EP2283075A1 - Wässrige dispersionen aufweisend mindestens ein alkyd-harz - Google Patents

Wässrige dispersionen aufweisend mindestens ein alkyd-harz

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Publication number
EP2283075A1
EP2283075A1 EP09757360A EP09757360A EP2283075A1 EP 2283075 A1 EP2283075 A1 EP 2283075A1 EP 09757360 A EP09757360 A EP 09757360A EP 09757360 A EP09757360 A EP 09757360A EP 2283075 A1 EP2283075 A1 EP 2283075A1
Authority
EP
European Patent Office
Prior art keywords
monomers
aqueous dispersion
formula
alkyd resin
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09757360A
Other languages
German (de)
English (en)
French (fr)
Inventor
Thorben SCHÜTZ
Joachim Knebel
Mario Gomez
Christine Maria BREINER
Matthias Beller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2283075A1 publication Critical patent/EP2283075A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • Aqueous dispersions comprising at least one alkyd resin
  • the present invention relates to aqueous dispersions comprising at least one alkyd resin. Furthermore, the present invention relates to processes for the preparation of these dispersions.
  • 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 generally 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 occurring through oxidation involving unsaturated groups.
  • Many of these alkyd resins include organic solvents or dispersants to coat the resins in a thin layer on the coating body.
  • 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 properties of many alkyd resins are not optimal. So the water intake is often too high. In addition, solvent resistance or hardness is too low for many applications.
  • a solution polymer based paint 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 publication DE-A-41 05 134 describes aqueous dispersions which can be used as binders in paints.
  • the preparation of these binders is carried out over several stages, initially a solution polymer is produced, 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 emulsion polymer shows high solubility.
  • aqueous dispersions comprising oxidatively drying polymers are disclosed in F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation II", Journal of Applied Polymer Science, Vol. 30, 4551-4570 (1985)
  • the polymers contain from 2 to 8% by weight of units derived from (Meth) acrylates with unsaturated, long-chain alcohol radicals are derived.
  • these polymers do not contain units obtained by polymerization of acid group-containing monomers. The durability of these dispersions and the hardness of the coatings are not sufficient for many applications.
  • US 5,750,751, EP-A-1 044 993 and WO 2006/013061 describe coating compositions comprising polymers based on vinyl monomers which are capable of crosslinking 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.
  • a disadvantage of the above-described coatings containing polymers based on (meth) acrylates is their high price.
  • coatings obtained from the coating agents set out above often exhibit low hardness. There is no evidence in these documents for the use of these polymers in alkyd resins.
  • Japanese Patent JP 59011376 describes emulsion polymers based on (meth) acrylates.
  • a disadvantage of the dispersions described in this document is their low storage life.
  • it has been found that the coatings obtained do not have sufficient stability for all requirements compared to all solvents.
  • US Pat. No. 6,599,972 discloses coating compositions based on polymers based on (meth) acrylates whose alcohol residue is derived from unsaturated fatty acid derivatives.
  • a disadvantage of the here in explicitly set out coating compositions is their shelf life and the stability of the coatings obtainable from the described compositions.
  • 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.
  • 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 preparation of the described resins is very expensive.
  • EP-A-1 578 864 discloses aqueous alkyd resins which have been modified with (meth) acrylate polymers.
  • To prepare the (meth) acrylic polymers large amounts of unsaturated fatty acids were used.
  • the complex production of these dispersions is disadvantageous.
  • the dispersions described lead to coatings with a relatively low hardness.
  • the coating compositions should have a very low residual monomer content. Furthermore, it was therefore an object of the present invention to provide a dispersion which has a particularly long shelf life and durability. Furthermore, the hardness of the coatings obtainable from coating agents should be able to be varied over a wide range. In particular, according to a particular aspect of the present invention
  • compositions that lead to very hard, scratch-resistant coatings.
  • the coatings obtainable from the coating compositions should have a high solvent resistance. This stability should be high compared to many different solvents. Another object is to provide coating compositions without volatile organic solvents.
  • the from the aqueous coatings available coatings 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 coating compositions according to the invention should be able to be prepared easily and inexpensively.
  • the present invention accordingly provides aqueous dispersion comprising at least one alkyd resin and at least one polymer comprising repeating units which are selected from monomers A according to formula (I)
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of formula NR ', wherein R' is hydrogen or a radical of 1 to 6 carbon atoms, provided that at least one of the groups X 1 and X 2 represent a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R 1 is an unsaturated radical having 9 to 25 carbon atoms.
  • the dispersions according to the invention have a very low residual monomer content.
  • the hardness of the coatings obtainable from dispersions of the invention can be varied over a wide range. In particular, very hard, scratch-resistant coatings can be obtained.
  • the coatings obtainable from the dispersions of the invention show a surprisingly high resistance to solvents, which is particularly evident in tests with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol.
  • MIBK methyl isobutyl ketone
  • the coatings obtained, in particular in tests according to the furniture test DIN 68861 -1 an excellent classification.
  • the dispersions according to the invention preferably have no volatile organic solvents.
  • the dispersions 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 aqueous dispersions show a high weather resistance, in particular a high UV resistance.
  • the films obtainable from the aqueous dispersions have a low tackiness after a short time.
  • the dispersions of the invention can be produced inexpensively on a large scale.
  • the dispersions of the invention are environmentally friendly and can be processed and produced safely and without great effort.
  • the dispersions of the invention show a very high shear stability.
  • the aqueous dispersions of the invention comprise at least one alkyd resin.
  • 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 which are derived from the long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds described above, for example fats or oils.
  • these derivatives are not necessarily polyvalent carboxylic acids, but can, for example, by
  • 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 of the invention include di- and tricarboxylic acids such as phthalic acid, isophthalic acid, 5- (nathium sulfo) isophthalic acid, terephthalic acid, trimellitic acid, 1,4-cyclohexanedicarboxylic acid, butanedioic acid, Maleic acid, fumaric acid, sebacic acid, adipic acid and azelaic acid. These 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-propanedio
  • trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol are preferred.
  • especially preferred are alcohols having three or more hydroxy groups.
  • the proportion of polyhydric alcohols 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.
  • 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.
  • 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, monovalent carboxylic acids, including valent 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-dimethylolpropionic acid. Dimethylol butyric acid and 2,2-Dimenthylolpentankla.
  • 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 free-radical polymerization can be used with preference.
  • Such resins 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 with 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 on Aug. 13, 1996 with the United States Patent Office (USPTO), application number 08 / 696,361, are incorporated herein by reference for purposes of disclosure. inserted application.
  • the resins set out in the publication DE-A-199 57 161 filed on 27.11.99 at the German Patent and Trademark Office with the application number DE 19957161.9 are incorporated in the present application for purposes of disclosure.
  • modified alkyd resins can be obtained, inter alia, by polymerizing a monomer mixture in the presence of an alkyd 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 groups which are 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 containing, based on its total amount, 0.1 to 10 wt .-% of pendant and / or terminal allyloxy groups, in
  • 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, based on the alkyd resin , 4 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 a constituent of a urethane group, an ester group or an ether group which links 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-, triallyl ether, mannitol mono-, di-, tri- or tetraallyl ether, dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid or 2,2-dimethylolpentanoic acid allyl ester or allyl urethane, of which Trimethylolpropane monoallyl ether is advantageous.
  • the dispersion 1 in one stage (2) can be graft-mixed with methacrylic acid and at least one further olefinically unsaturated monomer. be lymerinstrument.
  • 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.
  • reactive functional groups under the given reaction conditions and the subsequent storage of the dispersions according to the invention undergo no reactions with the carboxyl groups of methacrylic acid or with other optionally present reactive functional groups.
  • 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 in particular being suitable for the modification.
  • alkyd resins modified with polyethylene glycol may be used.
  • PEG polyethylene glycol
  • Preferred alkyd resins modified with polyethylene glycol are known inter alia from the document EP-A-0 029 145.
  • the resins set out in document EP-A-0 029 145 filed on 30 Oct. 1980 at the European Patent Office with the application number EP 80106672.1 are incorporated in the present application for the purpose 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 resin 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 of 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, especially difunctional onellen Isocyanaten A5 are derived.
  • the urethane alkyd resin is preferably prepared in a two-stage reaction, wherein the components A1 to A4 are esterified in the first stage, wherein the acid number of the first stage product is preferably at most 10 mg / g, more preferably at most 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 neutralized by reacting unsaturated fatty acids B1' with saturated carboxylic acids B2 'are produced.
  • 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 particularly preferably 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 number being determined according to DIN EN ISO 2114 can be.
  • 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 hydroxyl functionality of at least 1, 9, more preferably 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.
  • polyfunctional isocyanates include 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, allophanates and biurets.
  • alkyd resins based on urethanes.
  • urethane-alkyd resins can be obtained, for example, by reacting polyhydric alcohols with polyfunctional 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 are determined according to DIN EN ISO 4629 by means of a dispersion, wherein the value refers to the solids content.
  • aqueous dispersions according to the invention comprise at least one polymer comprising repeating units which are selected from monomers A according to formula (I)
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R 1 is an unsaturated radical having 9 to 25 carbon atoms, are derived.
  • polymer means that the dispersion contains compounds which can be obtained by reaction of monomers A with one another or with other monomers, this reaction being able to take place in one step or in stages.
  • the polymer may preferably be at least 2, more preferably at least 5 and most preferably at least 10 repeating units which may be derived from monomers A or comonomers. The upper limit of the number of repeating units depends on the type of reaction. For emulsion polymerization, values above 10 7
  • polymer is to be understood comprehensively, and within the scope of the invention also include compounds which are often referred to as oligomers.
  • the dispersion may contain one or more polymers which
  • Repeat units derived from monomers A may differ, for example, in the proportion of monomer A or in the chain length, the solubility behavior or other properties.
  • the polymer may preferably be obtained by radical polymerization. Accordingly, the term repeat unit results from the monomers used to prepare the polymer.
  • a dispersion according to the invention comprises at least one polymer which
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical with 1 to With the proviso that at least one of X 1 and X 2 is a group of formula NR 'wherein R' is hydrogen or a radical of 1 to 6 carbon atoms, Z is a linking group, and R 1 is an unsaturated radical with 9 to 25 carbon atoms are derived.
  • R is hydrogen or a methyl group
  • X 1 is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6
  • Carbon atoms, Z is a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R 1 is an unsaturated radical having 9 to 25 carbon atoms derived.
  • radical having 1 to 6 carbon atoms means a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups
  • the said groups may be branched or unbranched, furthermore these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the radicals R ' are preferably alkyl groups.
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl group.
  • the group Z preferably represents a linking group comprising 1 to 10, preferably 1 to 5 and most preferably 2 to 3 carbon atoms. These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as, for example, a methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, t-butylene or cyclohexylene group, where the Ethylene group is particularly preferred.
  • the group R 1 in formula (I) is an unsaturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkenyl, cycloalkenyl, alkenoxy, cycloalkenoxy, alkenoyl and heteroalipatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the preferred groups include in particular alkenyl groups, such as, for example, the nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, , Docosenyl, octanediazyl, nonanediazyl, decanediazyl, undecanedienyl, dodecanedienyl, tridecanediazyl, tetradecanedienyl , Pentadecanediazyl, hexadecanedienyl, heptadecanediazyl, octadecanedienyl, nonadecanediazyl, eicosanedienyl,
  • the preferred monomers A of the formula (I) or (III) include, but are not limited to, heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecane-dienyloxy-2-ethyl- (meth) acrylamide, heptadecane-triene-yloyloxy 2-ethyl (nneth) acrylic acid anide, heptadecenyloyloxy-2-ethyl (neth) acrylic acid anide, (meth) acryloyloxy-2-ethyl-palmitoleic acid anhydride, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy-2-ethyl-icosenic acid amide, ( Meth) acryloyloxy-2-ethyl-cetolenic acid amide, (meth) acryloyloxy-2-eth
  • the notation (meth) acryl stands for acrylic and methacrylic radicals, with methacrylic radicals being preferred.
  • Particularly preferred monomers A according to formula (I) or (III) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid anide.
  • the monomers A according to formula (I) which are used for the preparation of the polymer an iodine value in the range of 50 to 300 g of iodine / 100g, more preferably in the range of 100 to 200 g of iodine / 100g exhibit.
  • At least some of the monomers A according to formula (I) which are used for the preparation of the polymer have exactly one double bond in the unsaturated radical R 1 .
  • at least a portion of the monomers A of the formula (I) used to prepare the polymer may be two or more Have double bonds in the unsaturated radical R 1 .
  • Preferably mixtures of the monomers A can be used, whereby these mixtures can contain both monomers A with exactly one double bond in the remainder of R 1 as well as monomers A with two or more double bonds in the remainder of R 1 .
  • the weight ratio of the monomers A of the formula (I) which have exactly one double bond in the unsaturated radical R 1 to the monomers A of the formula (I) which have two or more double bonds in the unsaturated radical R 1 can be in the range of 100 : 1 to 1:10, more preferably in the range of 10: 1 to 1: 5.
  • the monomers A according to formula (I) or (III) can be obtained in particular by multi-stage processes.
  • a first stage for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine, for example ethylenediamine, ethanolamine, propylenediamine or propanolamine, to form an amide.
  • an amine for example ethylenediamine, ethanolamine, propylenediamine or propanolamine
  • the hydroxy group or the amine group of the amide is reacted with a (meth) acrylate, for example methyl (meth) acrylate, to obtain the monomers of the formula (I) or (III).
  • Valuable information on the preparation of these monomers can be found, inter alia, in the example of the present application.
  • intermediates obtained for example carboxamides which have hydroxyl groups in the alkyl radical
  • intermediates obtained can be converted to the monomers A according to formula (I) without expensive purification.
  • 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, among others, are among the preferred unsaturated fatty acids which can be used to prepare the present monomers A according to formula (I) and / or cervonic acid. These acids can preferably also be used as esters of alcohols having 1 to 4 carbon atoms, for example as ethyl, propyl, butyl and especially methyl esters.
  • the preferred amines for reacting the fatty acid or fatty acid ester include, in particular, ethylenediamine, ethanolamine, propanolamine and propylenediamine.
  • Advantages which in themselves are not obvious to the person skilled in the art can be achieved by polymers obtained by using a monomer mixture containing at least 2, preferably at least 5% by weight and more preferably at least 10% by weight of monomers A with 17 to 21 carbon atoms in the unsaturated radical R 1 , based on the total weight of the monomer mixture.
  • preferred polymers comprise repeat units derived from monomers B of the general formula (II)
  • R is hydrogen or a methyl group
  • X 1 and X 2 are independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X 1 and X 2 a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R 2 is a saturated radical having 9 to 25 carbon atoms, are derived.
  • monomer B for the preparation of the polymers to be used according to the invention, preference is hereby given to monomer B according to the general formula (IV) wherein R is hydrogen or a methyl group, X 1 is oxygen or a group of formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R 2 is a saturated A radical having 9 to 25 carbon atoms is included.
  • R is hydrogen or a methyl group
  • X 1 is oxygen or a group of formula NR '
  • R' is hydrogen or a radical having 1 to 6 carbon atoms
  • Z is a linking group
  • R is hydrogen or a radical having 1 to 6 carbon atoms
  • R 2 is a saturated A radical having 9 to 25 carbon atoms is included.
  • the group R 2 in formula (II) or (IV) is a saturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. Furthermore, these groups can
  • Substituents in particular halogen atoms or hydroxyl groups.
  • the preferred groups include in particular alkyl groups, such as the nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl Group.
  • the preferred monomers B according to formula (II) or (IV) include inter alia pentadecyloyloxy-2-ethyl (meth) acrylamide, heptadecyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-laurinklareamid .
  • Particularly preferred monomers B according to formula (II) or (IV) include methacryloyloxy-2-ethyl-palmitic acid amide and methacryloyloxy-2-ethyl-stearic acid amide.
  • monomers B according to formula (II) which have 15 or 17 carbon atoms in the radical R 2 are preferably used for the preparation of the polymers to be used according to the invention.
  • 2 or more monomers B of the formula (II) which are used to prepare the polymer are used in the monomer mixture, which differ in the number of carbon atoms in the radical R 2 .
  • the weight ratio of the monomers B of the formula (II) having 15 carbon atoms in the saturated radical R 2 to the monomers B of the formula (II) having 17 carbon atoms in the saturated radical R 2 is preferably in the range of 100: 1 to 1:10, more preferably in the range of 10: 1 to 1: 2.
  • a monomer mixture can be used for the preparation of the polymers, the at least 0.5, preferably at least 1 wt .-% and particularly preferably at least 3 wt .-% of monomers B having 11 to 17 carbon atoms in the saturated radical R 2 , based on the total weight of the monomer mixture.
  • Monomers B of the formula (II) can be prepared in a similar manner to the monomers A of the formula (I) set out above, but using saturated fatty acids or fatty acid esters.
  • the preferred fatty acids include, but are not limited to, capric, lauric, myristic, palmitic, margaric, arachidic, behenic, lignoceric, cerotic and stearic acids. These acids can preferably also be used as esters of alcohols having 1 to 4 carbon atoms, for example as ethyl, propyl, butyl and especially methyl esters.
  • Monomer mixtures comprising monomers A according to formula (I) and monomers B according to formula (II) can be obtained by mixing monomers A and monomers B.
  • these mixtures can be further obtained by reacting a fatty acid mixture or a fatty acid ester mixture which comprises unsaturated and saturated fatty acids or fatty acid esters with an amine and then with a (meth) acrylate or with a (meth) acrylamide in the manner described above a hydroxy group is reacted in the alkyl radical.
  • Preferred polymers may be obtained by a monomer mixture comprising monomer B as well as monomer A.
  • the weight ratio of the monomers A to the monomers B is not critical per se. However, surprising advantages can be achieved if the weight ratio of the monomers A to the monomers B is in the range from 100: 1 to 1:10, preferably in the range of 10: 1 to 1: 3, and more preferably in the range of 3: 1 to 1: 1.
  • a monomer mixture for the preparation of the polymers to be used according to the invention may comprise further monomers which are copolymerizable with the monomers A and B.
  • copolymerizable monomers include monomers having an acid group, monomers C comprising ester groups, which differ from the monomers of the formulas I or II, and styrene monomers.
  • Acid group-containing monomers are compounds which can be preferably radically copolymerized with the monomers A and B set forth above. 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.
  • Particularly preferred monomers C comprising ester groups include (meth) acrylates which are different from the monomers A or B, fumarates, maleates and / or vinyl acetate.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. 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;
  • (Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
  • mixtures comprising methacrylates and acrylates.
  • mixtures of methyl methacrylate and acrylates having 2 to 6 carbons such as ethyl acrylate, butyl acrylate and hexyl acrylate can be used.
  • these comonomers include, for example, (meth) acrylates having at least 7 carbon atoms in the alkyl radical, which are derived from saturated alcohols, such as 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,
  • saturated alcohols such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (
  • Aryl (meth) acrylates such as benzyl (meth) acrylate or phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times;
  • (Meth) acrylates having two or more (meth) acrylic groups glycol 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 1,1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycehndi (meth) acrylate; Dimethacrylates of ethoxylated bisphenol A; (Meth) acrylates having three or more double bonds, e.g
  • the monomers C comprising ester groups furthermore 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.
  • Another preferred group of comonomers are styrenic monomers, such as styrene, substituted styrenes having an alkyl substituent in the side chain, e.g.
  • ⁇ -methyl styrene and ⁇ -ethyl styrene substituted styrenes having an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • 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, A-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, Vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyl
  • Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride.
  • Preferred monomer mixtures for the preparation of the polymers to be used according to the invention comprise
  • the iodine value of the polymers to be used according to the invention is preferably in the range from 1 to 150 g of iodine per 100 g of polymer, more preferably in the range from 2 to 100 g of iodine per 100 g of polymer and most preferably from 5 to 40 g of iodine per 100 g of polymer in accordance with DIN 53241 -1.
  • the iodine number can in particular also be measured by means of a dispersion according to the invention.
  • the polymer to be used according to the invention has an acid number in the range of 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.
  • the acid number can also be determined by dispersion according to DIN EN ISO 2114.
  • the hydroxyl number of the polymer to be used according to the invention 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 polymer to be used according to the invention may preferably contain 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.
  • 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 may be dried, for example, under nitrogen or under vacuum.
  • the solution is separated from the insoluble fraction, for example by filtration.
  • 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.
  • a polymer to be employed may have a swelling of at least 1000%, more preferably at least 1400% and most preferably at least 1600% in tetrahydrofuran (THF) at 20 ° C.
  • the upper limit of the swelling is not critical per se, the swelling preferably being 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 polymers to be used according to the invention can be within a wide range.
  • emulsion polymers having a particle radius in the range of 1 to 500 nm, preferably 1 to 100 nm, preferably 5 to 59 nm can be used.
  • the radius of the particles is preferably in the range of 60 nm to 500 nm, particularly preferably 70 to 150 nm and most preferably 75 to 100 nm.
  • 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 can be used for this purpose.
  • the glass transition temperature of the polymer is preferably in the range of -30 0 C to 70 0 C, more preferably in the range of -20 to 40 0 C and most preferably in the range of 0 to 25 ° C.
  • the glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer.
  • 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: X 1
  • 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 in the Polymer Handbook 2 nd Edition, J. Wiley & Sons, New York (1975), which gives 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 which is obtainable by polymerization of 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 preferably the emulsion polymer, may be a homogeneous polymer which, for example, forms particles with a constant composition in an aqueous dispersion.
  • the emulsion polymer may consist of one or more segments. which are obtainable by polymerization of the monomers or monomer mixtures set out above.
  • the polymer may comprise multiple segments.
  • an emulsion polymer having a core-shell structure which may have one, two, three or more shells may be employed.
  • the segment which is obtainable by polymerization of the monomer mixture shown above 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 obtainable by polymerization of the monomers or monomer mixtures set forth above can be often separated and isolated from the core by suitable solvents.
  • the weight ratio of segment obtainable by polymerization of the monomer mixture shown above to core may range from 2: 1 to 1: 6, more preferably 1: 1 to 1: 3.
  • 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 to esters of (meth) acrylic acid whose alcohol radical preferably comprises 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms and very particularly 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, iso-propyl (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, iso-propyl (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 xylacrylat be used.
  • the polymers of the core may comprise the previously described comonomers.
  • the core may be crosslinked. This crosslinking can be achieved by the use of monomers having two, three or more free-radically polymerizable double bonds.
  • the shell of emulsion polymers to be used preferably comprises 15 to 50% by weight of units derived from monomers A of formula (I) which have at least one double bond in the radical R 1 .
  • the core may preferably have a glass transition temperature in the range from -30 to 200 ° C., more preferably in the range from -20 to 150 ° C.
  • the shell may preferably have 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 the range of 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 may suitably rature of the core at least 10 0 C, preferably at least 20 0 C above the glass transition temperature of the shell.
  • ATRP Atom Transfer Radical Polymerization
  • NMP Nonroxide Mediated Polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • the polymerization is carried out as 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 over a period of time can be added continuously or batchwise.
  • the emulsion polymerization can be carried out, for example, as a mini or as a microemulsion. Described in more detail in Chemistry and Technology of Emulsion Polymerization, AM van Herk (editor), Blackwell Publishing, Oxford 2005 and J. O'Donnell, EW Kaier, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454.
  • a miniemulsion is common by the Use of costabilizers or swelling agents characterized in that often long-chain alkanes or alkanols are used.
  • the droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns.
  • the droplet size in the case of microemulsions is preferably in the range below 1 ⁇ m, whereby particles below a size of 50 nm can be obtained in this way.
  • 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.
  • the composition of the monomer mixture can be changed stepwise, wherein before changing the composition, the polymerization is preferably up to a conversion of at least 80 wt .-%, particularly preferably at least 95 wt .-%, each based on the Total weight of the monomer mixture used is polymerized.
  • 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 mixture 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.
  • After the production of the core may be grafted onto this preferably a monomer mixture or polymerized onto the core, which comprises 15 to 40 wt .-% of monomers A according to formula (I).
  • 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 the ammonium salts of peroxydisulfuric, in particular ammonium, sodium and potassium peroxodisulfate.
  • Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate.
  • 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 half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms in the alkyl radical; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 ethylene oxide units; Partial phosphoric acid 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; Alkylpolyglykolether, preferably having 8 to 20 carbon atoms in the alkyl 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 the alkali metal salt, in particular as the sodium salt.
  • These compounds can be obtained commercially 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 tertiary
  • Octylphenolethoxylat with 30 ethylene oxide units and Fettal kholpolyethylen- glycol ether which preferably have 8 to 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. Preference is given to using mixtures of anionic emulsifier and nonionic emulsifier.
  • 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.
  • the emulsifiers can also be used in admixture with protective colloids.
  • Suitable protective colloids include u. a. partially hydrolyzed 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 - Re-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 metering in the initiator, preferably in aqueous solution.
  • the dosages of emulsifier and monomers can be carried out separately or as a mixture.
  • dosing Mixtures of emulsifier and monomer are used in such a way that emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor.
  • the residues of emulsifier and of monomer, which were not initially charged are metered in separately from one another after the start of the polymerization.
  • the dosage can be started 15 to 35 minutes after the start of the polymerization.
  • Preferred emulsion polymers having a high content of insoluble polymers can be obtained in the manner set forth above, wherein the reaction parameters to obtain a high molecular weight are known.
  • the use of molecular weight regulators can be dispensed with.
  • 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.
  • an aqueous alkyd resin can be mixed with the polymer described above.
  • an alkyd resin dispersion can also be initially charged, in which subsequently a polymer comprising repeating units derived from monomers A according to formula (I) is prepared.
  • At least a portion of the polymers comprising recurring units derived from monomers A of formula (I) may be covalently bonded to the alkyd resin.
  • at least a portion of the polymers comprising repeating units derived from monomers A of formula (I) not covalently bonded to the alkyd resin can be achieved through the use of alkyd resins having radically polymerizable double bonds.
  • (meth) acrylic acid or the compounds described above for introducing lateral and / or terminal allyloxy groups can be used in the preparation of the alkyd resin in order to achieve this.
  • a composition comprising at least one monomer A of formula (I) can be reacted.
  • the monomer A can be grafted onto the alkyd resin or polymerized in the form of a shell on a part of the alkyd resin.
  • a polymer which comprises monomers A of the formula (I).
  • a dispersion with this polymer can then be prepared an alkyd resin.
  • a reaction of the monomers A can be effected in particular by water-soluble initiators, which have been described above. Valuable information on the reaction of monomers with alkyd resins can be found inter alia in US Pat. No. 5,538,760, US Pat. No. 6,369,135 and DE-A-199 57 161.
  • the proportions by weight of alkyd resin and polymers comprising repeating units derived from monomers A according to formula (I) can be in a wide range, which can generally be adapted to the desired property profile.
  • the weight ratio of alkyd resin to polymers comprising recurring units derived from monomers A of formula (I) is in the range of 20: 1 to 1:20, more preferably 5: 1 to 1: 5, and most particularly preferably 3: 1 to 1: 3, based on the dry weight of the respective components.
  • the aqueous dispersions obtained by the process according to the invention can be used as coating agents.
  • 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.
  • a polymer dispersion which has a dynamic viscosity in the range from 0.1 to 180 mPas, preferably from 1 to 80 mPas and very particularly preferably from 10 to 50 mPas, measured in accordance with DIN EN ISO 2555 25 ° C (Brookfield).
  • the dispersions of the invention may contain additives or further components in order to adapt the properties of the coating composition to specific requirements.
  • additives include in particular drying aids, so-called siccatives, flow improvers, pigments and dyes.
  • siccatives can be added to the aqueous dispersions.
  • organometallic compounds for example metal soaps of transition metals, such as, for example, cobalt, manganese, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium.
  • transition metals such as, for example, 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.
  • coating compositions of the present invention have a minimum film formation temperature of at most 50 0 C, particularly preferably at most 35 ° C and most preferably at most 25 ° C, the measured overall DIN ISO 2115 can be measured.
  • an aqueous dispersion of the invention may have an iodine number 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 number of the aqueous dispersion can be in the range from 2 to 100 g of iodine per 100 g of aqueous dispersion, particularly preferably 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 aqueous dispersion 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 an aqueous dispersion 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 value can be determined in accordance with DIN EN ISO 4629 using a dispersion, the value relating to the solids content.
  • the aqueous dispersions of the present invention can be used in particular as a coating agent or as an additive. These include in particular paints, impregnating agents, adhesives and / or primers.
  • the aqueous dispersions can particularly preferably be used 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 300% by weight, particularly preferably at most 250% by weight, 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.
  • 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 fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl esters, 2.5% by weight of saturated C17 to C20 fatty acid methyl esters, 52% by weight of monounsaturated C18 fatty acid methyl ester, 1.5% by weight of monounsaturated C20 to C24 fatty acid methyl ester, 36% by weight of polyunsaturated C18 fatty acid methyl ester, 2% by weight of polyunsaturated C20 to C24 fatty acid methyl esters.
  • the reaction mixture was heated to 150 0 C. Within 2 h, 19.5 ml of methanol were distilled off. The resulting reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was further processed without purification. After cooling, 1919 g (19.2 mol) of methyl methacrylate, 3.1 g of LiOH and an inhibitor mixture consisting of 500 ppm hydroquinone monomethyl ether and 500 ppm phenothiazine were added.
  • reaction apparatus While stirring, the reaction apparatus was purged with nitrogen for 10 minutes. Thereafter, the reaction mixture was heated to boiling. The methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 0 C. After completion of the reaction, the reaction mixture was cooled to about 70 0 C and filtered.
  • the emulsion prepared had a solids content of 40 ⁇ 1%, a pH of 5.6, a viscosity of 37 mPas and an r N5 value of 70-75 nm.
  • the properties of the coating composition thus obtained were investigated by various methods. For this purpose, tests on solvent resistance, water absorption and scratch resistance were carried out on dried films.
  • Solvent resistance was determined using methyl isobutyl ketone (MIBK), swelling a sample with MIBK at room temperature for 4 hours. The sample was then removed from the solvent and excess solvent removed. Subsequently, the sample was dried for 1 hour at about 140 0 C. The weight loss is used to calculate the proportion of the sample removed by the solvent.
  • MIBK methyl isobutyl ketone
  • the swelling in ethanol indicated in Table 1 was similar to the experimental description set out above, but using ethanol as Solvent determined.
  • the value refers to the weight of the coating obtained after the experiment, the weight due to the weight loss being less than the weight of the starting sample.
  • a test specimen of untreated solid pine wood (dimensions: 45-50mmx45-50mmx17mm) can be used.
  • the test piece was coated and placed in water at room temperature so that only the coated area was in contact with water. From the increase in weight of the specimen, the water consumption is calculated. Furthermore, a furniture test was carried out in accordance with DIN 68861 -1.
  • Example 1 was substantially repeated except that 66.29 g of the aqueous dispersion prepared in Example 1 were mixed with 57.2 g of a polyurethane alkyd resin (commercially available from Worlee under the name E150W). Tests on solvent resistance, water absorption and scratch resistance were carried out on dried films. The results obtained are shown in Table 1.
  • Example 1 the alkyd resin used in Example 1 was tested without admixture of the previously described polymer based on (meth) acrylates. Dried films have been tested for medium resistance, water absorption and scratch resistance. The results obtained are shown in Table 1.
  • BA butyl acrylate
  • MMA methyl methacrylate
  • MAS methacrylic acid
  • APS ammonium peroxodisulfate
  • APS disponil FES 32
  • Example 1 was essentially repeated except that 117.15 g of the aqueous dispersion prepared in Example 1 were mixed with 33.7 g of a urethane-modified cosolvent-free short oil alkyd emulsion. Tests on solvent resistance, water absorption and scratch resistance were carried out on dried films.
  • Example 3 was essentially repeated except that 66.29 g of the aqueous dispersion prepared in Example 1 were mixed with 57.2 g of a urethane-modified cosolvent-free short oil alkyd emulsion. Tests on solvent resistance, water absorption and scratch resistance were carried out on dried films. The results obtained are shown in Table 1.
  • Example 3 was essentially repeated except that 33.7 g of the aqueous dispersion prepared in Example 1 was mixed with 117.15 g of a urethane-modified cosolvent-free short oil alkyd emulsion. Tests on solvent resistance, water absorption and scratch resistance were carried out on dried films. The results obtained are shown in Table 1. Comparative Example 3
  • Example 3 the alkyd resin used in Example 3 was tested without admixture of the previously described polymer based on (meth) acrylates. Tests on solvent resistance, water absorption and scratch resistance were carried out on dried films. The results obtained are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP09757360A 2008-06-06 2009-04-23 Wässrige dispersionen aufweisend mindestens ein alkyd-harz Withdrawn EP2283075A1 (de)

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PCT/EP2009/054862 WO2009146977A1 (de) 2008-06-06 2009-04-23 Wässrige dispersionen aufweisend mindestens ein alkyd-harz

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RU2010154394A (ru) 2012-07-20
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WO2009146977A1 (de) 2009-12-10
CN102056982A (zh) 2011-05-11
JP2011522094A (ja) 2011-07-28
KR20110027673A (ko) 2011-03-16

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