AMINOALKYLALKOXYSILANE

[0001] This invention relates to curable coating compositions comprising a binder containing unsaturated C=C group(s), for example a polysiloxane and a compound or polymer containing an aliphatically unsaturated group, which compositions can be cured for example using a curing agent or by the action of a siccative or by UV. 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. An aliphatically unsaturated group also called an aliphatically unsaturated hydrocarbon group is typically a chemical group containing at least one C=C unsaturation. A C=C unsaturation is also called a carbon to carbon unsaturation. An aliphatically unsaturated group is typically a group containing non aromatic C=C unsaturation(s). 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.

[0002] In particular it relates to the use of an unsaturated aminoalkylalkoxysilane additive in such coating compositions.

[0003] 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 (A) 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. Typically (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). (D) can for example be an aminoalkyl silane.

[0004] 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, stainless steel, galvanised steel, glass or plastic surfaces. These are used for buildings, steel structures, automobiles, aircraft and other vehicles. A finish coating or overcoat can be applied on a substrate bearing a primer coat previously applied on the substrate.

[0005] 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, a compound or polymer (B) containing at least one aliphatically unsaturated group and a curing agent (C) containing at least one primary or secondary amine group, is characterised in that the curing agent (C) comprises an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation.

[0006] The coating composition of the invention is curable for example by reaction of the compound or polymer (B) containing at least one aliphatically unsaturated group with the curing agent (C) containing at least one primary or secondary amine group by a Michael- type reaction. The curing agent (C) containing at least one primary or secondary amine group is preferably packaged separately from the coating composition comprising an organopolysiloxane (A) and a compound or polymer (B) containing at least one aliphatically unsaturated group 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. When the curable coating composition according to the invention is coated on a substrate, the coating may have improved properties compared to a coating which does not contain the aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation. The group having carbon to carbon unsaturation in the aminoalkylalkoxysilane (D) can react with the amine curing agent by a Michael-type reaction, and the silicon-bonded alkoxy groups of the aminoalkylalkoxysilane (D) can react with the organopolysiloxane (A) in the presence of moisture, so that the aminoalkylalkoxysilane (D) becomes bound into the cured coating.

[0007] The improved properties of the coating may be one or more of the following:

increased overcoating interval, increased surface hardness or scratch resistance

(measured for example by the Clemen test or by Pencil hardness test), increased weatherability, increased hydrophobicity, increased adhesion, easier application process (viscosity, drying time), higher solvent resistance, better slip, better visual appearance, increased abrasion resistance (measured for example by the ink rubber test) or other improved mechanical properties.

[0008] The invention thus includes the use of an aminoalkylalkoxysilane containing a primary or secondary amino group and a group having carbon to carbon unsaturation 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 (C) containing at least one primary or secondary amine group.

[0009] The invention also includes a process for coating a substrate characterised in that 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 aliphatically unsaturated group, a compound or polymer (C) containing at least one primary or secondary amine group and an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation.

[0010] The group containing carbon to carbon unsaturation can be, for example, an alkenyl group, such as vinyl or hexenyl, an acrylate group or a methacrylate group.

The coating composition of the invention can alternatively be cured by ultraviolet (UV) radiation. Alternatively, when 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.

[0011 ] In a 2-pack coating composition according to the invention, the

aminoalkylalkoxysilane (D) containing a group having carbon to carbon unsaturation is preferably packaged with another compound or polymer (C) containing at least one primary or secondary amine group, preferably an aminoalkylalkoxysilane, to form a curing agent composition. Thus according to one aspect of the invention an aminoalkylalkoxysilane curing agent composition for a coating 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 curing agent comprises an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation and an aminoalkyltrialkoxysilane containing at least one primary or secondary amine group and having no carbon-to-carbon unsaturation.

[0012] The invention includes the use of an aminoalkyltrialkoxysilane curing agent composition comprising an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation to harden 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

aliphatically unsaturated group in the presence of atmospheric moisture.

[0013] 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. Preferably R and R' are selected from alkyl groups, alkenyl groups, aryl groups, alkyl-aryl groups or aryl-alkyl groups. More preferably a substantial part, most preferably a majority of the R substituents will be alkyl groups having from 1 to 12 carbon atoms, most preferably methyl or ethyl groups. The organopolysiloxane can for example be a polydiorganosiloxane such as

polydimethylsiloxane (PDMS). Such 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.

[0014] Some of the R groups of the organopolysiloxane (A) can be alkyl groups bearing an alkoxysilyl moiety, for example a trialkoxysilyl moiety. An example of such an

organopolysiloxane is the dimethyl methyloctyl methyl(triethoxysilyl)propyl siloxane copolymer.

[0015] 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. Each substituent R can be selected for example from alkyl, aryl, alkenyl, acrylate, methacrylate and others. For example it can be an alkenyl group having 1 to 6 carbon atoms, for example a vinyl group or an hexenyl group.

[0016] 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.

[0017] Although it is preferred that 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. For example 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. [0018] 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.

[0019] The aliphatically unsaturated group in the compound or polymer (B) is preferably activated by an adjacent electron-withdrawing group, for example a carboxyl group. The aliphatically unsaturated group can be an ethylenically unsaturated group. Most preferably it comprises an ethylenically unsaturated double bond, that is a -CH=CH- bond, activated by an adjacent electron-withdrawing group, particularly an ethylenically unsaturated carboxylic ester group such as an acrylate or methacrylate. 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.

[0020] 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.

[0021] One preferred type of 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. Alternatively, 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.

[0022] An alternative oligomer or polymer (B) is a polyester oligomer containing maleate or fumarate ester units.

[0023] 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.

[0024] 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, 1 ,6-hexanediol diacrylate, 1 ,4-butanediol diacrylate, pentaerythritol triacrylate and/or pentaerythritol tetraacrylate, and/or a corresponding dimethacrylate.

[0025] 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 use of an

aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation in combination with an organopolysiloxane containing at least two aliphatically unsaturated hydrocarbon groups may be advantageous for increasing properties of the cured coating while maintaining the flexibility, hardness and scratch resistance of the cured coating.

[0026] 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 two, preferably at least three aliphatically unsaturated hydrocarbon groups, particularly at least two, preferably 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 two, preferably at least three substituents R in the branched siloxane being alkenyl groups. Examples of 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.

[0027] The component (B) can also include an acrylate-functional alkoxysilane such as 3- acryloxymethyltrimethoxysilane or 3-acryloxypropyltrimethoxysilane.

[0028] 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.

[0029] The curing agent (C) containing at least one primary or secondary amine group can be a compound or polymer and 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) in a siloxane condensation reaction and also with the aliphatically unsaturated group in the compound or polymer (B) by Michael-type addition. The aminoalkylalkoxysilane thus acts as an effective curing or hardening agent for the coating composition. The silane curing agent can have 2 or more amine groups.

[0030] The aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation is one example of a compound containing at least one primary or secondary amine group and generally forms part of the curing agent (C). The aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation can for example be a N-(substituted alkyl)- aminoalkylalkoxysilane in which the group having carbon to carbon unsaturation is present in the substituted alkyl group. An example of such a N-(substituted alkyl)- aminoalkylalkoxysilane is a bis(secondary amine) having an alkoxysilylalkyl group bonded to one amine nitrogen atom and a group having carbon to carbon unsaturation bonded to the other amine nitrogen atom. The group having carbon to carbon unsaturation can for example be a vinyl, allyl, butenyl, pentenyl or hexenyl group. The group having carbon to carbon unsaturation can for example comprise a vinyl group bonded to an aromatic ring.

[0031] The aminoalkylalkoxysilane (D) preferably contains at least two silicon-bonded alkoxy groups and is more preferably a trialkoxysilane. Examples of suitable

trialkoxysilanes include 2-(N'-vinylbenzyl)aminoethyl-3-aminopropyltrimethoxysilane of the formula:

CH ₂ =CH-C6H4-CH ₂ -NH-CH ₂ -CH ₂ -NH-C ₃ H ₆ -Si(OR)3

in which each R represents a methyl group or the corresponding triethoxysilane in which R represents an ethyl group. An example of a suitable dialkoxysilane is 2-(N'- vinylbenzyl)aminoethyl-3-aminopropylmethyldimethoxysilane.

[0032] The curing agent (C) also preferably comprises another aminoalkylalkoxysilane, more preferably a trialkoxysilane, for example an aminoalkyltrialkoxysilane containing at least one primary or secondary amine group and having no carbon-to-carbon unsaturation. A compound (C) 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 (C) containing at least one secondary amine group can for example be N-methyl-3- aminopropyltrimethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane. A compound (C) containing a primary amine group and a secondary amine group can for example be N-(2- aminoethyl)-3-aminopropyltrimethoxysilane. The aminoalkylalkoxysilane can alternatively be a dialkoxysilane or monoalkoxysilane. A compound (C) containing at least one primary amine group can for example be 3-aminopropylmethyldimethoxysilane or 3- aminopropylmethyldimethoxysilane.

[0033] The aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation can be the only amine compound or polymer used as curing agent (C). More usually however the aminoalkylalkoxysilane (D) is used in conjunction with another amine compound or polymer (C), preferably another

aminoalkylalkoxysilane. The aminoalkylalkoxysilane (D) may for example be present as 5 to 50% by weight of the amine curing agent composition. Thus an aminoalkyltrialkoxysilane curing agent composition according to the invention may comprise an

aminoalkylalkoxysilane (D) present as 5 to 50% by weight of the alkoxysilane content of the aminoalkyltrialkoxysilane curing agent composition.

[0034] The amine group of the amino-functional curing agent (C) can be present in blocked form, for example as a ketimine, to extend pot life, if this is desired. The compound (D) can also be blocked by ketimine if desired.

[0035] The molar ratio of amino groups of the amino-functional curing agent (C) to the total aliphatically unsaturated double bonds present in the compound or polymer (B) and the aminoalkylalkoxysilane (D) 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.

[0036] In a 2-pack curable coating composition, the aminoalkylalkoxysilane (D) is usually packaged as part of the curing agent (C). The other package of the coating composition comprises the organopolysiloxane (A) and the compound or polymer (B) containing at least one aliphatically unsaturated group. 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.

[0037] The aminoalkylalkoxysilane (D) may in some cases be packaged with the organopolysiloxane (A) and the compound or polymer (B) containing at least one aliphatically unsaturated group to form a curable coating composition. Such a curable coating composition can be cured by reaction with a curing agent (C), for example an aminoalkyltrialkoxysilane containing at least one primary or secondary amine group. The curable coating composition can alternatively be cured by UV radiation. Alternatively, when 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.

[0038] 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.

[0039] The coatings of the composition of this invention comprising the amine compound or polymer (C) 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), aminoalkylalkoxysilane curing agent (C) and

aminoalkylalkoxysilane (D).

[0040] The coating composition of the invention can be applied as a primer coat or as a top coat on a substrate.

[0041] 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.

[0042] The invention provides a curable coating composition, the composition containing a binder comprising

- an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule and optionally a compound or polymer (B) containing at least one aliphatically unsaturated C=C group provided that the binder contains at least one aliphatically unsaturated C=C group or

- a binder curable by radical reaction the binder containing an organopolysiloxane or a silane with at least one acrylate or methacrylate group or

- an alkyd binder containing at least one aliphatically unsaturated C=C group,

the composition containing optionally a curing agent (C) containing at least one primary or secondary amine group, characterised in that the composition also comprises an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation.

[0043] The invention provides a curable coating composition wherein the

aminoalkylalkoxysilane (D) is a N-(substituted alkyl)- aminoalkylalkoxysilane in which the group having carbon to carbon unsaturation is present in the substituted alkyl group.

The invention provides a curable coating composition wherein the aminoalkylalkoxysilane (D) is a bis(secondary amine) having an alkoxysilylalkyl group bonded to one amine nitrogen atom and a group having carbon to carbon unsaturation bonded to the other amine nitrogen atom. [0044] The invention provides a curable coating composition wherein the group having carbon to carbon unsaturation comprises a vinyl group bonded to an aromatic ring.

[0045] The invention provides a curable coating composition wherein the

aminoalkylalkoxysilane (D) contains at least two silicon-bonded alkoxy groups.

The invention provides a curable coating composition wherein the aminoalkylalkoxysilane (D) is a 2-(N'-vinylbenzyl)aminoethyl-3-aminopropyltrialkoxysilane of the formula:

CH ₂ =CH-C6H4-CH ₂ -NH-CH ₂ -CH ₂ -NH-C ₃ H ₆ -Si(OR)3

in which each R represents a methyl or ethyl group.

[0046] The invention provides a curable coating composition wherein the curing agent (C) comprises an aminoalkyltrialkoxysilane containing at least one primary or secondary amine group and having no carbon-to-carbon unsaturation

[0047] The invention provides a curable coating composition wherein the

aminoalkylalkoxysilane (D) is present at 1 to 10% by weight of the binder on a dry weight basis.

[0048] 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.

[0049] The invention provides an aminoalkyltrialkoxysilane curing agent composition for a coating comprising a binder which is:

an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule and optionally a compound or polymer (B) containing at least one aliphatically unsaturated group and optionally a curing agent (C) containing at least one primary or secondary amine group provided that the binder contains at least one aliphatically unsaturated C=C group or

- a binder curable by radical reaction the binder containing an organopolysiloxane or a silane with at least one acrylate or methacrylate group or

- an alkyd binder with at least one aliphatically unsaturated C=C group, characterised in that an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation is present preferably as 5 to 50% by weight of the alkoxysilane content of the aminoalkyltrialkoxysilane curing agent composition.

[0050] The invention provides the use of an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation in a curable coating composition the curable coating composition comprising a binder being - an organopolysiloxane (A) containing at least two silicon-bonded alkoxy groups per molecule, optionally a compound or polymer (B) containing at least one aliphatically unsaturated group, and optionally a compound or polymer (C) containing at least one primary or secondary amine group provided that the binder contains at least one aliphatically unsaturated C=C group or

- a binder curable by radical reaction the binder containing an organopolysiloxane or a silane with at least one acrylate or methacrylate group or

- an alkyd binder containing at least one aliphatically unsaturated C=C group, 13. The invention provides the use of an aminoalkyltrialkoxysilane curing agent composition comprising an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation to harden 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 aliphatically unsaturated group in the presence of atmospheric moisture.

[0051] The invention provides a process for coating a substrate, characterised in that the substrate is coated with a coating composition as defined above.

[0052] The invention provides a curable coating composition having a binder 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 curing agent (C) containing at least one primary or secondary amine group, characterised in that the curing agent (C) comprises an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation.

[0053] The invention provides an aminoalkyltrialkoxysilane curing agent composition for a coating 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, characterised in that an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation is present as 5 to 50% by weight of the alkoxysilane content of the aminoalkyltrialkoxysilane curing agent composition.

[0054] The invention provides the use of an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation 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 (C) containing at least one primary or secondary amine group.

[0055] The invention provides the use of an aminoalkyltrialkoxysilane curing agent composition comprising an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation to harden 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

aliphatically unsaturated group in the presence of atmospheric moisture.

The invention provides the use of an aminoalkyltrialkoxysilane curing agent composition comprising an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation to harden a coating composition comprising a binder curable by radical reaction the binder containing an

organopolysiloxane or a silane with at least one acrylate or methacrylate group.

[0056] The invention provides the use of an aminoalkyltrialkoxysilane curing agent composition comprising an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation to harden a coating composition comprising an alkyd binder containing at least one aliphatically unsaturated

C=C group.

Examples

[0057] The invention is illustrated by the following Examples, in which parts and

percentages are by weight.

[0058] In the Examples, coatings were evaluated by the following procedure.

[0059] 'Q-Panel' steel test panels were coated with a commercial primer and were allowed to dry in ambient temperature air for 7 days. The Dry Film Thickness of the primer is 100- 150 μπι.

[0060] The primer coat was overcoated with a 60μηι 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 an aminoalkylalkoxysilane (D) containing a primary or secondary amino group and a group having carbon to carbon unsaturation. The main package (part A) is a pigmented coating composition which is believed to comprise 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.

Example 1

[0061] 5% CH ₂ =CH-C ₆ H4-CH ₂ -NH-CH ₂ -CH ₂ -NH-C ₃ H ₆ -Si(OR)3 where R is methyl as added to part A of the paint described above. Test results are shown in Table 1 below. 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. Top coat Clemen hardness

Unmodified paint 800g

Example 1 1200g

[0062] Table 1 shows that the 2-(N'-vinylbenzyl)aminoethyl-3-aminopropyltrimethoxysilane substantially improved the Clemen hardness of the paint as compared with unmodified paint. An unmodified paint resisted without trace on the coating up to a load of 800g while a paint as of example 1 containing the additive of the invention resists up to a load of 1200g. The hardness of the surface as assessed by the Clemen test was thus improved. Example 2

[0063] A commercial UV curable composition containing a silane acrylate binder was modified by inclusion of 5% of 2-(N'-vinylbenzyl)aminoethyl-3-aminopropyltrimethoxysilane. The composition was applied on untreated aluminium panels.

In the following description, the terms "coating" and "film" are used to designate the same object i.e. a layer of paint applied on the surface of a substrate.

[0064] 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).

[0065] 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. 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The results are shown in the below table:

UV curable compositions (AY 42-260) Cros MEK Slip Visual Pencil Clemen Ink Water Pendulu

50 μπι - 500 mJ (H bulb) s cut (solvent appearan hardnes rubb conta m

resistanc ce hardnes s er ct Koenig e) s tester angle

REF ^* KO <5 Not very brittle 7H - <10 106° Not applicabl film applicabl e ^* e ^*

Example 2 GTO >100 + film ok 9H - >50 - -

^* the product is dedicated to be applied at 5 μηι. Higher thicknesses are problematic because of high stress leading to weak mechanical properties of the film .

DC1 1668 PCT 1