Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
  • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
  • C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
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  • 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
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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  • 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
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • 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
  • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
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  • 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
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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  • 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
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  • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

• the present invention relates to a (meth) acrylate monomer and a monomer mixture comprising a (meth) acrylate monomer.
• the present invention is directed to a polymer obtainable using this monomer or monomer mixture.
• the present invention relates to a coating agent.
• Coating agents in particular paints, have been produced synthetically for a long time.
• Many of these coating compositions are based on so-called alkyd resins, which are prepared using polybasic acids, alcohols and fatty acids and / or fatty acid derivatives.
• a particular group of these alkyd resins form crosslinked films upon exposure to oxygen, with crosslinking being by oxidation involving unsaturated groups.
• Many of these alkyd resins include organic solvents or dispersants to coat the resins in a thin layer on coating bodies.
• the use of these solvents should be omitted for reasons of environmental protection and occupational safety. Therefore, corresponding resins based on aqueous dispersions have been developed, but their storage stability is limited.
• the water absorption of many alkyd resins is too high or their solvent resistance and hardness is too low. Accordingly, attempts have been made to modify or replace the alkyd-based conventional paints set forth above.
• compositions comprising an alkyd resin modified with (meth) acrylate polymers, which is subsequently used in an emulsion polymerization.
• the preparation of the compositions described is carried out over several steps, so that the described resins are very expensive to produce.
• a solution polymer based coating composition based on vinyl monomers is described for example in DE-A-101 06 561.
• this composition comprises a high proportion of organic solvents.
• aqueous dispersions based on (meth) acrylate polymers are also known.
• the document DE-A-41 05 134 describes aqueous dispersions which can be used as binders in paints. The preparation of these binders, however, takes place over a plurality of stages, initially producing a solution polymer which is used after neutralization in an emulsion polymerization.
• DE-A-25 13 516 describes aqueous dispersions which comprise polymers based on (meth) acrylates, some of the (meth) acrylates being derived from unsaturated alcohol radicals.
• a disadvantage of the described dispersions is in particular their complicated preparation, wherein the polymers based on (meth) acrylates are obtained by solution polymerization. In this case, these polymers have a high proportion of acid groups, which is in the range of 5 to 20 wt .-%, based on the solution polymer.
• the document DE-A-26 38 544 describes oxidatively drying aqueous dispersions which comprise emulsion polymers based on (meth) acrylates, some of the (meth) acrylates used being derived from unsaturated alcohol radicals.
• chain transfer agents have been used to prepare the emulsion polymers so that the emulsion polymer shows high solubility.
• aqueous dispersions comprising oxidatively drying polymers are disclosed in F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation 30, 4551-4570 (1985)
• the polymers contain from 2 to 8% by weight of units derived from (meth) acrylates having unsaturated, long-chain alcohol radicals
• US Pat. No. 5,750,751 describes polymers based on vinyl monomers which can crosslink at room temperature.
• the polymers can be obtained both by solution polymerization and by emulsion polymerization.
• the monomer mixtures to be polymerized may include, inter alia, (meth) acrylates whose alcohol residues are modified by unsaturated fatty acids.
• the polymers obtained by solution and emulsion polymerization of modified (meth) acrylates show high solubility since chain transfer agents have been used.
• a disadvantage of the coating compositions described in US Pat. No. 5,750,751, however, is that softening solvents must be added which are to be avoided for reasons of environmental protection.
• document WO 2006/013061 describes dispersions comprising particles based on (meth) acrylates.
• the monomer mixtures used to prepare the particles include (meth) acrylates which are unsaturated by unsaturated fatty acids. were modified. However, the examples do not polymerize monomers comprising acid groups. Furthermore, the proportion of (meth) acrylates modified with unsaturated fatty acids is very high. Disadvantages of the dispersions described in WO 2006/013061 are, in particular, their complex preparation and the high proportion of residual monomers. Furthermore, the coatings obtained from the dispersions show a low stability against some solvents.
• dispersions are also known from the prior art which, in addition to polymers based on (meth) acrylates, may also comprise alkyd resins.
• document WO 98/22545 describes polymers with units derived from (meth) acrylates having unsaturated alcohol radicals. These polymers can be used together with alkyd resins.
• solvents are used to prepare paints from the described polymers.
• Aqueous dispersions are not described in WO 98/22545. Accordingly, these compositions suffer from the disadvantages set out above.
• Japanese Patent JP 59011376 describes emulsion polymers based on (meth) acrylates.
• the dispersions have a solids content of about 40% to a dynamic viscosity of at least 200 mPas.
• a particle size is not mentioned in this document. Due to the high viscosity of the dispersion, however, it can be assumed that the emulsion polymers have a particle size below 40 nm.
• a disadvantage of the dispersions described in this document is their low storage life. In addition, it has been found that the coatings obtained do not have sufficient stability for all requirements for elevated demands.
• (Meth) acrylate monomers which can be obtained by reacting 1,3-butadiene and (meth) acrylic acid are described, inter alia, in DE-A-19 43 453, US Pat. No. 3,562,314 and Baibulatova et al., Zhurnal Organicheskoi Khimii (1982), 18 (1), 46-52. However, no coating agents that can be obtained with these monomers are described. Instead, only applications in lubricants are presented. Furthermore, it is shown that the obtained (meth) acrylate monomers can be epoxidized.
• the monomers should be able to process into dispersions or to polymers, for example emulsion polymers, which have a very low residual monomer content.
• the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range.
• particularly hard, scratch-resistant coatings should be able to be obtained.
• a further object is to provide polymers, by the use of which coating compositions without volatile organic solvents are obtainable.
• the coatings obtainable from the coating compositions should have a high weather resistance, in particular a high UV resistance.
• the films obtainable from the coating compositions should have a low tackiness after a short time.
• the coatings obtainable from the polymers or monomer mixtures should have a particularly high resistance to solvents. This stability should be high compared to many different solvents.
• polymers it should be noted that they should have a small proportion of monomers which are complicated to prepare, while having the same performance.
• R 1 is hydrogen or a methyl group
• X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms
• R 2 is an alkylene group having 1 to 22 carbon atoms
• Y is oxygen, sulfur or a group of Formula NR ", wherein R" is hydrogen or a radical having 1 to 6 carbon atoms
• R 3 is an unsaturated radical having 8 carbon atoms and at least two double bonds.
• the monomer mixtures according to the invention can be processed into polymers, coating compositions and coatings which have a very low residual monomer content.
• the hardness of the coatings obtainable from coating compositions according to the invention can be varied over a wide range. According to a preferred modification, according to the invention, particularly particularly hard, scratch-resistant
• Coatings are obtained.
• the coatings obtainable from the coating compositions of the present invention show a surprisingly high solvent resistance, which is particularly evident in tests with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol. So show the coatings obtained in particular in experiments according to the furniture test DIN 68861 -1 excellent classification.
• MIBK methyl isobutyl ketone
• Coating agents obtainable using the monomer mixtures of the present invention generally do not require volatile organic solvents.
• the coating compositions of the invention show a high storage stability, a high durability and a very good shelf life. In particular, hardly any aggregate formation occurs.
• the coatings obtainable from the coating compositions of the invention show a high weather resistance, in particular a high UV resistance. Furthermore, the films obtainable from the coating compositions have a low tackiness after a short time.
• the monomers according to the invention, monomer mixtures, polymers and coating compositions can be produced inexpensively on a large scale.
• the polymers it should be noted that they can, with the same performance, have a smaller proportion of monomers which are complicated to prepare.
• the performance of the polymers results inter alia from the properties of the coating compositions and coatings obtainable therefrom.
• the coating compositions according to the invention are environmentally friendly and can be processed and produced safely and without great effort.
• the coating compositions of the invention show a very high shear stability.
• the (meth) acrylate monomer according to the invention corresponds to the general formula (I) wherein R 1 is hydrogen or a methyl group, X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 2 is an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of Formula NR ", wherein R" is hydrogen or a radical having 1 to 6 carbon atoms, and R 3 is an unsaturated radical having 8 carbon atoms and at least two double bonds.
• radical having 1 to 6 carbon atoms or “radical having 8 carbon atoms” represents a group having 1 to 6 or 8 carbon atoms. It includes aromatic and heteroaromatic groups and also alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups and heteroalipatic groups.
• the groups mentioned can be branched or unbranched. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxy groups.
• the radicals R ', R " are alkyl groups.
• the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert. butyl group.
• the radical R 2 is an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10, more preferably 2 to 6 carbon atoms.
• the radical R 2 represents an alkylene group having 2 to 4, more preferably 2 carbon atoms.
• the alkylene groups having 1 to 22 carbon atoms include in particular the methylene, Ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexyl groups, the ethylene group being particularly preferred.
• the radical R 3 comprises at least two C-C double bonds which are not part of an aromatic system.
• the radical R3 preferably represents a group with exactly 8 carbon atoms, which has exactly two double bonds.
• the radical R 3 preferably represents a linear hydrocarbon radical which has no heteroatoms.
• the radical R 3 in formula (I) may comprise a terminal double bond.
• the radical R 3 in formula (I) can not comprise a terminal double bond.
• the double bonds contained in the radical R 3 may preferably be conjugated. According to another preferred embodiment of the present invention, the double bonds contained in the radical R 3 are not conjugated.
• R 3 radicals which have at least double bonds are, inter alia, the octa-2,7-dienyl group, octa-3,7-dienyl group, octa-4,7-dienyl group, octa-5,7-dienyl group, Octa-2,4-dienyl group, octa-2,5-dienyl group, octa-2,6-dienyl group, octa-3,5-dienyl group, octa-3,6-dienyl group and octa-4,6-dienyl group.
• the preferred monomers according to formula (I) include, inter alia
• the (meth) acrylate mononers according to formula (I) can be used individually or as a mixture.
• the monomers of the formula (I) can have an iodine value in the range from 100 to 400 g of iodine / 100 g, more preferably in the range from 250 to 350 g of iodine / 100 g.
• the (meth) acrylate monomers of formula (I) can be obtained in particular by processes in which methacrylic acid, acrylic acid or a mixture thereof, hereinafter abbreviated as (meth) acrylic acid, or a (meth) acrylate, in particular methyl (meth) acrylate or Ethyl (meth) acrylate is reacted with an alcohol and / or an amine.
• the starting material to be reacted with the (meth) acrylic acid or the (meth) acrylate may advantageously correspond to the formula (II),
• HX-R-YR 3 (II), in which X is oxygen or a group of the formula NR ', in which R' is hydrogen or a radical having 1 to 6 carbon atoms, R 2 is an alkylene group having 1 to 22 carbon atoms, Y is oxygen, Sulfur or a group of the formula NR ", wherein R" is hydrogen or a radical having 1 to 6 carbon atoms, and R 3 is an at least double unsaturated radical having 8 carbon atoms.
• R ', R ", R 2 , Y and R 3 reference is made to the description of the formula (I).
• the preferred starting materials of the formula (II) include (methyl (octa-2,7-dienyl) amino) ethanol, (ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol, (methyl octa-2,7-dienyl) amino () ethylamine,
• the educts of formula (II) can be used individually or as a mixture.
• the starting materials of the formula (II) can be obtained inter alia by known methods of telomerizing 1,3-butadiene.
• telomerization means the reaction of compounds with conjugated double bonds in the presence of nucleophiles, filed in the publications WO 2004/002931 on 17.06.2003 at the European Patent Office with the application number
• the telomerization of 1, 3-butadiene using metal compounds comprising metals of the 8th to 10th group of the Periodic Table of the Elements can be carried out as a catalyst, wherein palladium compounds, in particular palladium-carbene complexes, which set forth in detail in the above-mentioned documents are, can be used with particular preference.
• nucleophiles are dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol; Diamines, such as ethylenediamine, N-methyl-ethylenediamine, N 1 N '
• Dimethylethylenediamine or hexamethylenediamine or aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
• aminoalkanols such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
• the temperature at which the telomerization reaction is carried out is between 10 and 180 ° C., preferably between 30 and 120 ° C., more preferably between 40 and 100 ° C.
• the reaction pressure is 1 to 300 bar, preferably 1 to 120 bar, especially preferably 1 to 64 bar and most preferably 1 to 20 bar.
• the monomer of the formula (I) set out above can advantageously be used in a monomer mixture which has one or more monomers which are copolymerizable with the monomer of the formula (I).
• a monomer mixture which comprises at least 2, preferably at least 5,% and more preferably at least 10% by weight of monomers of the formula (I) on the total weight of the monomer mixture.
• the monomer mixture comprises at least one further monomer which is copolymerisable.
• copolymerizable monomers include monomers having an acid group, monomers A comprising ester groups other than the monomers of formula I, and styrenic monomers.
• Acid group-containing monomers are compounds which can preferably be radically copolymerized with the above-described (meth) acrylate monomers of the formula (I). These include, for example, monomers having a sulfonic acid group, such as vinylsulfonic acid; Monomers having a phosphonic acid group, such as vinylphosphonic acid and unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, fumaric acid and maleic acid. Particularly preferred are methacrylic acid and acrylic acid.
• the Acid group-containing monomers can be used individually or as a mixture of two, three or more acid group-containing monomers.
• the preferred ester groups comprising monomers A include, in particular, (meth) acrylates which differ from the monomers of the formula (I), fumarates, maleates and / or vinyl acetate.
• (meth) acrylates include methacrylates and acrylates and mixtures thereof. These monomers are well known.
• (meth) acrylates having 1 to 6 carbons in the alkyl radical which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate , n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate; and (meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
• saturated alcohols such as methyl (meth) acrylate, ethyl
• mixtures for the preparation of polymers which comprise methacrylates and acrylates are particularly preferred.
• mixtures of methyl methacrylate and acrylates having 2 to 6 carbon atoms such as ethyl acrylate, butyl acrylate and hexyl acrylate.
• the comonomers include, for example, (meth) acrylates having at least 7 carbon atoms in the alkyl radical which are derived from saturated alcohols, for example 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadec
• monomers A comprising ester groups include vinyl esters such as vinyl acetate;
• Maleic acid derivatives such as, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride; and fumaric acid derivatives such as dimethyl fumarate.
• styrenic monomers such as styrene, substituted styrenes having an alkyl substituent in the side chain, e.g. For example, ⁇ -methylstyrene and ⁇ -ethyl styrene, substituted styrenes with a Alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
• styrenic monomers such as styrene, substituted styrenes having an alkyl substituent in the side chain, e.g. For example, ⁇ -methylstyrene and ⁇ -ethyl styrene, substituted styrenes with a Alkyl substituents on the ring such as vinyltoluene and
• polymers according to the invention which are obtained by the polymerization of monomer mixtures may comprise further monomers.
• monomers include, 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,
• Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride.
• Preferred monomer mixtures of the present invention comprise from 0.1 to 90% by weight, preferably from 0.5 to 30% by weight of (meth) acrylate monomer of the formula
• (I) From 10 to 90% by weight, preferably from 40 to 85% by weight, of monomers with ester groups A; 0 to 10 wt .-%, preferably 1 to 8 wt .-% monomer having an acid group, 0 to 50 wt .-%, preferably 0 to 30 wt .-% of styrene monomers and 0 to 50 wt .-%, preferably 0 to 30 %
• the data referring in each case to the total weight of the monomers.
• the present invention provides coating compositions which can be produced particularly inexpensively, since they can have a relatively low proportion of expensive monomers, without the properties of the coatings obtainable from the polymers or coating compositions being adversely affected.
• These mixtures preferably comprise
• the polymers obtainable thereby are new and therefore also subject of the present invention.
• the polymers of the invention comprise at least one unit derived from a (meth) acrylate monomer of the general formula (I).
• the monomers according to the invention can be reacted by free radical polymerization.
• the term "unit" results from the reaction of a double bond to form two covalent bonds, and these units are also commonly referred to as repeat units if two or more of these units are contained in a polymer.
• the abovementioned monomers or monomer mixtures can be reacted, for example, by solution polymerizations, bulk polymerizations or emulsion polymerizations, it being possible to achieve surprising advantages by free-radical emulsion polymerization.
• an aqueous phase is prepared for this purpose, which may comprise, in addition to water, customary additives, in particular emulsifiers and protective colloids, for stabilizing the emulsion.
• Monomers are then added to this aqueous phase and polymerized in the aqueous phase.
• a monomer mixture can be added continuously or batchwise over a time interval.
• the emulsion polymerization can be carried out, for example, as a miniemulsion or as a microemulsion, described in greater detail in Chemistry and Technology of Emulsion Polymerization, A.M. van Herk (editor), Blackwell Publishing, Oxford 2005, and J. O'Donnell, E.W. Kaier, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454.
• a miniemulsion is customary characterized by the use of costabilizers or swelling agents, many of which use long-chain alkanes or alkanols.
• the droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns.
• microemulsions are preferably in the range below 1 .mu.m, whereby particles below a size of 50 nm can thereby be obtained.
• Microemulsions often use additional surfactants, for example hexanol or similar compounds.
• the dispersing of the monomer-containing phase in the aqueous phase can be carried out by known means. These include, in particular, mechanical methods and the use of ultrasound.
• a monomer mixture which comprises from 5 to 50% by weight, particularly preferably from 10 to 40% by weight, of the (meth) acrylate monomer of the formula (I).
• the composition of the monomer mixture may be changed stepwise, prior to modification of the Composition, the polymerization is preferably up to a conversion of at least 80 wt .-%, more preferably at least 95 wt .-%, in each case based on the total weight of the monomer mixture used, polymehsiert.
• Core-shell polymer here stands for a polymer which has been prepared by a two-stage or multi-stage emulsion polymerization, without the core-shell structure being shown, for example, by electron microscopy.
• the tracking of the progress of the polymerization in each step may be carried out in a known manner, for example gravimetrically or by gas chromatography.
• the monomer composition for producing the core preferably comprises from 50 to 100% by weight of (meth) acrylates, with a mixture of acrylates and methacrylates being particularly preferably used.
• a monomer mixture which comprises 10 to 50% by weight, particularly preferably 15 to 40% by weight, of (meth) acrylate monomer of the formula (I) may preferably be grafted onto it or polymerized onto the core.
• the emulsion polymerization is preferably carried out at a temperature in the range from 0 to 120 ° C., more preferably in the range from 30 to 100 ° C.
• polymerization temperatures in the range from greater than 60 to less than 90 ° C., expediently 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., have proven to be particularly favorable.
• Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide.
• Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, in particular ammonium, sodium and potassium peroxodisulfate.
• Suitable redox initiator systems are, for example, combinations of ter- tiary amines with peroxides or Nathumdisulfit and alkali metal and the ammonium salts of peroxodisulfuric, especially sodium and potassium peroxodisulfate.
• the initiators mentioned can be used both individually and as a mixture. They are preferably used in an amount of 0.05 to 3.0 wt .-%, based on the total weight of the monomers of each stage. It is also possible with preference to carry out the polymerization with a mixture of different polymerization initiators having a different half-life in order to keep the free radical stream constant during the polymerization and at different polymerization temperatures.
• the stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids.
• the emulsion is stabilized by emulsifiers to obtain a low dispersion viscosity.
• the total amount of emulsifier is preferably 0.1 to 15 wt .-%, in particular 1 to 10 wt .-% and particularly preferably 2 to 5 wt .-%, based on the total weight of the monomers used.
• a part of the emulsifiers may be added during the polymerization.
• Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular Alkyl sulfates, preferably those having 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units; Sulfonates, preferably alkyl sulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylaryl sulfonates having 8 to 18 carbon atoms in the alkyl radical, esters and
• Alkylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units
• Alkylarylpolyglykolether 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, desirably with 8 to 40 ethylene oxide or propylene oxide units, respectively.
• the particularly preferred anionic emulsifiers include, in particular, fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15 paraffin sulfonate, these compounds generally being usable as alkali metal salt, in particular as sodium salt.
• These compounds can be commercially obtained in particular under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG.
• Suitable nonionic emulsifiers include tert-Octylphenolethoxylat with 30 ethylene oxide units and fatty alcohol polyethylene glycol, preferably 8 bis 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units. These emulsifiers are commercially available under the trade names Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® O 13/400 (Sasol Germany) available.
• the weight ratio of anionic emulsifier to nonionic emulsifier in the range of 20: 1 to 1: 20, preferably 2: 1 to 1: 10 and more preferably 1: 1 to 1: 5 are.
• mixtures containing a sulfate in particular a Fettal koholethersulfat, a lauryl sulfate, or a sulfonate, especially a Diisooctylsulfosuccinat or a Paraffinsulfonat as anionic emulsifier and an alkylphenol ethoxylate or a Fettalkoholpolyethylenglykolether, each preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 Ethylene oxide units have proven to be particularly suitable as a nonionic emulsifier.
• a sulfate in particular a Fettal koholethersulfat, a lauryl sulfate, or a sulfonate
• a sulfonate especially a Diisooctylsulfosuccinat or a Paraffinsulfonat as anionic emulsifier and an alkylphenol
• the emulsifiers can also be used in admixture with protective colloids.
• Suitable protective colloids include partially saponified polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene-maleic acid and vinyl ether maleic acid copolymers.
• protective colloids are used, this is preferably carried out in an amount of 0.01 to 1, 0 wt .-%, based on the total amount of the monomers.
• the protective colloids can be initially charged or added before the start of the polymerization.
• the initiator can be initially charged or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.
• the polymerization is preferably started by heating the batch to the polymerization temperature and initially and / or adding the initiator, preferably in aqueous solution. In this case, a part of the monomers can be initially charged in the reactor and the remainder added over a certain period of time.
• the feed can be interrupted for a few minutes after, for example, 1 to 5% of the monomers have been added.
• the dosages of emulsifier and monomers can be carried out separately or preferably as a mixture, in particular as an emulsion in water.
• Preferred emulsion polymers having a high content of polymers which are insoluble in THF can be obtained in the manner set forth above, the reaction parameters for obtaining a high molecular weight being known.
• the use of molecular weight regulators can be dispensed with.
• Polymers, especially high molecular weight emulsion polymers, result in particularly hard and solvent resistant paints.
• Paints that are particularly easy and easy to process can also have polymers with a lower molecular weight, the solvent resistance and the hardness of these coatings reaching a relatively high level.
• these polymers having a particularly good processability, a molecular weight below 250 000 g / mol, preferably below 150 000 g / mol and more preferably below 100 000 g / mol.
• the molecular weight can be determined by means of gel permeation chromatography (GPC) against a PMMA standard.
• Low molecular weight polymers especially low molecular weight emulsion polymers, can be prepared by adding molecular weight regulators to the reaction mixture or during the polymerization. Sulfur-free molecular weight regulators and / or sulfur-containing molecular weight regulators can be used for this purpose.
• the sulfur-free molecular weight regulators include, but are not limited to, dimeric ⁇ -methylstyrene (2,4-diphenyl-4-methyl-1-pentene), enol ethers of aliphatic and / or cycloaliphatic aldehydes, terpenes, ⁇ -terpinene, Terpinolene, 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1, 4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6-dihydro-2H-pyran, is preferred dimeric ⁇ -methylstyrene.
• the sulfur-containing molecular weight regulators used may preferably be mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
• the following polymerization regulators are exemplified: di-n-butylsulfide, di-n-octylsulfide, diphenylsulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide and dimethyl sulfoxide.
• Preferred compounds used as molecular weight regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, 2-ethylhexyl thioglycolate, cysteine, 2-mercaptoethanol, 1-mercaptopropan-3-ol, 3-mercaptopropane-1, 2-diol, 1-mercaptobutan-4-ol, mercaptoacetic acid, 3-mercaptopropionic acid, mercapto - succinic acid, thioglycerol, thioacetic acid, thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan. Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.
• the molecular weight regulators are preferably used in amounts of from 0.05 to 10, particularly preferably 0.1 to 5,% by weight, based on the amount used in the polymerization Monomers used. Of course, mixtures of polymerization regulators can also be used in the polymerization.
• the adjustment of the particle radii can be influenced inter alia by the proportion of emulsifiers. The higher this proportion, especially at the beginning of the polymerization, the smaller the particles are obtained.
• polymers obtainable by the process described above in particular the emulsion polymers which are preferably obtainable, form a further subject of the present invention.
• the emulsion polymer may have a content of from 2 to 60% by weight, more preferably from 10 to 50% by weight and most preferably from 20 to 40% by weight, based on the weight of the emulsion polymer dissolved in tetrahydrofuran (THF). at 20 0 C is soluble.
• THF tetrahydrofuran
• a sample of the polymer dried under exclusion of oxygen is stored in a 200-fold amount of solvent, based on the weight of the sample, at 20 ° C. for 4 hours.
• the sample can be dried, for example under nitrogen or under vacuum.
• the solution is separated from the insoluble fraction, for example by filtration. After evaporation of the solvent, the weight of the residue is determined.
• a 0.5 g sample of a vacuum-dried emulsion polymer can be stored in 150 ml of THF for 4 hours.
• an emulsion polymer may have a swelling of at least 800%, more preferably at least 1200%, and most preferably at least 1300% in tetrahydrofuran (THF) at 20 ° C.
• the upper limit of the swelling is not critical per se, with the swelling is preferably at most 5000%, more preferably at most 3000%, and most preferably at most 2500%.
• a dried under exclusion of oxygen sample of the emulsion polymer is stored at 20 0 C for 4 hours in a 200-fold amount of THF. As a result, the sample swells up. The swollen sample is separated from the supernatant solvent. Subsequently, the solvent is removed from the sample.
• the particle radius of the emulsion polymers can be in a wide range.
• emulsion polymers having a particle radius in the range of 10 to 500 nm, preferably 10 to 100 nm, particularly preferably 20 to 60 nm can be used.
• particle radii below 50 nm may be advantageous for film formation and coating properties.
• the radius of the particles can be determined by PCS (Photon Correlation Spectroscopy), with the data given refer to the d50 value (50% of the particles are smaller, 50% are larger).
• PCS Photon Correlation Spectroscopy
• a Beckman Coulter N5 Submicron Particle Size Analyzer may be used.
• the glass transition temperature of the polymer according to the invention is preferably in the range from -30 0 C to 70 0 C, more preferably in the range of -20 to 40 ° C and most preferably in the range of 0 to 25 ° C.
• the glass transition temperature can be determined by the nature and the proportion of the polymer used for the preparation of the polymer. be influenced.
• the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC).
• DSC differential scanning calorimetry
• the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. After Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
• Tg Tg 1 Tg Tg n 2 wherein X n is the mass fraction designated n (wt .-% / 100) of monomer n and Tg n is the glass transition temperature in Kelvin of the homopolymer of the monomer. Further helpful information can be found by the person skilled in the art in Polymer Handbook 2 nd Edition, J. Wiley & Sons, New York (1975), which indicates Tg values for the most common homopolymers. In this case, the polymer may have one or more different glass transition temperatures. These data therefore apply to a segment obtainable by polymerization of at least one (meth) acrylate monomer according to formula (I), preferably a monomer mixture according to the invention.
• the architecture of the polymer is not critical to many applications and properties. Accordingly, the polymers, in particular the emulsion polymers, can represent random copolymers, gradient copolymers, block copolymers and / or graft copolymers. Block copolymers or gradient copolymers can be obtained, for example, by discontinuously changing the monomer composition during chain growth. According to a preferred aspect of the present invention, the emulsion polymer is a random copolymer in which the monomer composition is substantially constant throughout the polymerization. However, since the monomers may have different copolymerization parameters, the exact composition may vary across the polymer chain of the polymer.
• the polymer may be a homogeneous polymer which, for example, forms particles with a constant composition in an aqueous dispersion.
• the polymer which is preferably an emulsion polymer, may consist of one or more segments obtainable by polymerization of at least one (meth) acrylate monomer according to formula (I), preferably a monomer mixture according to the invention.
• the emulsion polymer may be a core-shell polymer which may have one, two, three, or more shells.
• the segment which is obtainable by polymerization of the monomer mixture according to the invention or the (meth) acrylate monomer according to formula (I) preferably forms the outermost shell of the core-shell polymer.
• the shell may be connected to the core or inner shells via covalent bonds.
• the shell can also be polymerized on the core or an inner shell.
• the segment, which is obtainable inter alia by polymerization of the monomer mixture according to the invention can often be separated from the core by suitable solvents and isolated.
• the weight ratio of segment obtainable by polymerization of the monomer mixture according to the invention or of the (meth) acrylate monomer according to formula (I) to core can be in the range from 6: 1 to 1: 6.
• a ratio of 6: 1 to 2: 1, in the opposite case of 1: 1 to 1: 5, is particularly preferred.
• the core may preferably be formed from polymers comprising from 50 to 100% by weight, preferably from 60 to 90% by weight, of units derived from (meth) acrylates. Preference is given here to esters of (meth) acrylic acid whose alcohol radical is preferably 1 to 30 carbon atoms, more preferably 1 to 20 Carbon atoms, and most preferably 1 to 10 carbon atoms.
• (meth) acrylates which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate.
• saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate.
• a mixture comprising methacrylates and acrylates can be used to produce the core.
• methacrylates and acrylates having 2 to 6 carbons, such as ethyl acrylate, butyl acrylate and hexyl acrylate can be used.
• the polymers of the core may include the comonomers set forth above.
• the core may be crosslinked. This crosslinking can be achieved by using monomers having two, three or more radically polymerizable double bonds.
• the shell of an emulsion polymer of the present invention obtainable by polymerization of a monomer mixture of the present invention may preferably comprise 15 to 50% by weight of units derived from (meth) acrylate monomers of the formula (I).
• the core may preferably have a glass transition temperature in the range from -30 to 200 ° C., in particular in the range from -20 to 150 ° C. Particularly preferred is a glass transition temperature of> 50 0 C, in particular> 100 0 C.
• the shell of the emulsion polymer according to the invention which is preferably obtainable by polymerization of the monomer mixture according to the invention, preferably a glass transition temperature in the range of -30 0 C to 70 0 C. more preferably in the range of -20 to 40 ° C, and most preferably in Range from 0 to 25 0 C.
• the glass transition temperature of the core may be greater than the glass transition temperature of the shell.
• the glass transition temperature of the core at least 10 0 C, preferably at least 20 0 C. above the glass transition temperature of the shell.
• the iodine value of the polymers according to the invention is preferably in the range from 1 to 300 g of iodine per 100 g of polymer, more preferably in the range from 2 to 270 g of iodine per 100 g of polymer and very particularly preferably 5 to 250 g of iodine per 100 g of polymer. Measure according to DIN 53241 -1.
• the iodine number can in particular also be measured by means of a dispersion according to the invention.
• the polymer may have an acid number in the range of 0 to 50 mg KOH / g, preferably 0.1 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g exhibit.
• the acid number can also be determined by dispersion according to DIN EN ISO 2114.
• the hydroxyl number of the polymer may preferably be in the range from 0 to 200 mg KOH / g, more preferably 1 to 100 mg KOH / g and most preferably in the range from 3 to 50 mg KOH / g.
• the hydroxyl number can also be determined by dispersion according to DIN EN ISO 4629.
• the polymers obtainable by polymerization of (meth) acrylate monomers according to formula (I) or a monomer mixture according to the invention can be isolated.
• the dispersions obtainable by emulsion polymerization can be used as such as a coating agent.
• Coating compositions comprising the aforementioned polymers or compounds obtainable by reactions with the (meth) acrylate monomers set forth above are also provided by the present invention.
• Coating agents are compositions suitable for coating substrates.
• the coating compositions of the invention are oxidatively crosslinkable, so that crosslinked films are formed under the action of oxygen from the coating compositions, which in many cases have high solvent resistance.
• coating compositions comprising polymers set out above
• coating compositions based on alkyd resins which have been modified with the (meth) acrylate monomers or the monomer mixtures according to the invention may also be used successfully.
• modification is to be understood here comprehensively so that it is to be understood as meaning alkyd resins which have one or more units or repeating units derived from the (meth) acrylate monomers according to formula (I)
• modification Also alkyd resins or alkyd resin dispersions comprising the polymers set forth above.
• Alkyd resins have long been known, and are generally understood to mean resins obtained by condensation of polybasic carboxylic acids and polyhydric alcohols, these compounds generally having long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds, for example fats or oils are modified (DIN 55945, 1968).
• Alkyd resins are set forth, for example, in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM. In addition to these classic alkyd resins and resins can be used, which have similar properties.
• These resins are also characterized by a high content of groups of long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing Compounds, such as fats or oils derived. However, these derivatives do not necessarily have polybasic carboxylic acids but can be obtained, for example, by reacting polyols with isocyanates.
• the usable alkyd resins may preferably be mixed or diluted with water.
• Preferred polybasic carboxylic acids for preparing the alkyd resins preferably to be used in the dispersion according to the invention include dicarboxylic and tricarboxylic acids such as phthalic acid, isophthalic acid, 5- (sodium sulfo) isophthalic acid, terephthalic acid, trimellitic acid, 1,4-cyclohexanedicarboxylic acid,
• Butanedioic, maleic, fumaric, sebacic, adipic and azelaic acids can also be used as anhydrides for the production.
• aromatic dicarboxylic acids for the preparation of the alkyd resins.
• the proportion of polybasic carboxylic acids is preferably in the range of 2 to 50 wt .-%, particularly preferably 5 to 40 wt .-%, based on the weight of the starting materials used in the reaction mixture for the preparation of the resin.
• polyhydric alcohols are used to prepare the alkyd resins. These alcohols include trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, neopentyl glycol, ethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexyldimethanol, diethylene glycol, triethylene glycol, polyethylene glycol, Polytetrahydrofuran, polycaprolactone diol, polycaprolactone triol, trimethylol monoallyl ether, trimethylol diallyl ether, pentaerythritol triallyl ether, pentaerythritol diallyl ether, pentaerythritol monoallyl ether, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 2-methyl 1,3-propan
• propane hydrogenated bisphenol A
• propylene glycol dipropylene glycol
• polypropylene glycol polypropylene glycol
• glycerol glycerol
• sorbitol 2,2,4-trimethylpentanediol, 2,2,4-thymethyl-1,3-pentanediol, 2,2'-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A)
• propylene glycol dipropylene glycol
• polypropylene glycol polypropylene glycol
• glycerol glycerol
• sorbitol trimethylole
• fatty acids in particular can be used to prepare the alkyd resins set forth above.
• saturated and unsaturated fatty acids can be used, with particular preference being given to mixtures which contain unsaturated fatty acids.
• Preferred fatty acids have 6 to 30, more preferably 10 to 26 and most preferably 12 to 22 carbon atoms.
• the proportion of fatty acids is preferably in the range from 2 to 90% by weight, particularly preferably 10 to 70% by weight, based on the weight of the educts used in the reaction mixture for the preparation of the resin.
• Suitable saturated fatty acids include, but are not limited to, caprylic, capric, lauric, myristic, palmitic, margaric, arachidic, behenic, lignoceric, cerotic, palmitoleic and stearic acids.
• the preferred unsaturated fatty acids include, among others, undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and / or cervonic acid.
• the fatty acids set forth above can also be used in the form of their esters, for example in the form of triglycerides.
• the alkyd resins set forth above may contain other components. These include, for example, monohydric carboxylic acids, monohydric alcohols or compounds which lead to emulsifying groups in the resins, such as polyethylene oxides.
• the alkyd resins may contain hydroxycarboxylic acids, such as, for example, 2-, 3-, 4-hydroxybenzoic acid, ricinoleic acid, dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2- Dimethylol butyric acid and 2,2-Dimenthylolpentanklare.
• hydroxycarboxylic acids such as, for example, 2-, 3-, 4-hydroxybenzoic acid, ricinoleic acid, dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2- Dimethylol butyric acid and 2,2-Dimenthylolpentanklare.
• modified alkyd resins which have been modified with resins, in particular rosin, with styrene polymers, with acrylic polymers, with epoxides, with urethanes, with polyamides and / or with silicones.
• resins in particular rosin, with styrene polymers, with acrylic polymers, with epoxides, with urethanes, with polyamides and / or with silicones.
• alkyd resins modified with polymers obtainable by radical polymerization are known inter alia from the publications US 5,538,760, US 6,369,135 and DE-A-199 57 161.
• the resins set forth in US Pat. No. 5,538,760 filed May 22, 1995 in the United States Patent Office (USPTO) No. 446,130 are incorporated herein for purposes of disclosure.
• the resins set forth in US Pat. No. 6,369,135 B1 filed Aug. 13, 1996 with the United States Patent Office (USPTO) Serial No. 08 / 696,361 are incorporated herein for purposes of disclosure.
• the document DE-A-199 57 161 ranges on 27.11.99 at the German Patent and Trademark Office with the application number DE 19957161.9 set forth resins are included for purposes of disclosure in the present application.
• modified alkyd resins can be obtained, inter alia, by polymerizing a monomer mixture in the presence of an AI kyd resin.
• the weight ratio of monomer mixture to alkyd resin is preferably in the range from 100: 1 to 1: 4, preferably 5: 1 to 1: 1.
• alkyd resins are inter alia the acrylate-modified alkyd resins described in DE-A-199 57 161. These alkyd resins have, besides an alkyd core, groups obtained by polymerization of (meth) acrylates.
• acrylate-modified alkyd resins can be prepared by reacting in the presence of at least one water-miscible diol
• At least one alkyd resin which, based on its total amount, contains 0.1 to 10% by weight of pendant and / or terminal allyloxy groups, dispersed in water, resulting in the dispersion 1, (2) a mixture of methacrylic acid and at least a further carboxylic acid group-free olefinically unsaturated monomer in the dispersion 1 graft-polymerized, whereby the dispersion 2 results, and (3) once or n times (3.1) at least one acid group-free olefinically unsaturated monomer and / or (3.2) at least one mixture at least one acid group-containing olefinically unsaturated monomer and at least one acid group-free olefinically unsaturated monomer in the from step 2 (2) or (2) to (n-1) resulting dispersion 2 or 2 to n-1 graft copolymerized, with the proviso that in process step (3) or its repeats (3) to (n) acid groups are incorporated in an amount which corresponds to at most 90 MoI
• the lateral and / or terminal allyloxy groups set forth above may be present in the alkyd resin in an amount of from 0.1 to 10, preferably from 0.2 to 9, preferably from 0.3 to 8, more preferably 0.4, based on the alkyd resin to 7, very particularly preferably 0.5 to 6 and in particular 0.6 to 5% by weight.
• the oxygen atom of the allyloxy group can be part of a urethane group, an ester group or an ether group which connects the allyl radical to the main chain of the alkyd resin.
• Suitable compounds for introducing lateral and / or terminal allyloxy groups are allyl alcohol, 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, trimethylolpropane mono- or diallyl ether, glycerol mono- or diallyl ether, pentaerythritol mono-, di- or triallyl ether, mannitol mono-, di -, -trioder tetraallylether, dihydroxypropionic acid, Dihydroxybernsteinklakla-, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid or 2,2-Dimethylolpentanklaallylester or allyl urethane, of which trimethylolpropane monoallyl ether of Advantage is.
• the dispersion 1 can be graft copolymerized in a stage (2) with methacrylic acid and at least one further olefinically unsaturated monomer.
• the other olefinically unsaturated monomers may contain, in addition to the olefinically unsaturated double bonds, reactive functional groups, with the exception of carboxyl groups, for example isocyanate-reactive, carbamate-reactive, N-methylol or N-methylol ether reactive or alkoxycarbonylaminoreactive groups. It is essential in this case that these reactive functional groups under the given reaction conditions and the subsequent storage of Dispersi invention onen reactions with the carboxyl groups of methacrylic acid or with other optionally present reactive functional groups.
• hydroxyl group An example of reactive functional groups that meet these requirements is the hydroxyl group.
• These monomers are known per se, examples being given in DE 199 57 161. These include in particular hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acids, esters of acrylic acid, methacrylic acid, crotonic acid or ethacrylic acid having up to 20 carbon atoms in the alkyl radical.
• alkyd resins which are obtainable according to the document US Pat. No. 5,096,959 are preferred.
• the resins set forth in US Pat. No. 5,096,959 B1 filed Oct. 30, 1990 in the United States Patent Office (USPTO) No. 609,024 are incorporated herein for purposes of disclosure.
• These alkyd resins are modified by cycloaliphatic polycarboxylic acid, with cyclohexanedicarboxylic acids and cyclopentanedicarboxylic acids being particularly suitable for the modification.
• alkyd resins modified with polyethylene glycol can be used.
• a large number of patents describe the preparation of water-emulsifiable alkyd resins by modification with polyethylene glycol (PEG).
• PEG polyethylene glycol
• Preferred alkyd resins modified with polyethylene glycol are known inter alia from the document EP-AO 029 145.
• the in EP-AO 029,145 filed 30/10/80 at the European Patent Office with the application number EP 80106672.1 are incorporated in the present application for the purposes of disclosure.
• a polyethylene glycol can first be reacted with epoxide-containing carboxylic acid.
• the reaction product thus obtained can then be used in the reaction mixture for the preparation of the alkyd resin.
• Preferred polyethylene glycols for modifying the alkyd resins have, for example, a number average molecular weight of 500 to 5000 g / mol.
• Particularly preferred alkyd resins modified with polyethylene glycol can be further modified with copolymers obtainable by polymerization of methacrylic acid, unsaturated fatty acids and vinyl and / or vinylidene compounds.
• alkyd resins modified with urethane groups are disclosed inter alia in WO 2006/09221 1 and EP-A-1 533 342.
• the urethane-alkyd resins described in EP-A-1 533 342 can be used which contain building blocks which contain cycloaliphatic dicarboxylic acids from unsaturated fatty acids A1, aliphatic or aromatic or aromatic-aliphatic monocarboxylic acids A2 which are free from olefinic double bonds A3 or their anhydrides, at least trivalent, preferably at least tetrahydric alcohols A4, and aromatic or aliphatic polyfunctional, in particular difunctional isocyanates A5 are derived.
• the urethane-alkyd resin is preferably prepared in a two-stage reaction, the components A1 to A4 being esterified in the first stage, the acid number of the first-stage product preferably being at most 10 mg / g, particularly preferably times 5 mg / g.
• the hydroxyl-containing product of the first stage is reacted with the addition of a small amount (up to 1% of the mass of the first stage product, preferably up to 0.5% of its mass) of a tertiary amine with the isocyanate A5. under molecular enlargement.
• Preferred urethane alkyd resins have a Staudinger index, measured in chloroform at 23 0 C of at least 9 cm 3 / g, preferably at least 11 cm 3 / g.
• urethane-alkyd resins obtainable by reacting polyhydric alcohols A ', modified fatty acids B', fatty acids C, and polyfunctional isocyanates D '.
• the modified fatty acids B ' can be prepared by reacting unsaturated fatty acids B1' with unsaturated carboxylic acids B2 '.
• These urethane alkyds are known inter alia from WO 2006/092211.
• the resins set out in document WO 2006/092211 filed on 20.02.06 at the European Patent Office with the application number PCT / EP2006 / 001503 are incorporated in the present application for the purposes of disclosure.
• the modified fatty acid B ' preferably has an acid number of at least 80 mg / g.
• the increase in the acid number by the grafting is in the range from 80 mg / g to 250 mg / g and most preferably in the range from 100 mg / g to 150 mg / g, the acid value according to DIN EN ISO 2114 can be determined .
• the iodine value of the fatty acids C used to prepare the urethane alkyd resins is preferably at least 80 g / 100 g and preferably at least 120 g / 100 g.
• the components A ', B' and C are generally first reacted, the condensate preferably having a hydroxy functionality of at least 1.9, more preferably has at least 2.
• the condensate may have groups derived from polybasic carboxylic acids, especially the di- and tricarboxylic acids set forth above. This condensate is then reacted with a polyvalent isocyanate.
• the preferred polyfunctional isocyanates include, among others, 2,4- and 2,6-toluene diisocyanate and their technical mixtures, bis (4-isocyanatophenyl) methane, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane and 1,6-di -isocyanatohexane, and derived from these isocyanurates, allophanes and biurets.
• alkyd resins for the preparation of which polycarboxylic acids are generally used, it is also possible to use further alkyd resins, as already stated above.
• these alkyd resins include in particular alkyd resins based on urethanes.
• These urethane-alkyd resins can be obtained, for example, by reacting polyhydric alcohols with polyvalent isocyanates.
• Preferred urethane resins are known, for example, from EP-A-1 129 147. These can be obtained, for example, by reacting amide ester diols with polyols and polyfunctional isocyanates.
• Amidesterdiole can be obtained by reacting vegetable oils with N 1 N- dialkanolamines.
• the alkyd resin may have an iodine value according to DIN 53241 of at least 1 g of iodine / 100 g, preferably of at least 10 g of iodine / 100 g, more preferably of at least 15 g of iodine / 100 g.
• the iodine value of the alkyd resin may range from 2 to 100 g of iodine per 100 g of alkyd resin, more preferably 15 to 50 g of iodine per 100 g of alkyd resin.
• the iodine value can be determined by means of a dispersion, the value relating to the solids content.
• the alkyd resin may have an acid number in the range of 0.1 to 100 mg KOH / g, preferably 1 to 40 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g.
• the acid value can be determined in accordance with DIN EN ISO 2114 using a dispersion, the value relating to the solids content.
• the hydroxyl number of the alkyd resin may preferably be in the range of 0 to 400 mg KOH / g, more preferably 1 to 200 mg KOH / g, and most preferably in the range of 3 to 150 mg KOH / g.
• the hydroxyl number can be determined in accordance with DIN EN ISO 4629 using a dispersion, the value relating to the solids content.
• the alkyd resins set forth above without modification, but can be used together with polymers of the invention.
• this can preferably be achieved by polymerization of a (meth) acrylate monomer of the formula (I) or of a monomer mixture according to the invention, it being possible to obtain helpful information with regard to the reaction procedure, inter alia, from document EP-A-0 083 137 in the publication EP-AO 083 137, filed on 21.12.1987 at the European Patent Office with the application number 82201642.4 and reaction conditions alkyd resins are incorporated into the present application for the purposes of disclosure.
• the coating composition preferably comprises only small amounts of environmentally hazardous solvents, with aqueous dispersions being particularly preferred coating compositions.
• the aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight.
• the dynamic viscosity of the dispersion is dependent on the solids content and the particle size and can cover a wide range. For example, with finely divided dispersions with a high polymer content, it may in some cases be more than 10,000 mPas.
• aqueous dispersions according to the invention can be provided in a known manner with additives or further components in order to adapt the properties of the coating agent to specific requirements.
• additives include in particular drying aids, so-called siccatives, flow improvers, pigments and dyes.
• the coating compositions of the invention have a minimum film-forming temperature of at most 50 0 C, more preferably at most 35 ° C and most preferably at most 25 ° C, which can be measured according to DIN ISO 2115.
• a coating composition according to the invention in particular an aqueous dispersion, has an iodine number according to DIN 53241 of at least 1 g iodine / 100 g, preferably of at least 10 g iodine / 100 g, more preferably of at least 15 g iodine / 100 g exhibit.
• the iodine value of the aqueous dispersion can be in the range from 2 to 100 g of iodine per 100 g of aqueous dispersion, particularly preferably to 15 to 50 g of iodine per 100 g of aqueous dispersion.
• the iodine value can be determined by means of a dispersion, the value relating to the solids content.
• the coating agent preferably an aqueous dispersion, an acid number in the range of 0.1 to 100 mg KOH / g, preferably 1 to 40 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g.
• the acid value can be determined in accordance with DIN EN ISO 2114 using a dispersion, the value relating to the solids content.
• the hydroxyl number of a coating composition according to the invention may preferably be in the range from 0 to 400 mg KOH / g, more preferably 1 to 200 mg KOH / g and most preferably in the range from 3 to 150 mg KOH / g.
• the hydroxyl number can be determined in accordance with DIN EN ISO 4629 using a dispersion, the value relating to the solids content.
• siccatives can be added to the aqueous dispersions.
• organometallic compounds for example metal soaps of transition metals, such as cobalt, manganese, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium.
• transition metals such as cobalt, manganese, lead, zirconium
• Alkali or alkaline earth metals such as lithium, potassium and calcium.
• cobalt naphthalate and cobalt acetate can be used individually or as a mixture, with particular preference being given to mixtures containing cobalt, zirconium and lithium salts.
• the polymers of the present invention can be used in particular in coating compositions or as an additive.
• the coating compositions in particular the aqueous dispersions, can particularly preferably serve for the production of paints or impregnating agents for applications on wood and / or metal.
• the coatings obtainable from the coating compositions according to the invention show a high resistance to solvents, with only small amounts in particular being dissolved out of the coating by solvents.
• Preferred coatings show a high resistance, in particular to methyl isobutyl ketone (MIBK).
• MIBK methyl isobutyl ketone
• the weight loss after treatment with MIBK is preferably at most 50% by weight, preferably at most 35% by weight.
• the uptake of MIBK is preferably at most 400 wt .-%, more preferably at most 250 wt .-%, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, wherein a completely dried coating is measured. In this case, the drying takes place in the presence of oxygen, for example air, in order to allow crosslinking.
• the coatings obtained from the coating compositions of the invention show high mechanical resistance.
• the pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured in accordance with DIN ISO 1522.
• the dispersions according to the invention may contain other constituents in addition to the emulsion polymers.
• the present invention will be explained in more detail by means of an example and comparative examples, without this being intended to limit it.
• the solution was stirred for half an hour and transferred under argon to a 2-stainless steel autoclave (Parr Instruments).
• the autoclave was cooled with dry ice, whereby 220 g of butadiene (4.1 mol) were condensed.
• the autoclave was warmed to room temperature, producing a pressure of 20 bar with nitrogen.
• the mixture was then stirred at 80 ° C. for 20 h.
• the autoclave was cooled, the pressure released and the reaction solution again transferred to a 1 L Schlenk flask.
• the product obtained was purified by vacuum distillation, the boiling point was about 60 0 C. There are obtained 349 g (93%) of product.
• the product was analyzed by NMR spectroscopy.
• the reaction mixture was heated to boiling.
• the methyl methacrylate / methanol azeotrope was separated, with the head temperature gradually increasing to 100 ° C.
• the catalyst precipitated by addition of 20 ml of water and cooled with stirring to room temperature. After filtration, the excess methyl methacrylate was distilled off on a rotary evaporator.
• 2-octa-2,7-dienyloxyethanol was prepared. To this was added 33 mg of PddvdsIMes (1,3-dimesitylimidazol-2-ylidene-palladium (0) - ⁇ 2 , ⁇ 2 , -1, 1, 3,3-tetramethyl-1,3-divinyl-disiloxane 5.5 x 10 "5 moles) and 230 mg of 1,3-dimesityl-1H-imidazole-3-ium-methanesulfonate (5.7 x 10 " 4 moles) in a 1 L Schlenk flask under argon with 140 ml of THF and 120 ml of ethylene glycol (152 g , 2.45 mol).
• PddvdsIMes 1,3-dimesitylimidazol-2-ylidene-palladium (0) - ⁇ 2 , ⁇ 2 , -1, 1, 3,3-tetramethyl-1,3-divin
• the solution was stirred for half an hour and transferred under argon to a 2-stainless steel autoclave (Parr Instruments).
• the autoclave was cooled with dry ice to condense 300 g of butadiene (5.5 mol).
• the autoclave was warmed to room temperature, with
• the reaction mixture was heated to boiling.
• the methyl methacrylate / methanol azeotrope was separated, with the head temperature gradually increasing to 100 ° C.
• the reaction mixture was cooled to about 80 0 C.
• the catalyst precipitated by addition of 20 ml of water and cooled with stirring to room temperature. After filtration, the excess methyl methacrylate was distilled off on a rotary evaporator.
• the prepared emulsion had a solids content of 40 ⁇ 1%, a pH of 2.3, a viscosity of 12 mPas and an rN5 value of 96 nm.
• the properties of the coating composition thus obtained were examined by various methods. For this purpose, tests on solvent resistance were determined on dried films and the residual monomer content of the dispersions.
• MIBK methyl isobutyl ketone
• the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 2.3, a viscosity of 12 mPas and a r N5 value of 93 nm.
• the properties of the coating composition thus obtained were investigated by various methods. For this purpose, tests on solvent resistance were carried out on dried films and the residual monomer content was determined on the dispersions.
• MIBK methyl isobutyl ketone
• the produced emulsion had a solids content of 40 ⁇ 1%, a pH of 2.3, a viscosity of 13 mPas and an rN5 value of 92 nm.
• the properties of the coating composition thus obtained were investigated by various methods. For this purpose, experiments were carried out on dried films for solvent resistance and determined on the dispersions of the residual monomer content.
• MIBK methyl isobutyl ketone
• the dried film was completely soluble in MIBK. Therefore, no solvent uptake could be determined.

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