Classifications

• • 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
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
• • 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
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen

Definitions

• the invention relates to aqueous, hydroxy-functional binder dispersions with low solvent content based on hydroxy-functional copolymers, a process for the preparation of such binders, binder combinations on this basis and the use of the binders in paints.
• the emulsifiers affect the properties of the coatings or coatings, such as e.g. Water resistance, film optics (gloss), pigmentability negative.
• organic solvents in aqueous coating compositions lead to advantageous effects such as improved storage stability, pigment wetting, film optics and course.
• a subsequent reduction due to the process contained solvents from copolymers or dispersions is associated with high equipment and energy costs and thus high costs, so that there is a need for aqueous polymer dispersions, in the preparation of the use of organic solvents can be largely dispensed without deterioration the performance characteristics occurs.
• Copolymer dispersions which are to be cured by a chemical reaction for example with an aminoplast resin, a blocked polyisocyanate or a polyisocyanate, must contain a certain amount of reactive groups, for example hydroxyl groups.
• reactive groups for example hydroxyl groups.
• These groups are usually introduced by the concomitant use of hydroxy-functional (meth) acrylic acid ester in the copolymerization in the copolymer.
• these raw materials are very expensive compared to the non-functional (meth) acrylic esters or to styrene.
• larger amounts of these raw materials often have to be used in comparison with organically dissolved copolymers in order to compensate for the hydrophilicity of the coating films by means of a greater crosslinking density.
• aqueous copolymer dispersions can be prepared with low solvent content and high resistance level of the coating films based on hydroxy-functional copolymers if lactones are used, if appropriate, in conjunction with low molecular weight polyols as reactive diluents.
• the invention therefore provides a process for the preparation of copolymer dispersions in which
• A) one or more vinyl monomer mixtures comprising a) OH-free (meth) acrylic esters and / or vinylaromatics, b) hydroxy-functional vinyl monomers and / or hydroxyfunctional (meth) acrylic esters, c) ionic and / or potentially ionic monomers capable of free-radical copolymerization and d) optionally further free-radically copolymerizable monomers capable of free-radical copolymerization of the compounds of components a) -c) in the presence of e) of at least one lactone-containing compound and f) optionally free-molecular polyols having a number average molecular weight of from 62 to 250 Da and the copolymer thus obtained subsequently
• aqueous copolymer dispersions obtainable by the process described above.
• component a) As monomers of component a) are acrylates and methacrylates (hereinafter referred to as (meth) acrylates) having 1 to 18 carbon atoms in the alcohol portion of the ester group used.
• This alcohol part can be linear, branched or cycloaliphatic.
• suitable as monomers of component a) are methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, t-butyl, the isomeric pentyl, hexyl, 2-ethylhexyl, octyl -, dodecyl, hexadecyl, octadecyl or cyclohexyl, trimethylcyclohexyl and isobornyl (meth) acrylates or styrene.
• acetoacetoxyethyl methacrylate, acrylamide, acrylonitrile, vinyl ethers, methacrylonitrile, vinyl acetates, optionally substituted styrenes and vinyltoluenes can also be used in a).
• component b) it is possible to use polymerizable OH-containing monomers, for example hydroxyalkyl esters of unsaturated carboxylic acids, preferably hydroxyalkyl (meth) acrylates having 2 to 12, preferably 2 to 6, carbon atoms in the hydroxyalkyl radical.
• polymerizable OH-containing monomers for example hydroxyalkyl esters of unsaturated carboxylic acids, preferably hydroxyalkyl (meth) acrylates having 2 to 12, preferably 2 to 6, carbon atoms in the hydroxyalkyl radical.
• Examples of such compounds are 2-hydroxyethyl (meth) acrylate, the isomeric hydroxypropyl (meth) acrylates, 2-, 3- and 4-hydroxybutyl (meth) acrylates and the isomeric hydroxyhexyl (meth) acrylates.
• polymerizable hydroxy-functional monomers modified with alkylene oxides or chain-extended having a number-average molecular weight ⁇ 3,000 g / mol, preferably ⁇ 500 g / mol.
• alkylene oxides are preferably used for this purpose, ethylene, propylene or butylene oxide individually or in mixtures.
• ionic and / or potentially ionic monomers of component c) which are capable of radical copolymerization
• olefinically unsaturated monomers having carboxylic acid or carboxylic anhydride groups such as, for example, Acrylic acid, methacrylic acid, ⁇ -carboxyethyl acrylate, crotonic acid, fumaric acid, maleic anhydride, itaconic acid or monoalkyl esters of dibasic acids or anhydrides, e.g. Maleic acid monoalkyl esters are used, preference is given to acrylic acid and / or methacrylic acid.
• Also suitable as compounds of component c) are unsaturated, free-radically polymerizable compounds with phosphate or phosphonate or sulfonic acid or sulfonate groups, as described, for example, in WO-A 00/39181 (page 8 Z. 13 - page 9 Z. 19), in particular 2-acrylamido-2-methylpropanesulfonic acid.
• component d other monomers capable of free-radical copolymerization can also be used as compounds of component d).
• monomers capable of free-radical copolymerization may include, for example, di- or higher functional (meth) acrylate monomers and / or vinyl monomers, such as e.g. Hexanediol di (meth) acrylate or divinylbenzene.
• polymerizable, nonionically hydrophilicizing compounds such as acrylates of hydroxy-functional polyalkylene oxide ethers.
• the hydrophilization of the copolymers is preferably carried out only by ionic and / or potentially ionic groups.
• the proportions of the synthesis components a) to d) are typically chosen so that an OH number of 12 to 200 mg KOH / g, preferably from 25 to 150 mg KOH / g and more preferably from 50 to 150 mg KOH / g solid and an acid number of 0 to 50 mg KOH / g, preferably 10 to 30, particularly preferably from 15 to 25 mg KOH g based on the copolymer results.
• % Component d) is selected, so that copolymers are obtained which correspond to the above information in terms of OH and acid number and wherein the amounts of the above ranges add up to 100 wt .-%.
• Suitable lactone-containing compounds of component e) are all lactones which are known to the person skilled in the art. Preference is given to butyrolactone, valerolactone and e-caprolactone and any mixtures thereof with one another. Particular preference is given in e) to using 6-caprolactone.
• the low molecular weight polyols of component f) are the hydroxy-functional compounds known per se to a person skilled in the art having a molecular weight of from 62 to 250 Da with an average hydroxyl functionality of preferably greater than 1.5, more preferably from 2 to 4.
• low molecular weight polyols examples include ethanediol, di-, tri-, tetraethylene glycol, 1,2-propanediol, di-, tri-, tetra-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, butanediol.
• the procedure for the polymerization of the unsaturated monomers is familiar to the person skilled in the art.
• the components e) and f) are initially charged as reactive diluents and the unsaturated monomers are polymerized therein using a free-radical initiator.
• additional organic solvents can be used in a minor amount.
• Suitable co-solvents are any solvents known in the paint art, such as e.g. Alcohols, ethers, alcohols containing ether groups, esters, ketones, N-methylpyrrolidone or non-polar hydrocarbons or mixtures of these solvents.
• the solvents are used in amounts such that their content in the finished dispersion is from 0 to 5% by weight. If necessary, the solvents used can be partially removed by distillation again. In a preferred embodiment, however, completely dispenses with the use of additional organic solvents.
• the copolymerization is generally carried out at 40 to 200 ° C, preferably at 60 to 180 ° C, particularly preferably at 80 to 160 ° C.
• Suitable initiators for the polymerization reaction are organic peroxides such as di-tert-butyl peroxide or tert-butyl peroxy-2-ethylhexanoate and azo compounds such as azodiisobutyric acid nitrile (AEBN).
• organic peroxides such as di-tert-butyl peroxide or tert-butyl peroxy-2-ethylhexanoate
• azo compounds such as azodiisobutyric acid nitrile (AEBN).
• AEBN azodiisobutyric acid nitrile
• a two-stage addition and polymerization of unsaturated monomers of the type mentioned above takes place in the presence of the diluents e) and f).
• a hydroxy-functional copolymer having an OH number of 12 to 200 mg KOH / g solids and an acid number of 0 to 50 mg KOH / g solids consisting of 55 to 90 wt .-% of component a) , 2.5-50% by weight of component b), 0-6.5% by weight of component c) and 0-42.5% by weight of component d).
• a further polymer of monomers of components a) -d) is prepared in the reaction mixture obtained from step (I), this polymer having an OH number of 20 to 200 mg KOH / g solids and an acid number from 50 to 200 mg KOH / g solids.
• the polymer from step (11) consists of 45-80% by weight of component a), 5-50% by weight of component b), 6.5-25% by weight of component c) and 0-43.5 Wt .-% component d). The percentages of the polymer composition add up to 100% by weight per polymer.
• the monomer amounts of the two Polymerisather einen are to be chosen so that the mass ratio of the polymer from step (I) to that from step (II) is 10: 1 to 1: 2, preferably 6: 1 to 2: 1.
• a multistage polymerization process it is likewise possible to carry out the process continuously (gradient polymerization), ie adding a monomer mixture having a composition which changes in accordance with the composition of or of the copolymers A), the hydrophilic monomer proportions preferably being used according to components c) and optionally d) towards the end of the feed are higher than at the beginning.
• the copolymers obtainable by the process according to the invention have number-average molecular weights M n of 500 to 30,000 g / mol, preferably 1,000 to 15,000 g / mol, particularly preferably 1,500 to 10,000 g / mol.
• Suitable neutralizing agents are organic amines or water-soluble inorganic bases, e.g. soluble metal hydroxides, carbonates or hydrogencarbonates.
• Suitable amines are N-methylmorpholine, triethylamine, ethyldiisopropylamine, N, N-dimethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine, diethanolethanolamine, triethanolamine, butanolamine, morpholine, 2-aminomethyl-2-methyl-propanol or isophoronediamine , In mixtures, it is also possible to use ammonia proportionally. Particularly preferred are triethanolamine, N, N-dimethylethanolamine and ethyldiisopropylamine.
• the neutralizing agents are added in B) in amounts such that in total there is a theoretical degree of neutralization [of the acid groups] of 40 to 150%, preferably 60 to 120%.
• the degree of neutralization is understood to mean the ratio of added basic groups of the neutralization component from B) to acid functions of the copolymer.
• the pH of the aqueous binder dispersion according to the invention is 6 to 10, preferably 6.5 to 9.
• the aqueous, hydroxy-functional binder dispersions according to the invention have a solids content of from 25 to 70% by weight, preferably from 35 to 60% by weight, particularly preferably from 50 to 59% by weight, and from 0 to 12% by weight of organic solvents .-%, preferably 1 to 3.5 wt .-% on.
• the binder dispersions of the invention can be processed into aqueous coating compositions. Depending on the reactivity or, if appropriate, blocking of the crosslinkers, it is possible by combination with crosslinkers to prepare both one-component and two-component coatings.
• the term "interior component lacquers" is to be understood as meaning coating compositions in which binder component and crosslinker component can be stored together without a crosslinking reaction takes place in appreciable or harmful for the subsequent application extent.
• the crosslinking reaction takes place only after application after activation of the crosslinker. This activation can be effected, for example, by raising the temperature.
• two-component coatings are to be understood as coating compositions in which binder component and crosslinker component must be stored in separate vessels because of their high reactivity.
• the two components are mixed just before application and then generally react without additional activation. To accelerate the crosslinking reaction but can also be used catalysts or higher temperatures.
• the present invention therefore also provides aqueous coating compositions containing at least
• Suitable OH group-reactive crosslinkers are, for example, 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, aniline resins, as described in "Lackbuchharze", H. Wagner, H.F. Sarx, Carl Hanser Verlag Kunststoff, 1971.
• polyisocyanates typically have 2 or more NCO groups per molecule and are based, for example, on isophorone diisocyanate, hexamethylene diisocyanate, 1,4-diisocyanatocyclohexane, bis (4-isocyanatocyclohexane) methane, 1,3-diisocyanatobenzene, triisocyanatononane or the isomeric 2,4- and 2,6-TDI and may further comprise urethane, isocyanurate and / or biuret groups.
• low-viscosity optionally hydrophilized polyisocyanates of the aforementioned type based on aliphatic or cycloaliphatic isocyanates is particularly preferred.
• the polyisocyanates used as crosslinkers generally have a viscosity of from 10 to 5,000 mPas at 23 ° C. and can also be used, if desired for viscosity adjustment, in admixture with small amounts of inert solvents.
• the copolymers essential to the invention are generally sufficiently hydrophilic so that it is also possible to disperse hydrophobic crosslinker resins without additional emulsifiers. However, a use of external emulsifiers is not excluded.
• Water-soluble or dispersible polyisocyanates are e.g. by modification with carboxylate, sulfonate and / or polyethylene oxide groups and / or polyethylene oxide / polypropylene oxide groups. Hydrophilization of the polyisocyanates is e.g. by reaction with substancial amounts of monohydric, hydrophilic polyether alcohols possible. The preparation of such hydrophilicized polyisocyanates is described for example in EP-A 0 540 985 (page 3, Z 55 to page 4 Z.5).
• polyisocyanates containing allophanate groups described in EP-A 959 087 (pages 3 to 39 to 51), which are prepared by reacting low-monomer polyisocyanates with polyethylene oxide polyether alcohols under allophanatization conditions.
• the water-dispersible polyisocyanate mixtures based on triisocyanatononane described in DE-A 100 078 21 (page 2 Z. 66 to page 3 Z.5) are also suitable, as well as with ionic groups (sulfonate, phosphonate) hydrophiherte polyisocyanates, as they eg in DE 100 24 624 (page 3 Z. 13 to 33) are described.
• the customary auxiliaries and additives can be added to the coating technology, as described, for example, in US Pat. Defoaming agents, thickeners, pigments, dispersing agents, catalysts, anti-skinning agents, anti-settling agents or emulsifiers.
• auxiliaries and additives may also be added to the coating compositions containing the aqueous, hydroxy-functional binder dispersions of the invention.
• aqueous coating compositions comprising the aqueous, hydroxy-functional copolymer dispersions according to the invention are suitable for all fields of use in which aqueous coating and coating systems with high requirements for the durability of the films are used, e.g. for the coating of mineral building material surfaces, varnishing and sealing of wood and wood-based materials, coating of metallic surfaces (metal coating), coating and varnishing of asphalt or bituminous coatings, varnishing and sealing of various plastic surfaces (plastic coating) as well as high gloss varnishes.
• coating compositions comprising the copolymer dispersions essential to the invention lead to coatings having a very high level of properties, they are also suitable for production crack-bridging coatings, preferably in the construction sector and on mineral substrates.
• aqueous coating compositions containing the aqueous, hydroxy-functional binder dispersions according to the invention are used for the production of primers, fillers, pigmented or transparent topcoats, clearcoats and high gloss lacquers, and single-coat paints used in single and batch applications, e.g. in the field of industrial painting, automotive initial and repair paint application can be used.
• aqueous coating compositions comprising the aqueous, hydroxy-functional binder dispersions according to the invention for the coating or coating of mineral surfaces, of wood and plastics.
• the curing of the coating compositions according to the invention is typically carried out at temperatures of 0 to 140 ° C, preferably from 18 to 80 ° C.
• these coatings have a high level of resistance to solvents and chemicals, good weather resistance, high hardness and rapid drying.
• the coatings can be produced by the different spraying methods, such as, for example, air-pressure, airless or electrostatic spraying using single or optionally two-component spray systems.
• the lacquers and coating compositions containing the aqueous, hydroxy-functional binder dispersions according to the invention can also be applied by other methods, for example by brushing, rolling or knife coating.
• Viscosity measurements were carried out with a viscous viscometer Viscolab LC3 ISO from Physica, Stuttgart, Germany according to DIN 53019 at a shear rate of 40 s -1 .
• Dowanol ® PnB propylene glycol n-butyl ether, Dow Chemical, Midland, United States.
• Peroxan ® DB Di-tert-butyl peroxide, Pergan GmbH, Bocholt, Germany.
• Viscosity 1200 mPas (23 ° C, shear rate 40 "1 ) pH (10% in water) 8.1
• Component Film A Film B dispersion of Example 3 100 Dispersion from Example 4 100 Bayhydur XP ® 2451 36.3 20.8
• the binder according to the invention led to paint films with markedly improved resistance to aggressive media, in particular to ethanol and isopropanol.
• the binder according to the invention led to coating films with a significantly higher gloss than the comparable binder according to the prior art.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Dispersion Chemistry (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerisation Methods In General (AREA)
• Colloid Chemistry (AREA)
• Detergent Compositions (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Photoreceptors In Electrophotography (AREA)

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• 2003
  • 2003-12-24 DE DE10361274A patent/DE10361274A1/de not_active Withdrawn
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