WO2012038197A1 - Produit de revêtement à base de polymère (méth)acrylique et d'adjuvants de coalescence - Google Patents

Produit de revêtement à base de polymère (méth)acrylique et d'adjuvants de coalescence Download PDF

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Publication number
WO2012038197A1
WO2012038197A1 PCT/EP2011/064785 EP2011064785W WO2012038197A1 WO 2012038197 A1 WO2012038197 A1 WO 2012038197A1 EP 2011064785 W EP2011064785 W EP 2011064785W WO 2012038197 A1 WO2012038197 A1 WO 2012038197A1
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meth
octa
carbon atoms
acrylate
coating composition
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PCT/EP2011/064785
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German (de)
English (en)
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Gerold Schmitt
Christine Maria BREINER
Thorben SCHÜTZ
Wolfgang Klesse
Matthias Urbanek
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Evonik Röhm Gmbh
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Publication of WO2012038197A1 publication Critical patent/WO2012038197A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

  • the present invention relates to an aqueous coating composition
  • an aqueous coating composition comprising a dispersion of a (meth) acrylic polymer and a coalescing aid.
  • Coating agents in particular paints, have been produced synthetically for a long time. An important group of these funds is based on water
  • Dispersions that include multiple (meth) acrylate polymers.
  • the publication DE-A-41 05 134 describes aqueous dispersions which contain alkyl methacrylates as binders.
  • such paints from US 5,750,751, EP-A-1 044 993, WO 2006/013061 and WO 2008/094503 are known.
  • the coating agents described above already show a good
  • Coating agents should be added to organic solvents. These solvents are to be avoided for reasons of environmental protection. An improvement in this regard is made by the teaching of the document
  • Particles based on (meth) acrylates include. The for the production of
  • Particle monomer mixtures include (meth) acrylates modified by unsaturated fatty acids.
  • reactive paints form another group of known coating agents.
  • paints are for example off
  • EP-0 693 507 is known.
  • compositions are known which comprise so-called reactive diluents. For example, this describes
  • Coating agents with reactive solvents are disclosed, inter alia, in US 2009 / 151601A1, wherein said publications do not disclose polymers with (meth) acrylates which have been modified by unsaturated fatty acids.
  • the coating agent should be very environmentally friendly. This includes that they should have a very low residual monomer content and should release only small amounts of organic compounds into the environment during processing. Furthermore, it was therefore an object of the present invention
  • the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range.
  • Coatings can be obtained.
  • the coatings obtainable from the aqueous dispersions should have a high weather resistance, in particular a high UV resistance.
  • the films obtainable from the aqueous dispersions should have a low tackiness after a short time.
  • the coatings obtainable from the coating compositions should show a high chemical resistance.
  • a high stability compared to many different solvents and to bases and acids should be achieved.
  • a very good resistance to methyl isobutyl ketone (MIBK) should be given.
  • the coating compositions should continue to show a good processability, which is particularly clear by a low minimum film-forming temperature, without thereby affecting the mechanical properties or the
  • Coatings is adversely affected.
  • a further object can be seen in providing coating compositions which can be obtained very inexpensively and on an industrial scale.
  • the present invention accordingly provides an aqueous coating composition comprising at least one dispersion of a (meth) acrylic polymer and at least one auxiliary coalescence aid, which is characterized in that the (meth) acrylic polymer comprises units which are protected by (meth) acrylic Monomers are derived which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical, and
  • Coalescence auxiliary has at least one ethylenically unsaturated double bond and a molecular weight of less than 1000 g / mol.
  • the coating compositions of the invention have an excellent property profile.
  • the invention has an excellent property profile.
  • Coating agent very environmentally friendly, which have a very low content of residual monomers and release only small amounts of organic compounds into the environment during processing.
  • Coating may be available, which in turn are based on the polymers or compositions can be varied over a wide range. Surprisingly, in particular mechanically stable coatings can be obtained, which are characterized by a high elongation at break and / or a high tensile strength. Furthermore, coatings which consist of the inventive
  • Coating may be available, based on the hardness and the
  • the coating compositions of the present invention show, in particular, good processability, which becomes apparent in particular through a low minimum film-forming temperature, without adversely affecting the mechanical properties or the chemical resistance of the coatings obtainable from the coating compositions. At comparable
  • the coating compositions of the present invention exhibit a particularly low minimum film-forming temperature. At comparable
  • Minimum film-forming temperature of the dispersions show the coatings obtainable from these improved chemical resistance and increased pendulum hardness.
  • the coating compositions have an extremely low residual monomer content.
  • Coatings show a high weather resistance, in particular a high UV resistance. Furthermore, the films obtainable from the dispersions have a low tackiness after a short time.
  • the coating compositions according to the invention can be produced inexpensively on a large scale.
  • 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 coating compositions according to the invention are aqueous dispersions.
  • the aqueous coating compositions comprise at least one
  • Coalescence aid is known in the art, by which are meant additives that the
  • the presently used coalescence aids have a molecular weight of at most 1000 g / mol, preferably at most 800 g / mol.
  • Coalescence aid in the range from 120 to 600 g / mol, more preferably in the range from 140 to 500 g / mol.
  • the coalescing aid comprises at most 30, preferably at most 20, in particular at most 15 and more preferably at most 8
  • Coalescence aids are therefore of particular interest with a
  • the coalescing aid has at least one,
  • coalescing aids have a ratio of
  • the coalescing aid may have an HLB value in the range of 3 to 19, more preferably in the range of 9 to 16, calculated according to the method of Griffin (a) Griffin, W.C., J. Soc. Cosmetic Chem, 1, 31 1 (1949), b) ICI Bulletin, HLB System, 8, (1984).
  • the coalescence aid to be used according to the invention is an alcohol, an amine, an ether or an ester, particularly preferably an ester or an alcohol.
  • the coalescing aid comprises at least two ethylenically unsaturated double bonds. Accordingly, preference is given to compounds which have dienyl groups and / or are derived from polybasic compounds, for example dihydric or higher-valued alcohols and / or acids, in particular carboxylic acids.
  • coalescence aids which at least one Have octadienyl group.
  • the coalescing aid may be an alcohol, an amine, an ether or an ester.
  • R represents a residue of exactly 8 carbon atoms, which has two carbon-carbon double bonds. The preferred residues with exactly 8
  • carbon atoms and 2 double bonds include octa-2,7-dienyl groups, octa-3,7-dienyl groups, octa-4,7-dienyl groups, octa-5,7-dienyl groups, octa-2,4-dienyl groups, octa-2, 5-dienyl groups, octa-2,6-dienyl groups, octa-3,5-dienyl groups, octa-3,6-dienyl groups and octa-4,6-dienyl groups.
  • the preferred alcohols include in particular octa-2,7-dienol, octa-3,7-dienol, octa-4,7-dienol, octa-5,7-dienol, octa-2,4-dienol, octa-2, 5-dienol, octa-2,6-dienol, octa-3,5-dienol, octa-3,6-dienol and octa-4,6-dienol.
  • esters with one or more octadienyl groups are among the coalescence aids which are preferably used.
  • Suitable carboxylic acids from which the esters are derived may be linear, branched, cyclic, saturated or unsaturated.
  • aliphatic acids and aromatic acids can be used. These include, in particular, esters of the above-described octadienols which are derived from monocarboxylic acids.
  • Preferred monocarboxylic acids have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 4 carbon atoms.
  • Preferred monocarboxylic acids have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 4 carbon atoms.
  • Monocarboxylic acids include in particular formic acid, acetic acid,
  • Coalescence aids preferably have exactly one octadienyl group.
  • the molecular weight of preferred esters derived from monocarboxylic acids derived from monocarboxylic acids
  • preferably 1 to 20 carbon atoms are derived, is preferably 150 to 500 g / mol, particularly preferably 150 to 300 g / mol.
  • esters of carboxylic acids with two, three or more
  • Carboxylic acid groups are used, such as the esters of Oxalic acid, citric acid, terephthalic acid, fumaric acid, maleic acid or adipic acid.
  • Preferred polycarboxylic acids have 2 to 20, preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms.
  • Polycarboxylic acids having one, two or more octadienyl groups.
  • the molecular weight of preferred esters derived from polycarboxylic acids are particularly preferred.
  • the ethers include, in particular, compounds having an ether group derived from monoalcohols having preferably 1 to 10 carbon atoms. These monoalcohols may be linear, cyclic or branched.
  • unsaturated, saturated or aromatic alcohols can be used to prepare the ethers. These include, in particular, the methyl, ethyl, propyl, butyl, pentyl and hexyl ethers of the octadienols set forth above.
  • ethers examples include methoxyocta-2,7-diene (methyl octa-2,7-dienyl ether), ethoxy octa-2,7-diene and propoxy octa-2,7-diene.
  • methoxyocta-2,7-diene methyl octa-2,7-dienyl ether
  • ethoxy octa-2,7-diene ethoxy octa-2,7-diene
  • propoxy octa-2,7-diene propoxy octa-2,7-diene.
  • ethers are compounds derived from oligo- or polyalkylenes which, in addition to at least one octadienyl group, comprise alkylene oxide units, where, for example, ethers having 2 to 40, more preferably 3 to 10, ethylene oxide units and / or propylene oxide units are particularly preferred.
  • ethers of alcohols may be used which are two,
  • polyhydric alcohols preferably have 2 to 10 carbon atoms, which alcohols may be linear, branched, cyclic, saturated, unsaturated or aromatic.
  • These include in particular the ethers of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, di-pentaerythritol, mannitol, sorbitol, sucrose or mixtures of such alcohols.
  • the ethers of the polyhydric alcohols with octadienols set forth above may in this case have one, two, three or more octadienyl groups.
  • the preferred compounds include in particular
  • Monoocta-4,6-dienoxyethanol 1, 2-diocta-4,6-dienoxyethane, monoocta-4,6-dienoxy-propanediol, diocta-4,6-dienoxy-propanol, triocta-2,7-dienoxypropane, monoocta 2,7-dienoxyethanol, 1, 2-diocta-2,7-dienoxyethane, monoocta-2,7-dienoxy-propanediol, diocta-2,7-dienoxy-propanol and triocta-2,7-dienoxypropane.
  • These ethers may be used singly or as a mixture of two or more.
  • the molecular weight of preferred ethers derived from polyhydric alcohols having preferably 2 to 10 carbon atoms is preferably 170 to 800 g / mol, more preferably 170 to 600 g / mol.
  • amines can also be used.
  • amines comprise 8 to 20 carbon atoms.
  • the preferred amines include, in particular, octa-2,7-dienylamine, octa-3,7-dienylamine, octa-4,7-dienylamine, octa-5,7-dienylamine, octa-2,4-dienylamine, octa-2, 5-dienylamine, octa-2,6-dienylamine, octa-3,5-dienylamine, octa-3,6-dienylamine, octa-4,6-dienylamine, (methyl (octa-2,7-dienyl) amino) ethanol , (Ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol and
  • telomerization means the reaction of compounds with conjugated double bonds in the presence of
  • 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 Palladiumcarbenkomplexe, in the previously set forth
  • dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol;
  • Diamines such as ethylenediamine, N-methylethylenediamine, ⁇ , ⁇ '-dimethylethylenediamine or hexamethylenediamine;
  • Aminoalkanols such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol, or carboxylic acids, in particular the previously detailed mono- and polycarboxylic acids are used.
  • the publications WO 2004/002931, WO 03/031379 and WO 02/100803 are used.
  • 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, more preferably 1 to 64 bar and most preferably 1 to 20 bar.
  • the preparation of isomers from compounds having an octa-2,7-dienyl group can be carried out by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.
  • Coalescing aids which are particularly suitable according to the invention are obtained when alcohols having octadienyl ether groups are reacted with monocarboxylic or polycarboxylic acids or with polycarboxylic anhydrides in the sense of a
  • telomeres which are based on at least trihydric alcohols or randomly at least trifunctional alcohol mixtures, and which have on average per molecule at least one free hydroxyl group.
  • esterification reaction are the telomerization of glycerol and butadiene with a
  • Hydroxyl group content of 4.9 to 14.0 wt .-%.
  • coalescence aids with octadienyl groups are set forth in the document EP-A-0 546 417, with those described therein
  • esters of carboxylic acids with two, three or more can also be used in particular
  • Carboxylic acid groups are used as coalescing aids, such as the esters of oxalic acid, malonic acid, citric acid, the Terephthalic acid, fumaric acid, maleic acid or adipic acid having at least one, preferably at least two ethylenically unsaturated double bonds.
  • Preferred polycarboxylic acids have 2 to 20, preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms.
  • esters of ethylenically unsaturated alcohols which have 2 to 6, preferably 2 to 4, carbon atoms are particularly preferred.
  • diallyl malonate, divinyl malonate and tnallyl citrate are preferred, with diallyl malonate being particularly preferred.
  • Coating composition according to the invention at least one aqueous dispersion comprising at least one (meth) acrylic polymer with units derived from
  • (Meth) acrylic monomers are derived, which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical.
  • polymer means that the dispersion contains compounds which can be obtained by reaction of (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical with each other or with other monomers, this reaction being carried out in one step or in stages.
  • the dispersion may contain one or more polymers which
  • the polymer may preferably be obtained by radical polymerization. Accordingly, the term repeat unit results from the monomers used to prepare the polymer.
  • (Meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group are esters or amides of (meth) acrylic acid whose alkyl group has at least one carbon-carbon double bond and 8 to 40 carbon atoms.
  • the notation (meth) acrylic acid means methacrylic acid and acrylic acid and mixtures thereof.
  • the alkyl or alcohol or amide radical may preferably have 10 to 30 and more preferably 12 to 20 carbon atoms, this radical may include heteroatoms, in particular oxygen, nitrogen or sulfur atoms.
  • the alkyl radical may have one, two, three or more carbon-carbon double bonds.
  • the polymerization conditions in which the (meth) acrylic polymer is prepared are preferably chosen so that the largest possible proportion of the double bonds of the alkyl radical in the
  • Polymerization is maintained. This can be done, for example, by steric
  • the double bonds contained in the alcohol residue Prevent the double bonds contained in the alcohol residue. Furthermore, at least a part, preferably all of the double bonds contained in the alkyl radical of the (meth) acrylic monomer, has a lower reactivity in a free-radical polymerization than a (meth) acrylic group, so that preferably no further (meth) acrylic groups in the alkyl radical are included.
  • the iodine number of the (meth) acrylic monomers to be used in the alkyl radical having at least one double bond and 8 to 40 carbon atoms in the alkyl radical is preferably at least 50, more preferably at least 100, and most preferably at least 125 g of iodine / 100 g of (meth) acrylic monomer.
  • Such (meth) acrylic monomers generally correspond to the formula (I)
  • radical R is hydrogen or methyl
  • X is independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, and R 1 is a linear or branched radical having 8 to 40, preferably 10 to 30 and more preferably 12 to 20
  • Carbon atoms having at least one C-C double bond having at least one C-C double bond.
  • the notation (meth) acrylic stands for acrylic and methacrylic radicals, where
  • Methacryl radicals are preferred.
  • (Meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can be synthesized, for example, by esterification of (meth) acrylic acid, reaction of (meth) acryloyl halides and / or (meth) acrylic anhydride or transesterification of (meth) acrylates be obtained with alcohols containing at least one double bond and 8 to 40
  • (meth) acrylamides can be obtained by reaction with an amine.
  • Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, ikosenol, docosenol, octadiene-ol, nonanoedia-ol, deca- dien-ol, undecadiene-ol, dodecadiene-ol, trideca-dien-ol, tetradeca-dien-ol, pentadeca-dien-ol, hexadeca-dien-ol, heptadeca-dien-ol, octadeca-diene ol, Nonadeca-dien-ol, Ikosa-dien-ol and
  • fatty alcohols are partly commercially available or can be obtained from fatty acids, this reaction being carried out, for example, in F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985).
  • the preferred (meth) acrylates obtainable by this process include, in particular, octadiene-yl (meth) acrylate, octadeca-diene-yl (meth) acrylate, octadecanetrienyl (meth) acrylate, Hexadecenyl (meth) acrylate, octadecenyl (meth) acrylate and hexadecadienyl (meth) acrylate.
  • Epoxy groups Accordingly, for example, too
  • Hydroxylalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,5-dimethyl-1,6 hexanediol (meth) acrylate,
  • Suitable fatty acids for reaction with the abovementioned (meth) acrylates are often commercially available and are obtained from natural sources. These include 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 preferred (meth) acrylates obtainable by this process include, in particular, (meth) acryloyloxy-2-hydroxypropyl linoleic acid ester, (meth) acryloyloxy-2-hydroxypropyl linolenic acid ester and (meth) acryloyloxy-2-hydroxypropyl oleic acid ester.
  • 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 an unsaturated radical having 9 to 25 carbon atoms, are used.
  • 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
  • Z is a linking group
  • R is hydrogen or a radical having 1 to 6 carbon atoms and R 2 is an unsaturated radical having 9 to 25
  • radical having 1 to 6 carbon atoms means a group having 1 to 6 carbon atoms
  • 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 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 or 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 a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, wherein the Ethylene group is particularly preferred.
  • the group R 2 in formula (II) represents an unsaturated radical having 9 to 25 carbon atoms.
  • These groups include in particular alkenyl,
  • Cycloalkenyl, alkenoxy, cycloalkenoxy, alkenoyl and heteroalipatic groups may have substituents, in particular halogen atoms or hydroxyl groups.
  • the preferred groups include in particular alkenyl groups, such as the nonenyl,
  • the preferred (meth) acrylic monomers of the formula (II) or (III) include heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecadienyloxy-2-ethyl (meth) acrylamide, heptadeca- trienoyloxy-2-ethyl (meth) acrylamide, heptadecenyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-palmitoleic acid amide, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy 2-ethyl-icosenoic acid amide, (meth) acryloyloxy-2-ethyl-cetolenic acid amide,
  • the notation (meth) acryl stands for acrylic and methacrylic radicals, with methacrylic radicals being preferred.
  • Particularly preferred monomers of the formula (II) or (III) are methacryloyloxy-2-ethyl-oleic acid amide,
  • Methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide are examples of methacryloyloxy-2-ethyl-linolenic acid amide.
  • the (meth) acrylic monomers of formula (II) or (III) can be any suitable (meth) acrylic monomers of formula (II) or (III)
  • a first stage for example, one or more unsaturated fatty acids or
  • Fatty acid esters with an amine for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine, to be reacted to 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 give the To obtain monomers of the formula (II) or (III).
  • Monomers in which X 1 is a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, and X 2 is oxygen, may correspondingly first be an alkyl (meth) acrylate, for example
  • Methyl (meth) acrylate with one of the aforementioned amines to a
  • (Meth) acrylamide are reacted with a hydroxy group in the alkyl radical, which is then reacted with an unsaturated fatty acid to a (meth) acrylic monomer of formula (II) or (III).
  • Transesterification of alcohols with (meth) acrylates or the preparation of (meth) acrylic acid amides are described inter alia in CN 1355161, DE 21 29 425, DE 34 23 443 or
  • intermediates obtained for example carboxamides which have hydroxyl groups in the alkyl radical
  • intermediates obtained can be purified.
  • intermediates obtained can be reacted without expensive purification to the (meth) acrylic monomers of formula (II) or (III).
  • (meth) acrylic monomers with 8 to 40, preferably 10 to 30 and particularly prefers 12 to 20 carbon atoms and
  • R 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 3 is an alkylene group having 1 to 22 carbon atoms
  • Y is oxygen, sulfur or a group of the formula NR ", where R" is hydrogen or a radical having 1 to 6 carbon atoms
  • R 4 is an unsaturated radical having at least 8 carbon atoms and at least two double bonds.
  • radical R 3 is an alkylene group having 1 to 22
  • Carbon atoms preferably with 1 to 10, particularly preferably with 2 to 6 carbon atoms.
  • the radical R 3 represents according to a special
  • an alkylene group having 2 to 4, more preferably 2 carbon atoms an alkylene group having 1 to 22 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 cyclohexylene group, with the ethylene group being particularly preferred.
  • the radical R 4 comprises at least two CC double bonds which are not part of an aromatic system.
  • the radical R 4 represents a group with exactly 8 carbon atoms, which has exactly two double bonds.
  • the radical R 4 preferably represents a linear hydrocarbon radical which has no heteroatoms.
  • the radical R 4 in formula (IV) may comprise a terminal double bond.
  • the radical R 4 in formula (IV) can not comprise a terminal double bond.
  • the double bonds contained in the radical R 4 may preferably be conjugated.
  • the double bonds contained in the radical R 4 are not conjugated.
  • the at least two radicals R 4 are not conjugated.
  • the double bonds include, among others, 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 (meth) acrylic monomers of the general formula (IV) include, inter alia, 2 - [((2-E) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [( (2-Z) octa-2,7-dienyl) methylamino] ethyl-2-methylprop-2-enoate,
  • the (meth) acrylic monomers of the formula (IV) set out above can be obtained in particular by processes in which (meth) acrylic acid or a (meth) acrylate, in particular methyl (meth) acrylate or ethyl (meth) acrylate with an alcohol and / or an amine is reacted. These reactions have been previously stated.
  • the starting material to be reacted with the (meth) acrylic acid or the (meth) acrylate may advantageously correspond to the formula (V),
  • HX-R-YR 4 (V), wherein X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 3 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 4 is an at least double unsaturated radical having at least 8 carbon atoms.
  • the preferred starting materials of the formula (V) 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 the formula (V) can be used individually or as a mixture.
  • the educts of formula (V) can be, inter alia, by known
  • telomerization means the reaction of compounds with conjugated double bonds in the presence of nucleophiles
  • Reaction conditions such as pressure and temperature, are included in the present application for purposes of disclosure.
  • 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 Palladiumcarbenkomplexe, in the previously set forth References are set forth in more detail, can be used with particular preference.
  • dialcohols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol
  • Diamines such as ethylenediamine, N-methylethylenediamine, ⁇ , ⁇ '-dimethylethylenediamine or hexamethylenediamine
  • aminoalkanols such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
  • (meth) acrylic acid for example, octadienyl (meth) acrylates can be obtained, which are particularly suitable as (meth) acrylic monomers having 8 to 40 carbon atoms.
  • Preferred pressure and temperature values at which the telomerization can be carried out have been set forth above, so that reference is hereby made.
  • the preparation of isomers from compounds having an octa-2,7-dienyl group can be carried out by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.
  • the (meth) acrylic polymer to be used according to the invention comprises
  • the proportion by weight of the respective units which comprise these polymers results from that for the production % of the monomers used in the corresponding monomers, since the proportion by weight of groups derived from initiators or
  • Molecular weight regulators are derived, usually negligible.
  • the above-mentioned (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group may be used singly or as a mixture of two or more monomers.
  • preferred polymers contained in the dispersions of the present invention may include recurring units derived from more
  • Monomers are derived.
  • copolymerizable monomers include, but are not limited to, monomers having an acid group, monomers A comprising ester groups
  • Acid group-containing monomers are compounds which are preferably free-radical with the photoinitiator monomers set forth above
  • copolymerize 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 described above, fumarates, maleates and / or vinyl acetate.
  • the expression (Meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • the comonomers mentioned include, inter alia, (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical, which are not
  • the (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include, inter alia, (meth) acrylates having a linear or branched alkyl radical, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate,
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate
  • Cyclohexyl (meth) acrylate, bornyl (meth) acrylate, norbornyl (meth) acrylate and isobornyl (meth) acrylate may be used singly or as a mixture.
  • (meth) acrylic polymers which comprise a high proportion of (meth) acrylates having 1 to 6, preferably 1 to 4 and particularly preferably 1 or 2, carbon atoms in the alkyl radical, these monomers having no double bonds or heteroatoms in the alkyl radical. Accordingly, particularly preferred are (meth) acrylic polymers which are at least 20,
  • methyl methacrylate preferably have methyl methacrylate.
  • Alkyl radical which has no double bonds or heteroatoms in the alkyl radical can be at least 0.5: 1, more preferably at least 2: 1, this weight ratio preferably being in the range from 10: 1 to 1: 2, more preferably 6: 1 to 1: 1, and very particularly preferably 4: 1 to 3: 2.
  • Another class of comonomers are (meth) acrylates having at least 1 1 carbon atoms in the alkyl radical, which are derived from saturated alcohols and have no heteroatoms in the alkyl radical, such as
  • Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate;
  • heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate, 1- (2- (meth) acryloyloxyethyl) -2-pyrrolidone, 2- (3-oxazolidinyl) ethyl methacrylate, N- (2- (meth) acryloyloxyethyl) ethylene urea, N- (2- (meth) acrylamidoethyl) ethylene urea);
  • Carbonyl group-containing (meth) acrylates such as acetoacetyloxyethyl methacrylate (AAEMA);
  • Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as N- (methacryloyloxyethyl) diisobutylketimine, N-
  • Aryl (meth) acrylates such as benzyl (meth) acrylate, benzophenone methacrylate (BPMA) or phenyl (meth) acrylate, where the aryl radicals are each unsubstituted or up to may be substituted four times;
  • 2-hydroxyethyl (meth) acrylate preferably 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl (meth) acrylate, for example 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate
  • HEMA 2-hydroxyethyl methacrylate
  • hydroxypropyl (meth) acrylate for example 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate
  • HBMA hydroxybutyl methacrylate
  • Polyethylene glycol monomethacrylate having about 5 ethylene oxide units PEM5
  • polybutylene glycol mono (meth) acrylate polyethylene glycol polypropylene glycol mono (meth) acrylate
  • PEM5 Polyethylene glycol monomethacrylate having about 5 ethylene oxide units
  • DAAM Diacetone acrylamide
  • methacrylamide methacrylamide
  • acrylamide methacrylamide
  • Another class of comonomers are crosslinking monomers. These monomers have at least two double bonds with similar reactivity in a free-radical polymerization.
  • These include, in particular, (meth) acrylates derived from diols or higher alcohols such as 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, 1,3-butanediol (meth) acrylate,
  • Pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are also include vinyl esters, such as vinyl acetate,
  • Vinyl chloride vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride;
  • Maleic acid for example dimethyl maleate
  • Another group of comonomers are styrenic monomers, such as
  • Side chain such.
  • ⁇ -methylstyrene and ⁇ -ethylstyrene substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
  • Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride are further examples of comonomers.
  • (meth) acrylic polymers preferably 1 wt .-% to 99 wt .-%, preferably 20 wt .-% to 95 wt .-% and most preferably 40 wt .-% to 90 wt. -% of units derived from (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical, which have no double bonds or heteroatoms in the alkyl radical, based on the weight of the (meth) acrylic polymer.
  • (meth) acrylic polymers which contain 0 to 10% by weight, preferably 0.5 to 8% by weight and more preferably 1 to 5% by weight, of units derived from acid groups Monomers are derived, based on the weight of the (meth) acrylic polymer.
  • the (meth) acrylic polymer according to the invention may comprise 0 to 60% by weight, more preferably 5 to 50% by weight and most preferably 10 to 40% by weight of units derived from Styrene monomers, in particular of styrene, substituted styrenes having an alkyl substituent in the side chain, substituted styrenes with an alkyl substituent on the ring and / or halogenated styrenes are derived, based on the weight of the (meth) acrylic polymer.
  • (meth) acrylic polymers which have a very small proportion of (meth) acrylates having two or more carbon-carbon double bonds having a reactivity identical to a (meth) acrylate group. According to a special
  • Modification of the present invention is the proportion of compounds having two or more (meth) acrylate groups preferably at most 5 wt .-%, in particular at most 2 wt .-%, particularly preferably at most 1 wt .-%, particularly preferably at most 0 5 wt .-% and especially preferably at most 0, 1 wt .-% limited, based on the weight of the (meth) acrylic polymer.
  • Preferred polymers to be used according to the invention comprise
  • polymers to be used according to the invention comprise polymers
  • core-shell polymers can be used as (meth) acrylic polymer, wherein the outermost shell of the core-shell polymer preferably has a (meth) acrylate segment, the
  • (Meth) acrylic monomers are derived which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical,
  • Carbon atoms are derived in the alkyl radical, each based on the
  • the iodine number of the polymers to be used according to the invention is preferably in the range from 2 to 250 g of iodine per 100 g of polymer, more preferably 5 to 100 g of iodine per 100 g of polymer and most preferably 10 to 50 g of iodine per 100 g of polymer, measured 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 to be used according to the invention can be a
  • the acid number can also be determined according to DIN EN ISO 21 14 by means of a dispersion.
  • 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 lie.
  • the hydroxyl number can also be determined by dispersion according to DIN EN ISO 4629.
  • 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 10 to 100 nm, preferably 10 to 59 nm can be used.
  • the radius of the particles is preferably in the range of 60 nm to 500 nm, more preferably 70 to 150 nm, and all
  • the radius of the particles can be determined by PCS (Photon Correlation Spectroscopy), wherein the
  • Submicron Particle Size Analyzer can be used.
  • the glass transition temperature of the polymer is preferably in the range of 0 ° C to 70 ° C, more preferably in the range of 5 to 60 ° C and most preferably in the range of 10 to 50 ° C.
  • Glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer. It can the
  • DSC Differential scanning calorimetry
  • Center of the glass stage of the second heating curve can be determined with a heating rate of 10 ° C per minute. Furthermore, the glass transition temperature
  • Tg can also be calculated approximately in advance by means of the Fox equation.
  • x n is the mass fraction (wt .-% / 100) of monomer n and Tg n is the glass transition temperature in Kelvin of the homopolymer of the monomer n denotes. Further helpful hints can the expert the polymer Handbook 2 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. This information is therefore valid for a segment that is covered by
  • the dispersions of the (meth) acrylic polymers to be used according to the invention with units derived from (meth) acrylic monomers which in the alkyl radical have at least one double bond and 8 to 40
  • Coalescence aid contains.
  • the architecture of the polymer is not critical to many applications and properties. Accordingly, the polymers, in particular the emulsion polymers, can be random copolymers, gradient copolymers,
  • Block copolymers and / or graft copolymers can be obtained, for example, by reacting the monomer composition during chain growth
  • the emulsion polymer is a random copolymer in which the monomer composition is substantially constant throughout the polymerization.
  • the monomers are different
  • Copolymerization parameters may have the exact
  • Varying composition over the polymer chain of the polymer is achieved by Varying composition over the polymer chain of the polymer.
  • the polymer preferably the emulsion polymer, may be a homogeneous polymer which, for example in an aqueous dispersion, forms particles having a uniform composition.
  • the emulsion polymer may consist of one or more segments exist, which are obtainable by polymerization of the monomers or monomer mixtures set forth 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 be polymerized without grafting on the core or an inner shell.
  • the weight ratio of segment obtained by polymerizing a monomer mixture with (meth) acrylic monomers obtainable in the alkyl radical having at least one double bond and 8 to 40 carbon atoms to core in the range of 10: 1 to 1: 6 is particularly preferred 5: 1 to 1: 3 lie.
  • 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) acrylic acid whose alcohol radical preferably comprises 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbon atoms. These include in particular
  • 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.
  • polymers of the core may be those set forth above
  • Comonomers include.
  • 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. Allyl methacrylate is the preferred polyunsaturated monomer when shell grafting onto the core is desired.
  • the shell of preferred emulsion polymers to be used may preferably comprise from 15 to 50% by weight of units derived from (meth) acrylic monomers having at least one double bond and from 8 to 40 carbon atoms in the alkyl radical.
  • the core may preferably be a
  • the shell may preferably have a glass transition temperature in the range of -30 ° C to 70 ° C, more preferably in the range of -0 to 50 ° C and most preferably in the range of 10 to 40 ° C.
  • the glass transition temperature of the core may be greater than the glass transition temperature of the shell.
  • the polymerization is carried out as emulsion polymerization.
  • Additives, in particular emulsifiers and protective colloids for stabilizing the emulsion may include. Monomers are then added to this aqueous phase and polymerized in the aqueous phase. The addition of the monomers may be continuous or batchwise as a mixture or emulsion in water over a period of time. The emulsion polymerization can be carried out, for example, as a mini or as
  • Microemulsion be carried out. The more detailed 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.
  • Droplet size in miniemulsions is preferably in the range of 0.05 to 20 pm.
  • 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 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. In the preparation of homogeneous emulsion polymers can be carried out by known means. These include, in particular, mechanical methods and the use of ultrasound. In the preparation of homogeneous emulsion polymers can
  • a monomer mixture which preferably comprises 0.5 to 60 wt .-%, more preferably 1 to 40 wt .-% of (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 to 40 carbon atoms.
  • 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.
  • graft or polymerize onto the core a monomer mixture which comprises from 1 to 60% by weight, preferably from 15 to 25% by weight, of (meth) acrylic monomers which have at least one double bond in the alkyl radical and 8 to 40 carbon atoms.
  • the emulsion polymerization is preferably carried out at a temperature in the range of 0 to 120 ° C, particularly preferably in the range of 30 to 100 ° C.
  • polymerization temperatures in the range of greater than 60 to less than 90 ° C, suitably in the range of greater than 70 to less than 85 ° C, preferably in the range of greater than 75 to less than 85 ° C, proved to be particularly favorable.
  • the initiation of the polymerization is carried out with the for
  • Emulsion polymerization common initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide.
  • Suitable inorganic initiators are
  • Peroxodisulfuric especially ammonium, sodium and
  • 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,
  • the initiators mentioned can be used both individually and in mixtures. 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 preferable to carry out the polymerization with a mixture of different polymerization initiators having a different half-life, in order to keep the 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.
  • 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. According to a particular aspect of the present invention, 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
  • Alkyl, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl group and 1 to 50 ethylene oxide units;
  • Sulfonates preferably alkylsulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylarylsulfonates 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;
  • these alcohols or alkylphenols can also be from 1 to 40
  • 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
  • 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 may in particular be sold under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 are commercially available from Cognis GmbH, Cytec Industries, Inc. and Bayer AG.
  • Useful nonionic emulsifiers include tert-octylphenol ethoxylate with 30 ethylene oxide units and
  • Fatty alcohol polyethylene glycol ethers 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.
  • 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 fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a Diisooctylsulfosuccinat or a paraffin sulfonate as an anionic emulsifier and a
  • Alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ethers which in each case preferably have 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units, have proven particularly useful as nonionic emulsifier.
  • 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,
  • 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 submitted or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.
  • the polymerization by heating the batch on the
  • the dosages of emulsifier and monomers can be carried out separately or as a mixture, in particular as an emulsion in water.
  • the procedure is such that emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor or emulsified in water.
  • a portion of the monomers e.g. 1 - 10%, presented in the reactor and the polymerization started by addition of initiator.
  • With the dosage of the remaining monomers is preferably after the initiation of the polymerization, e.g. Started 5 to 15 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, the reaction parameters for obtaining a high molecular weight being known.
  • 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.
  • the dispersion is preferably adjusted to a pH of 7 to 10 after the preparation or during the preparation of a coating formulation by the addition of alkali.
  • Coalescence aid be mixed.
  • Coalescence aid may preferably be carried out at a temperature in the range from -10 to 50 ° C, more preferably in the range from 0 to 40 ° C. This can be done after the polymerization or only during the formulation into a coating medium.
  • Carbon atoms can be in a wide range, which can be generally adapted to the desired property profile.
  • the aqueous dispersions can be used as Be Anlagenungsm ittel.
  • 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 of 0, 1 to 10,000 mPas, preferably 1 to 1000 mPas and most preferably 10 to 500 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield) ,
  • coalescing aids and the above-described (meth) acrylic polymers comprising repeating units derived from (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical
  • the novel coating compositions or the aqueous compositions to be used according to the invention Dispersions contain additives or other components to the
  • Drying aids so-called siccatives, flow improvers, pigments and dyes.
  • compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions. Desiccatives can be particularly preferred for the aqueous
  • Dispersions are added. These include in particular
  • 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.
  • cobalt naphthalate and cobalt acetate As an example, mention may be made of cobalt naphthalate and cobalt acetate.
  • the siccatives can be used individually or as a mixture, with particular preference being given to mixtures containing cobalt, zirconium and lithium salts.
  • the coating compositions according to the invention preferably have a
  • aqueous dispersions with the abovementioned coalescence aids of the present invention can be used in particular as a coating agent or as an additive. These include in particular paints,
  • Impregnating agents for the production of paints or
  • Impregnating agents for applications on wood and / or metal serve.
  • Coatings show a high solvent resistance, in particular, only small proportions are dissolved by solvent from the coating.
  • Preferred coatings show a high resistance in particular to methyl isobutyl ketone (MIBK). So is the
  • Weight loss after treatment with MIBK preferably at most 50 wt .-%, preferably at most 35 wt .-%.
  • the uptake of MIBK is preferably at most 500% by weight, particularly preferably at most 300% by weight, based on the weight of the coating used. These values are measured at a temperature of approx. 25 ° C and a contact time of
  • 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 a high mechanical resistance.
  • the pendulum hardness is preferably at least 25 s, preferably at least 35 s, particularly preferably at least 50 s, measured in accordance with DIN ISO 1522.
  • Inventive coatings show surprisingly good mechanical properties.
  • coatings which have a nominal elongation at break of preferably at least 100%, particularly preferably at least 200%, measured in accordance with DIN EN ISO 527 Part 3.
  • Tensile strength measured according to DIN EN ISO 527 Part 3, of at least 0.5 MPa, more preferably at least 2 MPa show. Furthermore, the present invention surprisingly provides coatings which have a tensile strength of at least 1 MPa, particularly preferably at least 2 MPa, an elongation at break of at least 100%, particularly preferably at least 200%.
  • coating compositions according to the invention are available, a surprisingly high adhesive strength, which can be determined in particular according to the cross-cut test.
  • a classification of 0-1, particularly preferably of 0 according to the standard DIN EN ISO 2409 can be achieved.
  • Fatty acid methyl ester mixture 42.8 g (0.70 mol) of ethanolamine and 0.27 g (0.26%) submitted LiOH.
  • the fatty acid methyl ester mixture comprised 6% by weight saturated C12 to C16 fatty acid methyl ester, 2.5% by weight saturated C17 to C20 fatty acid methyl ester, 52% by weight monounsaturated C18
  • the reaction mixture was heated to 150 ° 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 without
  • Methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 ° C. After completion of the reaction, the reaction mixture was cooled to about 70 ° C and filtered.
  • Ammonium peroxodisulfate (APS) dissolved in 10 g of water. 5 minutes after the APS addition, the previously prepared emulsion was within 240 Minutes (interval: 3 minutes inflow, 4 minutes pause, 237 minutes remaining inflow).
  • the prepared dispersion had a solids content of 39.5%, a pH of 5.9, a viscosity of 1 1 m Pas, an r N 5 value of 91 nm and a minimum film-forming temperature of 52 ° C.
  • Preparation Example 1 was substantially repeated but using a monomer mixture comprising 350 g of butyl acrylate (BA), 826 g of methyl methacrylate (MMA), 210 g of methacryloyloxy-2-ethyl-fatty acid amide mixture, 14 g of methacrylic acid (MAS).
  • BA butyl acrylate
  • MMA methyl methacrylate
  • MAS methacrylic acid
  • the dispersion produced had a solids content of 39.7%, a pH of 5.8, a viscosity of 12.5 mPas, an r N 5 value of 73 nm and a minimum film-forming temperature of 36.5 ° C.
  • Ammonium peroxodisulfate (APS) dissolved in 10 g of water. 5 minutes after the addition of APS, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed).
  • the prepared dispersion had a solids content of 39.8%, a pH of 2.5, a viscosity of 14 mPas. a r N 5 value of 71 nm and a minimum film formation temperature of 44.0 ° C.
  • Preparation Example 3 was substantially repeated but using a monomer mixture comprising 350 g of butyl acrylate (BA), 826 g of methyl methacrylate (MMA), 210 g of methacryloyloxy-2-hydroxypropyl linoleic acid ester, 14 g of methacrylic acid (MAS).
  • BA butyl acrylate
  • MMA methyl methacrylate
  • MAS methacrylic acid
  • the dispersion produced had a solids content of 39.8%, a pH of 2.3, a viscosity of 13.5 mPas, an r N 5 value of 74 nm and a minimum film-forming temperature of 34.5 ° C.
  • Ammonium peroxodisulfate (APS) dissolved in 10 g of water. 5 minutes after the addition of APS, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed).
  • the dispersion produced had a solids content of 38.5%, a pH of 2.5, a viscosity of 14 m Pas, an r N 5 value of 59 nm and a minimum film-forming temperature of 41 ° C.
  • Coating medium prepared by addition of coalescence aids.
  • 2,7-octadienol and 2,7-octadienol * 5 PO were used for this purpose.
  • the data obtained and the amounts of 2,7-octadienol used are set forth in Tables 1 and 2.
  • the data relate to the weight of the respective components, wherein the data of the dispersion refer to the solids content.
  • MFT Minimum film forming temperature
  • MFT Minimum film forming temperature
  • MFT Minimum film forming temperature
  • TMPTMA Trimethylolpropane tri (meth) acrylate
  • TMPTMA trimethylolpropane tri (meth) acrylate
  • MFT minimum film forming temperature
  • Components, wherein the information of the dispersion refer to the solids content.
  • the properties of the coating composition thus obtained were examined by various methods. For this purpose, tests on solvent resistance, water absorption and hardness 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. Subsequently, the sample was removed from the MIBK
  • the values set forth in Table 7 refer to the weight of the coating after treatment with MIBK, also referred to herein as "true swelling.”
  • the hardness of the coating which is usually a measure of scratch resistance, was measured using the Pendulum Test according to König (DIN ISO 1522).
  • Weight percent refers to the solids content of the dispersion. Before testing the solvent resistance, the paints were dried for 10 days. The pendulum hardnesses were measured after different drying times.
  • Pendulum hardness was measured after different drying times.
  • Example 37 20 1, 5 57 63 63
  • Weight percent refers to the solids content of the dispersion. Before testing the solvent resistance, the paints were dried for 10 days. The pendulum hardnesses were measured after different drying times.
  • Weight percent refers to the solids content of the dispersion. Before testing the solvent resistance, the paints were dried for 10 days. Table 10
  • Weight percent refers to the solids content of the dispersion.
  • the pendulum hardnesses were measured after different drying times of the lacquers.
  • the dispersion described in Preparation Example 5 was admixed with 5% by weight of the coalescing aid indicated in Table 16 and 1.5% by weight of siccative (Nuodex®), the percentages being based on the solids content of the dispersion.
  • the pendulum hardnesses were measured after different drying times of the lacquers.

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

Abstract

L'invention concerne un produit de revêtement aqueux comprenant au moins une dispersion d'un polymère (méth)acrylique et au moins un adjuvant de coalescence. Le polymère (méth)acrylique contient des motifs dérivés de monomères (méth)acryliques dont le reste alkyle présente au moins une double liaison et de 8 à 40 atomes de carbone, tandis que l'adjuvant de coalescence présente au moins une double liaison éthyléniquement insaturée et une masse moléculaire inférieure à 1000 g/mole.
PCT/EP2011/064785 2010-09-23 2011-08-29 Produit de revêtement à base de polymère (méth)acrylique et d'adjuvants de coalescence WO2012038197A1 (fr)

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DE102010041272A DE102010041272A1 (de) 2010-09-23 2010-09-23 Beschichtungsmittel mit (Meth)acryl-Polymeren und Koaleszenzhilfsmitteln
DE102010041272.4 2010-09-23

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Publication number Priority date Publication date Assignee Title
JP2016204562A (ja) * 2015-04-24 2016-12-08 東邦化学工業株式会社 ポリカルボン酸系共重合体及びそれからなる分散剤

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US11884846B2 (en) * 2018-04-20 2024-01-30 Basf Se Adhesive composition having a gel content based on cross-linking via keto groups or aldehyde groups

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WO2008094503A2 (fr) 2007-01-30 2008-08-07 University Of South Mississippi Dérivés d'huile végétale fonctionnalisés dépourvus d'ester de glycérol et leurs compositions de latex
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016204562A (ja) * 2015-04-24 2016-12-08 東邦化学工業株式会社 ポリカルボン酸系共重合体及びそれからなる分散剤

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