1000 g / l.
55
00
5
Tabelle 15 Table 1
Tabelle 2Table 2
Für das Beschichten von teilchenförmigen Wasch- und Reinigungsmitteln können die gebräuchlichen Verfahren angewendet werden, z.B. Coaten in der Wirbelschicht oder im Horizontaltrommelcoater , Tauchschwertverfahren oder Kesselcoatingverfahren. Vorzugsweise beschichtet man Waschmitteltabletten, Reinigertabletten sowie Kugeln, Granulate und solche Formen von Wasch- und Reinigerformulierungen, von denen man beispielsweise 1 bis 5 Formkörper , wie Tabletten oder Kugeln, für einen Waschgang benötigt.The usual methods can be used for coating particulate detergents and cleaning agents, e.g. Coating in the fluidized bed or in the horizontal drum coater, immersion sword process or boiler coating process. Detergent tablets, detergent tablets and spheres, granules and such forms of detergent and cleaner formulations are preferably coated, of which 1 to 5 moldings, such as tablets or spheres, are required for a wash cycle.
Die Beschichtungsmittel werden beispielsweise in einer Stärke von 5 bis 1000 μ , bevorzugt 30 bis 500 μm und insbesondere in einer Stärke von 40 bis 100 μ auf die teilchenförmigen Wasch- und Reinigungsmittel aufgetragen.The coating compositions are applied, for example, to the particulate detergents and cleaners in a thickness of 5 to 1000 μm, preferably 30 to 500 μm and in particular in a thickness of 40 to 100 μm.
Gegenstand der Erfindung ist außerdem die Verwendung der oben beschriebenen Pfropfpolymerisate als Verpackungsmaterial für Wasch-, Reinigungs- und Wäschenachbehandlungsmittel zur Herstellung von einzelnen Portionen für die Dosierung der Mittel im Waschprozeß zusammen mit dem Verpackungsmaterial. Die jeweils für einen Waschgang einzeln portionierte und verpackte Menge an Wasch-, Reinigungs- oder Wäschenachbehandlungsmittel wird in der Literatur z.B. als "Einzelverpackung", "unit packaging detergent" oder "sachets for packaging measured portions of detergents" be- zeichnet.The invention also relates to the use of the graft polymers described above as packaging material for washing, cleaning and laundry aftertreatment compositions for the production of individual portions for metering the compositions in the washing process together with the packaging material. The amount of washing, cleaning or laundry aftertreatment agent individually portioned and packaged for a washing cycle is described in the literature e.g. referred to as "single packaging", "unit packaging detergent" or "sachets for packaging measured portions of detergents".
Aus den erfindungsgemäß zu verwendenden Pfropfpolymerisaten können, wie bereits oben beschrieben, Folien hergestellt werden, z.B. durch Extrudieren oder durch Gießen. Die Dicke der Folien beträgt beispielsweise 10 bis 1000 μm, vorzugsweise 30 bis 500 μm und liegt meistens in dem Bereich von 40 bis 100 μ . Aus den wasserlöslichen Folien von Pfropfpolymerisaten werden beispielsweise Beutel oder Säckchen für die Verpackung von pulverförmigen Waschmitteln, flüssigen Waschmitteln, Reinigungsmitteln und Wäsche- nachbehandlungsmitteln hergestellt. Nach dem Befüllen mit einem der genannten Mittel werden die Beutel oder Säckchen verschlossen, z.B. verschweißt, versiegelt oder mit Hilfe eines Klebers verklebt. Die Menge an aktivem Mittel, das jeweils in den Beuteln verpackt wird, ist vorzugsweise so bemessen, daß beispielsweise 1 bis 5, insbesondere 1 Beutel für einen einzigen Waschgang ausreicht. In manchen Fällen kann es in Abhängigkeit von der Wasserhärte erforderlich sein, mehrere Beutel, z.B. 2 bis 4, für einen Waschgang zu dosieren. Beim Kontakt mit Wasser zerfällt der Folienbeutel unter Freisetzung des darin verpackten Mittels. Das Verpackungsmaterial ist in Wasser bzw. in der Waschflotte sehr leicht löslich bzw. darin leicht dispergierbar . Mit Hilfe der in einzelne Portionen verpackten Wasch-, Reinigungs- und Wäschepfle-
gemittel ist es möglich, eine optimale Dosierung der Mittel zu erreichen, ohne daß für den Anwender die Gefahr besteht, beispielsweise mit alkalischen Bestandteilen einer Waschmittelformulierung in Berührung zu kommen.As already described above, films can be produced from the graft polymers to be used according to the invention, for example by extrusion or by casting. The thickness of the films is, for example, 10 to 1000 μm, preferably 30 to 500 μm and is usually in the range from 40 to 100 μm. Bags or sacks for the packaging of powder detergents, liquid detergents, cleaning agents and laundry aftertreatment agents, for example, are produced from the water-soluble films of graft polymers. After filling with one of the agents mentioned, the bags or sacks are closed, for example welded, sealed or glued with the aid of an adhesive. The amount of active agent which is packaged in the bags is preferably such that, for example, 1 to 5, in particular 1 bag is sufficient for a single wash cycle. In some cases, depending on the water hardness, it may be necessary to dose several bags, e.g. 2 to 4, for one wash. Upon contact with water, the foil pouch disintegrates, releasing the agent packed in it. The packaging material is very easily soluble or easily dispersible in water or in the wash liquor. With the help of the washing, cleaning and laundry care packaged in individual portions it is possible to achieve an optimal dosage of the agents without the risk of the user coming into contact with, for example, alkaline components of a detergent formulation.
Bevorzugt eingesetzte Pfropfpolymerisate sind durch Polymerisation vonGraft polymers preferably used are by polymerization of
(a) Vinylacetat in Gegenwart von(a) vinyl acetate in the presence of
(b) Polyalkylenoxiden, einseitig endgruppenverschlossenen Polyalkylenoxiden und/oder beidseitig endgruppenverschlossenen Polyalkylenoxiden(b) polyalkylene oxides, polyalkylene oxides capped at one end and / or polyalkylene oxides capped at both ends
und Hydrolyse von 20 bis 100 mol-% der Vinylacetateinheiten erhältlich.and hydrolysis of 20 to 100 mol% of the vinyl acetate units available.
Besonders bevorzugt sind solche Pfropfpolymere, die durch radika- lische Polymerisation vonThose graft polymers which are obtained by radical polymerization of
(a) Vinylacetat in Gegenwart von(a) vinyl acetate in the presence of
(b) Polyethylenglykolen eines Molekulargewichts (Zahlenmittel) von 500 bis 100 000, vorzugsweise 1000 bis 50 000 und(b) polyethylene glycols with a number average molecular weight of 500 to 100,000, preferably 1000 to 50,000 and
Hydrolyse von 20 bis 100 mol-% der Vinylacetateinheiten der Pfropfpolymerisate erhältlich sind.Hydrolysis of 20 to 100 mol% of the vinyl acetate units of the graft polymers are available.
Die Vinylacetateinheiten der bevorzugt in Betracht kommenden Pfropfpolymerisate werden meistens zu 80 bis 100 mol-% hydroly- siert .The vinyl acetate units of the preferred graft polymers are mostly hydrolyzed to 80 to 100 mol%.
Die K-Werte der Polymerisate wurden bestimmt nach H . Fikentscher, Cellulose-Chemie, Bd. 13, 58-64 und 71 bis 74 (1932) in N-Methyl- pyrrolidon bei einer Temperatur von 25°C und einer Polymerkonzentration von 1 Gew.-%.The K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71 to 74 (1932) in N-methylpyrrolidone at a temperature of 25 ° C. and a polymer concentration of 1% by weight.
BeispieleExamples
Herstellung der PfropfpolymerisateProduction of the graft polymers
Pfropfpolymerisat 1Graft polymer 1
In einem Polymerisationsgefäß wurden 72 g Polyethylenglykol (mittleres Molekulargewicht 6000, Pluriol® E 6000) vorgelegt und unter Rühren und leichtem Stickstoffström auf 80°C erhitzt. Unter Rühren wurde unter Aufrechterhaltung der 80°C ein Zulauf von 410 g
Vinylacetat in 3 h und gleichzeitig ein weiterer Zulauf von einer Lösung von 1,4 g tert . -Butylperpivalat in 30 g Methanol ebenfalls in 3 h zugetropft. Nach vollständiger Zugabe wurde noch 2 h bei 80°C gerührt. Nach dem Abkühlen wurde das Polymerisat in 450 ml 5 Methanol gelöst. Zur Verseifung wurden bei 30°C 50 ml einer 10 gew.-%igen methanolischen Natriu hydroxidlösung zugegeben. Nach ca. 40 min wurde die Reaktion durch Zugabe von 750 ml 1 gew.-%iger Essigsäure abgebrochen. Zur Entfernung des Methanols wurde die Lösung wasserdampfdestilliert . Nach anschließender Ge- 10 friertrocknung der klaren Lösung erhielt man ein weißes Pulver. Eine 20 gew.-%ige wäßrige Lösung des erhaltenen Polymeren wies eine Viskosität von 124 mPas auf. Der K-Wert des Pfropfpolymerisats betrug 54, die Reißdehnung 74 %.72 g of polyethylene glycol (average molecular weight 6000, Pluriol® E 6000) were placed in a polymerization vessel and heated to 80 ° C. with stirring and a gentle stream of nitrogen. With stirring, while maintaining the 80 ° C, an inlet of 410 g Vinyl acetate in 3 h and at the same time a further feed of a solution of 1.4 g tert. Butyl perpivalate in 30 g of methanol was also added dropwise in 3 h. After the addition was complete, the mixture was stirred at 80 ° C. for a further 2 h. After cooling, the polymer was dissolved in 450 ml of 5 methanol. For saponification, 50 ml of a 10% strength by weight methanolic sodium hydroxide solution were added at 30 ° C. After about 40 minutes, the reaction was stopped by adding 750 ml of 1% strength by weight acetic acid. The solution was steam distilled to remove the methanol. After subsequent freeze-drying of the clear solution, a white powder was obtained. A 20% by weight aqueous solution of the polymer obtained had a viscosity of 124 mPas. The K value of the graft polymer was 54 and the elongation at break 74%.
15 Beispiel 115 Example 1
Herstellung beschichteter TablettenManufacture of coated tablets
Auf 5000 g handelsübliche Geschirreinigertabletten Somat Profi 20 (Fa. Henkel) wurde in einem Horizontaltrommelcoater ("Accela-Cota 24", Fa. Manesty) eine wäßrige Lösung aufgesprüht, die 20 Gew.-% Pfropf olymerisat 1 und 0,5 Gew.-% Sicomet® RotP (BASF) enthielt. 625 g (inklusiv eines Zuschlags von 10 Gew.-% für Sprühverluste) wurden bei einer Zulufttemperatur von 60°C und einer Sprührate von 25 30 g/min mit einer 1,0 mm weiten Sprühdüse und einem Sprühdruck von 2,0 bar auf die Tabletten appliziert. Nach Beendigung des Sprühvorgangs wurden die mit der Lösung besprühten Tabletten noch 5 min bei 60°C getrocknet. Man erhielt mit einer roten Beschich- tung versehene Tabletten, die folgende Eigenschaften hatten:An aqueous solution containing 20% by weight of graft polymer 1 and 0.5% by weight was sprayed onto 5000 g of commercially available dishwasher tablets Somat Profi 20 (Henkel) in a horizontal drum coater ("Accela-Cota 24", Manesty). % Sicomet ® RotP (BASF) contained. 625 g (including a surcharge of 10% by weight for spray losses) were applied at a supply air temperature of 60 ° C and a spray rate of 25 30 g / min with a 1.0 mm wide spray nozzle and a spray pressure of 2.0 bar Tablets applied. After the end of the spraying process, the tablets sprayed with the solution were dried at 60 ° C. for a further 5 minutes. Tablets with a red coating were obtained which had the following properties:
3030
Aussehen: gleichmäßige körnige OberflächeAppearance: uniform granular surface
Griffgefühl : verringerte Oberflächenrauhigkeit, angenehmeres Greifgefühl gegenüber unbeschichteten TablettenGrip feeling: reduced surface roughness, more pleasant grip feeling compared to uncoated tablets
3535
Abrieb: kein Abrieb beim Reiben mit dem Finger, nach 10 minü- tigem Schütteln in einem Rotationsmischer (Fa. Gerhardt) mit je 1 Tablette in einem Schraubdeckelglas (500 ml) bei einer nach Beispiel 1 beschichteten Ta- 40 blette 50 mg und bei einer nichtbeschichteten Tablette 960 mg.Abrasion: no abrasion when rubbed with the finger, after shaking for 10 minutes in a rotary mixer (from Gerhardt) with 1 tablet each in a screw-cap glass (500 ml) with a tablet coated with 50 mg according to Example 1 and with one uncoated tablet 960 mg.
Beispiel 2Example 2
45 Herstellung von pulverbefüllten wasserlöslichen Folienbeuteln
Aus dem Pfropfpolymerisat 1 wurde jeweils durch Gießen eine Folie mit einer Stärke von 40 μm und eine Folie mit einer Stärke von 100 μm hergestellt. In jede Folie wurden 20 g eines handelsüblichen Vollwaschmittels mit Hilfe eines im Haushalt gebräuchlichen Folienschweißgerätes eingeschweißt. Die so hergestellten Waschmittel enthaltenden Folienbeutel wurden jeweils in ein mit Wasser (Temperatur 20°C) gefülltes Becherglas gegeben. Dann wurde die Zeit gemessen, in der sich die Verpackung (d.h. das Pfropfpolymerisat 1) rückstandsfrei auflöste.45 Manufacture of powder-filled water-soluble film bags A film with a thickness of 40 μm and a film with a thickness of 100 μm were produced from the graft polymer 1 by casting. 20 g of a commercially available heavy-duty detergent were welded into each film with the aid of a film welding device used in the household. The foil pouches prepared in this way were each placed in a beaker filled with water (temperature 20 ° C.). The time in which the packaging (ie the graft polymer 1) dissolved without residue was then measured.
Bei dem Folienbeutel aus einer Folie mit einer Stärke von 40 μ betrug die Lösezeit 20 Sekunden, bei dem Folienbeutel aus einer Folie mit einer Stärke von 100 μ dauerte die rückstandsfreie Auflösung 60 Sekunden.
The release time for the film bag made of a film with a thickness of 40 μ was 20 seconds, for the film bag made of a film with a thickness of 100 μ the residue-free dissolution took 60 seconds.
Claims
1. Verwendung von wasserlöslichen oder wasserdispergierbaren, filmbildenden Pfropfpolymerisaten, die erhältlich sind durch radikalische Polymerisation von1. Use of water-soluble or water-dispersible, film-forming graft polymers which are obtainable by free-radical polymerization of
(a) Vinylestern von aliphatischen C1-C2 -Carbonsäuren in Gegenwart von(a) Vinyl esters of aliphatic C 1 -C 2 carboxylic acids in the presence of
Polyethern eines mittleren Molekulargewichts (Zahlenmittel) von mindestens 300 der allgemeinen Formel IPolyethers with a number average molecular weight of at least 300 of the general formula I
^ fR-O^^O^Tf^O^A+R^O-^R^O-^R^O-^R8 ^ fR-O ^^ O ^ Tf ^ O ^ A + R ^ O- ^ R ^ O- ^ R ^ O- ^ R 8
in der die Variablen unabhängig voneinander folgende Bedeutung haben:in which the variables have the following meaning independently of one another:
R1 Hydroxy, A ino, Cχ-C24 -Alkoxy, R9-COO-, R9-NH-COO-, Polyalkoholrest;R 1 hydroxy, A ino, Cχ-C 24 alkoxy, R 9 -COO-, R 9 -NH-COO-, polyalcohol radical;
R8 Wasserstoff, Amino — Ci — C6-alkyl, C1-C24 — Alkyl, R9 - CO - , R9 - NH - CO - ;R 8 is hydrogen, amino - Ci - C 6 alkyl, C 1 -C 24 alkyl, R 9 - CO -, R 9 - NH - CO -;
R2 bis R7 R 2 to R 7
- (CH2.2-. - (CH2.3-» - (CH2) -. -CH2-CH(CH3) -, - CH2 - CH (CH2 - CH3 ) - , - CH2 - CHORl° - CH2 - ;- (CH2.2-. - (CH2.3- »- (CH 2 ) -. -CH 2 -CH (CH 3 ) -, - CH 2 - CH (CH 2 - CH 3 ) -, - CH 2 - CHORINE 1 - CH 2 -;
R9 Ci -C24- Alkyl;R 9 Ci -C 24 alkyl;
R10 Wasserstoff, C!-C2 - Alkyl, R9-CO-;R 10 hydrogen, C ! -C 2 - alkyl, R 9 -CO-;
A -CO-O-, -CO-B-CO-O-, -CO-NH-B-NH-CO-O- ;A -CO-O-, -CO-B-CO-O-, -CO-NH-B-NH-CO-O-;
B -(CH2)t_, gegebenenfalls substituiertes Arylen;B - (CH 2 ) t _ , optionally substituted arylene;
n 1 oder, wenn R1 einen Polyalkoholrest bedeutet, 1 bis 8;n 1 or, if R 1 is a polyalcohol radical, 1 to 8;
s 0 bis 500;s 0 to 500;
t 1 bis 12; u 1 bis 5000 ;t 1 to 12; u 1 to 5000;
v 0 bis 5000;v 0 to 5000;
w 0 bis 5000;w 0 to 5000;
x 1 bis 5000;x 1 to 5000;
y 0 bis 5000;y 0 to 5000;
z 0 bis 5000z 0 to 5000
als Beschichtungsmittel für teilchenförmige Wasch- und Reinigungsmittel und als Verpackungsmaterial für Wasch-, Reinigungs- und Wäschenachbehandlungsmittel zur Herstellung von einzelnen Portionen für die Dosierung der Mittel im Waschprozeß zusammen mit dem Verpackungsmaterial.as a coating agent for particulate washing and cleaning agents and as packaging material for washing, cleaning and laundry aftertreatment agents for the production of individual portions for dosing the agents in the washing process together with the packaging material.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Pfropfpolymerisate erhältlich sind durch Polymerisation von2. Use according to claim 1, characterized in that the graft polymers are obtainable by polymerization of
(a) Vinylacetat in Gegenwart von(a) vinyl acetate in the presence of
(b) Polyalkylenoxiden, einseitig endgruppenverschlossenen Polyalkylenoxiden und/oder beidseitig endgruppenverschlossenen Polyalkylenoxiden.(b) polyalkylene oxides, polyalkylene oxides capped at one end and / or polyalkylene oxides capped at both ends.
3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die Pfropfpolymerisate erhältlich sind durch Polymerisation von3. Use according to claim 1, characterized in that the graft polymers are obtainable by polymerization of
(a) Vinylacetat in Gegenwart von(a) vinyl acetate in the presence of
(b) Polyethylenglykolen eines Molekulargewichts (Zahlen - mittel) von 500 bis 100 000.(b) Polyethylene glycols with a number average molecular weight of 500 to 100,000.
4. Verwendung nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Vinylacetateinheiten der Pfropfpolymerisate zu 20 bis 100 mol-% hydrolysiert sind.4. Use according to claims 1 to 3, characterized in that the vinyl acetate units of the graft polymers are hydrolyzed to 20 to 100 mol%.
5. Verwendung nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Polymerisation in Gegenwart von 0,1 bis 30 Gew.-% an Comonomeren (c) , bezogen auf die Mischung aus Monomeren (a) und Comonomeren (c) , durchgeführt wird. 5. Use according to claims 1 to 4, characterized in that the polymerization in the presence of 0.1 to 30 wt .-% of comonomers (c), based on the mixture of monomers (a) and comonomers (c), carried out becomes.
6. Verwendung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Pfropfpolymerisate in Form von Folien mit einer Stärke von 10 bis 1000 μm als Verpackungsmaterial eingesetzt werden.6. Use according to claims 1 to 5, characterized in that the graft polymers in the form of films with a thickness of 10 to 1000 microns are used as packaging material.
7. Verwendung nach den Ansprüchen 1 bis 6, dadurch gekennzeichnet, daß die Pfropfpolymerisate in Form von Folien mit einer Stärke von 30 bis 500 μm eingesetzt werden.7. Use according to claims 1 to 6, characterized in that the graft polymers are used in the form of films with a thickness of 30 to 500 microns.
8. Verwendung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Pfropfpolymerisate zur Beschichtung von Waschmitteltabletten, Waschmittelgranulaten und Reinigertabletten eingesetzt werden. 8. Use according to claims 1 to 5, characterized in that the graft polymers are used for coating detergent tablets, detergent granules and detergent tablets.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10050958 | 2000-10-13 | ||
DE10050958A DE10050958A1 (en) | 2000-10-13 | 2000-10-13 | Use of vinyl ester/polyether (especially polyethylene glycol or capped polyalkylene oxide) graft polymers to give water-soluble or -dispersible coatings or packaging films for detergents |
PCT/EP2001/011761 WO2002031096A1 (en) | 2000-10-13 | 2001-10-11 | Use of water-soluble or water-dispersible polyether blocks containing graft polymers as coating material and packaging for washing, cleaning and for the treatment of laundry |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1326953A1 true EP1326953A1 (en) | 2003-07-16 |
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ID=7659785
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01976301A Withdrawn EP1326953A1 (en) | 2000-10-13 | 2001-10-11 | Use of water-soluble or water-dispersible polyether blocks containing graft polymers as coating material and packaging for washing, cleaning and for the treatment of laundry |
Country Status (8)
Country | Link |
---|---|
US (1) | US20040033929A1 (en) |
EP (1) | EP1326953A1 (en) |
JP (1) | JP2004511624A (en) |
AU (1) | AU2001295613A1 (en) |
CA (1) | CA2423518A1 (en) |
DE (1) | DE10050958A1 (en) |
MX (1) | MXPA03002247A (en) |
WO (1) | WO2002031096A1 (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10128531A1 (en) * | 2001-06-13 | 2002-12-19 | Basf Ag | Water soluble water dispersible film forming graft polymerisate consisting of vinyl esters of 1-24C carboxylic acids in presence of polyethers useful as coating agents, matrix builders, and agrochemical packaging materials |
AU2002344842A1 (en) * | 2001-06-22 | 2003-01-08 | Genencor International, Inc. | Highly impact-resistant granules |
DE10244802B4 (en) | 2002-09-26 | 2011-12-22 | Henkel Ag & Co. Kgaa | Plump detergent tablets |
DE10245260A1 (en) * | 2002-09-27 | 2004-04-15 | Henkel Kgaa | Process for the production of coated detergent or cleaning agent portions |
DE10253213B3 (en) * | 2002-11-15 | 2004-07-22 | Henkel Kgaa | Water-soluble portion packaging with filling and process for its production |
DE102005003122A1 (en) * | 2005-01-21 | 2006-07-27 | Henkel Kgaa | Anti-adhesive polymers to prevent the adhesion of microorganisms to textiles and to prevent laundry odor |
US7666963B2 (en) * | 2005-07-21 | 2010-02-23 | Akzo Nobel N.V. | Hybrid copolymers |
JP5345274B2 (en) | 2006-03-24 | 2013-11-20 | 株式会社日本触媒 | Hydrocarbon group-containing graft polymer and process for producing the same |
US20080020961A1 (en) * | 2006-07-21 | 2008-01-24 | Rodrigues Klin A | Low Molecular Weight Graft Copolymers |
NO20073834L (en) * | 2006-07-21 | 2008-01-22 | Akzo Nobel Chemicals Int Bv | Sulfonated graft copolymers |
ES2523029T3 (en) * | 2008-12-05 | 2014-11-20 | Dalli-Werke Gmbh & Co. Kg | Polymer coated detergent tablet |
AU2010278786B2 (en) | 2009-07-31 | 2014-04-10 | Akzo Nobel Chemicals International B.V. | Hybrid copolymer compositions |
US8679366B2 (en) | 2011-08-05 | 2014-03-25 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale |
US8853144B2 (en) | 2011-08-05 | 2014-10-07 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage |
US8841246B2 (en) | 2011-08-05 | 2014-09-23 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage |
US8636918B2 (en) | 2011-08-05 | 2014-01-28 | Ecolab Usa Inc. | Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale |
EP2773320B1 (en) | 2011-11-04 | 2016-02-03 | Akzo Nobel Chemicals International B.V. | Hybrid dendrite copolymers, compositions thereof and methods for producing the same |
EP2773321B1 (en) | 2011-11-04 | 2015-09-09 | Akzo Nobel Chemicals International B.V. | Graft dendrite copolymers, and methods for producing the same |
KR20140101842A (en) * | 2011-12-09 | 2014-08-20 | 바스프 에스이 | Use of formulations for machine dishwashing |
ES2587787T3 (en) * | 2012-03-09 | 2016-10-26 | Basf Se | Continuous procedure for synthesis of graft polymers based on polyethers |
US8945314B2 (en) | 2012-07-30 | 2015-02-03 | Ecolab Usa Inc. | Biodegradable stability binding agent for a solid detergent |
BR112015032804A2 (en) | 2013-07-03 | 2017-07-25 | Basf Se | process for preparing a polymer composition, polymer composition, use of a polymer composition, cleaning and washing composition, and adhesive composition |
US9365805B2 (en) | 2014-05-15 | 2016-06-14 | Ecolab Usa Inc. | Bio-based pot and pan pre-soak |
MX2019002880A (en) * | 2016-09-13 | 2019-07-04 | Procter & Gamble | Process for making a composition comprising benefit agent delivery particles. |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3168590D1 (en) * | 1980-05-09 | 1985-03-14 | Hoechst Ag | Polyvinyl alcohol composition, its preparation process, its use |
DE3536530A1 (en) * | 1985-10-12 | 1987-04-23 | Basf Ag | USE OF POLYALKYLENE OXIDES AND VINYL ACETATE GRAFT COPOLYMERISATS AS GRAY INHIBITORS IN THE WASHING AND TREATMENT OF TEXTILE GOODS CONTAINING SYNTHESIS FIBERS |
CA2029631A1 (en) * | 1989-11-22 | 1991-05-23 | Kathleen A. Hughes | Graft polymers as biodegradable detergent additives |
US5133892A (en) * | 1990-10-17 | 1992-07-28 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing detergent tablets |
GB9422924D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
US5534178A (en) * | 1994-12-12 | 1996-07-09 | Ecolab Inc. | Perforated, stable, water soluble film container for detersive compositions |
AU738231B2 (en) * | 1997-01-10 | 2001-09-13 | Hinton, Elizabeth Jane | Detergent |
US6037319A (en) * | 1997-04-01 | 2000-03-14 | Dickler Chemical Laboratories, Inc. | Water-soluble packets containing liquid cleaning concentrates |
DE10005942A1 (en) * | 2000-02-09 | 2001-08-16 | Basf Ag | Production of graft copolymers used e.g. as coatings by polymerizing vinyl esters in presence of solid polyether comprises using liquid polyalkylene glycol as solvent for radical initiator |
EP1124541B1 (en) * | 1998-09-30 | 2003-11-26 | Basf Aktiengesellschaft | Application of water-soluble or water-dispersible graft polymerizates which contain poly-ether and which are used as a coating agent, a binding agent and/or as a film-forming auxiliary agent in pharmaceutical forms of administration |
DE19940547A1 (en) * | 1999-08-26 | 2001-03-01 | Henkel Kgaa | Detergent tablets with partial coating |
AU5644400A (en) * | 1999-09-24 | 2001-03-29 | Rohm And Haas Company | Pellet compositions |
DE10015468A1 (en) * | 2000-03-29 | 2001-10-11 | Basf Ag | Hard capsules containing polymers and vinyl esters and polyethers, their use and production |
WO2001088079A1 (en) * | 2000-05-17 | 2001-11-22 | Henkel Kommanditgesellschaft Auf Aktien | Washing or cleaning agent shaped bodies |
-
2000
- 2000-10-13 DE DE10050958A patent/DE10050958A1/en not_active Withdrawn
-
2001
- 2001-10-11 US US10/399,141 patent/US20040033929A1/en not_active Abandoned
- 2001-10-11 JP JP2002534467A patent/JP2004511624A/en not_active Withdrawn
- 2001-10-11 CA CA002423518A patent/CA2423518A1/en not_active Abandoned
- 2001-10-11 EP EP01976301A patent/EP1326953A1/en not_active Withdrawn
- 2001-10-11 MX MXPA03002247A patent/MXPA03002247A/en unknown
- 2001-10-11 WO PCT/EP2001/011761 patent/WO2002031096A1/en not_active Application Discontinuation
- 2001-10-11 AU AU2001295613A patent/AU2001295613A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO0231096A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU2001295613A1 (en) | 2002-04-22 |
WO2002031096A1 (en) | 2002-04-18 |
CA2423518A1 (en) | 2003-03-25 |
US20040033929A1 (en) | 2004-02-19 |
DE10050958A1 (en) | 2002-04-18 |
JP2004511624A (en) | 2004-04-15 |
MXPA03002247A (en) | 2003-06-24 |
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