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
  • C08G18/28—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
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
  • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
  • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
  • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

• Aqueous 2-component PU systems with increased impact strength and good resistance properties a process for their production and their use
• the invention relates to aqueous two-component polyurethane systems, a process for their preparation and their use for the production of coatings with increased impact strength with good resistance to solvents.
• Polyisocyanates with free isocyanate groups aqueous two-component polyurethane Systems can be prepared by emulsifying the polyisocyanates with free isocyanate groups in the aqueous polymer solution or dispersion.
• the polyhydroxy compounds described in EP-A 0 358 979 are preferably radically polymerized in organic solution and then subsequently in the aqueous solution of a neutralizing agent - usually ammonia or tertiary
• the organic solvent can remain in the aqueous medium as required or can be removed by distillation.
• the morphology of the polymer polyols produced in this way is normally single-phase, that is to say they have either thermoplastic or elastomeric properties even after crosslinking and film formation with suitable hydrophobic and / or hydrophilized polyisocyanates.
• a single-phase construction of such a polymer polyol is generally not sufficient.
• the invention therefore relates to two-component polyurethane coating compositions which, as binder component a), are a polyol component consisting of at least two polymer polyols, the first being present as an elastic component a1) dispersed in a second thermoplastic component a2) as a discrete phase and b) one Polyisocyanate component with a viscosity of at most
• component a) is an aqueous solution and / or dispersion of a mixture of represents at least two vinyl polymer polyols of the above type, and in which the polyisocyanate component b) is emulsified or solubilized.
• component a) is a polyol component which consists of a mixture of at least two polyols a1) and a2) based on vinyl polymer. The polyols a1) and a2) are not chemically linked to one another before crosslinking with the isocyanate component b).
• Polyol al is an elastomer component which contains hydroxyl groups, sulfonate and / or carboxylate groups, preferably carboxylate groups and optionally sulfonic acid and / or carboxyl groups, preferably carboxyl groups.
• Component a1) is a polymer of olefinically unsaturated monomers which preferably has a molecular weight Mn (number average) of 500 to 500,000 g / mol, in particular 1,000 to 200,000 g / mol (based on the method of gel permeation chromatography) of the uncrosslinked portions), a hydroxyl number from 8 to 264, preferably 16 to 198 mg KOH / g solid resin, an acid number (based on the sum of the unneutralized and neutralized acid groups) of 0 to 100, preferably 3 to 50 mg KOH / g solid resin .
• the elastomer component a1) has a glass transition temperature (measured using the DSC or DMA method) of at most 0 ° C., preferably of at most -10 ° C.
• the thermoplastic component a2) is also a polyol which contains hydroxyl groups, sulfonate and / or carboxylate groups, preferably carboxylate groups and optionally sulfonic acid and / or carboxyl groups, preferably carboxyl groups.
• Component a2) is also a polymer of olefinically unsaturated monomers which preferably have a molecular weight Mn (number average) of 500 to 500,000 g / mol, in particular 1,000 to 200,000 g / mol (based on the uncrosslinked), which can be determined by the gel permeation chromatography method Proportions), a hydroxyl number of 16 to 264, preferably 33 to 198 mg KOH / g solid resin, an acid number (based on the sum of the unneutralized and neutralized acid groups) of 3 to 100, preferably 5 to 50 mg KOH / g solid resin.
• the thermoplastic component a2) has a glass transition temperature of at least 0 ° C., preferably at least + 10 ° C.
• Elastomer components a1) which are composed of the following comonomer components are very particularly preferred:
• the sum of the% by weight of al a) to al e) being 100 and the glass temperature being below -10 ° C.
• Thermoplastic components a2) which are composed of the following comonomer components are very particularly preferred: a2 a) 0.6-7.7% by weight of acrylic acid and / or methacrylic acid; a2 b) 6.8-50.8% by weight of 2-hydroxyethyl acrylate and / or hydroxypropyl acrylate and / or 2-hydroxyethyl methacrylate and / or hydroxypropyl methacrylate; a2 c) 30-80% by weight of methyl methacrylate and / or acrylonitrile and / or methacrylonitrile and / or styrene or substituted styrenes as comonomers which impart strength and hardness; a2 d) 5-40 wt .-% alkyl methacrylate with 2 to 12 carbon atoms in
• the elastomer component a1) and the thermoplastic component a2) are preferably mixed in weight ratios of 10:90 to 60:40 (with respect to solid resin).
• the invention also relates to a process for producing a two-component polyurethane coating composition which, as binder component a), comprises a polyol component consisting of at least two polyme ⁇ olyols, the first dispersing as an elastic component a) in a second thermoplastic component a2) as a discrete phase is present, and b) contains a polyisocyanate component with a viscosity of at most 10,000 mPa.s, consisting of at least one organic polyisocyanate in an NCO / OH equivalent ratio of Amounts corresponding to 0.2: 1 to 5: 1, characterized in that component a) is an aqueous solution and / or dispersion of a mixture of at least two vinyl polymer polyols of the type mentioned above, and in which the polyisocyanate component b) emulsifies or solubilizes is present.
• binder component a comprises a polyol component consisting of at least two polyme ⁇ olyols, the first
• the polymer components a1) and a2) containing hydroxyl groups are prepared by processes of free-radical polymerization in organic or aqueous phase which are known per se.
• the polymers are preferably prepared by the process of free-radical emulsion polymerization in an aqueous medium.
• Continuous or discontinuous polymerization processes are possible. Of the continuous processes, the batch and feed processes are to be mentioned, the latter being preferred.
• the feed process water is introduced alone or with part of an anionic emulsifier, if appropriate with admixture of a nonionic emulsifier, and with part of the monomer mixture, heated to the polymerization temperature, the polymerization is started radically in the case of a monomer charge, and the remaining monomer mixture together with an initiator mixture and the emulsifier in the course of 1 to 10 hours, preferably 3 to 6 hours. If necessary, it is subsequently reactivated in order to carry out the polymerization up to a conversion of at least 99%.
• the hydroxyl group-containing polymers a1) and a2) can be prepared by metering strategies in such a way that core-shell polymers are formed (cf.
• the core can be hard and hydrophobic and the shell can be soft and hydrophilic.
• a reverse structure with a soft core and a harder shell is also possible.
• the emulsifiers used here are anionic and / or nonionic in nature. Of the emulsifiers with an anionic nature, those with carboxylate groups, sulfate, sulfonate, phosphate or phosphonate groups can be used. Emulsifiers with sulfate, phosphate or phosphonate groups are preferred.
• the emulsifiers can be low molecular weight or high molecular weight. The latter are described, for example, in DE-A
• emulsifiers which have been neutralized with ammonia or amines are preferred.
• Emulsifiers which are composed of long-chain alcohols or substituted phenols and ethylene oxide chains with degrees of polymerization between 2 and 100 and a final monosulfuric acid ester group or phosphoric acid mono- and diester groups are particularly preferred.
• Ammonia is generally used as the neutralizing agent. They can be added to the emulsion batch individually or in any mixtures.
• Suitable nonionic emulsifiers which can mostly be used in combination with the above-mentioned anionic emulsifiers, are reaction products of aliphatic, araliphatic, cycloaliphatic or aromatic carboxylic acids, alcohols, phenol derivatives or amines with epoxides such as e.g. Ethylene oxide.
• Examples of this are reaction products of ethylene oxide with carboxylic acids such as e.g. Lauric acid, stearic acid, oleic acid, the carboxylic acids of castor oil, abietic acid, with longer-chain alcohols such as oleyl alcohol, lauryl alcohol, stearyl alcohol, with phenol derivatives such as e.g. substituted benzyl, phenylphenols, nonylphenol and with longer chain amines such as e.g. Dodecylamine and stearylamine.
• the reaction products with ethylene oxide are oligo- or
• Both water-soluble and water-insoluble solvents can be used as co-solvents.
• aromatics such as benzene, toluene, xylene, chlorobenzene
• esters such as ethyl acetate, butyl acetate
• ether esters such as methyl glycol acetate, ethyl glycol acetate, methoxypropyl acetate, methoxybutyl acetate
• ethers such as butyl glycol, tetrahydrofuran, dioxane, ethyl glycol ether, ethers of diglycol glycol, ethers of diglycol glycol such as acetone, methyl ethyl ketone, methyl isobutyl ketone, trichloromonofluoroethane, cyclic amides such as N-methylpyrrolidone or N-methylcaprolactam.
• the polymerization initiated by radicals can be triggered by water-soluble or water-insoluble initiators or initiator systems, the half-lives of the radical decomposition at temperatures from 10 ° C. to 100 ° C. between 0.01 and
• the polymerization is carried out in aqueous emulsion in the temperature range mentioned, preferably between 30 and 90 ° C., under a pressure of 10 3 to 2 ⁇ 10 4 mbar, the precise polymerization temperature depending on the type of initiator.
• the initiators are generally used in amounts of 0.05 to 6% by weight, based on the total amount of monomers.
• Suitable initiators are e.g. water-soluble and insoluble azo compounds such as azoisobutyronitrile or 4,4'-azo-bis- (4-cyanopentanoic acid) as well as inorganic and organic peroxides such as e.g. Dibenzoyl peroxide, t-butyl pe ⁇ ivalate, t-butyl per-2-ethylhexanoate, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicyclohexyl and dibenzyl peroxydicarbonate as well as the sodium, potassium and ammonium salts of peroxides Hydrogen peroxide.
• water-soluble and insoluble azo compounds such as azoisobutyronitrile or 4,4'-azo-bis- (4-cyanopentanoic acid
• inorganic and organic peroxides such as e.g. Dibenzoyl per
• the peroxodisulfates and hydrogen peroxides are often used in combination with reducing agents such as e.g. the sodium salt of formamidine sulfinic acid (Rongalit C), ascorbic acid or polyalkylene polyamines. This generally leads to a significant reduction in the polymerization temperature.
• reducing agents such as e.g. the sodium salt of formamidine sulfinic acid (Rongalit C), ascorbic acid or polyalkylene polyamines.
• Conventional regulators can be used to regulate the molecular weight of the polymers, e.g. n-dodecyl mercaptan, t-dodecyl mercaptan, diisopropyl xanthogen disulfide, di (methylene trimethylol propane) xanthogen disulfide and thioglycol.
• allylic compounds such as the dimer of ⁇ -methylstyrene possible. They are added in amounts of at most 3% by weight, based on the monomer mixture.
• the polymers present in aqueous dispersion are optionally mixed with neutralizing agents up to degrees of neutralization of 10 to 150% (arithmetically), preferably 30 to 100%.
• neutralizing agents up to degrees of neutralization of 10 to 150% (arithmetically), preferably 30 to 100%.
• inorganic bases ammonia or amines are added as neutralizing agents.
• inorganic bases e.g. Sodium hydroxide, potassium hydroxide, amines in addition to ammonia, trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine etc. are used.
• the neutralizing agents can be used both in the stoichiometric excess and in excess.
• cosolvents can remain in the aqueous dispersion in amounts of up to about 20% by weight, based on the aqueous phase.
• the cosolvents can also be removed by distillation as required after the polymerization.
• the polymer dispersions a1) and a2) generally have solids contents of 20 to 60% by weight, preferably 30 to 50% by weight, and viscosities of 10 to 10 5 , preferably 10 to 10 4 mPa.s at 23 ° C. and pH values from 5 to 10, preferably 6 to 9. They are preferably mixed in weight ratios from 10:90 to 60:40 (solid resins al: a2).
• the average particle diameters of each component present individually in the dispersion are generally between 50 and 500 nm, preferably from 80 to 250 nm.
• the polyisocyanate component b) is any organic polyisocyanate with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound free isocyanate groups which are liquid at room temperature.
• the polyisocyanate component b) generally has a viscosity of at most 10,000, preferably at most 1,000 mPa.s at 23 ° C.
• the polyisocyanate component b) is particularly preferably polyisocyanates or polyisocyanate mixtures with exclusively aliphatic and / or cycloaliphatic isocyanate groups having an (average) NCO functionality of between 2.2 and 5.0 and a viscosity at 23 ° C. of at most 500 mPa.s.
• the polyisocyanates can be used in a mixture with small amounts of inert solvents in order to lower the viscosity to a value within the ranges mentioned.
• the amount of such solvents is such that up to 20% by weight of solvent, based on the amount of water, is present in the coating compositions according to the invention, the solvent which may still be present in the polymer dispersions or solutions also containing in the calculation is received.
• Solvents suitable as additives for the polyisocyanates are, for example, aromatic hydrocarbons such as, for example, “solvent naphtha” or solvents of the type already mentioned above as examples.
• Polyisocyanates suitable as component b) are in particular the so-called “lacquer polyisocyanates” with aromatic or (cyclo) aliphatic isocyanate groups, the latter aliphatic polyisocyanates, as already stated, being particularly preferred.
• Polyisocyanates with (partially) hydrophilized character are very particularly preferred.
• Lacquer polyisocyanates based on hexamethylene diisocyanate or l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclo- hexane (IPDI) and / or bis (isocyanatocyclohexyl) methane, especially those based exclusively on hexamethylene diisocyanate.
• “Lacquer polyisocyanates” based on these diisocyanates are to be understood as meaning the known derivatives of these diisocyanates containing biuret, urethane, uretdione and / or isocyanurate groups, which, following their preparation, are known, preferably by distillation of excess starting diisocyanate have been exempted to a residual content of less than 0.5% by weight.
• the preferred aliphatic polyisocyanates to be used according to the invention include biuret groups which correspond to the abovementioned criteria
• Polyisocyanates based on hexamethylene diisocyanate such as can be obtained, for example, by the processes of US Pat. No. 3,124,605, 3,358,010, 3,903,126, 3,903,127 or 3,976,622, and which are obtained from mixtures of N, N ', N "-Tris- (6-isocyanato-hexyl) biuret with minor amounts of its higher homologues exist, as well as the cyclic trimer of hexamethylene diisocyanate corresponding to the criteria mentioned, as can be obtained according to US Pat. No.
• aromatic polyisocyanates which are also suitable according to the invention but are less preferred are, in particular, "paint polyisocyanates" based on 2,4-diisocyanatotoluene or its technical mixtures with 2,6-diisocyanatotoluene or on the basis of 4,4'-diisocyanatodiphenylmethane or its mixtures with its isomers and / or higher homologues.
• Aromatic lacquer polyisocyanates of this type are, for example, the iso- cyanates, such as those obtained by reacting excess amounts of 2,4-diisocyanatotoluene with polyhydric alcohols such as trimethylolpropane and subsequent removal of the unreacted excess diisocyanate by distillation.
• Further aromatic lacquer polyisocyanates are, for example, the trimerizates of the monomeric diisocyanates mentioned by way of example, ie the corresponding isocyanate isocyanurates, which have also been freed from excess monomeric diisocyanates by distillation, preferably after their preparation.
• Any water-dispersible polyisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups can be used as the crosslinking component for the binder dispersions according to the invention.
• ionic modified e.g. Carboxylate groups and optionally polyisocyanates containing polyether units of the in EP-A
• nonionic polyisocyanates which have been hydrophilically modified by reaction with polyethylene oxide polyether alcohols as crosslinker components for the binder dispersions according to the invention.
• Such polyisocyanates are, for example, from EP-A 206 059, EP-A 516 277, EP-B 540 985, EP-A 645 410, EP-A 680 983, US Pat. No. 5,200,489 and German Patent Application 19822891.0 known.
• suitable nonionic-hydrophilized polyisocyanates are the special emulsifiers mentioned in EP-B 486 881, comprising diisocyanates and polyisocyanates containing monofunctional polyether alcohols.
• water-dispersible polyisocyanates are the above-mentioned polyisocyanates which have been hydrophilically modified with the aid of polyethylene oxide polyether alcohols. cyanates with exclusively aliphatic and / or cycloaliphatic isocyanate groups.
• Water-dispersible polyisocyanates of the type mentioned with a uretdione and / or isocyanurate structure based on 1, 6-diisocyanatohexane (HDI), 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI) are very particularly preferred.
• HDI 1, 6-diisocyanatohexane
• IPDI isophorone diisocyanate
• IPDI isophorone diisocyanate
• / or 4,4'-diisocyanatodicyclohexyl methane are very particularly preferred.
• the polyisocyanate component b) can also consist of any mixtures of the polyisocyanates mentioned by way of example.
• the polyisocyanate component b) is emulsified in the aqueous dispersion of the polymers a), the dissolved or dispersed polymer simultaneously assuming the function of an emulsifier or of the reactive component for the added polyisocyanate.
• the mixing can be done by simply stirring at room temperature.
• the amount of the polyisocyanate component is such that an NCO / OH equivalent ratio, based on the isocyanate groups of component b) and the alcoholic hydroxyl groups of component a), is from 0.2: 1 to 5: 1, preferably 0.5: 1 to 2: 1 results.
• the polymer component a) i.e. the usual auxiliaries and additives of coating technology are incorporated into the dispersion or solution of the polymers. These include, for example, defoamers, flow control agents, pigments, dispersants for pigment distribution and the like.
• the polyol components crosslink with the polyisocyanates in such a way that the elastomer phase and the thermoplastic phase (a2) are fixed, thereby preventing thorough mixing.
• This is demonstrated in the examples using the separately detectable glass temperatures.
• Another object of the invention is the use of the coating compositions of the invention. They are suitable for practically all areas of application in which solvent-based, solvent-free or other types of aqueous coating and coating systems with an increased property profile are used today, eg coating of practically all mineral building material surfaces such as lime and / or
• Cement-bound plasters surfaces containing gypsum, fiber-cement building materials, concrete; Painting and sealing of wood and wood-based materials such as chipboard, wood fiber boards and paper; Painting and coating of metallic surfaces; Coating and painting of asphalt and bituminous road surfaces; Painting and sealing of various plastic surfaces; Coating of
• the coating of plastic surfaces is particularly preferred. Here coating systems with increased impact strength are required, even at low temperatures (down to -20 ° C) and at the same time good resistance to solvents and chemicals.
• the two-component system can be cured or crosslinked after application to the respective substrate at temperatures of 5 to 300 ° C., preferably between room temperature and 200 ° C.
• the templates I (see Table 1) are introduced and flushed with nitrogen. Then nitrogen is passed over in a steady stream and the receiver is heated to 80 ° C. with stirring at about 200 rpm. Then the monomer mixtures II given in Table 1 and the initiator solutions III are added quickly. After a reaction time of 30 min, the monomer mixtures
• Emulsifier A * (80%) 25 g -
• Ammonium peroxodisulfate 0.5 g 0.5 g deionized water 10 g 10 g
• Emulsifier A monosulfuric acid ester (ammonium salt) of a reaction product of dodecanol and oligoethylene oxide
• Emulsifier B dodecylbenzenesulfonic acid Examples C to F
• the templates I (see Table 2) are placed and flushed with nitrogen. Then nitrogen is passed in a steady stream and the initial charge with stirring at about 200 rpm. heated to 80 ° C. Then the monomer mixtures II given in Table 2 and the initiator solutions III are added very quickly. After a reaction time of 30 minutes, the feed of the monomer mixtures IV and the initiator solutions V is started; IV is metered in uniformly in 2 h, V in 4 h, after the end of the feed of the monomer mixtures IV, the feed of the monomer mixtures VI is started; VI is metered in uniformly in 2 h.
• the mixture is then stirred for 2 h and then reactivated with the initiator solutions VII. Then the mixture is stirred for 4 h. The mixture is then cooled to room temperature and solutions VIII are metered in for neutralization. The dispersions are then filtered and filled.
• Ammonium peroxodisulfate 0.5 g 0.5 g 0.5 g 0.5 deionized water 10 g 10 g 10 g 10 g
• Emulsifier A 6.25 g - - -
• Emulsifier A 12.5 g 12.5 g 12.5 g deionized water 700 g 700 g 700 g 700 g DE
• Emulsifier A 6.25 g - - -
• a receiver of 25 g of 80% emulsifier A and 450 g of deionized water is initially introduced and flushed with nitrogen. Then nitrogen is passed in a steady stream and the initial charge with stirring at about 200 rpm. heated to 65 ° C.
• the mixture is then stirred for 2 h, then cooled to 45 ° C. and reactivated with an initiator solution of 1 g of t-butyl hydroperoxide, 2 g of the above-mentioned iron sulfal solution and 3 g of deionized water and a reducing agent solution of 0.7 g of Rongalit C and 5 g of deionized water . Then the mixture is stirred at 45 ° C. for 4 h and then about 50 ml of one is applied under a light water jet vacuum of 200 to 300 mbar
• the physical-chemical characteristics of the aqueous polymer dispersions are: Solids content (% by weight) 41.6 pH 7.5
• Viscosity at RT and D 21.1 s " 1 (mPa.s) 2300 mean particle diameter (LKS) (nm) 96
• a receiver of 12.5 g of 80% emulsifier A and 700 g of deionized water is initially introduced and flushed with nitrogen. Then nitrogen is passed in a steady stream and the initial charge with stirring at about 200 rpm. heated to 80 ° C.
• 600 g of deionized water are metered in uniformly in 4 h.
• metering in of another monomer mixture of 27 g of acrylic acid, 115 g of methacrylate hydroxypropyl ester, 46 g of methacrylic acid methyl ester, 253 g of n-butyl acrylate and 6.25 g of 80% emulsifier A is started.
• This monomer mixture is metered in 2 hours.
• the mixture is then stirred for 2 hours and then reactivated with an initiator solution of 0.5 g ammonium peroxodisulfate and 10 g deionized water.
• the mixture is then stirred for 4 h, cooled to room temperature and neutralized with an aqueous solution of 16 g of 25% by weight ammonia and 20 g of deionized water. Then it is filtered and drained.
• the physical-chemical characteristics of the aqueous polymer dispersions are:
• Viscosity at RT and D 21.1 s " 1 (mPa.s) ⁇ 100 mean particle diameter (LKS) (nm) 112 acid number (mg KOH / g Lff) 12.8
• the impact resistance of plastics is usually impaired by painting because a crack in the painting can cause a break in the plastic part due to its notch effect.
• painted plastic parts in the biaxial puncture test according to DIN 53 443 have a lower work input than unpainted plastics.
• the crack-triggering effect of the coating can go so far that a tough fracture behavior of the plastic changes through the coating into a brittle fracture behavior with little work.
• comparison system 1 see Table 3
• application example 1 appear even more clearly in puncture tests according to DIN 53 443 on coated polybutylene terephthalate.
• the painting was done on Pocan®
• the parts by weight of the elastomer components C and D (corresponding to 30 parts of solid resin) given in Table 5 are mixed intensively with 169.1 parts by weight of the thermoplastic component H (corresponds to 70 parts by weight of solid resin) and with 16
• the parts by weight of the elastomer components D and F given in Table 6 are mixed intensively with 168.7 parts by weight of the thermoplastic component H (corresponds to 70 parts by weight of solid resin) and diluted with 11 parts by weight of water.
• the parts by weight of polyisocyanate 1 given in Table 6 are then added and mixed intensively. Films are then produced as in Example 1, conditioned and examined using the same methods in terms of application technology and physico-chemistry. The following results were obtained.
• thermoplastic elastomers systems 4 and 5 behave very similarly. System 5, however, has significantly better tar stain resistance.

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• Polyurethanes Or Polyureas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Saccharide Compounds (AREA)

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• 1998
  • 1998-12-18 DE DE19858733A patent/DE19858733A1/de not_active Withdrawn
• 1999
  • 1999-12-03 TW TW088121129A patent/TW593597B/zh not_active IP Right Cessation
  • 1999-12-06 KR KR1020017007593A patent/KR100611258B1/ko not_active Expired - Fee Related
  • 1999-12-06 US US09/868,206 patent/US6528573B1/en not_active Expired - Fee Related
  • 1999-12-06 EP EP99966915A patent/EP1141066B1/de not_active Expired - Lifetime
  • 1999-12-06 AT AT99966915T patent/ATE280793T1/de not_active IP Right Cessation
  • 1999-12-06 PT PT99966915T patent/PT1141066E/pt unknown
  • 1999-12-06 WO PCT/EP1999/009523 patent/WO2000037522A1/de not_active Ceased
  • 1999-12-06 JP JP2000589589A patent/JP2002533489A/ja not_active Abandoned
  • 1999-12-06 AU AU22807/00A patent/AU2280700A/en not_active Abandoned
  • 1999-12-06 ES ES99966915T patent/ES2232201T3/es not_active Expired - Lifetime
  • 1999-12-06 CA CA002355127A patent/CA2355127A1/en not_active Abandoned
  • 1999-12-06 DE DE59910952T patent/DE59910952D1/de not_active Expired - Lifetime

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