Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0895—Manufacture of polymers by continuous processes
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G4/00—Chewing gum
  • A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G4/00—Chewing gum
  • A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
  • A23G4/08—Chewing gum characterised by the composition containing organic or inorganic compounds of the chewing gum base
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G4/00—Chewing gum
  • A23G4/18—Chewing gum characterised by shape, structure or physical form, e.g. aerated products
  • A23G4/182—Foamed, gas-expanded or cellular products
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
  • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/046—Aerosols; Foams
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/0012—Galenical forms characterised by the site of application
  • A61K9/0053—Mouth and digestive tract, i.e. intraoral and peroral administration
  • A61K9/0056—Mouth soluble or dispersible forms; Suckable, eatable, chewable coherent forms; Forms rapidly disintegrating in the mouth; Lozenges; Lollipops; Bite capsules; Baked products; Baits or other oral forms for animals
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/0012—Galenical forms characterised by the site of application
  • A61K9/0053—Mouth and digestive tract, i.e. intraoral and peroral administration
  • A61K9/0056—Mouth soluble or dispersible forms; Suckable, eatable, chewable coherent forms; Forms rapidly disintegrating in the mouth; Lozenges; Lollipops; Bite capsules; Baked products; Baits or other oral forms for animals
  • A61K9/0058—Chewing gums
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/61—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints

Definitions

• the invention relates to new chewing gums for oral care based on polyurethane polyureas, a process for the preparation and their use.
• Organic polymers are widely used as raw materials in cosmetic products. They are used in many cosmetic products, such as in hair sprays, hair gels, mascara, lipsticks, creams etc.
• cosmetic products such as in hair sprays, hair gels, mascara, lipsticks, creams etc.
• oral care oral care
• polymers are e.g. in the form of toothbrushes, dental floss, etc.
• Dental care chewing gums consist essentially of so-called chewing gum base. This, in turn, consists of natural or artificial polymers, e.g. Latex, polyvinyl ethers, polyisobutylene vinyl ethers, polyisobutene, etc ..
• Such Zahnchevkaugummis contain as a tooth-care agents usually pH-controlling substances, which thus counteract the formation of tooth decay (tooth decay). Due to their plastic behavior, however, such Zahnchevkaugummis hardly contribute to cleaning the chewing surfaces or sides of the tooth.
• chewing gums generally have the disadvantage that they often have to be mechanically removed from public roads and places and disposed of, which leads to considerable cleaning effort - due to their adhesive properties - the floor and road surfaces.
• Dental wipes for example Oral-B Brush Aways TM, Gillette GmbH & Co. OHG, Germany
• Oral-B Brush Aways TM for example Oral-B Brush Aways TM, Gillette GmbH & Co. OHG, Germany
• They achieve a good cleaning effect of the sides of the teeth by applying the dental care cloth to a finger and by rubbing off the teeth.
• the nature of the application of such tooth wipes in public for aesthetic reasons is little accepted and thus does not represent an alternative to the use of a conventional toothbrush.
• the invention therefore chews of polyurethane-polyureas. _.
• An essential feature of the chewing masses is that they have a dimensional stability during chewing, i. do not suffer plastic deformation such as prior art chewing gums, but rather return to their original shape upon loading in a chewing operation due to the presence of polymeric restoring forces. Only then is it guaranteed that a tooth-cleaning effect (especially on the sides of the teeth) can occur.
• the chewing masses a 100% modulus of 0.1 to 8.0 MPa, with a tensile strength of 0.5 to 80 MPa and a ductility of 100 to 3000% (determined according to DIN 53504 on a free film of chewing gum with a layer thickness> 100 ⁇ m).
• the tensile tests were carried out in accordance with DIN 53504 with a test specimen shoulder rod S2 in accordance with DIN 53504.
• the tensile moduli were determined in accordance with DIN EN ISO 527.
• the layer thickness of the test specimens was 2.5 mm +/- 1 mm).
• the ratio of tensile strength and modulus of elasticity of the polymeric chewing gum according to the invention is greater than or equal to 1, preferably greater than 1.5 and particularly preferably greater than 2, and the ratio of the product of tear resistance (according to DIN ISO 34-1 (2004)). and Young's modulus to the square of the tensile strength is less than 4 mm, preferably less than 1.5 mm.
• the stability of the polymeric chewing mass under compression should be greater than 50 MPa, preferably greater than 75 MPa.
• Another object of the present invention is a process for the preparation of chews according to the invention, in which one or more polyurethane-polyurea dispersions (I) of the abovementioned type are optionally foamed together with further components of the chews and then dried.
• Such polyurethane-polyurea dispersions (I) are available in which _.
• polymeric polyols having number average molecular weights of 400 to 8000 g / mol and OH functionalities of 1.5 to 6,
• step B wherein optionally contained potentially ionic groups can be converted by partial or complete reaction with a neutralizing agent in the ionic form.
• Isocyanate-reactive groups are, for example, amino, hydroxy or thiol groups.
• organic polyisocyanates which can be used in component a1 are 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4 and / or
• 2,4,4-trimethylhexamethylene diisocyanate the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylenediisocyanate, 2,4- and / or 2, 6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate, 1,3- and / or l, 4-bis (2-isocyanato -prop-2-yl) -benzene (TMXDI), 1,3-bis (isocyanato-methyl) -benzene (XDI), (S) -alkyl 2,6-diisocyanatohexanoate, (L) -alkyl
• 2,6-diisocyanatohexanoates having branched, cyclic or acyclic alkyl groups with up to
• modified diisocyanates having a uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure and unmodified polyisocyanate having more than 2 NCO groups per molecule 4-isocyanatomethyl-l, 8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4 "triisocyanate are used with.
• polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups and an average NCO functionality of the mixture of 2 to 4, preferably 2 to 2.6 and particularly preferably 2 to 2.4 ,
• polymeric polyols having number-average molecular weights of from 400 to 6000 g / mol, more preferably from 600 to 3000 g / mol.
• These preferably have OH functionalities of from 1.8 to 3, more preferably from 1.9 to 2.1.
• Such polymeric polyols are the polyester polyols known per se in polyurethane lacquer technology, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethanepolyether polyols, polyurethane polycarbonate polyols and polyester polycarbonate polyols. These can be used in a2) individually or in any mixtures with one another.
• polyester polyols are the known polycondensates of di- and optionally tri - and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
• the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
• diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol ( 1, 6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, with hexanediol (1,6) and isomers, neopentyl glycol and neopentyl glycol hydroxypivalate being preferred.
• polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol ( 1, 6) and iso
• polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate. _.
• phthalic acid isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2,2 Dimethyl succinic acid are used.
• the acid source used may also be the corresponding anhydrides.
• monocarboxylic acids such as benzoic acid and hexanecarboxylic acid may additionally be used.
• Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and phthalic acid.
• Hydroxycarboxylic acids which may be used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
• Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.
• hydroxyl-containing polycarbonates preferably polycarbonatediols, having number-average molecular weights M n of from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol.
• carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene
• diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2- Methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethylpentanediol-1,3-dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A and lactone-modified diols of the above mentioned type in question. It is also possible to use mixtures of different diols.
• the diol component contains 40 to 100 wt .-% hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives.
• hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to terminal OH groups.
• Such derivatives are obtainable by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to di- or trihexylenglykol.
• polyether-polycarbonatediols which also contain polyetherdiols as diol component in addition to the diols described, in a2).
• Hydroxyl-containing polycarbonates are preferably of linear construction, but may also contain branches by the incorporation of polyfunctional components, in particular low molecular weight polyols.
• glycerol trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4-trimethylolpropane, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside or 1,3,4,6-dianhydrohexitols are suitable for this purpose.
• Suitable polyether polyols are, for example, the polytetramethylene glycol polyethers known per se in polyurethane chemistry, such as are obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.
• polyether polyols are the per se known addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxides and / or epichlorohydrin to di- or polyfunctional starter molecules.
• starter molecules it is possible to use all compounds known from the prior art, such as, for example, water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.
• polyurethane dispersions (I) comprise, as component a2), a mixture of polycarbonate polyols and polytetramethylene glycol polyols.
• the proportion of polycarbonate polyols in the mixture is 20 to 80 wt .-% and 80 to 20 wt .-% of polytetramethylene glycol polyols.
• Particular preference is given to a proportion of 35 to 70% by weight of polytetramethylene glycol polyols and 30 to 65% by weight of polycarbonate polyols, in each case with the proviso that the sum of the percentages by weight of the polycarbonate and polytetramethylene glycol polyols gives 100% by weight and the proportion the sum of the polycarbonate and polytetramethylene glycol polyether polyols on component a2) is at least 50% by weight, preferably 60% by weight and particularly preferably at least 70% by weight.
• polyols of the stated molecular weight range having up to 20 carbon atoms such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1 , 4-cyclohexanedimethanol, 1, 6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A, (2,2-bis (4-hydroxycyclohexyl) propane), trimethylolpropane, glycerol, pentaerythritol and any mixtures thereof.
• ethylene glycol diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,
• ester diols of the stated molecular weight range, such as ⁇ -hydroxybutyl- ⁇ -hydroxy-caproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
• monofunctional hydroxyl-containing compounds in a3).
• monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol mono-propyl ether, propylene glycol monobutyl ether,
• Suitable ionically or potentially ionically hydrophilic compounds are, for example, mono- and dihydroxycarboxylic acids, mono- and dihydroxysulfonic acids, and mono- and dihydroxyphosphonic acids and their salts, such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid propoxylated adduct of 2-butenediol and NaHSO 3 , for example described in DE-A 2 446 440 (page 5-9, formula I-ÜT) and compounds which can be converted into cationic groups, for example amine-based, blocks such as N-methyl Diethanolamine as hydrophilic structural components included.
• mono- and dihydroxycarboxylic acids such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid propoxylated adduct of 2-butenediol and NaHSO 3
• Preferred ionic or potentially ionic hydrophilicizing agents of component a4) are those of the abovementioned type which have an anionic, preferably hydrophilic, effect via carboxy or carboxylate and / or sulfonate groups.
• Particularly preferred ionic or potentially ionic hydrophilicizing agents are those which contain carboxyl and / or sulfonate groups as anionic or potentially anionic groups, such as the salts of dimethylolpropionic acid or dimethylolbutyric acid.
• Suitable nonionically hydrophilicizing compounds of component a4) are, for example, polyoxyalkylene ethers which contain at least one hydroxyl or amino group as the isocyanate-reactive group.
• Examples are the monohydroxy-functional, on average 5 to 70, preferably 7 to 55 ethylene oxide units per molecule having Polyalkylenoxidpolyetheralkohole, as they are accessible in a conventional manner by alkoxylation of suitable starter molecules (eg in Ullmann's Encyclopaedia of Industrial Chemistry, 4th Edition, Volume 19 , Verlag Chemie, Weinheim pp. 31-38).
• Particularly preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers which have 40 to 100 mol% of ethylene oxide and 0 to 60 mol% of propylene oxide units.
• Suitable starter molecules for such nonionic hydrophilicizing agents are saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-butanol.
• monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-butanol.
• Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or else as a mixture in the alkoxylation reaction.
• component bl) can di- or polyamines such as 1, 2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1,3- and 1,4-xylylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3,1,4-xylylenediamine and 4 , 4-diamino-dicyclohexylmethane and / or dimethylethylenediamine can be used. Also possible is the use of hydrazine or hydr
• component bl it is also possible to use compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups.
• primary / secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as N-amino ethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine.
• component bl) also mono-functional amine compounds may be used, such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, Mo ⁇ holin , Piperidine, or suitable substituted derivatives thereof, amide amines from diprimary amines and monocarboxylic acids, monodime of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
• amide amines from diprimary amines and monocarboxylic acids monodime of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
• Suitable ionically or potentially ionically hydrophilicizing compounds are, for example, mono- and diaminocarboxylic acids, mono- and diaminosulfonic acids and mono- and diaminophosphonic acids and their salts.
• ionic or potentially ionic hydrophilicizing agents are N- (2-aminoethyl) - ⁇ -alanine, 2- (2-aminoethylamino) -ethanesulfonic acid, ethylenediamine-propyl- or -butylsulfonic acid, 1,2-or- 1,3-propylenediamine- ⁇ -ethylsulfonic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid and the addition product of IPDI and acrylic acid (EP-A 0 916 647, Example 1). Furthermore, cyclohexylaminopropanesulfonic acid (CAPS) JQ
• WO-A 01/88006 can be used as anionic or potentially anionic hydrophilicizing agent.
• Preferred ionic or potentially ionic hydrophilicizing agents of component b2) are those of the abovementioned type which have a hydrophilizing effect via anionic, preferably carboxy or carboxylate and / or sulfonate groups.
• Particularly preferred ionic or potentially ionic hydrophilicizing agents b2) are those containing carboxyl and / or sulfonate groups as anionic or potentially anionic groups, such as the salts of N- (2-aminoethyl) - ⁇ -alanine, the 2- (2-amino -ethylamino) ethanesulfonic acid or the addition product of IPDI and acrylic acid (EP-A 0 916 647, Example 1).
• hydrophilization preference is given to using a mixture of anionic or potentially anionic hydrophilicizing agents and nonionic hydrophilicizing agents.
• the ratio of NCO groups of the compounds of component al) to NCO-reactive groups of components a2) to a4) in the preparation of the NCO-functional prepolymer is 1.05 to 3.5, preferably 1.2 to 3.0 particularly preferably 1.3 to 2.5.
• the amino-functional compounds in stage B) are used in such an amount that the equivalent ratio of isocyanate-reactive amino groups of these compounds to the free isocyanate groups of the prepolymer is 40 to 150%, preferably between 50 and 125%, particularly preferably between 60 and 120%.
• anionically and nonionically hydrophilicized polyurethane dispersions are used, the components al) to a4) and b1) to b2) being used for their preparation in the following amounts, the individual amounts adding up to 100% by weight:
• the amounts of component al) to a4) and bl) and b2) are particularly preferably:
• polyurethane dispersions (I) comprise as component as component al) isophorone diisocyanate and / or 1,6-hexamethylene diisocyanate and / or the isomeric bis (4,4'-isocyanatocyclohexyl) methanes in combination with a2) a mixture of polycarbonate polyols and polytetramethylene glycol polyols.
• the proportion of the polycarbonate polyols in the mixture a2) is 20 to 80 wt .-% and 80 to 20 wt .-% of polytetramethylene glycol polyols. Preference is given to a fraction of from 30 to 75% by weight of polytetramethylene glycol polyols and from 25 to 70% by weight of polycarbonate polyols.
• Particular preference is given to a proportion of 35 to 70% by weight of polytetramethylene glycol polyols and 30 to 65% by weight of polycarbonate polyols, in each case with the proviso that the sum of the percentages by weight of the polycarbonate and polytetramethylene glycol polyols gives 100% by weight and the proportion the sum of the polycarbonate and polytetramethylene glycol polyether polyols on component a2) is at least 50% by weight, preferably 60% by weight and particularly preferably at least 70% by weight.
• polyurethane dispersions can be carried out in one or more stages in homogeneous or multistage reaction, in some cases in disperse phase. After complete or partial polyaddition from al) to a4), a dispersing, emulsifying or dissolving step takes place. This is followed, if appropriate, by a further polyaddition or modification in disperse phase. ⁇
• Example prepolymer mixing method, acetone method or Schmelzdispergier Kunststoff can be used. Preference is given to proceeding by the acetone process.
• the components a2) to a4) which may have no primary or secondary amino groups and the polyisocyanate cyanate component al) for the preparation of an isocyanate-functional polyurethane prepolymer completely or partially and optionally with one with water miscible but opposite
• Isocyanate groups diluted inert solvent and to temperatures in the range of 50 to
• Suitable solvents are the customary aliphatic, ketofunctional solvents such as acetone, 2-butanone, which may be added not only at the beginning of the preparation, but optionally also in parts later. Preference is given to acetone and 2-butanone.
• solvents such as xylene, toluene, cyclohexane, butyl acetate, methoxypropyl acetate, N-methylpyrrolidone, N-ethylpyrrolidone, solvents with ether or ester units may additionally be used and distilled off in whole or in part or completely in the case of N-methylpyrrolidone , N-ethylpyrrolidone remain in the dispersion.
• solvents such as xylene, toluene, cyclohexane, butyl acetate, methoxypropyl acetate, N-methylpyrrolidone, N-ethylpyrrolidone, solvents with ether or ester units may additionally be used and distilled off in whole or in part or completely in the case of N-methylpyrrolidone , N-ethylpyrrolidone remain in the dispersion.
• cosolvent is completely dispensed with.
• bases such as tertiary amines, e.g. Trialkylamines having 1 to 12, preferably 1 to 6 carbon atoms used in each alkyl radical or alkali metal bases such as the corresponding hydroxides.
• alkyl radicals can, for example, also carry hydroxyl groups, as in the case of the dialkylmonoalkanol,
• Alkyl dialkanol and trialkanolamines are optionally also inorganic bases, such as aqueous ammonia solution or sodium or potassium hydroxide can be used.
• ammonia triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine and sodium hydroxide.
• the molar amount of the bases is 50 and 125 mol%, preferably between 70 and 100 mol% of the molar amount of the acid groups to be neutralized.
• the neutralization can also take place simultaneously with the dispersion in which the dispersing water already contains the neutralizing agent.
• the aminic components b1), b2) can optionally be used individually or in mixtures in the form of a dilute or diluted solvent in the process according to the invention, it being possible in principle for any order of addition to be possible.
• the diluent content in the chain extension component used in b) is preferably 70 to 95% by weight.
• the dispersion preferably takes place after the chain extension.
• the dissolved and chain extended polyurethane polymer is optionally sheared under high shear, e.g. vigorous stirring, either added to the dispersing water or, conversely, the dispersing water is stirred into the chain-extended polyurethane polymer solutions.
• the water is added to the dissolved chain-extended polyurethane polymer.
• the solvent still present in the dispersions after the dispersion step is then usually removed by distillation. A removal already during the dispersion is also possible.
• the residual content of organic solvents in the dispersions essential to the invention is typically less than 1.0% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight and very particularly preferably less than 0 , 05 wt .-% based on the total dispersion. ⁇
• the pH of the dispersions essential to the invention is typically less than 9.0, preferably less than 8.5, more preferably less than 8.0.
• the solids content of the polyurethane dispersion is typically 20 to 70 wt .-%, preferably 30 to 65 wt .-%, particularly preferably 40 to 63 wt .-% and most preferably from 50 to 63 wt .-%.
• polyurethane-polyurea dispersions (I) essential to the invention by polyacrylates.
• an emulsion polymerization of olefinically unsaturated monomers for. Esters of (meth) acrylic acid and alcohols having 1 to 18 carbon atoms, styrene, vinyl esters or butadiene, as described e.g. in DE-A-1 953 348, EP-A-0 167 188, EP-A-0 189 945 and EP-A-0 308 115.
• the monomers contain one or more olefinic double bonds.
• the monomers may contain functional groups such as hydroxyl, epoxy, methylol or acetoacetoxy groups.
• this modification is dispensed with.
• polyurethane-polyurea dispersions (I) essential to the invention may, for. Example of polyester, polyacrylate, polyepoxide or polyurethane polymers.
• aqueous binders may, for. Example of polyester, polyacrylate, polyepoxide or polyurethane polymers.
• the combination with radiation-curable binders, as z. As described in EP-A-O 753 531, is possible.
• this modification is dispensed with.
• Suitable foam assistants (E) are commercially available stabilizers, such as water-soluble fatty acid amides, sulfosuccinamides, hydrocarbon sulfonates, sulfates or fatty acid salts, the lipophilic radical preferably containing from 12 to 24 carbon atoms. ⁇
• Preferred foam assistants (H) are alkanesulfonates or sulfates having 12 to 22 carbon atoms in the hydrocarbon radical, alkylbenzenesulfonates or sulfates having 14 to 24 carbon atoms in the hydrocarbon radical or fatty acid amides or fatty acid salts having 12 to 24 carbon atoms.
• fatty acid amides are preferably fatty acid amides of mono- or di- (C 2-3 -alkanol) -amines.
• Fatty acid salts may be, for example, alkali metal salts, amine salts or unsubstituted ammonium salts.
• Such fatty acid derivatives are typically based on fatty acids such as lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, ricinoleic acid, behenic acid or arachidic acid, coconut fatty acid, tallow fatty acid, soybean fatty acid and their hydrogenation products.
• fatty acids such as lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, ricinoleic acid, behenic acid or arachidic acid, coconut fatty acid, tallow fatty acid, soybean fatty acid and their hydrogenation products.
• Particularly preferred foam auxiliaries (II) are sodium lauryl sulfate, sulfosuccinamides and ammonium stearates, and mixtures thereof.
• Suitable crosslinkers are, for example, unblocked polyisocyanate crosslinkers, amide and amine-formaldehyde resins, phenolic resins, aldehyde and ketone resins, such as e.g. Phenol-formaldehyde resins, resoles, furan resins, urea resins, carbamic acid ester resins, triazine resins, melamine resins, benzoguanamine resins, cyanamide resins or aniline resins.
• unblocked polyisocyanate crosslinkers amide and amine-formaldehyde resins
• crosslinkers is completely dispensed with.
• Thickener (IV) in the context of the invention are compounds which make it possible to adjust the viscosity of the resulting mixture of I-VI so that the production and processing of the foam according to the invention favors.
• Commercially available thickeners are suitable as thickeners, such as natural organic thickeners, eg dextrins or starch, organically modified natural substances, for example cellulose ethers or hydroxyethylcellulose, fully synthetic organic, for example polyacrylic acids, polyvinylpyrrolidones, poly (meth) acrylic compounds or polyurethanes (associative Thickener) and inorganic thickeners, eg Betonite or silicas. Preference is given to using organically fully synthetic thickeners.
• acrylate thickeners which are optionally further diluted with water before addition.
• Preferred commercially available thickeners are, for example, Mirox ® AM (BGB Stockhausen GmbH, Krefeld, Germany), Walocel® ® MT 6000 PV (Wolff Cellulosics GmbH & Co KG, Walsrode, Germany), Rhéolate ® 255 (Elementies Specialties, Gent, Belgium), Collacral® ® VL (BASF AG, Ludwigshafen, Germany) and Aristoflex® AVL (Clariant GmbH, Sulzbach, DE).
• Mirox ® AM BGB Stockhausen GmbH, Krefeld, Germany
• Walocel® ® MT 6000 PV Walolff Cellulosics GmbH & Co KG, Walsrode, Germany
• Rhéolate ® 255 Edlementies Specialties, Gent, Belgium
• Collacral® ® VL BASF AG, Ludwigshafen, Germany
• Aristoflex® AVL Chevronit
• V Aids
• Antioxidants and / or light stabilizers and / or other additives such as emulsifiers, fillers, plasticizers, pigments, silica sols, aluminum, clay, dispersions, leveling agents or thixotropic agents, etc ..
• Cosmetic additives (VI) are known e.g. Flavorings, abrasives, dyes, sweeteners, etc. as well as active ingredients such as fluoride compounds, teeth whitening agents etc.
• Foaming agent (II), crosslinker (HI), thickener (FV) and Hilsffen (V) can each account for up to 20 wt .-% and cosmetic additives (VI) up to 80 wt .-% based on the foamed and dried gum.
• component (I) 80 to 99.5 wt .-% of the polyurethane dispersion (I), 0 to 10 wt .-% of component (II), 0 to 10 wt .-% of component (IH), 0 to 10 wt % of component (IV), 0 to 10 wt .-% of component (V) and 0.1 to 20 wt .-% of component (VI) used, wherein the sum of the non-volatile components of the components (I. ) to (VI) and the sum of the individual components (I) to (VI) added to 100 wt .-%.
• 80 to 99.5% by weight of the polyurethane dispersion (I), 0 to 10% by weight of the component (H), 0 to 10% by weight of the component (IV), 0 to 10 are particularly preferred %
• component (V) and 0.1 to 15% by weight of component (VI) the sum relating to the non-volatile constituents of components (I) to (VI) and the sum of the individual components (I) to (VI) added to 100 wt .-%.
• Very particularly preferred are 80 to 99.5 wt .-% of the polyurethane dispersion (I), 0.1 to 10 wt .-% of component (II), 0.1 to 10 wt .-% of component (IV), 0 , 1 to 10 wt .-% of component (V) and 0.1 to 15 wt .-% of component (VI), wherein the sum refers to the nonvolatile components of the components (I) to (VI) and the Sum of the individual components (I) to (VI) added to 100 wt .-%.
• Foaming may be accomplished by the introduction of air or by the application of appropriate shear energy (e.g., mechanical stirring) or by commercial propellants. The entry of air is preferred.
• the foamed composition can be applied to various surfaces or shapes in a variety of ways. However, casting, knife coating, rolling, brushing, spraying or spraying is preferred.
• the mixture to be foamed or already foamed may first be placed on a surface or in a mold before it is further processed.
• the foamed material before drying has a preferred foam density of 200 to 800 g / l, more preferably 200 to 700 g / l, most preferably 300 to 600 g / l
• the density of the resulting gum according to the invention after drying is preferably 50 to 600 g / l, more preferably 100 to 500 g / l.
• the drying of the foamed material takes place at a temperature of 25 to 15O 0 C, preferably 30 0 C to 12O 0 C, more preferably at 40 to 100 0 C.
• the drying can be done in a conventional dryer. Also possible is drying in a microwave (HF) dryer.
• the chewing masses according to the invention typically have a thickness of 1 mm to 100 mm, 1 mm to 50 mm, preferably 1 mm to 30 mm after the drying step.
• the chewing gobs according to the invention can also be applied in a plurality of layers, for example to produce particularly high foam deposits, onto a wide variety of substrates or cast into molds.
• foamed compositions of the invention may also be used in combination with other carrier materials, e.g. textile backing, paper, etc., for example by prior application (e.g., coating).
• the chews according to the invention have excellent mechanical properties, in particular a high extensibility with high tensile strength; Thus returning to their original shape after the chewing process, have the ability to clean the chewing surfaces and tooth sides and do not stick to floor coverings.
• the solids contents were determined according to DEN-EN ISO 3251.
• NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909, unless expressly stated otherwise.
• Diaminosulphonate NH 2 -CH 2 CH 2 -NH-CH 2 CH 2 -SO 3 Na (45% in water)
• Desmophen ® C2200 polycarbonate polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)
• PolyTHF ® 2000 Polytetramethylenglykolpolyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (BASF AG, Ludwigshafen, DE)
• PolyTHF ® 1000 Polytetramethylenglykolpolyol, OH number 112 mg KOH / g, number-average number average molecular weight 1000 g / mol (BASF AG, Ludwigshafen, DE)
• Polyether LB 25 (monofunctional polyether based on ethylene oxide / propylene oxide number-average molecular weight 2250 g / mol, OH number 25 mg KOH / g (Bayer MaterialScience AG, Leverkusen, DE)
• Stokal ® STA Ammonium stearate-based foam additive, active substance content: 30% (Bozzetto GmbH, Krefeld, DE)
• Stokal ® SR Succinamate-based foaming agent, active substance content: approx. 34% (Bozzetto GmbH, Krefeld, DE)
• Mirox AM aqueous acrylic acid copolymer dispersion (BGB Stockhausen GmbH, Krefeld, DE)
• Borchigel ALA aqueous, anionic acrylic polymer solution (Borchers GmbH, Langenfeld, DE)
• Octosol SLS aqueous sodium lauryl sulfate solution (Tiarco Chemical Europe GmbH, Nuremberg, DE) Octosol 845.
• Sodium lauryl sulphate ether (Tiarco Chemical Europe GmbH, Nuremberg,
• the finished prepolymer was dissolved with 1040 g of acetone at 5O 0 C and then added a solution of 1.8 g of hydrazine hydrate, 9.18 g and 41.9 g of water diaminosulphonate min within 10 degrees. The stirring time was 10 min. After adding a solution of 21.3 g of isophorone diamine and 106.8 g of water was dispersed within 10 min by adding 254 g of water. This was followed by removal of the solvent by distillation in vacuo and a storage-stable dispersion having a solids content of 60.0% was obtained.
• the finished prepolymer was dissolved with 4800 g of acetone at 50 ° C and then added a solution of 29.7 g of ethylenediamine, 95.7 g of diaminosulfonate and 602 g of water within 5 min.
• the stirring time was 15 min. It was then dispersed within 20 min by adding 1169 g of water. This was followed by removal of the solvent by distillation in vacuo and a storage-stable PUR dispersion having a solids content of 60% was obtained.
• Example 4 Preparation of a chewing gum according to the invention
• Example S Preparation of a chewing gum according to the invention
• the modulus at 100% elongation was determined on films with a layer thickness> 100 ⁇ m.

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