EP2414462A1 - Composition de revêtement, polymère (méth)acryle et mélange de monomères pour la production du polymère (méth)acryle - Google Patents

Composition de revêtement, polymère (méth)acryle et mélange de monomères pour la production du polymère (méth)acryle

Info

Publication number
EP2414462A1
EP2414462A1 EP10711675A EP10711675A EP2414462A1 EP 2414462 A1 EP2414462 A1 EP 2414462A1 EP 10711675 A EP10711675 A EP 10711675A EP 10711675 A EP10711675 A EP 10711675A EP 2414462 A1 EP2414462 A1 EP 2414462A1
Authority
EP
European Patent Office
Prior art keywords
meth
coating composition
carbon atoms
monomers
acrylate
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Withdrawn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
EP10711675A
Other languages
German (de)
English (en)
Inventor
Christine Maria BREINER
Gerold Schmitt
Thorben SCHÜTZ
Joachim Knebel
Ina Zwierzchowski
Margarita Stein
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.)
Evonik Roehm GmbH
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 EP2414462A1 publication Critical patent/EP2414462A1/fr
Withdrawn legal-status Critical Current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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • Coating composition (meth) acrylic polymer and monomer mixture for producing the (meth) acrylic polymer
  • the present invention relates to a coating composition, a (meth) acrylic polymer and a monomer mixture for producing the (meth) acrylic polymer.
  • the present invention is directed to a process for producing a coating carried out using the coating agent and an article obtainable thereby.
  • Coating agents in particular paints, have been produced synthetically for a long time.
  • An important group of these agents is based on aqueous dispersions, many times
  • the coating compositions described above already show a good property spectrum. However, there is a permanent need to improve this property spectrum.
  • the compositions set forth above require a relatively long time for the resultant coatings to be dust-dry or tack-free. This applies in particular to the coating compositions which can be oxidatively crosslinked by oxygen. Although these drying times can be shortened by adding large amounts of siccatives.
  • this other properties of the coating materials in particular the processability, durability and, depending on the type of siccatives used, the environmental impact reduced. With regard to processability and durability, it should be noted that exposure to atmospheric oxygen very quickly leads to crosslinking of the unsaturated fatty acids, if high
  • UV radiation curable coating compositions set forth in WO 98/033855 must be cured with very high irradiation energies, excluding oxygen. Without these high light energies or in the presence of oxygen, coatings are often obtained which show a low resistance to solvents. Accordingly, the processing of these coating compositions is relatively expensive.
  • compositions to provide with excellent properties. These properties include in particular a very good workability and durability of the
  • Coating compositions are provided.
  • those obtainable from the coating compositions should
  • Coatings will be dust-dry and tack-free after a very short time. Further, the coating compositions should show a long pot life in terms of dust dry time, so that the coating composition can be processed for a relatively long time after opening the container.
  • 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 organic solvents should be given.
  • the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range.
  • particularly hard, scratch-resistant coatings should be obtainable from the coating compositions.
  • coatings obtainable from the coating compositions of the invention should have a relatively low brittleness in terms of hardness.
  • the coatings obtainable from the coating compositions should have a high weather resistance, in particular a high UV resistance.
  • the coating compositions should show improved environmental compatibility.
  • the smallest possible amounts of organic solvents should be released into the environment by evaporation.
  • the coating compositions should have a low residual monomer content.
  • Another object can be seen in providing coating compositions that can be obtained very inexpensively and on an industrial scale.
  • Coating composition may be included, monomer mixtures for the preparation of preferred polymers, a process for the preparation of a coating and a coated article, the claims 14, 17, 21 and 23 provide a solution to the underlying problems.
  • the subject of the present invention is accordingly a
  • a coating composition characterized in that the composition comprises at least one photoinitiator and at least one (meth) acrylic polymer having units derived from (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl radical ,
  • the coating compositions according to the invention show excellent processability.
  • films formed from the coating compositions of the invention become dust-dry and tack-free after a relatively short time.
  • the coating compositions according to the invention have a long pot life, so that the coating compositions can be stored for a long time even after opening the storage container.
  • the coatings obtainable from the coating compositions of the present invention exhibit high chemical resistance and increased weathering stability as well as high blocking resistance and fast adhesion and dust-free properties.
  • a high stability to water and many different organic solvents as well as to bases and acids can be achieved.
  • the coating shows a high wet adhesion.
  • the coatings available from the coating agent are characterized by a low water absorption.
  • the coated article furthermore has a high water permeability, in particular with respect to water vapor.
  • textiles can be provided with the coating compositions without the permeability to water vapor would be too much affected.
  • the hardness of the coatings obtainable from the coating compositions can be varied over a wide range.
  • particularly hard, scratch-resistant coatings can be obtained.
  • coatings which are obtainable from the coating compositions according to the invention, based on the hardness and the chemical resistance, a relatively low brittleness.
  • the coating compositions show improved environmental compatibility. Thus, extremely small amounts of organic solvents are released into the environment through evaporation. Particularly preferred embodiments show no release of organic solvents into the atmosphere. Furthermore, the coating compositions have a low residual monomer content. Here, the coating compositions may comprise a high solids content. In addition, inventive lead
  • Coating compositions to coatings with a high gloss exhibit particularly long shelf life and durability.
  • the coatings obtainable from the coating compositions show a high weather resistance, in particular a high UV resistance.
  • the novel coating compositions are particularly cost-effective and commercially available.
  • a coating composition according to the invention comprises at least one photoinitiator.
  • Photoinitiators are compounds that can form active species upon irradiation with electromagnetic waves. Without intending to be limited, it is commonly believed that the active species can initiate radical processes that promote hardening of the coating composition.
  • Preferred photoinitiators can be activated by irradiation with light having a wavelength in the range of 200 to 800 nm.
  • Preferred photoinitiators are characterized in particular by the fact that a composition comprising at least 95% by weight, preferably at least 98% by weight, of ethoxylated pentaerythritol tetraacrylate having the CAS no. 51728-26-8 (PPTTA), commercially available from Akcros Chemicals under the tradename Actilane 440, commercially available from Cytec under the tradename Ebecryl 40, commercially available from Rahn AG under the tradename Genome 1456, and commercially available from Sartomer under the tradename SR 494).
  • PPTTA ethoxylated pentaerythritol tetraacrylate having the CAS no. 51728-26-8
  • a coating obtainable from this composition preferably has a pendulum hardness of at least 40 s, more preferably at least 90 s, measured in accordance with DIN ISO 1522.
  • Preferred photoinitiators may often include a ketone functionality and an aromatic group. In many cases, photoinitiators are distinguished by the assumed mechanism of action, without this being intended to limit them.
  • type I photoinitiators believed to undergo ⁇ -cleavage include thioxanthone and derivatives of this compound, particularly isopropylthioxanthone (ITX), fluorenone and derivatives of this compound, anthraquinone and derivatives of this compound, xanthone and derivatives of this compound , Benzoins and benzoin derivatives, in particular benzoin ethers, such as benzoin alkyl ethers, benzil ketals, in particular benzil dimethyl ketals, acylphosphine oxides, in particular 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, alpha-
  • Type II photoinitiators believed to undergo hydrogen transfer include, but are not limited to, benzophenone and derivatives of this compound, such as alkylbenzophenones, diphenoxybenzophenones, aminofunctionalized benzophenones, for example, 4,4'-bis (dimethylamino) benzophenone (Michler's Ket ), and halogenated benzophenones and anthrone, camphorquinone and derivatives of this compound, benzil and phenylpropanedione.
  • the photoinitiators of type II can preferably be used in combination with amines, preferably tertiary amines.
  • Norrish II type photoinitiators which can preferably be used in combination with an amine.
  • low molecular weight photoinitiators can be used, which preferably have a molecular weight of less than 1000 g / mol, particularly preferably up to 800 g / mol.
  • the preferred photoinitiators include, in particular, mono- or bisacylphosphine oxides, for example diphenyl 2,4,6-trimethylbenzoylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ( ⁇ IRGACU-RE 819), bis (2,6- dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; ⁇ -hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone ( ⁇ IRGACURE 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone ( ⁇ DAROCUR 1173), 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone ( ⁇ IRGACURE 2959); ⁇ -aminoketones such as 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone ( ⁇ I
  • Methylphenylglyoxylic acid ester 5,5'-oxo di (ethyleneoxydicarbonylphenyl) or 1,2-
  • photoinitiators having a molecular weight greater than or equal to 1000 g / mol, in particular greater than or equal to 2000 g / mol.
  • Photoinitiators having a molecular weight of at least 1000 g / mol can be obtained by polymerization of mixtures comprising photoinitiator monomers.
  • Photoinitiator monomers are photoinitiators having at least one carbon-carbon double bond that is free-radically polymerizable.
  • Polymeric photoinitiators or copolymerized photoinitiators lead to particularly environmentally friendly and harmless coatings, since these photoinitiators do not lead to a migration of components into the environment. This property is particularly useful in printing inks or coatings for
  • polymeric photoinitiators lead to coatings which have a particularly high solvent resistance and excellent mechanical properties. Furthermore, coating compositions comprising these polymeric photoinitiators exhibit particularly good processability and durability.
  • Preferred photoinitiator monomers include (meth) acrylates having a keto group of general formula I. wherein R 1 is hydrogen or methyl, X 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 bond or a linking group, R 2 is hydrogen, halogen, hydroxy or a 1 to 20 carbon atoms, m is an integer in the range of 0 to 4 and R 3 is a radical having 1 to 20 carbon atoms.
  • the group Z in formula (I) represents a bond or a group having 1 to 2000 carbon atoms, preferably 1 to 1000 carbon atoms, and more preferably 1 to 500 carbon atoms.
  • the preferred compound groups Z include, in particular, groups of the formula (II)
  • R 4 is a bond, oxygen, sulfur, or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, O-CO-O, HN-CO-O, HN-CO-NH or a linking group of 1 to 20 carbon atoms stands; R 5 , R 6 , R 7 are independently hydrogen or methyl, n is an integer from 0 to 200, preferably 1 to 100, o and p are independently an integer from 0 to 2.
  • the radical R 2 in formula (I) preferably represents hydrogen or a radical having 1 to 20 carbon atoms.
  • the group R 3 in formula (I) preferably denotes an aromatic or heteroaromatic radical, with aryl radicals, in particular phenyl radicals, being particularly preferred.
  • the group R 3 represents an aromatic or heteroaromatic radical and the linking group Z represents a bond.
  • R 1 is hydrogen or methyl
  • X 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 bond or a linking group
  • R 2 is hydrogen, halogen, hydroxy or a radical having 1 to 20 carbon atoms
  • m is an integer in the range of 0 to 4
  • R 8 is Is hydrogen, halogen, hydroxy or a radical having 1 to 20 carbon atoms and r represents an integer in the range of 0 to 5.
  • the radicals having 1 to 20 carbon atoms include, but are not limited to, (C1-C20) alkyl, (C1-C20) alkoxy, (C1-C20) -althio, (C2-C20) -alkenyl, (C 2 -C 20) -alkynyl, aryl or heterocyclyl, where the aryl or heterocyclyl radicals may be unsubstituted or may be provided with up to three, in the case of fluorine also up to the maximum number of identical or different radicals, and in said alkyl, Alkenyl or alkynyl radicals one or more, preferably up to three nonadjacent saturated carbon units may be replaced by heteroatom units such as oxygen or sulfur, and further wherein 3 to 6 atoms of these optionally as modified hydrocarbon radicals form a cycle can and these hydrocarbon radicals with or without the specified variations, optionally with one or more, preferably up to three, in the case of halogen to the
  • (C 1 -C 20) -alkyl means an unbranched or branched hydrocarbon radical having 1 to 20 carbon atoms, such as. As the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical; as well as As the pentyl, 2-methylbutyl, 1,1-
  • Aryl is an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, C atoms, for example phenyl, naphthyl or biphenylyl, preferably phenyl.
  • aryloxy is meant, for.
  • arylthio or 1- or 2-naphthylthio group by the term “(C 3 -C 8) -cycloalkoxy” a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group which is linked via an oxygen
  • (C 3 -C 8) -cycloalkylthio a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group linked via a sulfur atom.
  • heterocyclyl means a heteroaromatic or heteroaliphatic ring system, wherein
  • heteromatic ring system is an aryl radical in which at least one CH group is replaced by N and / or at least two adjacent CH groups are replaced by S, NH or O, to understand, for.
  • Cinnoline 1,8-naphthyridine, 1,5-naphthyridine, 1,6-
  • heteroaliphatic ring system means a cycloalkyl radical in which at least one carbon unit is substituted by O, S or a
  • Group NR "is replaced and R" is hydrogen, (C 1 -C 4) -alkyl or aryl; the term “heterocyclyloxy” denotes one of the abovementioned heterocyclic radicals which are linked via an oxygen atom; and under (C 1 -C 2) -alkoxycarbonyl the methoxycarbonyl or ethoxycarbonyl group.
  • a 4-hydroxybenzophenone methacrylate preferably 4-hydroxybenzophenone * 13EO-methacrylate and / or a methacryloxybenzophenone, in particular 4-methacryloyloxybenzophenone, is particularly expediently used.
  • the (meth) acrylates having a keto group of the general formulas (I) or (III) set out above can be prepared, for example, by transesterification of (meth) acrylates or esterification of (meth) acrylic acid with corresponding aromatic keto compounds, in particular benzophenone compounds, which have a
  • aromatic keto compounds in particular benzophenone compounds which comprise hydroxyl or amine groups, can be reacted with reactive (meth) acrylates, in particular (meth) acryloyl halides or (meth) acrylic anhydrides.
  • photoinitiator monomers are described in EP-A-333 291, filed in the European Patent Office on Under Application No. 89200652.9, the photoinitiators set forth therein and methods for their preparation being included in this application for purposes of disclosure.
  • photoinitiator monomers according to the above formula (I) can be commercially obtained, for example, under the trade name Ebecryl® P36 and Ebecryl® P38.
  • Photoinitiator monomers can preferably be copolymerized free-radically.
  • These copolymerizable monomers include, but are not limited to, monomers having an acid group, monomers A comprising ester groups, and styrenic monomers.
  • Acid group-containing monomers are compounds which can be preferably radically copolymerized with the photoinitiator monomers set forth above. These include, for example, monomers with 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 photoinitiator monomers, fumarates, maleates and / or vinyl acetate.
  • the term includes (meth) acrylates Methacrylates and acrylates and 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 have no double bonds or heteroatoms in the alkyl radical.
  • 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, tert.
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, norbornyl (meth) acrylate and isobornyl (meth) acrylate.
  • the above-described (meth) acrylates having 1 to 10 carbon atoms in the alkyl group may be used singly or as a mixture.
  • Another class of comonomers are (meth) acrylates having at least 11 carbon atoms in the alkyl radical, which are derived from saturated alcohols and have no heteroatoms in the alkyl radical, such as undecyl (meth) acrylate, 5-methyl undecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, Tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate,
  • Cycloalkyl (meth) acrylates such as 2, 4, 5-tri-t-butyl
  • 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 a hydroxy group in the alkyl radical, in particular
  • Hydroxyethyl methacrylate HEMA
  • Hydroxypropyl (meth) acrylate for example, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate (HPMA), hydroxybutyl (meth) acrylate, preferably hydroxybutyl methacrylate (HBMA), 3,4-dihydroxybutyl (meth) acrylate , 2, 5-Dimethyl-l, 6-hexanediol (meth) acrylate, 1, 10-decanediol (meth) acrylate, glycerol mono (meth) acrylate and polyalkoxylated derivatives of (meth) acrylic acid, in particular polypropylene glycol mono (meth) acrylate with 2 to 10, preferably 3 to 6 propylene oxide units, preferably polypropylene glycol monomethacrylate with about 5 propylene oxide units (PPM5), polyethylene glycol mono (meth)
  • (Meth) acrylamides in particular N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, tert. Butylaminoethyl methacrylate, methacrylamide and acrylamide; Glycerol carbonate methacrylate; 2-carbamoyloxyethyl methacrylate and
  • (Meth) acrylates derived from saturated fatty acids or fatty acid amides such as (meth) acryloyloxy-2-hydroxypropyl-palmitic acid ester, (meth) acryloyloxy-2-hydroxypropyl-stearic acid ester and (meth) acryloyloxy-2-hydroxypropyl-laurin ester, pentadecyloyloxy- 2-ethyl- (meth) acrylamide, heptadecyloyloxy-2-ethyl- (meth) acrylamide, (meth) acryloyloxy-2-ethyl-lauric acid amide, (meth) acryloyloxy-2-ethyl- myristic acid amide, (meth) acryloyloxy-2-ethyl-palmitic acid amide, (meth) acryloyloxy-2-ethylstearic acid amide, (meth) acryloyloxy-2-
  • Monomers These monomers have at least two double bonds with similar reactivity in a radical polymerization.
  • These monomers include in particular (meth) acrylates derived from diols or higher alcohols, e.g.
  • Glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
  • Double bonds e.g. Glycerol tri (meth) acrylate
  • the comonomers also include vinyl esters such as vinyl acetate, vinyl chloride, vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride; Maleic acid derivatives, such as
  • Maleic anhydride esters of maleic acid, for example Maleic acid dimethyl ester, methylmaleic anhydride; and fumaric acid derivatives such as dimethyl fumarate.
  • styrenic monomers such as styrene, substituted styrenes having an alkyl substituent in the side chain, such as e.g. For example, D-methylstyrene and D-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; Maleimide, methylmaleimide;
  • Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride are further examples of comonomers.
  • accelerator amines having at least one ethylenically unsaturated double bond.
  • monomers include but are not limited to
  • DMAEMA Dimethylaminoethyl methacrylate
  • DMAPMA dimethylamino-propyl methacrylate
  • the polymeric photoinitiator may comprise from 0 to 10% by weight, more preferably from 1 to 5% by weight and most preferably from 1.5 to 4% by weight of units derived from monomers having one accelerating effect on photoinitiation are derived.
  • the molecular weight of polymeric photoinitiators can be in a wide range. In general this is
  • Weight average molecular weight usually at least 1000 g / mol, preferably at least 2000 g / mol and most preferably at least 5000 g / mol.
  • polymeric photoinitiators having a relatively high molecular weight can be used. These polymeric photoinitiators can be obtained in particular by emulsion polymerization, wherein these polymeric photoinitiators, for example, a weight average molecular weight, for example in
  • Emulsion polymers are distinguished, in particular, by high environmental compatibility since they often require no organic solvents and can have a particularly low residual monomer content.
  • the proportion of units derived from photoinitiator monomers in the polymeric photoinitiators can be in a wide range.
  • compounds can be used which consist entirely of units derived from photoinitiator monomers.
  • the polymeric photoinitiator may comprise from 0.1% to 100%, preferably from 0.5% to 50%, and most preferably from 1% to 10% by weight of units derived from photoinitiator monomers, based on the weight of the polymeric photoinitiator.
  • the polymeric photoinitiators can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective units comprising these polymers results from the proportions by weight of corresponding monomers used to prepare the polymers, since the proportion by weight of groups derived from initiators or molecular weight regulators can usually be neglected.
  • a coating composition according to the invention comprises at least one (meth) acrylic polymer having units derived from (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical.
  • (Meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical are esters or amides of (meth) acrylic acid whose alkyl radical has at least one carbon-carbon double bond which is not part of an aromatic system, and 8 to Has 40 carbon atoms.
  • (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 selected so that the largest possible proportion of the double bonds of the alkyl radical is maintained during the polymerization. This can be done for example by steric hindrance of the double bonds contained in the alcohol radical.
  • at least one part, preferably all of the double bonds contained in the alkyl radical of the (meth) acrylic monomer has a lower one
  • the iodine value of the (meth) acrylic monomers to be used for the preparation of the (meth) acrylic polymers which have 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 iodine / 100 g of (meth) acrylic monomer.
  • Such (meth) acrylic monomers generally correspond to the formula (IV)
  • radical R 1 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
  • R 9 is a linear or branched radical having 8 to 40, preferably 10 to 30 and more preferably 12 to 20 carbon atoms, which has at least one CC double bond.
  • (Meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can be obtained, for example, by esterification of
  • (Meth) acrylic acid reaction of (meth) acryloyl halides or of (meth) acrylic anhydride or transesterification of (meth) acrylates with alcohols having at least one double bond and 8 to 40 carbon atoms. Accordingly, (meth) acrylamides by
  • Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, ikosenol, docosenol, octadiene-ol, nonanoedia-ol, deca- dien-ol, undeca-dien-ol, dodecadiene-ol, trideca-diene-ol, tetradecadiene-ol, pentadeca-diene-ol, hexadeca-diene-ol, heptadecadiene-ol, octadeca-diene ol, Nonadeca-dien-ol, Ikosa-dien-ol and
  • acrylates obtainable by this process are octa-dienyl (meth) acrylate, octadeca-dienyl (meth) acrylate, octadecanetrienyl (meth) acrylate, Hexadecenyl (meth) acrylate, octadecenyl (meth) acrylate and hexadecadienyl (meth) acrylate.
  • (meth) acrylates which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can also be obtained by reacting unsaturated fatty acids with (meth) acrylates which have reactive groups in the alkyl radical, in particular alcohol radical.
  • the reactive groups include in particular hydroxy groups and epoxy groups. Accordingly, for example, hydroxyalkyl (meth) acrylates, such as 3-hydroxypropyl (meth) acrylate, 3,4-
  • 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 1 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 represents a group of the formula NR ', where R' is hydrogen or a radical having 1 to 6
  • R 1 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 1 is a linking group, R 'is hydrogen or a radical having 1 to 6 carbon atoms, and R 0 1100 is a uunnggeessaturated residue with 9 to 25 carbon atoms, achieve.
  • radical having 1 to 6 carbon atoms represents a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups and also alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl,
  • Alkanoyl, alkoxycarbonyl and heteroaliphatic groups 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 1 in the formulas (V) and (VI) preferably represents a linking group which is 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, isobutyl,
  • the group R 10 in formula (V) and (VI) represents 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, octadiene-yl, nonanediazyl, decadiene-yl, undecanediazyl, dodecadienyl, tridecadienyl, tetradecadienyl , Pentadeca-diene-yl, hexadeca-dien-yl, heptadeca-dien-yl, octadeca-dien-yl, nonadeca-dien-yl,
  • the preferred (meth) acrylic monomers of the formula (V) or (VI) include heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecadienyloxyloxy-2-ethyl (meth) acrylamide, heptadeca- trienyloxy-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-cetoleic acid amide, (meth) acryloyloxy-2-ethyl-erucic acid amide,
  • Particularly preferred monomers according to formula (V) or (VI) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.
  • the (meth) acrylic monomers of the formula (V) or (VI) can be obtained in particular by multistage processes.
  • a first step 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 amine group of the amide is reacted with a (meth) acrylate, for example
  • Methyl (meth) acrylate reacted to obtain the monomers of the formula (V) or (VI).
  • 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
  • X 1 is a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms
  • X 2 is oxygen
  • Embodiment of the present invention can be reacted intermediates without extensive purification to the (meth) acrylic monomers according to formula (V) or (VI).
  • the (meth) acrylic monomers having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms and at least one double bond in the alkyl radical include, in particular, monomers of the general formula (VII) wherein R 1 is hydrogen or a methyl group, X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 11 is an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of Wherein R '' is hydrogen or a radical having 1 to 6 carbon atoms, and R 12 is an unsaturated radical having at least 8 carbon atoms and at least two CC double bonds.
  • VI monomers of the general formula (VII) wherein R 1 is hydrogen or a methyl group, X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R 11 is an alkylene group having 1 to 22 carbon
  • the radical R 11 is an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10, more preferably 2 to 6 carbon atoms.
  • the radical R 11 represents an alkylene group having 2 to 4, more preferably 2 carbon atoms.
  • the alkylene groups having 1 to 22 carbon atoms include in particular the methylene, ethylene, propylene, isopropylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, with the ethylene group being particularly preferred.
  • the radical R 12 comprises at least two CC double bonds which are not part of an aromatic system.
  • the radical R 12 represents a group with exactly 8 carbon atoms, which has exactly two carbon-carbon double bonds.
  • the radical R 12 is preferably a linear hydrocarbon radical which has no heteroatoms.
  • the radical R 12 in formula (VII) may comprise a terminal double bond.
  • the radical R 12 in formula (VII) can not comprise a terminal carbon-carbon double bond.
  • the double bonds contained in the radical R 12 may preferably be conjugated.
  • the double bonds contained in the radical R 12 are not conjugated.
  • R 12 radicals which have at least two 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 (VII) include, inter alia, 2- [((2-E) octa-2,7-dienyl) methylamino] ethyl-2-methylprop-2-enoate,
  • the (meth) acrylic monomers of the formula (V) 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 (VIII),
  • HXR-YR 12 (VIII), 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 11 is an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group R '' is hydrogen or a radical having 1 to 6 carbon atoms, and R 12 is an at least double unsaturated radical having at least 8 carbon atoms.
  • the preferred starting materials of the formula (VIII) 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 according to formula (VIII) can be obtained inter alia by known methods of telomerization of 1,3-butadiene.
  • the term means
  • Telomerization means the reaction of compounds with conjugated double bonds in the presence of nucleophiles, filed in WO 2004/002931 17.06.2003 to the European Patent Office with the application number PCT / EP2003 / 006356, WO 03/031379 filed on 01.10.2002 with the application number PCT / EP2002 / 10971 and WO 02/100803 filed on 04.05.2002 with the application number PCT / EP2002 / 04909
  • the methods set forth, in particular the catalysts used for the reaction and the reaction conditions, such as pressure and temperature, are incorporated into the present application for purposes of disclosure.
  • the telomerization of 1,3-butadiene can be carried out using metal compounds comprising metals of groups 8 to 10 of the Periodic Table of the Elements, as catalyst, with palladium compounds, in particular palladium-carbene complexes, which are set forth in more detail in the publications set out above, can be used with particular preference.
  • nucleophiles are dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol; Diamines such as ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine or hexamethylenediamine; or aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
  • Diamines such as ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine or hexamethylenediamine
  • aminoalkanols such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.
  • (meth) acrylic acid as a nucleophile
  • octadienyl (meth) acrylates can be obtained, which are particularly suitable as (meth) acrylic monomers having 8 to 40 carbon atoms.
  • 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.
  • the (meth) acrylic polymer to be used according to the invention comprises preferably 0.5 to 60% by weight, preferably 1 to 30% by weight, more preferably 1.5 to 20% by weight and most preferably 2 to 15% by weight. -% of units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 to 40 carbon atoms, based on the weight of the (meth) acrylic polymer.
  • the (meth) acrylic polymers can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective units which comprise these polymers results from the proportions by weight of corresponding monomers used for the preparation of the polymers, since the proportion by weight of
  • 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.
  • a monomer mixture may contain other monomers which are copolymerizable with them.
  • copolymerizable monomers include, but are not limited to, photoinitiator monomers, monomers having an acid group, ester groups
  • Monomers B which are different from the above-mentioned (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group, and styrenic monomers.
  • a group of preferred monomers for the preparation of (meth) acrylic polymers which can be used according to the invention have an acid group. These monomers have previously been described in connection with the polymeric photoinitiators, so that reference is hereby made.
  • Particularly preferred monomers B comprising ester groups include (meth) acrylates, fumarates, maleates and / or vinyl acetate.
  • the comonomers mentioned include, among others
  • (meth) acrylic polymers which are preferably 1% by weight to 99% by weight, preferably 10% by weight to 70% by weight and very particularly preferably 20% by weight to 60% by weight.
  • (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 total weight of the (meth) acrylic polymer.
  • (meth) acrylates having at least 11 carbon atoms in the alkyl radical which are derived from saturated alcohols and have no heteroatoms in the alkyl radical; heterocyclic (meth) acrylates; Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates; Aryl (meth) acrylates; (Meth) acrylates having a hydroxy group in the alkyl radical; polyalkoxylated derivatives of (meth) acrylic acid; Glycerol carbonate methacrylate; 2-carbamoyloxyethyl methacrylate; (Meth) acrylates derived from saturated fatty acids or fatty acid amides; Vinylester; styrene; heterocyclic
  • the (meth) acrylic polymer may contain from 0 to 60% by weight, more preferably from 5 to 50% by weight and most preferably from 10 to 40% by weight of units derived from styrenic monomers , in particular of styrene, substituted styrenes having an alkyl substituent in the side chain, substituted styrenes having an alkyl substituent on Ring and / or halogenated styrenes are derived, based on the total weight of the (meth) acrylic polymer.
  • monomer mixtures are preferred which have a very low content of (meth) acrylates having two or more carbon-carbon double bonds which have a reactivity identical to a (meth) acrylate group.
  • the proportion of compounds having two or more (meth) acrylate groups is preferably at most 5 wt .-%, in particular at most 2 wt .-%, particularly preferably at most 1 wt .-%, particularly preferred at most 0.5% by weight and most preferably at most 0.1% by weight, based on the total weight of the monomers.
  • the photoinitiator and the (meth) acrylic polymer may be bonded together via a bond such that the (meth) acrylic polymer has units derived from photoinitiator monomers.
  • a monomer mixture for preparing (meth) acrylic polymers may contain photoinitiator monomers. These monomers have been previously described so that reference is made to them. Of particular interest are, in particular, (meth) acrylic polymers which have from 0 to 10% by weight, preferably from 0.5 to 8% by weight and more preferably from 1 to 5% by weight, of units derived from photoinitiator monomers based on the total weight of the (meth) acrylic polymer. Monomer mixtures which comprise at least one (meth) acrylic monomer which has at least one carbon-carbon double bond and 8 to 40 carbon atoms in the alkyl radical and at least one photoinitiator monomer are new and are therefore likewise provided by the invention.
  • the (meth) acrylates set out above with a keto group of the general formula (I) can be used.
  • the weight ratio of (meth) acrylic monomers having in the alkyl group at least one double bond and 8 to 40 carbon atoms to the photoinitiator monomers may be particularly preferred range from 20: 1 to 5: 1.
  • monomers which exhibit an accelerating effect on photoinitiation can be used to prepare the (meth) acrylic polymer.
  • These monomers include, in particular, accelerator amines which have at least one ethylenically unsaturated double bond.
  • These monomers include, inter alia, 2-dimethylaminoethyl methacrylate (DMAEMA) and dimethylamino-propyl methacrylate (DMAPMA).
  • monomer mixtures which contain from 0.5 to 60% by weight, more preferably from 1 to 30% by weight, of (meth) acrylate having at least one double bond and from 8 to 40 carbon atoms in the alkyl radical, 1 to 5 wt .-%, particularly preferably 1.5 to 4 wt .-% photoinitiator monomer,
  • (Meth) acrylate having 1 to 10 carbon atoms in the alkyl radical, each based on the weight of the monomers.
  • the molecular weight of (meth) acrylic polymers to be used according to the invention can be within a wide range.
  • the weight-average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol.
  • the weight-average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol.
  • (Meth) acrylic polymers are used which have a relatively high molecular weight. These (meth) acrylic polymers can be obtained in particular by emulsion polymerization, these (meth) acrylic polymers being, for example, a weight-average molecular weight, for example in the range from 100,000 to 10,000,000 g / mol, particularly preferably in the range from 200,000 to 500,000 g / mol can.
  • Emulsion polymers are notable in particular for their high environmental compatibility, since they often require no organic solvents and can have a particularly low residual monomer content.
  • low molecular weight (meth) acrylic polymers may also be used.
  • These (meth) acrylic polymers can be, for example, a weight-average molecular weight, for example in the range from 1000 to 150000 g / mol, in particular 4000 to 100000 g / mol, particularly preferably in the range from 5000 to 50,000 g / mol.
  • Low molecular weight polymers are widely used in organic solvent coating compositions. Coating compositions comprising organic solvents exhibit good processability over a wide temperature and humidity range. In relation to performance, coating compositions containing these (meth) acrylic polymers show improved environmental compatibility. Thus, extremely small amounts of organic solvents are released into the environment by evaporation, since the solvent content can be selected relatively low for a given workability.
  • M w / M n in the range of 1 to 5, particularly preferably in the range of 2 to 3.
  • the molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.
  • the glass transition temperature of or used according to invention polymer is preferably in the range from -60 0 C to 100 0 C, in particular -30 ° C to 70 0 C., particularly preferably in the range from -20 to 40 0 C and most preferably in the range of 0 to 25 0 C.
  • 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), in particular according to DIN EN ISO 11357.
  • DSC differential scanning calorimetry
  • the glass transition temperature as the center of the glass stage of the second heating curve can be determined with a heating rate of 10 0 C per minute.
  • Tg glass transition temperature can also be calculated approximately in advance by means of the Fox equation. After Fox T.G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:
  • Tg Tg 1 Tg Tg n 2 wherein X n is the mass fraction designated n (wt .-% / 100) of monomer n and Tg n is the glass transition temperature in Kelvin of the homopolymer of the monomer. Further helpful information can be found in the Polymer Handbook 2 nd Edition, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers. For example, according to this handbook, poly (methyl methacrylate) has a glass transition temperature of 378 K, poly (butyl methacrylate) of 297 K, poly (isobornyl methacrylate) of 383 K, poly (isobornyl acrylate) of 367 K and
  • the polymer may have one or more different glass transition temperatures. This information therefore applies to a segment obtainable by polymerization of a mixture comprising at least one (meth) acrylic monomer which has at least one double bond and 8 to 40 carbon atoms in the alkyl radical, preferably a monomer mixture according to the invention. If a polymeric photoinitiator is used, preferred glass transition temperatures are also in the ranges set forth above.
  • the architecture of the (meth) acrylic polymer and / or the polymeric photoinitiator is not critical to many applications and properties.
  • the Polymers, in particular the emulsion polymers are 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.
  • the emulsion polymer, in particular the (meth) acrylic polymer is a random copolymer in which the monomer composition is substantially constant throughout the polymerization. However, since the monomers may have different copolymerization parameters, the exact composition may vary across the polymer chain of the polymer.
  • the polymer may be a homogeneous polymer which, for example, forms particles with a constant composition in an aqueous dispersion.
  • the polymer which is preferably an emulsion polymer, may consist of one or more segments obtainable by polymerization of a monomer mixture.
  • the polymer may be a core-shell polymer which may have one, two, three, or more shells.
  • 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 outermost shell of preferably used emulsion polymers may preferably comprise from 5 to 50% by weight, more preferably from 15 to 28% by weight, of units, are derived from (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl radical, based on the weight of the outermost shell.
  • a polymeric photoinitiator having a core-shell structure can be employed, the outermost shell of which comprises 0 to 15% by weight, more preferably 1 to 7% by weight, of units derived from photoinitiator monomers on the weight of the outermost shell.
  • the iodine number of (meth) acrylic polymers to be used preferably lies in the range from 1 to 300 g of iodine per 100 g of polymer, 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 very particularly preferably 10 to 50 g of iodine per 100 g of polymer, measured in accordance with DIN 53241-1.
  • the (meth) acrylic polymer may have 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. If a polymeric photoinitiator is used, it may preferably have an acid number which is in the ranges set out above for the (meth) acrylic polymers.
  • the hydroxyl number of the (meth) acrylic polymer may preferably be in the range of 0 to 150 mg KOH / g, more preferably 20 to 120 mg KOH / g, and most preferably in the range of 40 to 100 mg KOH / g.
  • the hydroxyl number can be determined according to DIN EN ISO 4629.
  • a polymeric photoinitiator may be employed which preferably has a hydroxyl number in the range of 0 to 150 KOH / g, more preferably 20 to 120 mg KOH / g and most preferably in the range of 40 to 100 mg KOH / g.
  • the (meth) acrylic polymers and / or polymeric photoinitiators to be used according to the invention can be obtained in particular by solution polymerizations, bulk polymerizations or emulsion polymerizations, it being possible to achieve surprising advantages by free-radical emulsion polymerizations. These are set forth in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition.
  • 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.
  • 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 microemulsion, as 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 customary characterized by the use of costabilizers or swelling agents, many of which use long-chain alkanes or alkanols.
  • the droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns.
  • 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.
  • core-shell polymers can also be prepared.
  • the composition of the monomer mixture can be changed step by step, wherein prior to changing the composition, the polymerization is preferably polymerized 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 .
  • Core-shell polymer here stands for a polymer that passes through a two- or multi-stage emulsion polymerization was prepared, without the core-shell structure has been shown, for example, electron microscopy.
  • the tracking of the progress of the polymerization in each step may be carried out in a known manner, for example gravimetrically or by gas chromatography.
  • the monomer composition for producing the core preferably comprises from 50 to 100% by weight of (meth) acrylates, with a mixture of acrylates and methacrylates being used with particular preference. According to a particular aspect of the present invention, the
  • Weight ratio of acrylates to methacrylates in the core greater than or equal to 1, more preferably greater than or equal to 2.
  • a monomer mixture which is preferably grafted onto or polymerised onto the core can be grafted onto the core and contains from 0.5 to 60% by weight, particularly preferably from 2 to 30% by weight, in particular from 5 to 20% by weight (meth ) acrylic monomer having at least one double bond and 8 to 40 carbon atoms in the alkyl group.
  • 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. More details can the
  • 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 of different half-life in order to obtain the
  • 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 to 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.
  • 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
  • Alkylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;
  • Alkylarylpolyglykolether preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units; Ethylene oxide / propylene oxide copolymers, preferably block copolymers, desirably with 8 to 40 ethylene oxide or propylene oxide units, respectively.
  • the particularly preferred anionic emulsifiers include, in particular, fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15 paraffin sulfonate, these compounds generally being usable as the alkali metal salt, in particular as the sodium salt.
  • These compounds can in particular be commercially obtained under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® Kl from the companies 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 moieties. These emulsifiers are among the
  • Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® O 13/400 (Sasol Germany) are commercially 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 an 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 saponified polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, styrene-maleic acid and vinyl ether maleic acid copolymers. If 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.
  • 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 is preferably carried out by heating the
  • a part of the monomers can be initially charged in the reactor and the remainder added over a certain period of time.
  • the feed is interrupted for a few minutes after, for example, 1-5% of the monomers are added.
  • the dosages of emulsifier and monomers can be carried out separately or preferably as a mixture, in particular as an emulsion in water.
  • the emulsion polymerization can be carried out in a wide pH range. It is preferably between 2 and 9. In a particular embodiment, the polymerization is carried out at pH values between 4 and 8, in particular between 6 and 8. Likewise, the dispersion after the polymerization can be adjusted to a preferred pH range for the application. For pigmented coating systems, the range is generally 8 - 9 or above.
  • the molecular weight of the polymers is initially uncritical within wide limits.
  • Preferred emulsion polymers having a high content of polymers which are insoluble in THF may be obtained in the manner set forth above.
  • the reaction parameters to obtain a high molecular weight are known.
  • the use of molecular weight regulators can be dispensed with.
  • Coating compositions that are particularly easy and easy to process may also have lower molecular weight polymers, with solvent resistance and hardness of these Coatings reached a relatively high level.
  • these polymers having a particularly good processability, a molecular weight below 1 000 000 g / mol, preferably below 500 000 g / mol and more preferably below 250 000 g / mol.
  • Molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.
  • Polymers in particular low molecular weight emulsion polymers, can be prepared by the addition of
  • Molecular weight regulators are obtained in the reaction mixture before or during the polymerization. Sulfur-free molecular weight regulators and / or sulfur-containing molecular weight regulators can be used for this purpose.
  • the sulfur-free molecular weight regulators include, but are not limited to, dimeric ⁇ -methylstyrene (2,4-diphenyl-4-methyl-1-pentene), enol ethers of aliphatic and / or cycloaliphatic aldehydes, terpenes, ⁇ -terpinene,
  • Terpinolene 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1,4,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6-dihydro-2H-pyran dimeric ⁇ -methylstyrene.
  • Mercury compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides can preferably be used as the sulfur-containing molecular weight regulator.
  • the following polymerization regulators are given by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide,
  • Preferred compounds used as molecular weight regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
  • Examples of these compounds are ethyl thioglycolate, 2-ethylhexyl thioglycolate, cysteine, 2-mercaptoethanol, 3-mercaptopropanol, 3-mercaptopropan-1, 2-diol, 1,4-mercaptobutanol, mercaptoacetic acid,
  • Mercaptopropionic acid mercaptosuccinic acid, thioglycerol, thioacetic acid, thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.
  • the molecular weight regulators are preferably used in amounts of 0.05 to 10, more preferably 0.1 to 5 wt .-%, based on the monomers used in the polymerization. Of course, mixtures of polymerization regulators can also be used in the polymerization.
  • polymerizations using molecular weight regulators can be used to reduce the minimum film-forming temperature (MFT) of the polymers obtainable thereby.
  • the proportion of molecular weight regulators can be such that the (meth) acrylic polymers or coating compositions of the invention, a minimum film-forming temperature (MFT) of at most 60 0 C, particularly preferably at most 50 0 C, and most preferably at most 40 0 C, which can be measured according to DIN ISO 2115. The higher the proportion of
  • the minimum film-forming temperature is preferably in the ranges set out above.
  • 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 emulsion polymer particularly the (meth) acrylic polymer uncrosslinked or slightly crosslinked so that the (THF) in tetrahydrofuran at 20 0 C over soluble fraction 60 wt .-% based on the weight of the emulsion polymer lies.
  • the emulsion polymer may have a content of from 2 to 60% by weight, particularly preferably from 10 to 50% by weight and very particularly preferably from 20 to 40% by weight, based on the weight of the emulsion polymer in THF at 20 ° 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,
  • the particle radius of the emulsion polymers can be in a wide range.
  • emulsion polymers having a particle radius in the range of 10 to 500 nm, preferably 10 to 100 nm, particularly preferably 20 to 60 nm are used.
  • particle radii below 50 nm may be advantageous for film formation and coating properties.
  • the radius of the particles can be determined by PCS (Photon Correlation Spectroscopy), the data given refer to the r50 value (50% of the particles are smaller, 50% are larger).
  • PCS Photon Correlation Spectroscopy
  • a Beckman Coulter N5 Submicron Particle Size Analyzer may be used.
  • emulsion polymers having a high swelling factor Preferred emulsion polymers, in particular (meth) acrylic polymers, exhibit a swelling factor of at least 2, in particular at least 4, particularly preferably at least 6 and very particularly preferably at least 8.
  • the particle radius of the emulsion polymers in water r water
  • THF tetrahydrofuran
  • Emulsion polymers which have low crosslinking. Accordingly, in particular, emulsion polymers obtained from a monomer mixture having a low content of compounds having two or more (meth) acrylate groups show a high swelling factor.
  • coating compositions which are preferably 40 to 80% by weight, particularly preferably 50 to 75% by weight, of at least one (meth) acrylic polymer having units derived from (meth) acrylic
  • Monomers are derived which in the alkyl radical at least one
  • the coating compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions.
  • siccatives include in particular organometallic compounds, for example metal soaps of transition metals, such as cobalt, manganese, vanadium, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium.
  • transition metals such as cobalt, manganese, vanadium, 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 agents may preferably be in the range of greater than 0 to 5 wt .-%, more preferably in the range of 1 to 3 wt .-% based on the polymer content.
  • an accelerator amine can be used. These compounds have been described previously and are set forth, inter alia, in WO 2003/091287, filed on 17.04.2003 at the European Patent Office with the application number PCT / EP03 / 04035, so that this document, in particular the accelerator set forth therein for purposes of disclosure in the present Registration will be inserted.
  • Preferred accelerator amines include low molecular weight amines, polymeric amines, and polymerizable amines.
  • NDEA N-methyl-diethanolamine
  • DMAEMA 2-diethylaminoethyl methacrylate
  • the coating agents may comprise solvents. These coating agents can be processed over a particularly broad temperature and humidity range.
  • the term of the solvent is to be understood here broadly.
  • the preferred solvents include in particular aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, in particular isopropanol, n-butanol, isobutanol; Ether, in particular
  • glycol monomethyl ether glycol monoethyl ether
  • glycol monobutyl ether Aliphatic, preferably pentane, hexane, cycloalkanes and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also plasticizers such as low molecular weight polypropylene glycols or phthalates.
  • the proportion of solvent in preferred coating compositions may in particular be in the range from 0 to 50% by weight, more preferably in the range from 1 to 20% by weight.
  • a surprisingly good processability also show coating compositions whose
  • Solid content preferably at least 50 wt .-% is particularly preferably at least 60 wt .-%.
  • the coating compositions of the present invention comprise a relatively high level of water, with aqueous dispersions being particularly preferred coating compositions.
  • the aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight.
  • These coating compositions often comprise only a very small, preferably no fraction of organic solvents.
  • Preferred aqueous dispersions comprise at most 5% by weight, more preferably at most 2% by weight, of volatile organic constituents (VOC), such as residual monomers or organic solvents.
  • Coating compositions are therefore characterized by a particularly high environmental friendliness.
  • the coating compositions of the invention may contain conventional additives, in particular UV stabilizers, flow control agents and biocides.
  • the dynamic viscosity of the coating agent is dependent on the solids content and may include a wide range. So this can be more than 10,000 mPas at high polymer content.
  • the present invention provides a method for producing a coating in which a coating composition of the invention is applied to a substrate and cured.
  • the coating composition according to the invention can be applied by conventional application methods, in particular by roller application or spraying. Furthermore, dipping methods are also suitable for applying the coating composition.
  • the curing of the coating composition is carried out by drying and by oxidative crosslinking by means of atmospheric oxygen.
  • the coating composition applied to the substrate may additionally be cured by irradiation with light having a wavelength in the range of 100 to 800 nm, preferably 200 to 800 nm and more preferably 350 to 780 nm, illuminance preferably in the range of 0.1 to 100 mW / cm 2 , more preferably in the range of 0.5 to 80 mW / cm 2 , measured according to DIN 5050-1 1992-05.
  • the irradiation can be done with natural light.
  • the irradiation can be carried out with a commercially available system. These are marketed for example by Cetelon nanotechnology under the name LUMIFORM®.
  • the present coating composition can be used in particular for the production of paints, varnishes, sealants, adhesives and printing inks.
  • the substrates which can preferably be provided with a coating composition according to the invention include, in particular, wood, metals, in particular iron and steel, and also plastics.
  • the present invention provides coated articles obtainable by a method according to the invention.
  • the coating of these objects is characterized by an excellent property spectrum.
  • 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 level of resistance to methyl isobutyl ketone (MIBK) in particular
  • 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 1000 wt .-%, more preferably at most 600 wt .-%, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and a contact time of at least 4 hours, with a complete dried coating that has been cross-linked.
  • 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.
  • preferred coatings which are obtainable from the coating compositions of the invention have 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.
  • the mixture was then stirred for 1 h at 6O 0 C, then the mixture was poured with stirring (metal paddle stirrer, stirring motor) in a thin stream in 3 1 of water. It was stirred H and the precipitate was then filtered off with suction through a glass filter frit, washed twice with 2 1 H 2 O (stirred for about 15 min in a beaker with a stirrer with metal paddle) and then sucked dry on the suction filter. The solid was then air dried for 5 days.
  • Equipped with a sump thermometer and a distillation bridge was 206.3 g (0.70 mol)
  • 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 fatty acid methyl ester, 1.5% by weight 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.
  • 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 produced emulsion had a solids content of 40 + 1%, a pH of 5.8, a viscosity of 11 mPas and a r N5 value of 64 nm.
  • the coating agent was adjusted to a pH of about 9 with an NH 3 solution and provided with a siccative (2.5% Nuodex Web Combi AQ).
  • the properties of the coating composition thus obtained were examined by means of solvent resistance tests.
  • the distance between radiator and dispersion film was about 5.5 cm.
  • Solvent resistance was determined using methyl isobutyl ketone (MIBK), swelling a sample with MIBK at room temperature for 4 hours has been. The sample was then removed from the solvent and excess solvent removed.
  • MIBK methyl isobutyl ketone
  • the emulsion prepared had a solids content of 40 + 1%, a pH of 6.0, a viscosity of 12 mPas and a rN5 value of 67 nm.
  • the coating agent was adjusted to a pH of about 9 with an NH 3 solution and provided with a siccative (2.5% Nuodex Web Combi AQ).
  • butyl acrylate (BA), 156 g of methyl methacrylate (MMA), 60 g of methacryloyloxy-2-ethyl-2-ethyl-amide mixture, 4 g of methacrylic acid (MAS), 1.2 g of ammonium chloride were initially used in a 2 l PE beaker.
  • peroxodisulfate (APS), 12.0 g of Disponil FES 32 (30%) and 359.18 g of water were emulsified by Ultra-Turrax at 4000 rpm for 3 minutes.
  • the emulsion prepared had a solids content of 40 + 1%, a pH of 5.6, a viscosity of 22 mPas and a rN5 value of 70 nm.
  • the coating agent was adjusted to a pH of about 9 with an NH3 solution and fitted with a siccative (2.5% Nuodex Web Combi AQ).
  • the emulsion prepared had a solids content of 50 + 1%, a pH of 9.3 (after adjustment with an NH 3 solution), a viscosity of 90 mPas and an r N 5 value of 74 nm.
  • the properties of the coating composition thus obtained were investigated by means of the solvent resistance tests set forth in Example 1. The results obtained are shown in Table 1.
  • the emulsion prepared had a solids content of 50 + 1%, a pH of 9.2 (after adjustment with an NH3 solution), a viscosity of 103.5 mPas and an rN5 value of 70 nm.
  • the produced emulsion had a solids content of 50 ⁇ 1%, a pH of 7.65, a viscosity of 125 mPas and a rN5 value of 67 nm.
  • Example 1 The properties of the coating composition thus obtained were investigated on the basis of the solvent resistance tests set forth in Example 1, the coating composition having been previously adjusted to a pH of about 9 with an NH 3 solution. The results obtained are shown in Table 1.
  • the dispersion was cooled to 50 0 C and treated with 25% ammonia solution (0.055 wt .-%, based on the water content). Subsequently, 3% by weight of Triton X305, based on the water content, was added. Subsequently, the emulsion was cooled to room temperature and treated with 25% ammonia solution (0.145 wt .-%, based on the water content). After the addition of ammonia, the dispersion was filtered through a screen mesh of 125 ⁇ m mesh size.
  • the emulsion produced had a solids content of 49 ⁇ 1%, a pH of 9.1, a viscosity of 289 mPas and a particle radius of 63 nm.
  • the coating agent was applied with a siccative (2.5% Nuodex Web Combi AQ, based on the solids content).
  • Another dispersion of the invention was prepared by mixing the dispersions of Comparative Examples 5 and 6 using a 50:50 weight ratio. However, the siccative was added after mixing the polymer dispersions.
  • the performance of the obtained coating compositions obtained in Examples 3 to 5 and Comparative Examples 5 and 6 was determined by various methods. This was a block test, a Scouring test, an experiment to determine the pendulum hardness (according to König), cross-cut test according to the standard DIN EN ISO 2409 and a gloss test carried out. Furthermore, the drying time was determined.
  • the block point was determined with 0.5 mm thick polymer films, the calculated amounts of clearcoats (over area and dry content) to the corresponding
  • Lamp type / power Philips, TL 20W / 05
  • the block point indicates the temperature at which the film adheres but not yet glued, so that the surface is not damaged when pulling apart.
  • Pendulum hardness films were drawn onto glass plates having a nominal wet film thickness of 200 ⁇ m by means of a quadruple film drawing frame and then subjected to exposure to daylight or UV radiation as previously stated (see attempt to determine the blocking point). The exposure time was 7 days.
  • Case 1 Number of double strokes required until a piece of film flakes off / rubs off. The exposed area must still be completely surrounded by the film (maximum 1500 double strokes).
  • Case 2 (value in parentheses): The film is completely rubbed off in the direction of scouring in about one line (this value is given if case 1 does not occur, max 2500 2500 double strokes).
  • the pendulum hardness determination films were coated on glass plates having a target wet film thickness of 200 ⁇ m by means of a quadruple film drawing frame, and then subjected to UV exposure as previously described (see experiment for determination of the blocking point).
  • the Exposure time was 28 days.
  • the measurement was carried out according to König with the pendulum hardening device from BYK Mallinckrodt. In each case, a duplicate determination was carried out at different points of the coated films with subsequent averaging. The result was given after conversion of the required oscillations by multiplication by a factor of 1.4 in seconds. The values given refer to a measurement after 28 days.
  • the test was carried out using films with a wet film thickness of 200 ⁇ m using a
  • Films with a wet film thickness of 200 ⁇ m were applied using a quadruple-film draw frame.
  • the substrate used was a black test panel (Metopac, Lenetta).
  • the films were exposed to UV light for 4 weeks (see attempt to determine the blocking point).
  • the gloss of the films was after 28 days with the device Picogloss (model 503) from Erichsen under a Einstrahlwinkel determined by 85 °. Five-fold determinations were carried out, the highest and lowest value were canceled and the average of the remaining measured values was determined.
  • Drying time (tack-free time, based on DIN 53150)
  • the films were applied by means of a quadruple Filmziehrahmens on aluminum plates (Henkel, Alodine 1200) in a climate chamber at 23 ° C and about 25% rel. Humidity with a nominal wet film thickness of 100 microns drawn up and then immediately subjected to the tests.
  • a piece of paper (80 g / cm 2 ) and a rubber disc were placed on the film surface and loaded with a weight (20 g) for 60 s. Subsequently, the weight and rubber disc were removed and the aluminum plate dropped vertically from a height of 3-5 cm onto a surface. Drying grade 2 was reached when the piece of paper fell off.
  • Example 3 shows the highest pendulum hardness and the best rating in the abrasion test.
  • Examples 4 and 5 show that these coating compositions are superior to those of the comparative examples
  • the films of Examples 4 and 5 show a block temperature which corresponds to that of Comparative Example 5.
  • the film of Comparative Example 6 shows a much lower temperature, but this film performs better in the cross-cut test than that of Comparative Example 5.
  • This decrease in adhesion does not show the films of Examples 4 and 5.
  • the very high pendulum hardness and the excellent abrasion resistance compared to both Comparative Examples suggest that the adhesion due to the assumed brittleness would have to be lower than that of the Comparative Example 5.
  • the paint according to Example 3 has a slightly better adhesion than that of Comparative Example 5.
  • the film of Example 5 shows very high gloss values.

Abstract

L'invention concerne une composition de revêtement, comprenant au moins un photo-initiateur et au moins un polymère (méth)acryle comprenant des motifs qui sont dérivés de monomères (méth)acryle qui présentent dans un reste alkyle, au moins une double liaison et 8 à 40 atomes de carbone. L'invention concerne en outre un mélange de monomères comprenant au moins un monomère (méth)acryle présentant dans un reste alkyle, au moins une double liaison et 8 à 40 atomes de carbone, et au moins un monomère photo-initiateur, et un polymère (méth)acryle, qui est obtenu par polymérisation de ce mélange de monomères. En outre, l'invention concerne un procédé de production d'un revêtement. L'invention concerne également un objet revêtu, qui comprend un revêtement qui est obtenu par ledit procédé.
EP10711675A 2009-03-30 2010-03-30 Composition de revêtement, polymère (méth)acryle et mélange de monomères pour la production du polymère (méth)acryle Withdrawn EP2414462A1 (fr)

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DE200910001966 DE102009001966A1 (de) 2009-03-30 2009-03-30 Beschichtungszusammensetzung,(Meth)acryl-Polymer und Monomermischung zur Herstellung des(Meth)acryl-Polymers
PCT/EP2010/054139 WO2010112474A1 (fr) 2009-03-30 2010-03-30 Composition de revêtement, polymère (méth)acryle et mélange de monomères pour la production du polymère (méth)acryle

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US20110318595A1 (en) 2011-12-29
CN102369245A (zh) 2012-03-07
JP2012522087A (ja) 2012-09-20
WO2010112474A1 (fr) 2010-10-07
US8420709B2 (en) 2013-04-16
RU2011143587A (ru) 2013-05-10
KR20120006013A (ko) 2012-01-17
TW201105758A (en) 2011-02-16
DE102009001966A1 (de) 2010-10-07

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