WO2015097064A1 - Compositions de revêtement durcissables contenant un alcoxysilane insaturé - Google Patents

Compositions de revêtement durcissables contenant un alcoxysilane insaturé Download PDF

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Publication number
WO2015097064A1
WO2015097064A1 PCT/EP2014/078485 EP2014078485W WO2015097064A1 WO 2015097064 A1 WO2015097064 A1 WO 2015097064A1 EP 2014078485 W EP2014078485 W EP 2014078485W WO 2015097064 A1 WO2015097064 A1 WO 2015097064A1
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Prior art keywords
group
binder
compound
coating composition
polymer
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PCT/EP2014/078485
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English (en)
Inventor
David Pierre
Gina DI GIOVANNI
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Dow Corning Corporation
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Publication of WO2015097064A1 publication Critical patent/WO2015097064A1/fr

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    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the coating compositions can be cured by a radical reaction i.e. a chemical reaction between radicals. Such radical reaction is for example initiated by UV.
  • a binder as defined herein is a compound or mixture of compounds able to bind and form a coating on a substrate.
  • a binder as defined herein can be a precured macromolecule able to react to form a polymer coating.
  • the binder as defined herein can alternatively be a system, for example a mixture of compounds, able to cure and form a coating after curing.
  • a siloxane or polysiloxane or organopolysiloxane is a silicon containing compound containing repeating Si-O-Si bonds.
  • a silane is a silicon containing compound which does not contain repeating Si-O-Si bonds.
  • the curable coating composition is especially suitable for metallic or overcoated metallic substrates. In particular it relates to the use of an unsaturated alkoxysilane additive in such coating compositions.
  • Curable polysiloxane coating compositions having a binder comprising a compound or polymer (D) containing at least one primary or secondary amine group, a compound or polymer (B) containing at least one ethylenically unsaturated double bond activated by an adjacent electron-withdrawing group, and a polymer (A) containing at least two silicon- bonded alkoxy groups are known.
  • a compound or oligomer or polymer or component is a compound which can be polymeric or non-polymeric.
  • (D) contains at least one silicon-bonded alkoxy group in its molecule.
  • the coating is capable of curing at ambient temperature and humidity both by hydrolysis and condensation of the Si-O-C bonds of the polyorganosiloxane (A) and of the silicon-bonded alkoxy group in (D) and by Michael-type addition reaction of the amine (D) with the activated ethylenically unsaturated double bonds of (B).
  • (A) can for example be an aminoalkyl silane.
  • Such polysiloxane coating compositions have high gloss which is retained remarkably well on weathering and UV exposure. They are particularly suitable for coating substrates which are exposed to the weather, e.g. sunlight, for long periods before recoating.
  • the coating compositions can for example be used as a finish coating on substrates such as metal like zinc or aluminium, or stainless steel, galvanised steel, glass or plastic surfaces. These are used for buildings, steel structures, automobiles, aircraft and other vehicles.
  • a finish coating can be applied on a substrate bearing a primer coat previously applied on the substrate.
  • a curable coating composition according to the invention having a binder comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule and a compound or polymer (B) containing at least one aliphatically unsaturated group, is characterised in that the binder also comprises (C) an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule and a compound or polymer (B) containing at least one aliphatically unsaturated group, is characterised in that the binder also comprises (C) an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule and a compound or polymer (B) containing at least one aliphatically unsaturated group, is characterised in that the binder also comprises (C) an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule and a compound or polymer (B) containing
  • the coating composition of the invention is curable for example by reaction with a compound or polymer (D) containing at least one primary or secondary amine group.
  • the compound or polymer (D) containing at least one primary or secondary amine group is preferably packaged separately from the coating composition of the invention as defined above to form a 2-pack coating composition in which the packages can be mixed a short time before the coating composition is coated on the substrate.
  • the curable coating composition according to the invention is mixed with a compound or polymer (D) containing at least one primary or secondary amine group and coated on a substrate, the coating may have improved properties compared to a coating which does not contain the
  • acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane C.
  • the acryloxy or methacryloxy groups of the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane can react with the amine curing agent by a Michael-type reaction, and the silicon-bonded alkoxy groups of the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane can react with the organopolysiloxane (A) in the presence of moisture, so that the
  • the improved properties of the coating may be one or more of the following: increased overcoating interval, increased surface hardness or scratch resistance
  • the invention thus includes the use of an acryloxymethylalkoxysilane or
  • methacryloxymethylalkoxysilane containing at least two silicon-bonded alkoxy groups in a curable coating composition comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and a compound or polymer (D) containing at least one primary or secondary amine group.
  • A organopolysiloxane
  • B containing at least one aliphatically unsaturated group
  • D compound or polymer
  • the invention also includes a process for coating a substrate characterised in that the substrate is coated with a coating composition comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one ethylenically unsaturated carboxylic ester group, an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one ethylenically unsaturated carboxylic ester group, an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one ethylenically unsaturated carboxylic ester group, an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one ethy
  • the coating composition of the invention can alternatively be cured by ultraviolet (UV) radiation. Coatings of the invention cured by UV radiation also have improved properties.
  • the binder is an alkyd resin
  • the coating composition can be cured by the action of a siccative (Cobalt based or similar) and oxygen from air.
  • the organopolysiloxane (A) is a material based on a Si-O-Si polymer chain and may comprise mono-functional, di-functional, tri-functional and/or tetra-functional siloxane units. It is preferred that the majority of siloxane units are di-functional units having the general formula RR'Si0 2 /2 wherein R and R' each independently denotes an organic component or a hydroxyl or hydrogen substituent.
  • R and R' are selected from alkyl groups, alkenyl groups, aryl groups, alkyl-aryl groups or aryl-alkyl groups.
  • the organopolysiloxane can for example be a polydiorganosiloxane such as
  • polydimethylsiloxane PDMS
  • a polydiorganosiloxane can for example have terminal silicon-bonded alkoxy groups.
  • the terminal groups of the organopolysiloxane can for example be dimethylmethoxysilyl groups, dimethylethoxysilyl groups, methyldimethoxysilyl groups, methyldiethoxysilyl groups, triethoxysilyl groups or trimethoxysilyl groups.
  • the organopolysiloxane (A) can for example comprise 3 to 100 siloxane units, preferably 4 to 25 siloxane units.
  • R groups of the organopolysiloxane (A) can be alkyl groups bearing an alkoxysilyl moiety, for example a trialkoxysilyl moiety.
  • alkoxysilyl moiety for example a trialkoxysilyl moiety.
  • organopolysiloxane is the dimethyl methyloctyl methyl(triethoxysilyl)propyl siloxane copolymer.
  • the organopolysiloxane (A) can be an organopolysiloxane comprising at least one of the following units: M unit (mono-functional), D unit (di-functional), T unit (tri-functional), Q unit (tetra-functional).
  • a M unit has the formula R3Si01 /2 wherein R is a substituent, preferably an organic substituent and each R can be the same or different on a single Si atom.
  • a D unit has the formula R2Si02/2 wherein R is a substituent, preferably an organic substituent and each R can be the same or different on a single Si atom.
  • a Q unit has the formula Si0 4/2 .
  • a T unit has the formula RSi0 3/2 , wherein R is a substituent, preferably an organic substituent.
  • R is a substituent, preferably an organic substituent.
  • R can be selected for example from alkyl, aryl, alkenyl, acrylate, methacrylate and others.
  • R can be an alkenyl group having 1 to 6 carbon atoms, for example a vinyl group or an hexenyl group.
  • a branched organopolysiloxane typically contains at least one T unit and/or at least one Q unit.
  • a linear organopolysiloxane typically contains D units and optionally M units.
  • the majority of siloxane units of the organopolysiloxane (A) are di-functional siloxane units other units such as tri-functional or tetra-functional units may also be present resulting in the polymer chain exhibiting a certain amount of branching.
  • resinous organopolysiloxane materials may be used such as a condensation product of a partially hydrolysed trialkoxysilane.
  • the organopolysiloxane (A) can alternatively be a resinous oligomeric alkyl silicate, for example the material sold under the trade mark DOW CORNING ® US/CF/2403 resin. Blends of such resinous
  • organopolysiloxane materials with an alkoxy-tipped linear polyorganosiloxane such as PDMS can be used.
  • the organopolysiloxane (A) is preferably present as at least 25% by weight of the binder of the curable coating composition, and may for example be present at from 40% up to 85% of the binder.
  • the aliphatically unsaturated group in the compound or polymer (B) is preferably activated by an adjacent electron-withdrawing group, for example a carboxyl group.
  • Acrylate ester groups are preferred because they are more reactive in the Michael reaction than methacrylate groups, particularly at ambient temperature.
  • Compounds or polymers (B) containing other olefinically unsaturated groups activated by an adjacent carboxyl group, for example containing a maleate or fumarate ester group can also be used effectively.
  • the compound or polymer (B) preferably contains at least two aliphatically unsaturated groups, more preferably at least two aliphatically unsaturated groups each activated by an adjacent electron-withdrawing group.
  • (B) can for example be an oligomer or polymer, for example of molecular weight at least 300 up to 5000, preferably up to 3000, containing at least two acrylate or methacrylate groups.
  • the acrylate or methacrylate groups are preferably present in the oligomer or polymer as terminal groups.
  • oligomer or polymer (B) is a urethane acrylate. This can be formed for example by the reaction of an isocyanate-tipped prepolymer with a hydroxyalkyl acrylate or methacrylate such as hydroxyethyl acrylate.
  • the oligomer or polymer (B) can be an epoxy resin acrylate or methacrylate, a polyether acrylate or methacrylate, a polyester acrylate, a melamine resin acrylate, a polyamide acrylate, or an acrylic polymer having pendent acrylate or methacrylate groups.
  • An alternative oligomer or polymer (B) is a polyester oligomer containing maleate or fumarate ester units.
  • the compound or polymer (B) can alternatively be a drying alkyd resin.
  • Alkyd resins are polyesters derived from polyols such as trimethylolpropane, glycerol, or pentaerythritol and a dicarboxylic acid or carboxylic acid anhydride such as phthalic anhydride or maleic anhydride modified by the addition of fatty acids.
  • Drying alkyd resins include polyunsaturated fatty acids such as linolenic acid or linoleic acid, or drying oils which comprise triglycerides of polyunsaturated fatty acids. Examples of drying oils include linseed (flax seed) oil, tung oil, poppy seed oil, perilla oil, and walnut oil.
  • the compound or polymer (B) can alternatively be an acrylate or methacrylate ester of a polyol, for example propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate,
  • a polyol for example propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate,
  • the component (B) can be a blend of a compound and a polymer, for example a blend of an acrylate or methacrylate ester of a polyol with an oligomer or polymer containing at least two acrylate or methacrylate groups.
  • the compound or polymer (B) is preferably present as at least 10% by weight of the binder of the curable coating composition and may be present at up to 40 or 50% by weight of the binder.
  • An oligomer or polymer containing acrylate or methacrylate groups can for example be present at 15% up to 50% by weight of the binder.
  • the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) containing at least two silicon-bonded alkoxy groups is preferably a trialkoxysilane.
  • acryloxymethylalkoxysilanes are preferred.
  • the acryloxymethylalkoxysilane can for example be an acryloxymethyltrialkoxysilane of the formula:
  • each R represents a methyl or ethyl group, for example
  • the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane can be any suitable acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane.
  • dialkoxysilane for example an acryloxymethyldialkoxysilane of the formula:
  • each R represents a methyl or ethyl group and R' represents an alkyl group, preferably a methyl or ethyl group.
  • the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) is preferably present in the curable coating composition at 1 to 15% or up to 99.9% by weight of the binder on a dry weight basis, more preferably 2 to 7%.
  • the curable coating composition of the invention comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule
  • acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) containing at least two silicon-bonded alkoxy groups can for example be cured by reaction with a compound or polymer (D) containing at least one primary or secondary amine group.
  • a curable coating composition of the invention comprises an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, an acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) containing at least two silicon-bonded alkoxy groups and a compound or polymer (D) containing at least one primary or secondary amine group.
  • A organopolysiloxane
  • B containing at least one aliphatically unsaturated group
  • an acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane C
  • D compound or polymer
  • the compound or polymer (D) containing at least one primary or secondary amine group is preferably an amino-functional alkoxysilane, for example an
  • aminoalkylalkoxysilane Such an aminoalkylalkoxysilane can react in the presence of moisture with the silicon-bonded alkoxy groups of the organopolysiloxane (A) and of the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) in a siloxane condensation reaction and also with the aliphatically unsaturated group in the compound or polymer (B) and the acryloxy or methacryloxy group of (C) by Michael-type addition.
  • the aminoalkylalkoxysilane thus acts as an effective curing or hardening agent for the coating composition.
  • the aminoalkylalkoxysilane (D) is more preferably a trialkoxysilane.
  • the compound (D) containing at least one primary amine group can for example be 3- aminopropyltrimethoxysilane, 3-amino-2-methyl-propyltrimethoxysilane or 3- aminopropyltriethoxysilane, or can be a disilane such as bis(3-aminopropyl)- tetramethoxysilane.
  • a disilane compound contains a Si-O-Si bond.
  • a compound (D) containing at least one secondary amine group can for example be N-methyl-3- aminopropyltrimethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane.
  • a compound (D) containing a primary amine group and a secondary amine group can for example be N- (2-aminoethyl)-3-aminopropyltrimethoxysilane.
  • the aminoalkylalkoxysilane (D) can alternatively be a dialkoxysilane or monoalkoxysilane.
  • a compound (D) containing at least one primary amine group can for example be 3-aminopropylmethyldimethoxysilane or 3- aminopropylmethyldimethoxysilane.
  • the amine group of the amino-functional compound or polymer (D) can be present in blocked form, for example as a ketimine, to extend pot life, if this is desired.
  • the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) can be used in the curable coating composition together with an organopolysiloxane containing at least two aliphatically unsaturated hydrocarbon groups to form a coating composition having excellent flexibility and hardness of the cured coating film.
  • the aliphatically unsaturated hydrocarbon groups of such an organopolysiloxane are preferably silicon-bonded alkenyl groups but can alternatively be alkynyl groups. Examples of alkenyl groups include vinyl, hexenyl, allyl, butenyl, pentenyl and hexenyl groups.
  • the aliphatically unsaturated hydrocarbon groups can be terminal groups on the organopolysiloxane and/or can be groups pendant on the siloxane polymer chain.
  • the organopolysiloxane containing at least two aliphatically unsaturated hydrocarbon groups can for example be a branched organopolysiloxane containing at least three aliphatically unsaturated hydrocarbon groups, particularly at least three alkenyl groups.
  • the branched organopolysiloxane can for example comprise one or more Q units of the formula Si0 4/2 and/or one or more T units of the formula RSi0 3/2 , up to 1000 D units of the formula R 2 Si0 2/2 and M units of the formula R 3 Si0 1/2, wherein the substituents R are selected from alkyl, aryl and alkenyl groups having 1 to 6 carbon atoms, at least three substituents R in the branched siloxane being alkenyl groups.
  • suitable branched organopolysiloxanes include those described in EP-A-1070734.
  • the branched organopolysiloxane can include both vinyl and hexenyl groups; it can for example contain at least two, preferably at least three, dimethylvinylsiloxy M units, with at least 1 molar % of the groups R in the D units of the formula R 2 Si0 2/2 being hexenyl groups.
  • An organopolysiloxane containing at least two aliphatically unsaturated hydrocarbon groups can alternatively be a linear organopolysiloxane, for example a short chain (degree of polymerisation less than 100 siloxane units) polydimethylsiloxane having terminal dimethylvinylsiloxy units, optionally having pendant alkenyl groups, for example it can include methylvinylsiloxane or hexenylmethylsiloxane units.
  • the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) can if desired be mixed with an organopolysiloxane (C) containing at least two aliphatically unsaturated hydrocarbon groups to form an additive package for improving the properties of the cured coating to a substrate while maintaining the flexibility, hardness and scratch resistance of the cured coating.
  • the molar ratio of amino groups of the amino-functional compound or polymer (D) to the total aliphatically unsaturated double bonds present in the compound or polymer (B) and the acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) of the coating composition is usually in the range 1 :10 to 10:1 , preferably at least 1 :2 up to 3:1 or 5:1 molar.
  • the curable coating composition of the invention comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per
  • acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) containing at least two silicon-bonded alkoxy groups can alternatively be cured by UV radiation or initiated by oxygen from air with the help of a siccative.
  • the compound or polymer (D) is preferably packaged separately from the organopolysiloxane (A), the aliphatically unsaturated compound or polymer (B) and the acryloxymethylalkoxysilane or
  • methacryloxymethylalkoxysilane (C) to form a 2-pack coating composition.
  • the two packages of the coating composition can be mixed a short time before the coating composition is coated on the substrate, for example a short time before the coating is applied by brush, spray or roller.
  • the separately packaged components can alternatively be applied by twin-feed spray.
  • the coating compositions of the invention usually contain one or more pigments, and can contain other ingredients such as a siloxane condensation catalyst, a thickening agent, a plasticiser, a pigment dispersant, a stabiliser, a flow aid or a solvent.
  • coatings of the composition of this invention are usually capable of curing at ambient temperatures of for example 5 to 30 5 C. Coatings can be cured at elevated temperatures, for example in the range 30 to 130 5 C, is heat curing is practical and is desired. Atmospheric moisture generally provides sufficient moisture for hydrolysis and reaction of the silicon-bonded alkoxy groups of organopolysiloxane (A), acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) and an
  • aminoalkylalkoxysilane curing agent (D) if present.
  • the coating composition of the invention can be applied as a primer coat or as a top coat on a substrate. Coatings formed from the compositions of the invention may have improved properties.
  • Coatings formed from the coating compositions of the invention retain the high gloss, flexibility, hardness, scratch resistance and long term resistance to weathering and UV exposure and may have other improved properties.
  • the invention provides a curable coating composition, the composition containing a binder comprising
  • binder curable by radical reaction the binder containing an organopolysiloxane or a silane with at least one acrylate or methacrylate group or
  • the binder also comprises (C) an acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane containing at least two silicon-bonded alkoxy groups.
  • the invention provides a curable coating composition wherein the
  • acryloxymethylalkoxysilane (C) is an acryloxymethyltrialkoxysilane of the formula
  • each R represents a methyl or ethyl group.
  • the invention provides a curable coating composition wherein the
  • acryloxymethylalkoxysilane (C) is acryloxymethyltrimethoxysilane.
  • the invention provides a curable coating composition wherein the
  • acryloxymethylalkoxysilane (C) is present at 1 to 1 5% by weight of the binder on a dry weight basis.
  • the invention provides a curable coating composition wherein the compound or polymer (B) contains at least one ethylenically unsaturated carboxylic ester group.
  • the invention provides a curable coating composition wherein the compound or polymer (B) comprises a drying alkyd resin.
  • the invention provides a curable coating composition further comprising as curing agent a compound (D) containing at least one primary or secondary amine group.
  • the invention provides a curable coating composition wherein the compound (D) containing at least one primary or secondary amine group is an aminoalkyltrialkoxysilane.
  • the invention provides the use of an an acryloxymethylalkoxysilane or
  • methacryloxymethylalkoxysilane containing at least two silicon-bonded alkoxy groups in a curable coating composition comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated carboxylic ester group, and a compound or polymer (D) containing at least one primary or secondary amine group.
  • A organopolysiloxane
  • B containing at least one aliphatically unsaturated carboxylic ester group
  • D compound or polymer
  • the invention provides a process for coating a substrate, characterised in that the substrate is coated with a coating composition as defined above.
  • the invention provides an additive composition for a curable coating composition comprising an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, a compound or polymer (B) containing at least one aliphatically unsaturated group, and a compound or polymer (D) containing at least one primary or secondary amine group, said additive composition comprising an acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) containing at least two silicon-bonded alkoxy groups and an organopolysiloxane containing at least two aliphatically unsaturated hydrocarbon groups.
  • A organopolysiloxane
  • B containing at least one aliphatically unsaturated group
  • D compound or polymer containing at least one primary or secondary amine group
  • said additive composition comprising an acryloxymethylalkoxysilane or methacryloxymethylalkoxysilane (C) containing at least two silicon-bonded alkoxy groups and
  • the invention provides the use of an acryloxymethylalkoxysilane or
  • methacryloxymethylalkoxysilane containing at least two silicon-bonded alkoxy groups in a curable coating composition having a binder comprising
  • binder curable by radical reaction the binder containing an organopolysiloxane or a silane with at least one acrylate or methacrylate group or
  • the primer coat was overcoated with a 50 ⁇ layer (dry film thickness) of a coating according to the invention and the coated panels were allowed to dry in ambient temperature air for 7 days.
  • the coating according to the invention was a 2-pack paint modified by the addition of acryloxymethyltnmethoxysilane to the main package of the paint.
  • the main package (part A) is believed to be a pigmented coating composition comprising 25-50% of a silicone resin having dimethylsiloxane units, methoxy groups and phenyl groups and silicon-bonded alkoxy groups, 10-25% acrylate-functional urethane oligomer, 10-25% 1 ,6-hexanediol diacrylate and 13-55% pigments.
  • the curing agent package (part B) is believed to comprise a primary aminoalkyltrialkoxysilane.
  • Test panels overcoated with unmodified paint were also tested by the same process.
  • the Clemen hardness test is done to measure the scratch resistance of the surface of a coating. The test was conducted with an "Elcometer 3000 Motorised Clemen"
  • K0003000M003 (SN300012040007) tester.
  • the sample is hold down with a clamp in the equipment.
  • a load of defined weight is put on the sample and one observes which weight is needed to leave a trace on the coating.
  • Table 1 shows that the acryloxymethyltrimethoxysilane improved the Clemen hardness of the paint as compared to unmodified paint.
  • a commercial UV curable composition containing a silane acrylate binder was modified by inclusion of 5% of acryloxymethyltrimethoxysilane. The composition was applied on untreated aluminium panels.
  • coating and “film” are used to designate the same object i.e. a layer of paint applied on the surface of a substrate.
  • the cross cut test is a test to measure the resistance of paints and coatings from substrates.
  • a lattice pattern is made in the coating with a cross cut tool. Two passes are made, the second pass being perpendicular to the first. The cut is brushed in diagonal direction. A tape is applied on the grid, pressed and removed. The grid area is then observed. KO means the coating is fully destroyed.
  • GtO means the best result (ISO2409).
  • the MEK test is a test to measure the solvent resistance of a coating.
  • the surface of the coating is rubbed with cloth soaked with MEK (methyl ethyl ketone) until failure or breakthrough of the film occurs.
  • MEK methyl ethyl ketone
  • Methyl Ethyl Ketone is rubbed across the surface of the part with a cloth (100 double rubs). The rubs are counted as a double rub (one rub forward and one rub backward constitutes a double rub). The higher the number, the better the solvent resistance of the coating is.
  • the slip test is a haptic test to evaluate the sensory touch of a film. A finger is applied on the film and the feeling is subjectively estimated by the operator. + means the feeling is good.
  • the pencil hardness test is a test to evaluate the hardness of a film.
  • a pencil of defined hardness is applied to the film.
  • the pencils are classified from 6B (the softer) to 6H (the hardest): 6B 5B 4B 3B 2B B HB F H 2H 3H 4H 5H 6H.
  • the pencil hardness of the film is the hardness of the hardest pencil that does not mark the film.
  • the ink rubber test also called ink rub test is a test to evaluate the abrasion resistance of a film.
  • Sand paper is applied back and forth to a film sample by an ink rubber tester equipment. The number of strokes is programmed in the equipment. The tester stops automatically when the preset number of strokes is achieved. The samples are then evaluated visually for print degradation and ink transfer.
  • the water contact angle is measured with a VCA Optima equipment from AST Products, Inc S/N Optima 10200221019. A drop of water is applied on the film with the syringe incorporated into the equipment. The equipment calculates the contact angle which is the angle between the tangent to the drop at the point of contact and the solid surface of the film. This permits to evaluate the hydrophobic/hydrophilic nature of the film. A high contact angle is linked to a hydrophobic film while a low contact angle will be linked to a more hydrophilic film.
  • the pendulum Koenig test is a test to evaluate the hardness of a film.
  • a Koenig tester equipment from Sheen Instruments S969320 707KP is used.
  • the damping time of an oscillating pendulum is measured.
  • the pendulum is oscillating between 3 and 6 degrees.
  • the time (in seconds) taken for the pendulum to decrease from 6 to 3 degrees is measured.
  • UV curable compositions (AY 42-260) Cross MEK Slip Visual Pencil Clemen Ink Water Pend 50 ⁇ - 500 mJ (H bulb) cut (solvent appearance hardness hardness rubber contact Koen resistance) tester angle

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention concerne une composition de revêtement durcissable, la composition contenant un liant comprenant un organopolysiloxane (A) contenant au moins deux groupes alcoxy liés par un silicium par molécule et éventuellement un composé ou un polymère (B) contenant au moins un groupe à insaturation aliphatique à condition que le liant contienne au moins un groupe C=C à insaturation aliphatique ou un liant durcissable par une réaction radicalaire, le liant contenant un organopolysiloxane ou un silane ayant au moins un groupe acrylate ou méthacrylate ou un liant de type alkyde contenant au moins un groupe C=C à insaturation aliphatique, le liant comprenant également (C) un acryloxyméthylalcoxysilane ou un méthacryloxyméthylalcoxysilane contenant au moins deux groupes alcoxy liés par un silicium. Les propriétés améliorées du revêtement selon l'invention peuvent être l'une ou plusieurs des suivantes : intervalle entre l'application des couches, dureté de surface ou résistance aux rayures, résistance aux intempéries, hydrophobicité, adhérence, procédé d'application, résistance aux solvants, glissement, aspect visuel, résistance à l'abrasion ou autres propriétés mécaniques améliorées.
PCT/EP2014/078485 2013-12-23 2014-12-18 Compositions de revêtement durcissables contenant un alcoxysilane insaturé WO2015097064A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1323041.2A GB201323041D0 (en) 2013-12-23 2013-12-23 Curable coating compositions containing an unsaturated alkoxysilane
GB1323041.2 2013-12-23

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WO2015097064A1 true WO2015097064A1 (fr) 2015-07-02

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018052645A1 (fr) 2016-09-19 2018-03-22 Dow Corning Corporation Adhésif de contact avec la peau et procédés associés à sa préparation et à son utilisation
WO2018052646A1 (fr) 2016-09-19 2018-03-22 Dow Corning Corporation Composition de copolymère pour applications d'adhésif et de revêtement
US11142639B2 (en) 2016-09-19 2021-10-12 Dow Silicones Corporation Polyurethane-polyorganosiloxane copolymer and method for its preparation
US11672768B2 (en) 2016-09-19 2023-06-13 Dow Silicones Corporation Skin contact adhesive and methods for its preparation and use

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5466999A (en) * 1977-11-07 1979-05-29 Japan Atom Energy Res Inst Transparent thermosetting resin composition
EP1070734A2 (fr) 1999-07-23 2001-01-24 Dow Corning Corporation Compositions de revêtement de silicone anti-adhésives
WO2004037868A1 (fr) * 2002-10-23 2004-05-06 Henkel Corporation Compositions de sechage double uv-humidite et de sechage rapide de l'humidite
EP2067800A1 (fr) * 2006-09-29 2009-06-10 Asahi Kasei Corporation Composition de polyorganosiloxane
EP2412756A1 (fr) * 2009-03-23 2012-02-01 Cemedine Co., Ltd. Composition durcissable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5466999A (en) * 1977-11-07 1979-05-29 Japan Atom Energy Res Inst Transparent thermosetting resin composition
EP1070734A2 (fr) 1999-07-23 2001-01-24 Dow Corning Corporation Compositions de revêtement de silicone anti-adhésives
WO2004037868A1 (fr) * 2002-10-23 2004-05-06 Henkel Corporation Compositions de sechage double uv-humidite et de sechage rapide de l'humidite
EP2067800A1 (fr) * 2006-09-29 2009-06-10 Asahi Kasei Corporation Composition de polyorganosiloxane
EP2412756A1 (fr) * 2009-03-23 2012-02-01 Cemedine Co., Ltd. Composition durcissable

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018052645A1 (fr) 2016-09-19 2018-03-22 Dow Corning Corporation Adhésif de contact avec la peau et procédés associés à sa préparation et à son utilisation
WO2018052646A1 (fr) 2016-09-19 2018-03-22 Dow Corning Corporation Composition de copolymère pour applications d'adhésif et de revêtement
US11142639B2 (en) 2016-09-19 2021-10-12 Dow Silicones Corporation Polyurethane-polyorganosiloxane copolymer and method for its preparation
US11672768B2 (en) 2016-09-19 2023-06-13 Dow Silicones Corporation Skin contact adhesive and methods for its preparation and use
WO2018151780A1 (fr) 2017-02-15 2018-08-23 Dow Silicones Corporation Copolymère de silicone-uréthane-urée, sa préparation et son utilisation
US11041042B2 (en) 2017-02-15 2021-06-22 Dow Silicones Corporation Silicone urethane urea copolymer and preparation and use thereof

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