WO1999062978A1 - Powder-paint binder composition - Google Patents

Powder-paint binder composition Download PDF

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Publication number
WO1999062978A1
WO1999062978A1 PCT/NL1999/000340 NL9900340W WO9962978A1 WO 1999062978 A1 WO1999062978 A1 WO 1999062978A1 NL 9900340 W NL9900340 W NL 9900340W WO 9962978 A1 WO9962978 A1 WO 9962978A1
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WO
WIPO (PCT)
Prior art keywords
block
group
polymer
meth
acrylate
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Application number
PCT/NL1999/000340
Other languages
French (fr)
Inventor
Johan Rietberg
Jan Henderikus Udding
Saskia Udding-Louwrier
Original Assignee
Dsm N.V.
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
Priority claimed from EP98201851A external-priority patent/EP0962473A1/en
Priority claimed from EP98203137A external-priority patent/EP0987283A1/en
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU42925/99A priority Critical patent/AU4292599A/en
Publication of WO1999062978A1 publication Critical patent/WO1999062978A1/en

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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
    • 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

Definitions

  • the invention relates to a powder-paint binder composition
  • a powder-paint binder composition comprising a polymer based on an ethylenically unsaturated monomer and optionally a crosslinker .
  • Polymers comprising ethylenically unsaturated monomer units can be obtained through radical polymerization, in which functional groups are randomly distributed across the polymer.
  • Such polymers are described in Paint and Surface Coatings (R. Lambourne, pp. 68-74, 1987, Ellis Horwood Limited), the complete disclosure of which is incorporated herein by reference.
  • powder coatings obtained after curing of a powder paint composition containing a binder composition which includes a polyacrylate and a crosslinker are known to be too brittle and too sensitive to damage upon exposure to solvents.
  • It is the object of the present invention to provide a curable powder paint binder composition comprising an ethylenically unsaturated monomer based polymer, which results in a powder coating exhibiting good mechanical properties and a superior resistance to chemicals.
  • the powder paint binder composition comprises an A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having crosslmkable functional groups, said B block being essentially free of reactive functional groups.
  • the functional groups are located at the end blocks A and C of the polymer.
  • the combined weight percent of the end blocks A and C is generally less than 30 wt . % of the total weight of the A-B-C- block copolymer .
  • the invention also relates to the A-B-C block polymer having functional end groups.
  • the polymer has been obtained through controlled radical polymerization m the presence of an initiator and a metal complex or a metal -containing compound .
  • the method of producing the A-B-C block polymer for use m a curable powder-paint binder composition can comprise the steps of: a) providing a mixture, said mixture comprising an effective amount of an initiator and an effective amount of a catalyst; b) adding a first functionalized monomer to said mixture, said first functionalized monomer comprising for example an ethylenically unsaturated mono- or dicarboxylic acid derivative; c) polymerizing said first functionalized monomer at a suitable temperature and pressure to effectively polymerize said first functionalized monomer to form A block of said A-B-C block polymer; d) adding a non- functionalized monomer to said mixture, said non- functionalized monomer having essentially no reactive functional groups which are crosslinkable to said first functionalized monomer, and polymeriziging said non- functionalized monomer to form B block of said A-B-C block polymer; e) adding a second functionalized monomer to said mixture, said second functionalized monomer having no functional groups which are crosslink
  • the location of the functional groups in the end blocks A and C is contrary to the random distribution of functional units across the whole of poly (meth) acrylates conventionally used in powder-paint binder compositions.
  • the block B contains essentially no reactive or crosslinkable functional groups.
  • Block B may however include various monomer units such as, for example, alkyl (meth) acrylates and styrene .
  • suitable functional monomers in blocks A and C include (meth) acrylic acid, (meth) acrylic acid esters, glycidyl (meth) acrylate and hydroxyethyl (meth) acrylate .
  • the functional monomers in A and C may be the same or different.
  • the monomers in blocks A and C are epoxy, carboxyl and hydroxyl groups .
  • Suitable ethylenically unsaturated monomers include, for example, styrene, acrylonitrile and ethylenically unsaturated mono- or dicarboxylic acid derivatives. These derivatives include preferably esters, of (C 3 -C 3 ) monoethylenically unsaturated monocarboxylic acids, such as for example (meth) acrylic acid and crotonic acid, and (C 4 -C 6 ) monoethylenically unsaturated dicarboxylic acids such as, for example, maleic acid, maleic anhydride, itaconic acid and fumaric acid.
  • (Meth) acrylic acid ester and styrene are preferred.
  • Suitable (meth) acrylic acid derivatives include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, benzyl
  • (meth) acrylate and hydroxyalkyl (meth) acrylates such as hydroxyethyl and hydroxypropyl (meth) acrylate and/or glycidyl esters or glycidyl ethers of alkyl (meth) acrylates .
  • Acrylate-based polymers containing different reactive functional groups can be used in the binder composition according to the invention. Examples of suitable functional groups are carboxyl groups , epoxy groups , anhydride groups , hydroxyl groups, acetoacetonate groups and combinations thereof .
  • the degree of branching of the polymer is generally between 2 and 6. Branching refers to the extensions of the polymer chain (s) attached to the polymer backbone .
  • the molecular weight (Mn) of the polymer is usually higher than 800 and is preferably higher than 1500. To obtain good flow behaviour at temperatures between 100°C and 200°C, the molecular weight (Mn) is usually lower than about 10,000 and preferably lower than about 7000.
  • the polydispersity is generally lower than
  • the polydispersity (Mw/Mn) has been determined with the aid of size exclusion chromatography using a viscosimeter detector .
  • the Tg of the polyacrylate is generally between about 30°C and about 120°C. Relatively larger amounts of crosslinker can be used in the binder composition if the Tg lies at the upper limit of this range. To obtain an optimum storage stability, the Tg is preferably higher than 50°C. With a view to the processing of the polymer the Tg is preferably lower than 100°C.
  • the viscosity of the polyacrylate is generally between 100 and 8000 dPas (measured at 160°C using a Rheometric Plate-Plate) .
  • the polymerization according to the invention generally takes place at temperatures between 60°C and 180°C and preferably between 80°C and 170°C.
  • the pressure is generally between 1 and 10 atmospheres.
  • the polymerization is carried out under an inert atmosphere .
  • Suitable examples of initiators used in producing the A-B-C block polymer include halogen containing compounds, for example, ⁇ -halo-substituted carboxylic (C ⁇ -C 6 )alkyl esters.
  • Suitable halogen atoms e.g. halo- subsituents are for example chloro and bromo.
  • initiators are ⁇ - (mono- , di-, or tri-) chloro or bromo acetic methyl ester, ⁇ - (mono- or di-) chloro- or bromo propionic methyl ester, ⁇ -chloro or bromo butyric methyl ester and ⁇ -chloro or bromo malonic dimethyl ester.
  • the initiators may also be multifunctional, such as, for example, 4 -vinyl benzyl chloride, ⁇ , ⁇ ' -dibromo-p-xylene , ⁇ , ⁇ -dichloro-p-xylene, 2 , 4-mesitylene disulphonyl chloride, tosyl chloride, mesylchloride, 1 , 3 , 5-tris (bromomethyl) benzene, tetrakis (bromomethyl) benzene , hexakis (bromomethyl) -benzene ,
  • esters of the aforementioned ⁇ -halogen-substituted carboxylic acids with diols and polyols such as, for example, the tri (dichloroacetic acid) ester of trimethylol propane, the di (alpha-bromo propionic acid) ester of ethylene glycol and the di (dichloroacetic acid) ester of ethylene glycol .
  • dichloro methyl acetate is used as the initiator.
  • the metals may be present in a compound with a covalent or ionic bond or in a complex with a coordination bond.
  • the metal containing compound or the metal complex may act as a catalyst .
  • Suitable metallic elements are Cu, Fe, Ag, Ti, W, U, Al, Mo, Pd, Ru, Rh and Ni .
  • Cu, Fe, Ru and Ni are used.
  • the catalyst is a metal complex based on one or more metal ions or salts with exchangeable counte ⁇ ons and ligands.
  • the number of counte ⁇ ons lies between 0 and 6 and preferably between 1 and 4.
  • tetravalent metals it is possible to use, for example, four monovalent counterions, two divalent counterions or a combination of a trivalent and a monovalent counte ⁇ on.
  • four monovalent counterions are used.
  • the number of counterions is between 1 and 3. Preferably three monovalent counterions are used.
  • Suitable counterions include halides, preferably chloride and bromide, (C ⁇ -C 2 o) alkoxides, preferably (C ⁇ -C 8 ) alkoxide, (C 2 -C 2 o) carboxylates, preferably (C 2 -C 8 ) carboxylates, enolates, preferably of 2 , 4 -pentanedione (acetylacetonates) and alkyl esters of malonic acid and acetyl acetic acid, phenolates, naphthenates, cresylates and mixtures of said counterions .
  • halides preferably chloride and bromide
  • (C ⁇ -C 2 o) alkoxides preferably (C ⁇ -C 8 ) alkoxide
  • C 2 -C 2 o) carboxylates preferably (C 2 -C 8 ) carboxylates
  • enolates preferably of 2 , 4 -pentanedione (acet
  • Suitable ligands include, for example, (substituted) bipy ⁇ dmes, py ⁇ dmes, bi- and t ⁇ dentate amines, mono-, bi- and tridentate phosphmes, lmmes and nit ⁇ les.
  • bipy ⁇ dmes examples include 2 , 2 ' -bipyridme and 4 , 4 ' -d ⁇ alkyl-2 , 2 ' -bipyridme .
  • amines are tetramethylethylene diamine (TMEDA) , tetramethylpropylene diamine and pentamethylene diethylene triamme.
  • Suitable phosphmes include for example triphenylphosphme, 1 , 2-b ⁇ s (diphenylphosphmo) ethane, 1, 3 -bis (diphenylphosphmo) propane, 1, 4 -bis (diphenylphosphmo) butane, R (+) -2 , 2 ' -bis (diphenylphosphmo) 1,1- bmaphthyl , S (-) 2 , 2 ' -bis (diphenylphosphmo) 1,1- bmaphthyl, PPh 3 and 1 , 2-b ⁇ s (dimethylphosphmo) ethene .
  • Suitable mtriles include for example acetonitrile and succmonitrile .
  • Suitable pyridmes include for example pyridme, alkylpy ⁇ dme, 2 , 2 ' -bipyridme, 4,4'd ⁇ alkyl- 2 , 2 ' -bipyridme, 2-py ⁇ dyl acetonitrile and 2,2' :6 ',2'- terpy ⁇ dme.
  • Suitable lmmes can be obtained by the reaction of salicylaldehyde with a compound containing nitrogen atoms.
  • the nitrogen compound is a polyamme such as, for example, ethylenediamme, cis- 1 , 2-cyclohexaned ⁇ amme, trans-1 , 2 -cyclohexanediamme (racemic), [S , S] -trans-1 , 2 -cyclohexanediamme , [R,R]- trans- 1 , 2 -cyclohexanediamme , N-methylbisethylene- triamme, triethylenetetraamme , 3 , 3 ' -diammo-N- methyldipropylamme, 1 , 2-phenylened ⁇ amme, 1,1,2,2,- tetramethylethylenediamme and propylene lmme dendrimers .
  • Suitable substituents include for example alkyl , aryl , halogen, nitrile, nitroxyl, dialkylphosphmo, diarylphosphmo, py ⁇ dyl , ammoalkyl , ammoaryl , carboxyl , hydroxyl and carbonyl groups .
  • a small amount, for example between 0.001 and 2 mol.%, of metal salts can be added during the production of the A-B-C-block polymer. Examples of such salts include CuCl 2 , CuBr 2 or FeCl 3 .
  • the catalysts can also be applied to a carrier such as, for example, silica.
  • the controlled living radical polymerization may take place by bulk polymerization or by solvent polymerization m the presence of solvents such as, for example, toluene, acetonitrile, xylene, 1 , 2-d ⁇ chloroethane, tert -butyl benzene, methyl ethyl ketone, dimethyl formamide, dimethyl sulphoxide, mesitylene, butyl acetate and benzene.
  • solvents such as, for example, toluene, acetonitrile, xylene, 1 , 2-d ⁇ chloroethane, tert -butyl benzene, methyl ethyl ketone, dimethyl formamide, dimethyl sulphoxide, mesitylene, butyl acetate and benzene.
  • Controlled living radical polymerizations are described m J. Am. Chem. Soc . 1997, 119, 674-680, and m Macromolecules , 1995, 28, 7901-7910, the complete reference of which is incorporated herein by means of reference .
  • a preferred embodiment of producing the A- B-C block polymer comprises adding the functionalized monomer or a mixture of a functionalized monomer and a non- functionalized monomer to a mixture, consisting of the catalyst and the initiator, m a solvent.
  • Suitable solvents include, for example, toluene, butyl acetate and methyl isobutyl ketone.
  • the amount of initiator used is between about 0.01 and about 10 mol.% relative to the monomers.
  • the amount of catalyst used is between about 0.001 and about 10 mol.% relative to the monomers.
  • Block A can also be formed by initiator with functional groups such as, for example, 2-bromo-2- methyl-hydroxy ethylpropionate, 2-bromo-hydroxy ethylpropionate , hydroxyethyldichloroacetate , t ⁇ chloroethanol , t ⁇ chlorobutanol , t ⁇ chloropropanol , t ⁇ bromoethanol , tribromopropanol , and/or tribromobutanol .
  • functional groups such as, for example, 2-bromo-2- methyl-hydroxy ethylpropionate, 2-bromo-hydroxy ethylpropionate , hydroxyethyldichloroacetate , t ⁇ chloroethanol , t ⁇ chlorobutanol , t ⁇ chloropropanol , t ⁇ bromoethanol , tribromopropanol , and/or tribromobutanol
  • Block C can also be formed by addition of a functional alkene compound.
  • Suitable alkene compounds include allylalcohol , methylbutenol and allylglycidyl- ether .
  • thermosettmg powder-pamt binder composition can contain more than 50 wt . % polymer and less than 50 wt . % crosslinker. In general more than 2 wt . % crosslinker is used although the use of less than 15 wt . % crosslinker is preferred. These amounts are defined as wt . % relative to the total amount the combined weight of the of polymer and crosslinker.
  • the crosslinker has to be capable of reacting with the functional groups being present m blocks A and C of the A-B-C block polymer.
  • crosslmkers examples include triglycidyl isocyanurate (TGIC) , polybisphenol-A epoxides, compounds containing (blocked) isocyanate groups, compounds containing ⁇ -hydroxyalkylamide groups, ammo resins, crosslmkers containing acid groups and crosslmkers (as described m EP-A-600546) comprising at least one aliphatic branched or linear chain with an epoxy functionality containing 5-26 carbon atoms such as, for example, epoxidized oils.
  • TGIC triglycidyl isocyanurate
  • polybisphenol-A epoxides compounds containing (blocked) isocyanate groups
  • compounds containing ⁇ -hydroxyalkylamide groups examples include ammo resins, crosslmkers containing acid groups and crosslmkers (as described m EP-A-600546) comprising at least one aliphatic branched or linear chain with an epoxy functionality containing 5-26 carbon atoms such as,
  • the polyacrylates obtained according to the present process also offer the possibility of using a "full-acrylic" system.
  • an oligomer or polymer containing acrylate groups takes over the function of the crosslinker.
  • an acid-functional polyacrylate obtained via the living polymerization described above can be combined with a state of the art glycidyl methacrylate copolymer .
  • the curing reaction between the polymer and the crosslinker which results m the ultimate cured coating will be a function of the polymer and the crosslinker which is selected.
  • This curing reaction can be effectuated, if desired, m the presence of an effective amount of catalyst.
  • the binder composition according to the invention it is possible to choose the desired curing time by adjusting the type and amounts of catalyst used and/or the curing agent. The importance of the ratio of the polymer and the crosslinker described above and of the amount of catalyst is explained m Misev, Powder Coatings, Chemistry and Technology pp. 174-223 (1991, John Wiley) , the complete disclosure of which is incorporated herein by reference.
  • A-B-C polymers with several branches that are linked to one another via one or more branching points can also be made.
  • the multifunctional initiators already described above can be used to this end during the preparation.
  • These materials too, may consist of one or more polymer blocks each consisting of various monomers .
  • the materials thus formed can be used as viscosity regulators in, for example, coatings and polymer mixtures .
  • These mixtures may contain polymers based on monomers that can be cured with the aid of radicals such as, for example, styrene acrylonitrile, styrene or methyl (meth) acrylate .
  • the relatively large number of terminal groups can be used to provide materials with improved adhesion properties. These materials moreover show improved UV and melting resistance in comparison with linear materials.
  • the invention is directed to a powder paint binder composition containing an A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having functional groups, said B block being essentially free of reactive functional groups and wherein at least one of the functional groups of the A block and the C block is modified into a functional group with a different chemical reactivity.
  • the modification of the starting A-B-C block polymer can, for example, take place by reaction of this A-B-C block polymer and a compound comprising an ethylenically unsaturated group, an acid group, an hydroxy group, an isocyanate group, an acetoacetate group, an epoxide group, a vmylether group or a fatty acid group.
  • Said modification with an ethylenically unsaturated groups will result m a polymer having, for example, (meth) acrylate, vmylether, fumaric or maleic end groups.
  • the selection of the ethylenically unsaturated groups depends on the functionality m blocks A and C.
  • the present invention can result, for example, m that a polymer having carboxyl groups m A or C may be modified with glycidyl (meth) acrylate, a polymer having epoxy groups m A or C may be modified with (meth) acrylic acid and a polymer having hydroxyl groups A or C may be modified with a polyisocyanate and a hydroxyvmylether or hydroxy
  • a polymer containing hydroxylgroups may also be modified with an unsaturated carboxylic acid such as for example fumaric acid or maleic acid anhydride and may also be functionalised with a saturated anhydride to an acid.
  • an unsaturated carboxylic acid such as for example fumaric acid or maleic acid anhydride and may also be functionalised with a saturated anhydride to an acid.
  • the end blocks A and C of the A-B-C polymer functional groups are located.
  • suitable functional groups are carboxyl groups, epoxy groups, anhydride groups, hydroxyl groups, acetoacetonate groups and combinations thereof.
  • the combined weight percent of the end blocks A and C is generally less than 30 wt . % of the total weight of the A-B-C block copolymer.
  • the A-B-C polymer can be obtained through controlled radical polymerization in the presence of an initiator and a metal complex or a metal -containing compound after which the modification takes place in a second step.
  • a method of producing this functionalised A-B-C block polymer can comprise the steps of: a) providing a mixture, said mixture comprising an effective amount of an initiator and an effective amount of a catalyst; b) adding a first functionalized monomer to said mixture, said first functionalized monomer comprising for example an ethylenically unsaturated mono- or dicarboxylic acid derivative; c) polymerizing said first functionalized monomer at a suitable temperature and pressure to effectively polymerize said first functionalized monomer to form A block of said A-B-C block polymer; d) adding a non- functionalized monomer to said mixture, said non-functionalized monomer having essentially no reactive functional groups which are crosslinkable to said first functionalized monomer, and polymerising said non-functionalized monomer to form B block of said A-B-C block polymer; e) adding a functionalised alkene compound to said mixture or adding a second functionalized monomer to said mixture, said second functionalized monomer having functional groups which are not crosslinkable to
  • B-C block polymer can, for example, also comprise the steps of : a) providing a mixture, comprising a functionalized initiator, a catalyst and a non-functionalized monomer, said non-functionalized monomer having essentially no reactive functional groups which are crosslinkable to said functionalized initiator, and polymerizing said non-functionalized monomer to form the A and B blocks of said A-B-C block polymer; b) adding a functional alkene compound to said initiator or adding a functionalized monomer to said mixture, said functionalized monomer having functional groups which are not crosslinkable to said non-functionalized monomer, and polymerizing said functionalized monomer to obtain C block of said A-B-C block polymer, thereby obtaining said A- B-C block polymer, wherein said A block and said C block of said A-B-C block polymer are terminally disposed and said B block is interposed between said A block and said C block, said B block being essentially free of reactive functional groups which are crosslinkable with those on said A block and
  • the A-B-C blockpolymer can be functionalised with different components.
  • the reaction conditions and the reagents depend on the selection of the reaction components and the intended application.
  • the molecular weight (Mn) of the modified polymer is usually higher than 400 and is preferably higher than 600. To obtain good flow behaviour at temperatures between 100°C and 200°C, the molecular weight (Mn) is usually lower than about 10,000 and preferably lower than about 7000.
  • the Tg of the modified A-B-C polymer for example a polyacrylate, is generally between about 30°C and about 120°C. To obtain an optimum storage stability, the Tg is preferably higher than 50°C. With a view to the processing of the polymer the Tg is preferably lower than 100°C.
  • the modified polymer can be applied m a powder pamt composition as a polymer, as a crosslinker and as the binder system.
  • a carboxylic acid functional polymer obtained by modification of an hydroxy functional A-B-C block polymer with an anhydride or diacid, may be crossl ked with t ⁇ glycidyl isocyanurate (TGIC) , polybisphenol-A epoxides, compounds containing (blocked) isocyanate groups, compounds containing ⁇ -hydroxyalkylamide groups, ammo resins, crosslmkers containing acid groups and crosslmkers (as described m EP-A-600546) comprising at least one aliphatic branched or linear chain with an epoxy functionality containing 5-26 carbon atoms such as, for example, epoxidized oils.
  • TGIC t ⁇ glycidyl isocyanurate
  • polybisphenol-A epoxides compounds containing (blocked) isocyanate groups
  • compounds containing ⁇ -hydroxyalkylamide groups ammo resins
  • crosslmkers containing acid groups and crosslmkers (as described m
  • a binder composition according to the invention yields a good coating after thermal curing under the influence of a catalyst at a temperature ranging from, for instance, about 80 °C to about 200 °C, depending on the selected polymer
  • the powder pamt binder composition according to the mvention can also be applied m a radiation curable powder pamt composition if the modification with, for example, an ethylenically unsaturated group takes place which results a polymer with vmylether, allyl or propenyl, (meth) acrylate , itaconate, maleate or fumarate functional groups.
  • a radiation-curable system can comprise for example a resm, a crosslinker, a photomitiator, a flow agent and pigments.
  • Suitable polymers or crosslmkers which can be added to the radiation curable powder pamt compositions according to the invention include for example (meth) acrylated polyesters, (meth) acrylated polyurethanes , (meth) acrylated polyethers, polyepoxides, polyv ylethers, polyallylethers , unsaturated polyesters and poly (meth) acrylates .
  • crosslinker comprising units of a prepolymer having a molecular weight (Mn) higher than 400 and units of a vinyl ether or an unsaturated alcohol, the number of polyme ⁇ zable unsaturations of the crosslinker being higher than or equal to 2 , is very suitable. It is also possible to apply combinations of several polymers and/or crosslmkers.
  • UV curing of the binder composition according to the invention preferably takes place through UV and EB curing.
  • compositions according to the invention can be cured by, for example, radical polymerization and by catiomc UV polymerization.
  • a photomitiator can, at a temperature ranging from, for instance, 40°C to 120°C, be mixed with a binder composition according to the invention.
  • a polymer which the functional, for example, hydroxyl -group is modified mto a vinyl ether, allyl or propenyl, (meth) acrylate, itaconate, maleate or fumarate is preferred for this application.
  • An important advantage due to the present invention is the high cure speed, and the possibility of a low temperature curing for example at temperatures lower than 140 °C.
  • the pamt can subsequently be applied to the substrate or be sprayed electrostatically. After application, the powder pa t is molten at temperatures ranging from, for instance, 40°C to 170°C by being placed m an oven, exposure to mfra-red radiation, or a combination of both, so that a closed, smooth coating film is formed with a layer thickness ranging from, for instance, 20 to 200 ⁇ m, after which the still warm panel is cured under a UV light source. Afterwards post-heatmg may take place.
  • Photomitiators initiate curing of the compositions according to the invention upon exposure to light.
  • Suitable initiators for radical polymerizations are ketomc and may be aromatic such as, for instance, benzophenone.
  • Irgacure 184 ® (Ciba) is an aryl ketone with hydroxycyclohexyl -phenyl -ketone as active component and is, like Irgacure 369 ® (active component 2 -benzyl-2 -d ⁇ methylammo-1- (4- morphol ophenyl) -butanone-1) , a suitable photomitiator.
  • Acyl phosphme such as 2 , 4 , 6-t ⁇ methyl benzoyl diphenyl phosphme oxide (Lucerme TPO ® , BASF) can also be used. Chemical derivatives of this photomitiator are also suitable, as are combinations of these initiators.
  • a suitable combination of photomitiators is formed by Irgacure 1800 ® (Ciba) , which consists of 75 wt . % Irgacure 184 ® and 25 wt . % (bis (2 , 6-d ⁇ methoxy benzoyl) -2 , 4 , 4-tr ⁇ methylpentyl phosphme oxide) .
  • suitable additives include pigments, fillers, degassing agents, flow agents, stabilizers and t ⁇ bochargmg improving agents .
  • suitable pigments include for example inorganic pigments, such as titanium dioxide, zmc sulphide, iron oxide and chromium oxide, and also organic pigments such as azo compounds .
  • Suitable fillers include for example metal oxides, silicates, carbonates and sulphates.
  • Suitable stabilizers include for example primary and/or secondary antioxidants and UV stabilizers such as qu ones, (ste ⁇ cally hindered) phenolic compounds, phosphonites , phosphites, thioethers and HALS compounds (hindered amme light stabilizers) .
  • UV stabilizers such as qu ones, (ste ⁇ cally hindered) phenolic compounds, phosphonites , phosphites, thioethers and HALS compounds (hindered amme light stabilizers) .
  • Examples of degassing agents m include benzoin and cyclohexane dimethanol bisbenzoate.
  • flow agents include polyalkylacrylates , fluorohydrocarbons and silicon oils.
  • Suitable additives are for example additives to improve the tribo-chargmg properties, include for example sterically hindered tertiary amines.
  • Powder paints according to the invention can be applied to a susbtrate m the usual manner, for example by means of electrostatic spraying of the powder onto an earthed substrate and curing of the coating such as through exposure to heat at a suitable temperature for a sufficiently long period.
  • the applied powder can for example be heated m a gas oven, an electric oven or with the aid of infrared radiation.
  • Thermosettmg coatings of powder pamt (coating) compositions intended for industrial applications are described further m general terms the already mentioned Powder Coatings by Misev, pp. 141-173 (1991) .
  • compositions according to the present invention can be used m powder coatings intended for use on for example metal, wood, aluminium, paper, cardboards and plastic substrates.
  • the coatings are also very suitable for use the automotive industry for coating external and/or internal parts.
  • the invention will be further elucidated with reference to the following, non-limiting examples.
  • the reaction was continued for another 3 hours to bring about complete conversion.
  • the solution was cooled and filtered. Toluene was removed through distillation and the product obtained, with a molecular weight Mn of 3250, was heated to 200°C, after which the tertiary butyl ester decomposed.
  • the carboxyl -functional polyacrylate obtained had an acid number of 52.4 mg of KOH/g of resin and a glass transition temperature of 92°C.
  • the temperature was kept at 105°C. After 90% conversion 2.13 g of tert . -butyl acrylate was added.
  • the solution was cooled and filtered. Toluene was removed through distillation and the product, with a molecular weight (Mn) of 3320, was heated to 200°C.
  • the carboxyl -functional polyacrylate obtained had an acid number of 52.4 mg of KOH/g of resin and a glass transition temperature of 93°C.
  • 940 acrylate polymer obtained according to Example I was dissolved in 500 g of butyl acetate. The solution was heated to 120°C, after which 2 g of catalyst was added. Next, 60 g of propylene oxide was dosed in 2 hours. After additional 3 hours afterreaction at 120°C butyl acetate was removed by vacuum distillation up to 180°C.
  • the polymer obtained had an acid number of ⁇ 1 mg of KOH/g of resin and a hydroxyl value of 48 mg of KOH/g of resin.
  • the polymer's glass transition temperature was 78°C.
  • the polyacrylates obtained according to Examples I -II I (Acrylate 1, Acrylate 2 and Acrylate 3, respectively, in Table 2) were mixed with a crosslinker as indicated in Table 2. This mixture was dosed to a kneader at 120°C. After the resin had melted completely, titanium dioxide was dispersed in the resin, after which the other additives were added. After cooling, the product obtained was reduced in size, pulverized and sieved to a maximum particle size of 90 mm. The powder-paint composition was electrostatically applied to an earthed metal substrate and was cured to a powder coating .

Abstract

The invention relates to a powder paint composition comprising an A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having cross-linkable functional groups, said B block being essentially free of reactive functional groups.

Description

POWDER-PAINT BINDER COMPOSITION
The invention relates to a powder-paint binder composition comprising a polymer based on an ethylenically unsaturated monomer and optionally a crosslinker .
Polymers comprising ethylenically unsaturated monomer units, such as for example polyacrylates, can be obtained through radical polymerization, in which functional groups are randomly distributed across the polymer. Such polymers are described in Paint and Surface Coatings (R. Lambourne, pp. 68-74, 1987, Ellis Horwood Limited), the complete disclosure of which is incorporated herein by reference. However powder coatings obtained after curing of a powder paint composition containing a binder composition which includes a polyacrylate and a crosslinker are known to be too brittle and too sensitive to damage upon exposure to solvents.
It is the object of the present invention to provide a curable powder paint binder composition comprising an ethylenically unsaturated monomer based polymer, which results in a powder coating exhibiting good mechanical properties and a superior resistance to chemicals.
The invention is characterized in that the powder paint binder composition comprises an A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having crosslmkable functional groups, said B block being essentially free of reactive functional groups. The functional groups are located at the end blocks A and C of the polymer. The combined weight percent of the end blocks A and C is generally less than 30 wt . % of the total weight of the A-B-C- block copolymer . After curing of the powder paint composition comprising the binder composition according to the invention the powder coating has a good resistance to yellowing and to weather influences, and exhibits good flow behaviour, good storage stability, good resistance to chemicals, a high gloss, high scratch resistance and good mechanical properties.
The invention also relates to the A-B-C block polymer having functional end groups.
According to a preferred embodiment of the invention the polymer has been obtained through controlled radical polymerization m the presence of an initiator and a metal complex or a metal -containing compound .
The method of producing the A-B-C block polymer for use m a curable powder-paint binder composition, can comprise the steps of: a) providing a mixture, said mixture comprising an effective amount of an initiator and an effective amount of a catalyst; b) adding a first functionalized monomer to said mixture, said first functionalized monomer comprising for example an ethylenically unsaturated mono- or dicarboxylic acid derivative; c) polymerizing said first functionalized monomer at a suitable temperature and pressure to effectively polymerize said first functionalized monomer to form A block of said A-B-C block polymer; d) adding a non- functionalized monomer to said mixture, said non- functionalized monomer having essentially no reactive functional groups which are crosslinkable to said first functionalized monomer, and polymeriziging said non- functionalized monomer to form B block of said A-B-C block polymer; e) adding a second functionalized monomer to said mixture, said second functionalized monomer having no functional groups which are crosslinkable to said non- functionalized monomer, and polymerizing said second functionalized monomer to obtain C block of said A-B-C block polymer, thereby obtaining said A-B-C block polymer, wherein said A block and said C block of said A-B-C block polymer are terminally disposed and said B block is interposed between said A block and said C block, said B block being essentially free of reactive functional groups which are crosslinkable with those on said A block and said C block.
The location of the functional groups in the end blocks A and C is contrary to the random distribution of functional units across the whole of poly (meth) acrylates conventionally used in powder-paint binder compositions.
The block B contains essentially no reactive or crosslinkable functional groups. Block B may however include various monomer units such as, for example, alkyl (meth) acrylates and styrene . Examples of suitable functional monomers in blocks A and C include (meth) acrylic acid, (meth) acrylic acid esters, glycidyl (meth) acrylate and hydroxyethyl (meth) acrylate . The functional monomers in A and C may be the same or different. Preferably, the monomers in blocks A and C are epoxy, carboxyl and hydroxyl groups .
Suitable ethylenically unsaturated monomers include, for example, styrene, acrylonitrile and ethylenically unsaturated mono- or dicarboxylic acid derivatives. These derivatives include preferably esters, of (C3-C3) monoethylenically unsaturated monocarboxylic acids, such as for example (meth) acrylic acid and crotonic acid, and (C4-C6) monoethylenically unsaturated dicarboxylic acids such as, for example, maleic acid, maleic anhydride, itaconic acid and fumaric acid.
(Meth) acrylic acid ester and styrene are preferred. Suitable (meth) acrylic acid derivatives include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, benzyl
(meth) acrylate and hydroxyalkyl (meth) acrylates such as hydroxyethyl and hydroxypropyl (meth) acrylate and/or glycidyl esters or glycidyl ethers of alkyl (meth) acrylates . Acrylate-based polymers containing different reactive functional groups can be used in the binder composition according to the invention. Examples of suitable functional groups are carboxyl groups , epoxy groups , anhydride groups , hydroxyl groups, acetoacetonate groups and combinations thereof . The degree of branching of the polymer is generally between 2 and 6. Branching refers to the extensions of the polymer chain (s) attached to the polymer backbone .
The molecular weight (Mn) of the polymer is usually higher than 800 and is preferably higher than 1500. To obtain good flow behaviour at temperatures between 100°C and 200°C, the molecular weight (Mn) is usually lower than about 10,000 and preferably lower than about 7000. The polydispersity is generally lower than
2 and usually lies between 1.1 and 1.8. The polydispersity (Mw/Mn) has been determined with the aid of size exclusion chromatography using a viscosimeter detector . The Tg of the polyacrylate is generally between about 30°C and about 120°C. Relatively larger amounts of crosslinker can be used in the binder composition if the Tg lies at the upper limit of this range. To obtain an optimum storage stability, the Tg is preferably higher than 50°C. With a view to the processing of the polymer the Tg is preferably lower than 100°C.
The viscosity of the polyacrylate is generally between 100 and 8000 dPas (measured at 160°C using a Rheometric Plate-Plate) .
The polymerization according to the invention generally takes place at temperatures between 60°C and 180°C and preferably between 80°C and 170°C. The pressure is generally between 1 and 10 atmospheres. The polymerization is carried out under an inert atmosphere .
Suitable examples of initiators used in producing the A-B-C block polymer include halogen containing compounds, for example, α-halo-substituted carboxylic (Cι-C6)alkyl esters.
Suitable halogen atoms e.g. halo- subsituents are for example chloro and bromo. Examples of such initiators are α- (mono- , di-, or tri-) chloro or bromo acetic methyl ester, α- (mono- or di-) chloro- or bromo propionic methyl ester, α-chloro or bromo butyric methyl ester and α-chloro or bromo malonic dimethyl ester. The initiators may also be multifunctional, such as, for example, 4 -vinyl benzyl chloride, α, α ' -dibromo-p-xylene , α, α-dichloro-p-xylene, 2 , 4-mesitylene disulphonyl chloride, tosyl chloride, mesylchloride, 1 , 3 , 5-tris (bromomethyl) benzene, tetrakis (bromomethyl) benzene , hexakis (bromomethyl) -benzene ,
1, 4-dibromo-2 -butene , and esters of the aforementioned α-halogen-substituted carboxylic acids with diols and polyols such as, for example, the tri (dichloroacetic acid) ester of trimethylol propane, the di (alpha-bromo propionic acid) ester of ethylene glycol and the di (dichloroacetic acid) ester of ethylene glycol .
Preferably dichloro methyl acetate is used as the initiator.
The metals may be present in a compound with a covalent or ionic bond or in a complex with a coordination bond. The metal containing compound or the metal complex may act as a catalyst .
Suitable metallic elements are Cu, Fe, Ag, Ti, W, U, Al, Mo, Pd, Ru, Rh and Ni . Preferably Cu, Fe, Ru and Ni are used.
Preferably, the catalyst is a metal complex based on one or more metal ions or salts with exchangeable counteπons and ligands.
The number of counteπons lies between 0 and 6 and preferably between 1 and 4. In the case of tetravalent metals it is possible to use, for example, four monovalent counterions, two divalent counterions or a combination of a trivalent and a monovalent counteπon. Preferably four monovalent counterions are used.
In the case of trivalent metals the number of counterions is between 1 and 3. Preferably three monovalent counterions are used.
Examples of suitable counterions include halides, preferably chloride and bromide, (Cι-C2o) alkoxides, preferably (Cι-C8) alkoxide, (C2-C2o) carboxylates, preferably (C2-C8) carboxylates, enolates, preferably of 2 , 4 -pentanedione (acetylacetonates) and alkyl esters of malonic acid and acetyl acetic acid, phenolates, naphthenates, cresylates and mixtures of said counterions .
Suitable ligands include, for example, (substituted) bipyπdmes, pyπdmes, bi- and tπdentate amines, mono-, bi- and tridentate phosphmes, lmmes and nitπles.
Examples of suitable bipyπdmes include 2 , 2 ' -bipyridme and 4 , 4 ' -dιalkyl-2 , 2 ' -bipyridme . Examples of amines are tetramethylethylene diamine (TMEDA) , tetramethylpropylene diamine and pentamethylene diethylene triamme.
Suitable phosphmes include for example triphenylphosphme, 1 , 2-bιs (diphenylphosphmo) ethane, 1, 3 -bis (diphenylphosphmo) propane, 1, 4 -bis (diphenylphosphmo) butane, R (+) -2 , 2 ' -bis (diphenylphosphmo) 1,1- bmaphthyl , S (-) 2 , 2 ' -bis (diphenylphosphmo) 1,1- bmaphthyl, PPh3 and 1 , 2-bιs (dimethylphosphmo) ethene . Suitable mtriles include for example acetonitrile and succmonitrile .
Suitable pyridmes mclude for example pyridme, alkylpyπdme, 2 , 2 ' -bipyridme, 4,4'dιalkyl- 2 , 2 ' -bipyridme, 2-pyπdyl acetonitrile and 2,2' :6 ',2'- terpyπdme.
Suitable lmmes can be obtained by the reaction of salicylaldehyde with a compound containing nitrogen atoms. Preferably, the nitrogen compound is a polyamme such as, for example, ethylenediamme, cis- 1 , 2-cyclohexanedιamme, trans-1 , 2 -cyclohexanediamme (racemic), [S , S] -trans-1 , 2 -cyclohexanediamme , [R,R]- trans- 1 , 2 -cyclohexanediamme , N-methylbisethylene- triamme, triethylenetetraamme , 3 , 3 ' -diammo-N- methyldipropylamme, 1 , 2-phenylenedιamme, 1,1,2,2,- tetramethylethylenediamme and propylene lmme dendrimers .
It is also possible to use, for example, substituted o-hydroxybenzaldehydes instead of salicylaldehyde . Suitable substituents include for example alkyl , aryl , halogen, nitrile, nitroxyl, dialkylphosphmo, diarylphosphmo, pyπdyl , ammoalkyl , ammoaryl , carboxyl , hydroxyl and carbonyl groups . Optionally a small amount, for example between 0.001 and 2 mol.%, of metal salts can be added during the production of the A-B-C-block polymer. Examples of such salts include CuCl2, CuBr2 or FeCl3. The catalysts can also be applied to a carrier such as, for example, silica.
The controlled living radical polymerization may take place by bulk polymerization or by solvent polymerization m the presence of solvents such as, for example, toluene, acetonitrile, xylene, 1 , 2-dιchloroethane, tert -butyl benzene, methyl ethyl ketone, dimethyl formamide, dimethyl sulphoxide, mesitylene, butyl acetate and benzene.
Controlled living radical polymerizations are described m J. Am. Chem. Soc . 1997, 119, 674-680, and m Macromolecules , 1995, 28, 7901-7910, the complete reference of which is incorporated herein by means of reference .
A preferred embodiment of producing the A- B-C block polymer comprises adding the functionalized monomer or a mixture of a functionalized monomer and a non- functionalized monomer to a mixture, consisting of the catalyst and the initiator, m a solvent. Suitable solvents include, for example, toluene, butyl acetate and methyl isobutyl ketone.
The amount of initiator used is between about 0.01 and about 10 mol.% relative to the monomers. The amount of catalyst used is between about 0.001 and about 10 mol.% relative to the monomers. After the percentage of conversion of the functionalized monomer m block A has passed, for example, 90%, non-functionalized monomer B can be added . After the percentage of conversion of the total amount of monomers A + B has passed for example, 85% funtionalized monomer C can be added.
Block A can also be formed by initiator with functional groups such as, for example, 2-bromo-2- methyl-hydroxy ethylpropionate, 2-bromo-hydroxy ethylpropionate , hydroxyethyldichloroacetate , tπchloroethanol , tπchlorobutanol , tπchloropropanol , tπbromoethanol , tribromopropanol , and/or tribromobutanol .
Block C can also be formed by addition of a functional alkene compound. Suitable alkene compounds include allylalcohol , methylbutenol and allylglycidyl- ether . On completion of the polymerization metal salts and/or ligands can be removed via filtration over silica or washing with water.
A thermosettmg powder-pamt binder composition can contain more than 50 wt . % polymer and less than 50 wt . % crosslinker. In general more than 2 wt . % crosslinker is used although the use of less than 15 wt . % crosslinker is preferred. These amounts are defined as wt . % relative to the total amount the combined weight of the of polymer and crosslinker. The crosslinker has to be capable of reacting with the functional groups being present m blocks A and C of the A-B-C block polymer.
Examples of suitable crosslmkers include triglycidyl isocyanurate (TGIC) , polybisphenol-A epoxides, compounds containing (blocked) isocyanate groups, compounds containing β-hydroxyalkylamide groups, ammo resins, crosslmkers containing acid groups and crosslmkers (as described m EP-A-600546) comprising at least one aliphatic branched or linear chain with an epoxy functionality containing 5-26 carbon atoms such as, for example, epoxidized oils.
The polyacrylates obtained according to the present process also offer the possibility of using a "full-acrylic" system. In this case an oligomer or polymer containing acrylate groups takes over the function of the crosslinker. As an example of such a system an acid-functional polyacrylate obtained via the living polymerization described above can be combined with a state of the art glycidyl methacrylate copolymer .
The curing reaction between the polymer and the crosslinker which results m the ultimate cured coating will be a function of the polymer and the crosslinker which is selected. This curing reaction can be effectuated, if desired, m the presence of an effective amount of catalyst. With the binder composition according to the invention it is possible to choose the desired curing time by adjusting the type and amounts of catalyst used and/or the curing agent. The importance of the ratio of the polymer and the crosslinker described above and of the amount of catalyst is explained m Misev, Powder Coatings, Chemistry and Technology pp. 174-223 (1991, John Wiley) , the complete disclosure of which is incorporated herein by reference.
In addition to the aforementioned A-B-C tπblock copolymers, A-B-C polymers with several branches that are linked to one another via one or more branching points can also be made. The multifunctional initiators already described above can be used to this end during the preparation. These materials, too, may consist of one or more polymer blocks each consisting of various monomers . On account of their improved flow behaviour, the materials thus formed can be used as viscosity regulators in, for example, coatings and polymer mixtures . These mixtures may contain polymers based on monomers that can be cured with the aid of radicals such as, for example, styrene acrylonitrile, styrene or methyl (meth) acrylate . In addition, the relatively large number of terminal groups can be used to provide materials with improved adhesion properties. These materials moreover show improved UV and melting resistance in comparison with linear materials.
The invention is directed to a powder paint binder composition containing an A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having functional groups, said B block being essentially free of reactive functional groups and wherein at least one of the functional groups of the A block and the C block is modified into a functional group with a different chemical reactivity.
By selecting a specific reagent or a type of reagent it is possible, to obtain a polymer which has, with respect to the starting A-B-C polymer, at least one other desired functional group having a different chemical reactivity than the starting functional group. Consequently a broad range of polymers and a broad range of crosslmkers can be combined to obtain powder paint formulations with desired properties. In Table I a survey of examples of possible modifications is given:
Table I
Figure imgf000015_0001
Regarding Table I, the modification of the starting A-B-C block polymer can, for example, take place by reaction of this A-B-C block polymer and a compound comprising an ethylenically unsaturated group, an acid group, an hydroxy group, an isocyanate group, an acetoacetate group, an epoxide group, a vmylether group or a fatty acid group.
Said modification with an ethylenically unsaturated groups will result m a polymer having, for example, (meth) acrylate, vmylether, fumaric or maleic end groups. The selection of the ethylenically unsaturated groups depends on the functionality m blocks A and C.
Furthermore, the present invention can result, for example, m that a polymer having carboxyl groups m A or C may be modified with glycidyl (meth) acrylate, a polymer having epoxy groups m A or C may be modified with (meth) acrylic acid and a polymer having hydroxyl groups A or C may be modified with a polyisocyanate and a hydroxyvmylether or hydroxy
(meth) acrylate or allylalcohol.
A polymer containing hydroxylgroups may also be modified with an unsaturated carboxylic acid such as for example fumaric acid or maleic acid anhydride and may also be functionalised with a saturated anhydride to an acid.
At the end blocks A and C of the A-B-C polymer functional groups are located. Examples of suitable functional groups are carboxyl groups, epoxy groups, anhydride groups, hydroxyl groups, acetoacetonate groups and combinations thereof. The combined weight percent of the end blocks A and C is generally less than 30 wt . % of the total weight of the A-B-C block copolymer.
The A-B-C polymer can be obtained through controlled radical polymerization in the presence of an initiator and a metal complex or a metal -containing compound after which the modification takes place in a second step.
A method of producing this functionalised A-B-C block polymer can comprise the steps of: a) providing a mixture, said mixture comprising an effective amount of an initiator and an effective amount of a catalyst; b) adding a first functionalized monomer to said mixture, said first functionalized monomer comprising for example an ethylenically unsaturated mono- or dicarboxylic acid derivative; c) polymerizing said first functionalized monomer at a suitable temperature and pressure to effectively polymerize said first functionalized monomer to form A block of said A-B-C block polymer; d) adding a non- functionalized monomer to said mixture, said non-functionalized monomer having essentially no reactive functional groups which are crosslinkable to said first functionalized monomer, and polymerising said non-functionalized monomer to form B block of said A-B-C block polymer; e) adding a functionalised alkene compound to said mixture or adding a second functionalized monomer to said mixture, said second functionalized monomer having functional groups which are not crosslinkable to said non-functionalized monomer, and polymerizing said second functionalized monomer to obtain C block of said A-B-C block polymer, thereby obtaining said A-B-C block polymer, wherein said A block and said C block of said A-B-C block polymer are terminally disposed and said B block is interposed between said A block and said C block, said B block being essentially free of reactive functional groups which are crosslinkable with those on said A block and said C block and f) functionalising the A-B-C blockpolymer . A method of producing the functionalised A-
B-C block polymer can, for example, also comprise the steps of : a) providing a mixture, comprising a functionalized initiator, a catalyst and a non-functionalized monomer, said non-functionalized monomer having essentially no reactive functional groups which are crosslinkable to said functionalized initiator, and polymerizing said non-functionalized monomer to form the A and B blocks of said A-B-C block polymer; b) adding a functional alkene compound to said initiator or adding a functionalized monomer to said mixture, said functionalized monomer having functional groups which are not crosslinkable to said non-functionalized monomer, and polymerizing said functionalized monomer to obtain C block of said A-B-C block polymer, thereby obtaining said A- B-C block polymer, wherein said A block and said C block of said A-B-C block polymer are terminally disposed and said B block is interposed between said A block and said C block, said B block being essentially free of reactive functional groups which are crosslinkable with those on said A block and said C block and c) functionalismg the A-B-C blockpolymer .
As shown m Table I the A-B-C blockpolymer can be functionalised with different components. The reaction conditions and the reagents depend on the selection of the reaction components and the intended application.
The molecular weight (Mn) of the modified polymer is usually higher than 400 and is preferably higher than 600. To obtain good flow behaviour at temperatures between 100°C and 200°C, the molecular weight (Mn) is usually lower than about 10,000 and preferably lower than about 7000. The Tg of the modified A-B-C polymer, for example a polyacrylate, is generally between about 30°C and about 120°C. To obtain an optimum storage stability, the Tg is preferably higher than 50°C. With a view to the processing of the polymer the Tg is preferably lower than 100°C.
The modified polymer can be applied m a powder pamt composition as a polymer, as a crosslinker and as the binder system.
In case the polymer acts as a crosslinker a suitable polymer has to be selected, m case the polymer acts as the polymer a suitable crosslinker has to be selected and m case the polymer acts as the binder system there is no need for a further polymer or crosslinker . Preferably a carboxylic acid functional polymer, obtained by modification of an hydroxy functional A-B-C block polymer with an anhydride or diacid, may be crossl ked with tπglycidyl isocyanurate (TGIC) , polybisphenol-A epoxides, compounds containing (blocked) isocyanate groups, compounds containing β-hydroxyalkylamide groups, ammo resins, crosslmkers containing acid groups and crosslmkers (as described m EP-A-600546) comprising at least one aliphatic branched or linear chain with an epoxy functionality containing 5-26 carbon atoms such as, for example, epoxidized oils.
A binder composition according to the invention yields a good coating after thermal curing under the influence of a catalyst at a temperature ranging from, for instance, about 80 °C to about 200 °C, depending on the selected polymer
The powder pamt binder composition according to the mvention can also be applied m a radiation curable powder pamt composition if the modification with, for example, an ethylenically unsaturated group takes place which results a polymer with vmylether, allyl or propenyl, (meth) acrylate , itaconate, maleate or fumarate functional groups.
A radiation-curable system can comprise for example a resm, a crosslinker, a photomitiator, a flow agent and pigments. Suitable polymers or crosslmkers which can be added to the radiation curable powder pamt compositions according to the invention include for example (meth) acrylated polyesters, (meth) acrylated polyurethanes , (meth) acrylated polyethers, polyepoxides, polyv ylethers, polyallylethers , unsaturated polyesters and poly (meth) acrylates . In this application also a crosslinker comprising units of a prepolymer having a molecular weight (Mn) higher than 400 and units of a vinyl ether or an unsaturated alcohol, the number of polymeπzable unsaturations of the crosslinker being higher than or equal to 2 , is very suitable. It is also possible to apply combinations of several polymers and/or crosslmkers.
Radiation curing of the binder composition according to the invention preferably takes place through UV and EB curing. These methods are described m more detail , for instance, the article "UV and
EB-cuπng" by S.J. Bett et al . in JOCCA 1990 (11), pp. 446-453.
The compositions according to the invention can be cured by, for example, radical polymerization and by catiomc UV polymerization.
For the UV radiation curing of a powder pamt formulation a photomitiator can, at a temperature ranging from, for instance, 40°C to 120°C, be mixed with a binder composition according to the invention. A polymer which the functional, for example, hydroxyl -group is modified mto a vinyl ether, allyl or propenyl, (meth) acrylate, itaconate, maleate or fumarate is preferred for this application. An important advantage due to the present invention is the high cure speed, and the possibility of a low temperature curing for example at temperatures lower than 140 °C.
Mixing can take place both m a solvent and m the melt, for instance m an extruder or a static mixer. Further, pigments and the desired auxiliary materials such as, for instance, flow agents can be added. The pamt can subsequently be applied to the substrate or be sprayed electrostatically. After application, the powder pa t is molten at temperatures ranging from, for instance, 40°C to 170°C by being placed m an oven, exposure to mfra-red radiation, or a combination of both, so that a closed, smooth coating film is formed with a layer thickness ranging from, for instance, 20 to 200 μm, after which the still warm panel is cured under a UV light source. Afterwards post-heatmg may take place.
Examples of suitable photomitiators are described m Volume 3 "Photomitiators for free radical and cationic polymerisation" of "Chemistry and Technology of UV and EB formulations" by K. Dietliker (1991; SITA Technology Ltd . , London).
Photomitiators initiate curing of the compositions according to the invention upon exposure to light. Suitable initiators for radical polymerizations are ketomc and may be aromatic such as, for instance, benzophenone. Irgacure 184® (Ciba) is an aryl ketone with hydroxycyclohexyl -phenyl -ketone as active component and is, like Irgacure 369® (active component 2 -benzyl-2 -dιmethylammo-1- (4- morphol ophenyl) -butanone-1) , a suitable photomitiator. Acyl phosphme, such as 2 , 4 , 6-tπmethyl benzoyl diphenyl phosphme oxide (Lucerme TPO®, BASF) can also be used. Chemical derivatives of this photomitiator are also suitable, as are combinations of these initiators. A suitable combination of photomitiators is formed by Irgacure 1800® (Ciba) , which consists of 75 wt . % Irgacure 184® and 25 wt . % (bis (2 , 6-dιmethoxy benzoyl) -2 , 4 , 4-trιmethylpentyl phosphme oxide) .
The preparation of a powder-pamt composition and the chemical curing reactions of powder-pamt compositions mto cured coatings are described m general terms , for example, Misev, Powder Coatings, Chemistry and Technology, pp. 44-54, p. 148 and pp. 225-226, the complete disclosure of which is incorporated herein by reference.
Optionally one or more other additives . suitable for use m paints may also be used. Examples of suitable additives include pigments, fillers, degassing agents, flow agents, stabilizers and tπbochargmg improving agents . Suitable pigments include for example inorganic pigments, such as titanium dioxide, zmc sulphide, iron oxide and chromium oxide, and also organic pigments such as azo compounds . Suitable fillers include for example metal oxides, silicates, carbonates and sulphates.
Suitable stabilizers include for example primary and/or secondary antioxidants and UV stabilizers such as qu ones, (steπcally hindered) phenolic compounds, phosphonites , phosphites, thioethers and HALS compounds (hindered amme light stabilizers) .
Examples of degassing agents mclude benzoin and cyclohexane dimethanol bisbenzoate. Examples of flow agents include polyalkylacrylates , fluorohydrocarbons and silicon oils. Suitable additives are for example additives to improve the tribo-chargmg properties, include for example sterically hindered tertiary amines. Powder paints according to the invention can be applied to a susbtrate m the usual manner, for example by means of electrostatic spraying of the powder onto an earthed substrate and curing of the coating such as through exposure to heat at a suitable temperature for a sufficiently long period. The applied powder can for example be heated m a gas oven, an electric oven or with the aid of infrared radiation. Thermosettmg coatings of powder pamt (coating) compositions intended for industrial applications are described further m general terms the already mentioned Powder Coatings by Misev, pp. 141-173 (1991) .
Compositions according to the present invention can be used m powder coatings intended for use on for example metal, wood, aluminium, paper, cardboards and plastic substrates. The coatings are also very suitable for use the automotive industry for coating external and/or internal parts. The invention will be further elucidated with reference to the following, non-limiting examples.
Example I
Preparation of a carboxyl -functional acrylate polymer A mixture consisting of 14.1 g of 2,2'- bipyridme and 288 g of toluene was degassed and inertlzed with nitrogen. Next, 4.5 g of CuCl was added after which the mixture was heated no 105°C. Next, 15 g of dichloroacetic methyl ester, 31.5 g of methyl methacrylate and 27 g of tert . -butyl acrylate were added. The temperature was Kept at 105°C. After 4 hours the tert . -butyl acrylate present had reacted. Next, 210 g of methyl methacrylate was added at 105°C. Subsequently, after 90% conversion, a mixture consisting of 27 g of tert . -butyl acrylate and 31.5 g of methyl methacrylate was added.
The reaction was continued for another 3 hours to bring about complete conversion. The solution was cooled and filtered. Toluene was removed through distillation and the product obtained, with a molecular weight Mn of 3250, was heated to 200°C, after which the tertiary butyl ester decomposed. The carboxyl -functional polyacrylate obtained had an acid number of 52.4 mg of KOH/g of resin and a glass transition temperature of 92°C.
Example II Preparation of an acrylate polymer
A mixture consisting of 1.562 g of
2 , 2 ' bipyridme and 50 g of toluene was degassed and ertized with nitrogen. Next, 0.496 g of CuCl was added, after which the mixture was heated to 105°C. Then 3.1 g of dichloroacetic tert-butyl ester and 50 g of methyl methacrylate were added.
The temperature was kept at 105°C. After 90% conversion 2.13 g of tert . -butyl acrylate was added.
After 4 hours and 105°C complete conversion was realized. The solution was cooled and filtered. Toluene was removed through distillation and the product, with a molecular weight (Mn) of 3320, was heated to 200°C. The carboxyl -functional polyacrylate obtained had an acid number of 52.4 mg of KOH/g of resin and a glass transition temperature of 93°C.
Example III Preparation of a hydroxyl -functional acrylate polymer
940 acrylate polymer obtained according to Example I was dissolved in 500 g of butyl acetate. The solution was heated to 120°C, after which 2 g of catalyst was added. Next, 60 g of propylene oxide was dosed in 2 hours. After additional 3 hours afterreaction at 120°C butyl acetate was removed by vacuum distillation up to 180°C.
The polymer obtained had an acid number of <1 mg of KOH/g of resin and a hydroxyl value of 48 mg of KOH/g of resin. The polymer's glass transition temperature was 78°C.
Examples IV-XII Powder coatings
The polyacrylates obtained according to Examples I -II I (Acrylate 1, Acrylate 2 and Acrylate 3, respectively, in Table 2) were mixed with a crosslinker as indicated in Table 2. This mixture was dosed to a kneader at 120°C. After the resin had melted completely, titanium dioxide was dispersed in the resin, after which the other additives were added. After cooling, the product obtained was reduced in size, pulverized and sieved to a maximum particle size of 90 mm. The powder-paint composition was electrostatically applied to an earthed metal substrate and was cured to a powder coating .
The curing conditions and properties obtained are shown in Table 3. From this it can be concluded that powder coatings were obtained that possess the desired combination of elasticity, hardness and resistance to chemicals .
Figure imgf000027_0001
Figure imgf000028_0001
1) epoxidized linseed oil (Union Carbide) 2) epoxidized soybean oil (Henkel) 3) triglycidyl isocyanurate (CIBA) 4) tetramethoxymethyl glycoluril (Cyanamid) 5) tolonate HDT blocked with triazole 6) tetramethylguanidine 7) dimethylbenzyl amine
Table 3
Figure imgf000029_0003
) Curing temperature 200°C ) Kόnig pendulum hardness - DIN 53 157 ) Reverse impact test - ASTM-2794/69 ) Erichson slow penetration ISO 1520 - DIN 53156
') : Acetone double rubs
Figure imgf000029_0001
Figure imgf000029_0002

Claims

C L A I M S
1. Powder paint binder composition comprising a A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having crosslinkable functional groups, said B block being essentially free of reactive functional groups and a crosslinker.
2. Composition according to Claim 1, characterized in that the combined weight percent of said A block and said C block is less than about 30 wt . % of said A-B-C block polymer.
3. Composition according to any one of Claims 1-2, characterized in that the polymer is a poly (meth) acrylate or a polystyrene.
4. Composition according to any one of Claims 1-3 wherein at least one of the A block and the C block of the A-B-C block polymer is modified into a functional group with a different chemical reactivity (with regard to the starting A-B-C polymer) .
5. Composition according to Claim 4 characterized in that the functional group in the starting A block and/or C block is a hydroxyl group, a carboxylic acid group or an epoxy group and the resulting functional group in the modified A-B-C blockpolymer is a carboxylic acid, an acetoacetate, an alkoxysilane , a vinylether, an allyl or propenyl group, a (meth) acrylate, an itaconate, a maleate or a fumarate, a hydroxyl, an oxazoline, an amide or a carbonate group. 6. A radiation curable powder paint binder composition containing an A-B-C block polymer according to any one of Claims 1-5 in which the functional group in the A and/or C group is modified into a vinyl ether, allyl, propenyl, (meth) acrylate , itaconate, maleate or fumarate group . 7. A thermal curable powder paint binder compositon containing an A-B-C block polymer according to any of Claims 1-5 in which the functional group in the A and/or C block is modified into a carboxylic acid group. 8. Powder paint containing a composition according to any one of Claims 1-7 and optionally pigment, catalyst, filler and additives. 9. Powder coating obtained after curing of a powder paint according to Claim 8. 10. Entirely or partly coated substrate, characterized in that a powder coating according to Claim 9 has been used as the coating. 11. A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having crosslinkable functional groups, said B block being essentially free of reactive functional groups wherein the combined weight percent of said A block and said C block is less than about 30 wt . % of said A-B-C block polymer and wherein, the polymer is a poly (meth) crylate or a polysterene. 13. A-B-C block polymer according to Claim 12 wherein at least one of the A block and the C block is modified into a functional group with a different chemical reactivity (with regard to the starting A-B-C polymer) and wherein the functional group in the starting A block and/or C block is a hydroxyl group, a carboxylic acid group or an epoxy group and the resulting functional group in the modified A-B-C blockpolymer is a carboxylic acid, an acetoacetate, an alkoxysilane, a vinylether, an allyl or propenyl group, a (meth) acrylate, an itaconate, a maleate or fumarate, a hydroxyl, an oxazoline, an amide or a carbonate group.
AMENDED CLAIMS
[received by the International Bureau on 4 October 1999 (04.10.99); original claims 1-13 replaced by amended claims 1-11 (3 pages)]
Powder paint binder composition comprising a
A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having crosslinkable functional groups, said
B block being essentially free of reactive functional groups and a crosslinker.
Composition according to Claim 1, characterized in that the combined weight percent of said A block and said C block is less than about 30 wt . % of said A-B-C block polymer.
Composition according to any one of Claims 1-2, characterized in that the polymer is a poly (meth) acrylate or a polystyrene .
Composition according to any one of Claims 1-3 wherein at least one of the A block and the C block of the A-B-C block polymer is modified into a functional group with a different chemical reactivity (with regard to the starting A-B-C polymer) .
Composition according to Claim 4 characterized in that the functional group in the starting A block and/or C block is a hydroxyl group, a carboxylic acid group or an epoxy group and the resulting functional group in the modified A-B-C blockpolymer is a carboxylic acid, an acetoacetate, an alkoxysilane, a vinylether, an allyl or propenyl group, a (meth) acrylate, an itaconate, a maleate or a fumarate, a hydroxyl, an oxazoline, an amide or a carbonate group .
6. A radiation curable powder paint binder composition containing an A-B-C block polymer according to any one of Claims 1-5 in which the functional group in the A and/or C group is modified into a vinyl ether, allyl, propenyl,
(meth) acrylate, itaconate, maleate or fumarate group.
7. A thermal curable powder paint binder compositon containing an A-B-C block polymer according to any of Claims 1-5 in which the functional group in the A and/or C block is modified into a carboxylic acid group.
8. Powder paint containing a composition according to any one of Claims 1-7 and optionally pigment, catalyst, filler and additives.
9. Powder coating obtained after curing of a powder paint according to Claim 8.
10. Entirely or partly coated substrate, characterized in that a powder coating according to Claim 9 has been used as the coating.
11. A-B-C block polymer formulated from an ethylenically unsaturated monomer, said A block and said C block being terminally disposed and said B block being interposed between said A block and said C block; said A block and said C block having crosslinkable functional groups, said B block being essentially free of reactive functional groups wherein the combined weight percent of said A block and said C block is less than about 30 wt . % of said A-B-C block polymer and wherein, the polymer is a poly (meth) acrylate or a polystyrene and wherein at least one of the A block and the C block is modified into a functional group with a different chemical reactivity (with regard to the starting A-B-C polymer) and wherein the functional group in the starting A block and/or C block is a hydroxyl group, a carboxylic acid group or an epoxy group and the resulting functional group in the modified A-B-C blockpolymer is a carboxylic acid, an acetoacetate, an alkoxysilane, a vinylether, an allyl or propenyl group, a (meth) acrylate, an itaconate, a maleate or fumarate, a hydroxyl, an oxazoline, an amide or a carbonate group.
PCT/NL1999/000340 1998-06-04 1999-06-01 Powder-paint binder composition WO1999062978A1 (en)

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EP98201851A EP0962473A1 (en) 1998-06-04 1998-06-04 Block polymer and powder-paint binder composition
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WO2002051947A2 (en) * 2000-12-22 2002-07-04 Basf Corporation, Please See General Appointment Of Representative Water-based coating composition having carbonate-amine cross-linking, method of preparing the same, and a cured film thereof
US6699943B2 (en) 2000-06-16 2004-03-02 Basf Corporation Water-based coating composition having carbamate-melamine cross-linking, method of preparing the same, and a cured film thereof
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US6916877B2 (en) 2000-06-16 2005-07-12 Basf Corporation Coating composition including a water-based copolymer cross-linking with a water-dispersible cross-linking agent, method of preparing the same, and a cured film thereof
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WO2006138311A1 (en) * 2005-06-17 2006-12-28 E. I. Du Pont De Nemours And Company Rapid drying lacquers containing triblock copolymer for rheology control
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6699943B2 (en) 2000-06-16 2004-03-02 Basf Corporation Water-based coating composition having carbamate-melamine cross-linking, method of preparing the same, and a cured film thereof
US6881791B2 (en) 2000-06-16 2005-04-19 Basf Corporation Poly-electrolyte free block copolymers and their use in crosslinking coatings applications
US6916877B2 (en) 2000-06-16 2005-07-12 Basf Corporation Coating composition including a water-based copolymer cross-linking with a water-dispersible cross-linking agent, method of preparing the same, and a cured film thereof
WO2002051947A2 (en) * 2000-12-22 2002-07-04 Basf Corporation, Please See General Appointment Of Representative Water-based coating composition having carbonate-amine cross-linking, method of preparing the same, and a cured film thereof
WO2002051947A3 (en) * 2000-12-22 2003-01-16 Basf Corp Water-based coating composition having carbonate-amine cross-linking, method of preparing the same, and a cured film thereof
EP1714993A1 (en) * 2004-01-30 2006-10-25 Kaneka Corporation Thermoplastic elastomer composition and molded article
EP1714993A4 (en) * 2004-01-30 2007-01-24 Kaneka Corp Thermoplastic elastomer composition and molded article
US7799869B2 (en) 2004-01-30 2010-09-21 Kaneka Corporation Thermoplastic elastomer composition and molded article
WO2006138311A1 (en) * 2005-06-17 2006-12-28 E. I. Du Pont De Nemours And Company Rapid drying lacquers containing triblock copolymer for rheology control
US8906461B2 (en) 2005-06-17 2014-12-09 Axalta Coating Systems Ip Co., Llc Rapid drying lacquers containing triblock copolymer for rheology control

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