WO2011009228A1 - Polymères acryliques, compositions de revêtement et procédés de préparation associés - Google Patents

Polymères acryliques, compositions de revêtement et procédés de préparation associés Download PDF

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Publication number
WO2011009228A1
WO2011009228A1 PCT/CN2009/000825 CN2009000825W WO2011009228A1 WO 2011009228 A1 WO2011009228 A1 WO 2011009228A1 CN 2009000825 W CN2009000825 W CN 2009000825W WO 2011009228 A1 WO2011009228 A1 WO 2011009228A1
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meth
polymer
acrylate
weight
coating composition
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PCT/CN2009/000825
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English (en)
Inventor
Zhengfeng Zhang
Yan Li
Pinfeng Bao
Gerold Schmitt
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Evonik Röhm Gmbh
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Priority to PCT/CN2009/000825 priority Critical patent/WO2011009228A1/fr
Publication of WO2011009228A1 publication Critical patent/WO2011009228A1/fr

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    • 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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention describes waterborne acrylic polymers and coating compositions. Furthermore, the present invention relates to a method of preparing these coating compositions and to a coating being obtainable by application of the coating
  • Metallic coating films sparkle when metallic flake pigments contained therein reflect incident light. The reflection, in combination with the colours of the coating films, produces an attractive, unique appearance full of variations.
  • the metallic coating films are formed chiefly on exterior panels of automobiles, motorcycles, etc. Recent compositions for preparing these films comprise polymers having phosphate groups for stabilizing the metal flakes.
  • compositions useful as an adhesion promoting primer activator for curable acrylic monomer formulations particularly for anaerobic curable formulations which comprise a solution in a volatile organic solvent of a metal salt of an acid phosphate acrylic monomer.
  • the use of organic solvents comprises environmental disadvantages. Therefore, efforts have been made to minimize to use of organic solvents in coating compositions.
  • the compositions disclosed are based on the monomers and must be polymerized for their applications. Such compositions must be applied very carefully in order to obtain a continuous quality of the obtained coating. In the Examples a composition comprising the acid phosphate acrylic monomer and an adhesive are applied in two steps.
  • aqueous metallic coating composition comprising (A) 100 parts, based on solids, of a film-forming aqueous acrylic polymer obtained by neutralizing a copolymer having a number average molecular weight of 2,000 to 200,000, an acid value of 10 to 110 mg KOH/g and a hydroxyl value of 20 to 100 mg KOH/g, the copolymer being obtained by copolymerizing (a) 10 to 35 wt.% of styrene, (b) 5 to 25 wt.% of C6-18 alkyl (meth)acrylate, (c) 0.1 to 10 wt.% of phosphoric ester group-containing monomer, (d) 2 to 10 wt.% of carboxyl-containing monomer, (e) 5 to 20 wt.% of hydroxyl-containing monomer, and (A) 100 parts, based on solids, of a film-forming aqueous acrylic polymer obtained by neutralizing a copolymer having a number average molecular
  • the copolymer is preferably made by a solution polymerization. No hints are made regarding an emulsion polymerization. Furthermore, the films according to EP 960 917 are relatively sensitive against weathering and are very complicated in their manufacture. Therefore, the preparation of the composition according to EP 960 917 is complex and elaborate. In addition thereto, the adhesion of the coatings on the most important metals is low.
  • JP 2007/269846 describes a manufacture method of dispersions including emulsion polymerization of OH-containing, carboxy-containing and phosphoric acid-containing vinyl monomers, and other vinyl monomers in water in the presence of chain-transfer agents and surfactants.
  • a sample of phosphoric acid-containing vinyl monomers is methacryloyloxyethyl phosphate.
  • 2007/269846 is obtained by two polymerization steps. Therefore, the preparation of the composition according to JP 2007/269846 is complex and elaborate. In addition thereto, the adhesion of the coatings on the most important metals is low.
  • the polymers should have a high adhesion performance, especially on metals such as aluminum flakes. Furthermore, the coating materials ought to have a very low residual monomer content. Additionally, it was an object of the present invention to provide a dispersion which has a particularly long storage life and suitability for storage. Moreover, the coating materials should have low viscosity, especially in relation to the solid content. Furthermore, the intention was that the hardness of the coatings obtainable from coating materials could be varied over a wide range. In accordance with one particular aspect of the present invention, more particularly, it was intended that compositions be provided that lead to very hard, scratch-resistant coatings.
  • the coatings obtainable from the coating materials have a high solvent resistance.
  • a further object can be seen in the provision of coating materials without high amounts of volatile organic solvents.
  • the coating materials should be environmentally acceptable.
  • the coatings obtainable from the coating compositions ought to have a high weathering stability, more particularly a high UV stability.
  • the films obtainable from the coating materials ought after a short time to feature a low tack.
  • the coating materials of the invention ought to be able to be prepared easily and inexpensively.
  • special embodiments of the coatings being obtainable from the polymers and the coating materials, respectively should have a high gloss.
  • the present invention accordingly provides an acrylic polymer for a coating
  • composition the polymer comprising
  • the polymers according to the present invention have a high adhesion performance, especially on metals such as aluminum flakes. Moreover, the polymers and the coating materials are environmentally acceptable.
  • the coating compositions of the invention have a very low residual monomer content.
  • the hardness of the coatings obtainable from the polymers and the coating compositions of the invention can be varied over a wide range. Thus it is possible more particularly to obtain very hard, scratch-resistant coatings.
  • the coatings obtainable from the polymers and the coating compositions of the invention exhibit a surprisingly high solvent resistance, which is manifested more particularly in tests with methyl isobutyl ketone (MIBK) or ethanol. In this context it is even possible to clean the coatings with non-polar solvents, more particularly cleaning solvent (petroleum ether), without the coating being damaged irreversibly as a result.
  • MIBK methyl isobutyl ketone
  • the coating compositions of the invention preferably contain merely very small amounts of volatile organic solvents. Furthermore, coating compositions of the invention exhibit a high level of storage stability, a long shelf life and very good storage properties. More particularly virtually no aggregate is formed.
  • the coatings obtainable from the polymers and the coating compositions exhibit a high weathering stability, more particularly a high UV stability.
  • the films obtainable from the coating compositions, furthermore, after a short time feature a low tack. Furthermore, the coating materials of the invention exhibit high wet-film stability and an increased open time.
  • the coatings obtainable from the dispersions of the invention exhibit particularly high strength of adhesion, abrasion resistance and durability.
  • Preferred coatings and substrates coated with the coatings of the invention may be exposed in particular to high mechanical loads without the coating cracking.
  • the dispersions of the invention can be prepared inexpensively on a large scale.
  • the dispersions of the invention are eco-friendly and can be prepared and processed safely and without great cost and complexity.
  • the dispersions of the invention exhibit a very high shear stability.
  • special embodiments of the coatings being obtainable from the polymers and the coating materials, respectively have a high gloss.
  • the polymer of the present invention comprises 10% to 55% by weight, preferably 15 to 45 % by weight of units derived from high solid (meth)acrylate monomers, based on the weight of the polymer.
  • the polymer may be obtained preferably by free-radical polymerization. Accordingly the weight fraction of the units of the polymer as mentioned in the present application is a product of the weight fractions of corresponding monomers that are used for preparing the (meth)acrylate polymer.
  • (meth)acrylates encompasses methacrylates and acrylates and also mixtures of both.
  • High solid monomers or bulky side chain (meth)acrylate monomers provide a low viscosity to a (meth)acrylic polymer.
  • High solid (meth)acrylate monomers are known in the art. These monomers include cycloalkyl (meth)acrylates.
  • Preferred high solid (meth)acrylate monomers are cycloalkyl (meth)acrylates, such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate having a ring substituent, such as tert-butylcyclohexyl (meth)acrylate and trimethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, methyl norbornyl (meth)acrylate and dimethyl norbornyl (meth)acrylate, 1-adamantyl
  • the polymer of the present invention comprises 0.1% to 10% by weight, preferably 1 to 5 % by weight of units derived from phosphorus (meth)acrylate
  • the phosphorus (meth)acrylate monomer is a (meth)acrylate having the following formula (I)
  • R 1 is H or methyl
  • Organic groups containing 2 to 20 carbon atoms are known in the art.
  • the expression embraces alkylene, cycloalkylene, divalent aromatic groups, alkenylene groups and alkynyl groups having 2 to 20 carbon atoms, and also heteroaliphatic and
  • heteroaromatic groups which besides carbon atoms and hydrogen atoms contain, in particular, oxygen, nitrogen, sulfur, and phosphorus atoms. Said groups may be branched or unbranched, and the radical R 2 can be substituted or unsubstituted.
  • the substituents include, in particular, halogens, nitro, sulfonic acid, alkoxy, cycloalkoxy, alkanoyl, alkoxycarbonyl, sulfonic ester, sulfinic acid, sulfinic ester, thiol, cyanide, epoxy, (meth)acryloyl, amino, and hydroxyl groups.
  • halogen denotes a fluorine, chlorine, bromine or iodine atom.
  • Preferred compounds according to formula (I) are disclosed, e.g. in the document EP-A-O 074 708, filed with the European Patent Office at 26.07.82 with the application number 82303942.5. These compounds disclosed in EP-A-O 074 708 and methods for their preparation are enclosed herein by reference.
  • the residue R 2 is an alkylene group having 2 to 20, more preferably 2 to 10 and most preferably 2 to 4 carbon atoms.
  • These residues include, e.g. ethylene, propylene, butylenes, 2-methyl propylene, hexylene, cyclohexylene.
  • the residue A is preferably OH.
  • the phosphorous monomer is methacryloyloxyethyl phosphate. Therefore, R 1 preferably is a methyl group, R 2 is -CH 2 CH 2 - and A is OH in the formula (I).
  • the polymer comprises comonomers.
  • a comonomer is a monomer being different from the units of the polymer that have been set out above, but can be copolymerized with the monomers set out above.
  • monomers containing acid groups include 2 to 7 carbon atoms and also one terminal double bond. They include, for example, monomers having a sulphonic acid group, such as vinylsulphonic acid, for example; monomers having a phosphonic acid group, such as vinylphosphonic acid, for example; and unsaturated carboxylic acids, such as
  • methacrylic acid acrylic acid, fumaric acid and maleic acid, for example.
  • Methacrylic acid and acrylic acid are particularly preferred.
  • the monomers containing acid groups can be used individually or as a mixture of two, three or more monomers containing acid groups.
  • the polymer may comprise 0.1 % to 10% by weight, more preferably 1 to 5 % by weight of units derived from monomers containing acid groups, preferably derived from (meth)acrylic acid.
  • the weight ratio of the units derived from monomers containing acid groups to the units derived from phosphorus (meth)acrylate monomers could be in the range from 50:1 to 0:1 , more preferably 2:1 to 1 :4.
  • preferred polymers comprise units being derived from (meth)acrylate comonomers.
  • (Meth)acrylate comonomers are esters of methacrylic acid, acrylic acids or mixtures of both being different to the high solid (meth)acrylates and phosphorus (meth)acrylate monomers as mentioned above.
  • Preferred comonomers include (meth)acrylates having 1 to 6 carbon atoms in the alkyl radical deriving from saturated alcohols, such as methyl (meth)acrylate, ethyl
  • (meth)acrylate n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate and pentyl (meth)acrylate, hexyl (meth)acrylate.
  • the polymer may comprise 0.1 % to 89.9% by weight, more preferably 10 to 80 % by weight and more preferably 40 to 75 % by weight of units derived from
  • (meth)acrylates having 1 to 6 carbon atoms in the alkyl radical deriving from saturated alcohols.
  • the weight ratio of the units derived from (meth)acrylates having 1 to 6 carbon atoms in the alkyl radical deriving from saturated alcohols to the units derived from phosphorus (meth)acrylate monomers could be in the range from 500:1 to 6:1 , more preferably 50:1 to 20:1.
  • the (meth)acrylate comonomers include hydroxyalkyl (meth)acrylates, such as
  • the polymer may contain 0 to 50 % by weight, more preferably 0.1 to 10 % by weight of units derived from hydroxyalkyl (meth)acrylates, based on the weight of the polymer.
  • these comonomers include, for example, (meth)acrylates having at least 7 carbon atoms in the alkyl radical and deriving from saturated alcohols, such as, for example, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl
  • (meth)acrylamide and derivatives thereof, such as N-methylol (meth)acrylamide,
  • aryl (meth)acrylates such as benzyl (meth)acrylate or phenyl (meth)acrylate, it being possible for each of the aryl radicals to be unsubstituted or to be substituted up to four times;
  • di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra- and polyethylene glycol di(meth)acrylate, 1 ,3-butanediol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1 ,6- hexanediol di(meth)acrylate, glycerol di(meth)acrylate;
  • (meth)acrylates having three or more double bonds such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and
  • vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride, for example;
  • heterocyclic (meth)acrylates such as 2-(1-imidazolyl)ethyl (meth)acrylate,
  • styrene substituted styrenes having an alkyl substituent in the side chain, such as, for example, ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, and halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes, for example;
  • heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5- vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-viny!butyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles,
  • vinyloxazoles and hydrogenated vinyloxazoles vinyl ethers and isoprenyl ethers; maleic acid derivatives such as, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride, maleimide, methylmaleimide; and fumaric acid derivatives, such as dimethyl fumarate.
  • maleic acid derivatives such as, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride, maleimide, methylmaleimide
  • fumaric acid derivatives such as dimethyl fumarate.
  • a preferred polymer may contain a low amount of units deriving from styrene monomers and/or aryl
  • the polymer may contain 20 % by weight or less, preferably 10 % or less and more preferably 5 % by weight or less of units deriving from styrene monomers and/or aryl (meth)acrylate monomers.
  • the polymer does not contain any amount of units deriving from styrene monomers and/or aryl (meth)acrylate monomers.
  • the polymer comprises units being derived from at least one methacrylate and at least one acrylate as comonomers.
  • such polymers may comprise units derived from methyl methacrylate and butyl acrylate.
  • Unexpected improvements can be achieved by mixtures having a weight ratio of the methacrylate comonomers to the acrylate comonomers being in the range of from 20:1 to 1 :40, preferably from 2:1 to 1 :4.
  • the acrylic polymer of the present invention is useful for a coating composition.
  • the present polymer can be used in a coating composition for forming a coating.
  • Polymers for a coating composition are preferably obtainable by an emulsion polymerization.
  • the present invention provides a polymer having units derived from monomers as mentioned above.
  • the polymers are obtainable by free radical polymerization such as solution, bulk or emulsion polymerization, the preparation taking place preferably by way of emulsion polymerization, these processes being set out in sources including Ullmanns's Encyclopaedia of Industrial Chemistry, Fifth Edition.
  • the polymer is an emulsion polymer.
  • An emulsion polymer is a polymer being obtainable by way of emulsion polymerization. Accordingly, the polymers are preferably obtainable by mixing at least one high solid (meth)acrylate monomer, at least one phosphorus (meth)acrylate monomer and at least one comonomer and polymerize the mixture obtained in an emulsion polymerization. This process is set out in reference books including Ullmanns's Encyclopaedia of Industrial Chemistry, Fifth Edition.
  • aqueous phase which as well as water may include typical additives, more particularly emulsifiers and protective colloids for stabilizing the emulsion.
  • This aqueous phase is then admixed with monomers, and polymerization is carried out.
  • a monomer mixture batchwise or continuously over a time interval.
  • the dispersing of the monomer phase in the aqueous phase can take place using known agents. These include, more particularly, mechanical methods and also the application of ultrasound.
  • the monomer mixture for preparing the emulsion polymers in accordance with the invention comprises preferably
  • the monomer mixture preferably contains 0.1 to 10% by weight, more preferably 1% to 5% by weight of monomers containing acid groups.
  • the monomer mixture preferably contains 0.1 % to 89.9% by weight, more preferably 10 to 80 % by weight and most preferably 40 to 75 % by weight of (meth)acrylates having 1 to 6 carbon atoms in the alkyl radical deriving from saturated alcohols
  • Core-shell polymer here stands for a polymer which has been prepared by a two- stage or multistage emulsion polymerization, without the core-shell structure having been shown by means, for example, of electron microscopy. Monitoring of the progress of the polymerization reaction in each step can be effected in a known way, such as by gravimetry or gas chromatography, for example.
  • the emulsion polymerization is conducted preferably at a temperature in the range from 0 to 120 0 C, more preferably in the range from 30 to 100 0 C.
  • temperatures which have proved to be especially favourable in this context are temperatures in the range from greater than 60 to less than 90°C, judiciously in the range from greater than 70 to less than 85°C, preferably in the range from greater than 75 to less than 85°C.
  • the polymerization is initiated with the initiators that are customary for emulsion polymerization.
  • Suitable organic initiators are, for example, hydroperoxides such as tert- butyl hydroperoxide or cumene hydroperoxide.
  • Suitable inorganic initiators are hydrogen peroxide and also the alkali metal salts and the ammonium salts of
  • peroxodisulphuric acid more particularly ammonium, sodium and potassium
  • Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulphite and alkali metal salts and the ammonium salts of peroxodisulphuric acid, more particularly sodium and potassium peroxodisulphate. Further details can be taken from the technical literature, more particularly H. Rauch-Puntigam, Th. Volker, "Acryl- und Methacryltagen", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopaedia of Chemical Technology, Vol. 1 , pages 386ff, J. Wiley, New York, 1978. Particular preference in the context of the present invention is given to the use of organic and/or inorganic initiators.
  • the stated initiators may be used both individually and in a mixture. They are preferably used in an amount of 0.05% to 3.0% by weight, based on the total weight of the monomers of the respective stage. It is also possible with preference to carry out the polymerization with a mixture of different polymerization initiators having different half- lives, in order to keep the flow of free radicals constant over the course of the
  • Stabilization of the batch is accomplished preferably by means of emulsifiers and/or protective colloids.
  • the dispersion is preferably stabilized by emulsifiers, in order to obtain a low dispersion viscosity.
  • the total amount of emulsifier is preferably 0.1% to 15% by weight, more particularly 1% to 10% by weight and more preferably 2% to 5% by weight, based on the total weight of the monomers used. In accordance with one particular aspect of the present invention it is possible to add a portion of the emulsifiers during the polymerization.
  • Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, more particularly
  • alkyl sulphates preferably those having 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulphates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;
  • sulphonates preferably alkylsulphonates having 8 to 18 carbon atoms in the alkyl radical, alkylarylsulphonates having 8 to 18 carbon atoms in the alkyl radical, diesters and monoesters of sulphosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms in the alkyl radical; where appropriate these alcohols or alkylphenols may also have been ethoxylated with 1 to 40 ethylene oxide units;
  • phosphoric acid partial esters and their alkali metal and ammonium salts preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units;
  • alkyl polyglycol ethers preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
  • alkylaryl polyglycol ethers preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units;
  • ethylene oxide/propylene oxide copolymers preferably block copolymers, favourably having 8 to 40 ethylene and/or propylene oxide units.
  • the particularly preferred anionic emulsifiers include, more particularly, fatty alcohol ether sulphates, diisooctyl sulphosuccinate, lauryl sulphate, C15-paraffinsulphonate, it being possible to use these compounds generally in the form of the alkali metal salt, more particularly the sodium salt.
  • These compounds may be obtained commercially, more particularly, under the commercial designations Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG.
  • Judicious nonionic emulsifiers include tert-octylphenol ethoxylate with 30 ethylene oxide units and fatty alcohol polyethylene glycol ethers which have preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units. These emulsifiers are available commercially under the commercial designations Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and
  • the weight ratio of anionic emulsifier to nonionic emulsifier can judiciously be in the range from 20:1 to 1 :20, preferably 2:1 to 1 :10 and more preferably 1 :1 to 1 :5.
  • Mixtures which have proven to be especially appropriate are those comprising a sulphate, more particularly a fatty alcohol ether sulphate, a lauryl sulphate, or a sulphonate, more particularly a diisooctyl sulphosuccinate or a paraffin sulphonate, as anionic emulsifier, and an alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ether having in each case preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units, as nonionic emulsifier.
  • a sulphate more particularly a fatty alcohol ether sulphate, a lauryl sulphate, or a sulphonate, more particularly a diisooctyl sulphosuccinate or a paraffin sulphonate, as anionic emulsifier
  • emulsifiers can also be used in a mixture with protective colloids.
  • Suitable protective colloids include partially hydrolysed polyvinyl acetates,
  • polyvinylpyrrolidones carboxymethyl-, methyl-, hydroxyethyl and hydroxypropyl- cellulose, starches, proteins, poly(meth)acrylic acid, poly(meth)acrylamide,
  • protective colloids are used they are used preferably in an amount of 0.01 to 1.0% by weight, based on the total amount of the monomers.
  • the protective colloids may be included in the initial charge before the start of the polymerization, or metered in.
  • the initiator may be included in the initial charge or metered in. It is also possible, furthermore, to include a portion of the initiator in the initial charge and to meter in the remainder.
  • the polymerization is preferably started by heating the batch to the polymerization temperature and metering in the initiator, preferably in aqueous solution.
  • the metered feeds of emulsifier and monomers may be carried out separately or as a mixture.
  • the approach taken is to premix emulsifier and monomer in a mixer upstream of the polymerization reactor.
  • the remainders of emulsifier and of monomer which have not been included in the initial charge are metered in separately from one another after the start of the polymerization. With preference it is possible to commence the metered feed 5 to 35 minutes after the start of the polymerization.
  • Emulsion polymers having a high fraction of insoluble fraction can be obtained in the manner set out above, the reaction parameters for obtaining a high molecular weight being known. Thus it is possible more particularly in this context to omit the use of molecular weight regulators.
  • the processability of the coating compositions e.g. the minimum temperature at which the film binds, also known as minimum film form temperature (MFFT) can be lowered by using a molecular weight regulator, also known as chain transfer agent.
  • MFFT minimum film form temperature
  • chain transfer agents include e.g.
  • 2-mercaptoethanol mercaptoacetic acid, 2-mercaptobenzimidazole, 2-mercaptobenzoic acid, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 3-mercapto-2-butanol, 2- mercaptosulfonic acid, 2-mercaptonicotinic acid, 4-hydroxythiopheno3-mercapto-1 ,2- propanediol, 1-mercapto-2-propanol, 2-mercaptopropionic acid, N-(2- mercaptopropionyl)glycine, 3-mercaptopropyltrimethoxysilane, 2-mercaptopyridine, 2- mercaptopyridine-N-oxide, 2-mercaptopyridinol, mercaptosuccinic acid, 2,3- mercaptopropanesulfonic acid, 2,3-dimercaptopropanol, 2,3-dimercaptosuccinic acid, cystine, cystine hydrochloride, cysteine e
  • Preferred functionalized end- capping agents include 2-mercaptoethanol, 3-mercapto-1 ,2-propanediol, 4- mercaptobutanol, 11-mercaptoundecanol, mercaptoacetic acid, 3-mercaptopropionic acid, 12-mercaptododecanoic acid, 2-mercaptoethylamine, 1-chloro-6-mercapto-4- oxahexan-2-ol, 2,3-dimercaptosuccinic acid, 2,3-dimercaptopropanol, 3- mercaptopropyltrimethoxysilane, 2-chloroethanethiol, 2-amino-3-mercaptopropionic acid, and compounds such as the adduct of 2-mercaptoethylamine and caprolactam.
  • the amounts of chain transfer agents are preferably in the range of 0.001 % by weight to 5 % by weight, more preferably 0.01 % by weight to 3 % by weight, based on the total amount of monomers.
  • One of the ways in which the adjustment of the particle radii of the emulsion polymer can be influenced is via the fraction of emulsifiers. The higher this fraction, more particularly at the beginning of the polymerization, the smaller the particles obtained.
  • the polymer preferably the emulsion polymer of the present invention can have a weight average molecular weight in the range of from 10000 to 5000000 g/mol, more preferably from 50000 to 1000000 g/mol.
  • the number average molecular weight of the polymer can be in the range of from 5000 to 2500000 g/mol, more preferably in the range of from 25000 to 1300000 g/mol.
  • the molecular weight of the emulsion polymer can be determined by gel permeation chromatography (GPC) using a PMMA standard.
  • the emulsion polymer can have a fraction of 2% to 60%, more preferably 10% to 50% and very preferably 20% to 40%, by weight, based on the weight of the emulsion polymer according to the present invention, which is soluble in tetrahydrofuran (THF) at 20 0 C.
  • THF tetrahydrofuran
  • a sample of the emulsion polymer that has been dried is stored in 200 times the amount of solvent, based on the weight of the sample, at 2O 0 C for 4 h. Subsequently the solution is separated, by filtration for example, from the insoluble fraction. After the solvent has been evaporated the weight of the residue is determined.
  • a 0.5 g sample of an emulsion polymer dried under reduced pressure can be stored in 150 ml of THF for 4 hours.
  • the particle radius of the emulsion polymer may vary over a wide range.
  • the emulsion polymer may have a particle radius in the range from 10 to 500 nm, preferably 10 to 200 nm, more preferably 20 to 100 nm. Particle radii below 50 nm in particular may be advantageous for film formation and the coating properties.
  • the emulsion polymer according to the present invention may have a particle radius of at least 50 nm.
  • the radius of these particles is situated preferably in the range from 60 nm to 500 nm, more preferably 70 to 150 nm and very preferably 75 to 100 nm.
  • the radius of the particles can be determined by means of PCS (Photon Correlation Spectroscopy), the data given relating to the r50 value (50% of the particles are smaller, 50% are larger). This can be done using, for example, a Beckman Coulter N5 Submicron Particle Size Analyzer.
  • the glass transition temperature of the polymer is situated preferably in the range from -30 0 C to 70 0 C, more preferably in the range from -20 to 40 0 C and very preferably in the range from 0 to 25°C.
  • the glass transition temperature may be influenced via the nature and the fraction of the monomers used to prepare the (meth)acrylate segment.
  • the glass transition temperature, Tg, of the polymer may be determined in a known way by means of Differential Scanning Calorimetry (DSC).
  • DSC Differential Scanning Calorimetry
  • the glass transition temperature may be determined according to DIN EN ISO 11357. E.g. the glass transition temperature may be determined as center of the second heating curve with a heating rate of 10 0 C per minute.
  • the glass transition temperature Tg may also be calculated approximately in advance by means of the Fox equation. According to Fox T. G., Bull. Am. Physics Soc. 1 , 3, page 123 (1956) it is the case that
  • Tg n identifies the glass transition temperature, in kelvins, of the homopolymer of the monomer n. Further useful information can be found by the skilled person in the Polymer Handbook, 2nd Edition, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers.
  • the polymer may accordingly comprise random copolymers, gradient copolymers, block copolymers and/or graft copolymers.
  • Block copolymers and gradient copolymers can be obtained, for example, by discontinuously altering the monomer composition during chain propagation.
  • the emulsion polymer comprises a random copolymer in which the monomer composition over the polymerization is substantially constant. Since, however, the monomers may have different copolymerization parameters, the precise composition may fluctuate over the polymer chain of the polymer.
  • the emulsions described above can be used as a coating composition. These coating compositions are new and subject matter of the present invention.
  • the acrylic polymers according to the present invention and coating compositions comprising the present polymers can be used as a binder resin of a paint composition for automobile industry, architecture industry and wood coating industry. It can be used also as binder resin for metallic paints for above mentioned industries.
  • the water- resistance, gloss and other properties of a dried coating layer and an alignment of metallic particles may be improved.
  • the coating compositions may comprise further components and additives, e.g. anti- foamer, pH adjusting agents, organic solvents, thickener, fillers, pigments, fungicides, flow improvers and dyes etc.
  • additives e.g. anti- foamer, pH adjusting agents, organic solvents, thickener, fillers, pigments, fungicides, flow improvers and dyes etc.
  • the stability of the coating composition can be improved by adjusting the pH-value of the water phase of the coating composition within the range of 6 to 10, preferably 7 to 9.
  • the pH value is defined as minus the decimal logarithm of the hydrogen ion activity in an aqueous solution.
  • the coating compositions of the present invention may comprise metallic pigments, e.g. aluminum pigment, bronze pigment, mica, gold pigment or silver pigment.
  • metallic pigments e.g. aluminum pigment, bronze pigment, mica, gold pigment or silver pigment.
  • a metallic flake pigment is used, more preferably an aluminum flake pigment is used.
  • the proportion of the metallic pigment may preferably range from about 1 to 20 parts by weight, more preferably from 2 to 10 parts by weight per 100 parts by weight, based on solids, of the film-forming acrylic polymer.
  • composition may comprise a stabilizing agent.
  • the stabilizing agent prevents a settling of the mixture and promotes the orientation of a flake pigment. This component is preferably used in combination with a metallic flake pigment.
  • the stabilizing agent includes e.g. water borne waxes, cellulose acetate butyrate, and carboxylmethyl cellulose acetate butyrate.
  • the coating composition preferably comprises 1 to 15 % by weight, more preferably 3 to 8 % by weight carboxylmethyl cellulose acetate butyrate.
  • such compositions have improved flow and leveling characteristics, reduced dry-to-touch time, no sagging, excellent redissolve resistance, and superior aluminum pigment control in metallic paints.
  • the coating composition may include small amounts of organic solvents, e.g. for improving the dispersion of the metallic pigment in the coating composition.
  • organic solvents include alcohol solvents, such as ethanol, methanol, isopropanol, butanol, ether solvents, such as ethylene glycol, propylene glycol, butyl glycol ether, ester solvents and hydrocarbon solvents e.g., aromatic hydrocarbons, ketones, such as acetone, methyl ethyl ketone.
  • the coating compositions of the present invention comprise butyl glycol ether.
  • a preferred coating composition is described in the following table 1. The additives mentioned in Table 1 can be used singly or as a mixture of two, three or more components as mentioned in Table 1.
  • Table 1 The amounts in Table 1 are based on the solids content, if the component is used as a solution or dispersion.
  • Coating composition comprising metallic pigments can be prepared by adding metallic particles to a polymer solution or an aqueous dispersion of a polymer, preferably an emulsion polymer according to the present invention.
  • the metallic pigment, especially flake pigments can be predispersed in an organic solvent, e.g. butyl glycol ether and deionized water.
  • the dispersion comprising the metallic pigment is mixed with the water borne acrylic emulsion polymer.
  • the water-borne acrylic emulsion polymer is neutralized with a pH adjusting agent, such as AMP-95, and then further additives, like dispersants, anti-foamers, antiseptics, stabilizing agent, such as water-borne wax (preferably used as 10% dispersion) and the rest of the deionized water is added and mixed.
  • a pH adjusting agent such as AMP-95
  • further additives like dispersants, anti-foamers, antiseptics, stabilizing agent, such as water-borne wax (preferably used as 10% dispersion) and the rest of the deionized water is added and mixed.
  • stabilizing agent such as water-borne wax (preferably used as 10% dispersion) and the rest of the deionized water is added and mixed.
  • the predispersed aluminum pigment may be added in the resin mixture, and mixed with thickener.
  • the coating materials of the invention preferably have a minimum film formation temperature of not more than 50 0 C, with particular preference not more than 35°C and very particular preference not more than 25°C, a temperature which can be measured in accordance with DIN ISO 2115.
  • the aqueous dispersion may judiciously have an acid number in the range from 0.1 to 100 mg KOH/g, preferably 1 to 40 mg KOH/g and very preferably in the range from 2 to 10 mg KOH/g.
  • the acid number may be determined in accordance with DIN EN ISO 2114 from a dispersion, the figure being based on the solids content.
  • the hydroxyl number of an aqueous dispersion of the invention may be situated preferably in the range from 0 to 400 mg KOH/g, more preferably 1 to 200 mg KOH/g and very preferably in the range from 3 to 150 mg KOH/g.
  • the hydroxyl number can be determined in accordance with ASTM E222 from a dispersion, the figure being based on the solids content.
  • the coating composition according to the present invention preferably comprises a solid content in the range of 20 to 70 % by weight, more preferably in the range of 35 to 55 % by weight.
  • the coatings obtainable by the coating compositions of the present invention are new and a further subject matter of the present invention.
  • the coatings obtainable from the coating materials of the invention exhibit high solvent resistance: more particularly, only small fractions are dissolved from the coating by solvents.
  • Preferred coatings exhibit a high resistance, more particularly, to methyl isobutyl ketone (MIBK).
  • MIBK methyl isobutyl ketone
  • the weight loss after treatment with MIBK amounts preferably to not more than 50% by weight, more preferably not more than 35% by weight.
  • the absorption of MIBK amounts preferably to not more than 300% by weight, with particular preference not more than 250% by weight, based on the weight of the coating employed. These values are measured at a temperature of approximately 25°C over an exposure time of at least 4 hours, the coating subjected to measurement being a fully dried coating.
  • the coatings obtained from the coating materials of the invention display a high mechanical stability.
  • the pendulum hardness is preferably at least 20 s, more preferably at least 25 s, measured in accordance with DIN ISO 1522.
  • the coatings of the present invention preferably have a high adhesion.
  • the coating may have a classification of 0 to 2, preferably 0 to 1 determined according to DIN EN ISO 2409, especially on an aluminium substrate.
  • the thickness of the dry coating is preferably in the range of 10 to 200 ⁇ m, more preferably in the range of 20 to 80 ⁇ m.
  • HEMA-P methacryloyloxyethyl phosphate
  • GMAA methacrylic acid
  • APS ammonium peroxodisulphate
  • emulsifier Disonil FES 32 (30% form)
  • a 2 I glass reactor which had a water bath heating facility and was equipped with a blade stirrer was charged with 400 g of water and 0.3 g of Disponil FES 32 (30% form) and this initial charge was heated to 80 0 C and admixed with 0.3 g of ammonium peroxodisulphate (APS) in solution in 10 g of water. 5 minutes after the addition of the APS 1 the emulsion prepared beforehand was metered in over the course of 240 minutes (interval: 3 minutes' feed, 4 minutes' pause, 237 minutes' feed of remainder).
  • APS ammonium peroxodisulphate
  • the batch was stirred at 80 0 C for 1 hour. Thereafter it was cooled to room temperature and the dispersion was filtered through VA screen fabric of 0.125 mm mesh size. The dispersion was filled in a glass bottle.
  • the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 2.6, a viscosity of 35 mPas and an r N5 value of 75 nm.
  • the properties of the resulting coating material were investigated by a cross cut test used for the examination of the adhesive performance. For this purpose, a film had been formed on an aluminium substrate having a thickness of about 40 ⁇ m (dry film). Additionally, a film having the same thickness had been formed on a phosphated steel substrate.
  • a lattice pattern in the film with the multi-cut tool (BYK Gardner, Model D-5120) had been made, cutting to the substrate. Brush in diagonal direction 5 times each, using a brush pen or tape over the cut and remove with Permacel tape Examine the grid area using an illuminated magnifier.
  • the adhesion grade was evaluated according to the cross cut test (DIN EN ISO
  • the film formed with the emulsion polymer achieved a classification of about 1 on aluminium and about 0 on phosphated steel.
  • Example 1 was essentially repeated, but using a monomer mixture comprising 420 g of butyl acrylate (BA), 168 g of methyl methacrylate (MMA), 210 g of cyclohexyl
  • BA butyl acrylate
  • MMA methyl methacrylate
  • cHMA methacrylate
  • HEMA-P methacryloyloxyethyl phosphate
  • BA butyl acrylate
  • MMA methyl methacrylate
  • cHMA cyclohexyl methacrylate
  • HEMA-P methacryloyloxyethyl phosphate
  • GMAA methacrylic acid
  • the film formed with the emulsion polymer achieved a classification of about 1 on aluminium and about 1 on phosphated steel.
  • Example 1 was essentially repeated, but using a monomer mixture comprising 420 g of butyl acrylate (BA), 184.8 g of methyl methacrylate (MMA), 210 g of isobornyl methacrylate (IBOMA), 16.8 g of methacryloyloxyethyl phosphate (HEMA-P) and 8.4g of methacrylic acid (GMAA) rather than a mixture of 420 g of butyl acrylate (BA), 184.8 g of methyl methacrylate (MMA), 210 g of cyclohexyl methacrylate (cHMA), 16.8 g of methacryloyloxyethyl phosphate (HEMA-P) and 8.4 g of methacrylic acid (GMAA).
  • the film formed with the emulsion polymer achieved a classification of about 1 on aluminium and about 1 on phosphated steel.
  • MMA methacrylate
  • cHMA cyclohexyl methacrylate
  • HEMA-P methacryloyloxyethyl phosphate
  • GMAA methacrylic acid
  • AIBN Azobisisobutyronitrile
  • a 2 I glass reactor which had a water bath heating facility and was equipped with a blade stirrer was charged with 375 g of n-butanol and 375 g of toluene and heated to 90 0 C.
  • the first mixture prepared beforehand was metered in over the course of 240 minutes at nitrogen atmosphere.
  • the batch was stirred at 90 0 C for 0.5 hour. Thereafter the second mixture prepared beforehand was added into the reactor for the post-reaction. The batch was stirred at 90 0 C for further 2 hour. Thereafter a mixture of 35 g of n- butanol and 35 g of toluene was added and the batch was stirred at 90 0 C for 0.5 hour. It was cooled to room temperature and the solution resin was filled in a glass bottle.
  • the film formed with the solution polymer achieved a classification of about 1 on aluminium and about 1 on phosphated steel.
  • HEMA-P methacryloyloxyethyl phosphate
  • GMAA methacrylic acid
  • the film formed with the emulsion polymer achieved a classification of about 2 on aluminium and about 5 on phosphated steel.
  • Example 1 was essentially repeated, but using a monomer mixture comprising 420 g of butyl acrylate (BA), 184.8 g of methyl methacrylate (MMA), 210 g of cyclohexyl methacrylate (cHMA) and 25.2 g of methacrylic acid (GMAA) rather than the mixture mentioned in Example 1.
  • BA butyl acrylate
  • MMA methyl methacrylate
  • cHMA cyclohexyl methacrylate
  • GMAA methacrylic acid
  • the film formed with the emulsion polymer achieved a classification of about 5 on aluminium and about 1 on phosphated steel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un polymère acrylique destiné à une composition de revêtement, ledit polymère comprenant 10 % à 55 % en poids de motifs dérivés de monomères (méth)acrylates à teneur élevée en solides, 0,1 % à 10 % en poids de motifs dérivés de monomères (méth)acrylates phosphorés, et 35 % à 89,9 % en poids de motifs dérivés de comonomères, rapporté dans chaque cas au poids du polymère. De plus, l'invention décrit une composition de revêtement comprenant ledit polymère et un procédé de préparation de la composition de revêtement.
PCT/CN2009/000825 2009-07-23 2009-07-23 Polymères acryliques, compositions de revêtement et procédés de préparation associés WO2011009228A1 (fr)

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WO2014074854A1 (fr) * 2012-11-09 2014-05-15 Wang Tongxin Copolymères à blocs pour la protection de l'émail des dents
CN103881495A (zh) * 2014-01-09 2014-06-25 北京展辰化工有限公司 一种高固含水性清面漆及其制备方法
US9399708B2 (en) 2012-04-12 2016-07-26 Howard University Polylactide and calcium phosphate compositions and methods of making the same
JPWO2016121241A1 (ja) * 2015-01-28 2017-11-02 関西ペイント株式会社 水性塗料組成物
CN108641029A (zh) * 2018-04-19 2018-10-12 常州顺斯康复合新材料有限公司 一种金属防护用水性丙烯酸酯自干纳米乳液及其制备方法
US20190292399A1 (en) * 2016-06-03 2019-09-26 Dow Global Technologies Llc Aqueous polymer dispersion and aqueous coating composition comprising the same
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US9399708B2 (en) 2012-04-12 2016-07-26 Howard University Polylactide and calcium phosphate compositions and methods of making the same
US11267950B2 (en) 2012-04-12 2022-03-08 Howard University Polylactide and apatite compositions and methods of making the same
US10400083B2 (en) 2012-04-12 2019-09-03 Howard University Polylactide and apatite compositions and methods of making the same
CN105431465B (zh) * 2012-11-09 2018-04-27 高露洁-棕榄公司 用于牙釉质防护的嵌段共聚物
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US20150283061A1 (en) * 2012-11-09 2015-10-08 Tongxin Wang Block copolymers for tooth enamel protection
CN105431465A (zh) * 2012-11-09 2016-03-23 高露洁-棕榄公司 用于牙釉质防护的嵌段共聚物
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US10918588B2 (en) 2012-11-09 2021-02-16 Colgate-Palmolive Company Block copolymers for tooth enamel protection
CN103881495A (zh) * 2014-01-09 2014-06-25 北京展辰化工有限公司 一种高固含水性清面漆及其制备方法
JPWO2016121241A1 (ja) * 2015-01-28 2017-11-02 関西ペイント株式会社 水性塗料組成物
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EP3252118A4 (fr) * 2015-01-28 2018-07-04 Kansai Paint Co., Ltd Composition de revêtement aqueuse
US20190292399A1 (en) * 2016-06-03 2019-09-26 Dow Global Technologies Llc Aqueous polymer dispersion and aqueous coating composition comprising the same
EP3555217B1 (fr) 2016-12-19 2021-02-17 Celanese International Corporation Dispersions aqueuses acryliques présentant un contenu biorenouvelable élevé
CN108641029A (zh) * 2018-04-19 2018-10-12 常州顺斯康复合新材料有限公司 一种金属防护用水性丙烯酸酯自干纳米乳液及其制备方法

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