HK1134310A - Silane-modified binder dispersions - Google Patents

Description

Silane-modified binder dispersions

RELATED APPLICATIONS

This application claims priority to german patent application No. 102007061871.0 filed on 12/19/2007, the entire contents of which are hereby incorporated by reference for all useful purposes.

Technical Field

The present invention relates to a water-based formulation (aquous formation) comprising a silane-modified polymeric binder and inorganic nanoparticles, wherein the silane-modified polymeric binder has a siloxane content (siloxanecontent), a process for its preparation and its use in the preparation of water-based coating compositions.

Background

In modern automobile painting concepts, clear lacquer (clear lacquer) plays an essential role as a surface layer. In this context, in addition to aesthetic effects such as high gloss and transparency, the protective function of clear lacquers is also an important aspect. The clear lacquer protects the underlying lacquer layer from external influences such as sunlight, water, solvents and aggressive chemicals and last but not least against mechanical stresses. The scratch resistance of automotive clearcoats is therefore still an essential criterion for the quality of automotive clearcoats.

Nanoparticles in polymer coatings can be targeted to improve properties such as scratch resistance, UV protection or electrical conductivity. Control over the surface modification and dispersion of the nanoparticles determines the desired transparent appearance of the coating and its properties.

Various attempts have been made in the past to incorporate nanoparticles into coating composition formulations. In this case, the particles may be incorporated directly into the resin or curing agent component, or into the coating composition to be applied. In water-based systems, it is possible to disperse the particles in the aqueous phase. The preparation of the particles in situ in one of the binder components and the adaptation of the surface to the resin or curing agent component have been described further on.

From a practical point of view, it is advantageous to disperse the nanoparticles as a stable master batch (masterbatch) in one of the components, so that long-term storage stability and ease of handling of the paint formulation can be ensured. In end use, the nanoparticles must also be readily dispersible in finely divided form to give advantageous properties such as transparency, scratch resistance or electrical conductivity.

In practice, the nanoparticles are typically dispersed into the resin component, into the aqueous phase, or into the final mixture of curing agent and resin shortly before curing. In this connection, it is generally necessary to adapt the surface of the nanoparticles to the particular matrix of the coating composition or binder. A disadvantage of simply mixing modified nanoparticles is that the stability depends on the overall formulation, i.e. on all formulation ingredients. A change in one parameter may lead to stratification of the mixture in this regard (Pilotek, Steffen; Tabellion, Frank (2005), European Coatings Journal, 4, 170 and below).

WO-a 2006/008120 discloses aqueous based dispersions of polymeric and/or oligomeric organic binders with inorganic nanoparticles. The nanoparticles are surface modified by the addition of silane-functional (silane-functional) compounds. However, a disadvantage is that the gloss and haze of the coatings obtained do not meet the high requirements of automotive clearcoats.

The modification of lacquer systems using Polydimethylsiloxane (PDMS) is known in the prior art. PDMS has a high surface tension, which results in specific properties such as good surface wettability, slip resistance and easy-to-clean surfaces (Reusmann in Farbe und Lack, Vol. 105, 8/99, pp. 40-47, Adams in Paindidia, 1996, 10 months, pp. 31-37).

To ensure good incorporation of PDMS and to avoid migration of PDMS as much as possible, organofunctional PDMS types, such as alkyleneamine-or alkylenehydroxy-functional PDMS derivatives, are often used. Such paint systems are described, for example, in WO91/18954, EP-A0329260 or US 4774278.

However, amine-functional PDMS types have the disadvantage that, because the tendency to form urea is very high, the pot life (pot life) of polyurethane systems based on these becomes extremely short.

The known types of hydroxyl-functional PDMS actually result in improved pot life, but they generally show incompatibility with the polyisocyanate component, thus failing to produce a homogeneous film and crosslinking only incompletely. Thus, free unbound PDMS is present in the lacquer, which in time migrates out of the coating and leads to a deterioration of the coating properties.

WO-a 2007/025670 discloses two-component coating compositions comprising a polyisocyanate component as binder in combination with a reactive component which is a component reactive towards isocyanate groups, in particular a polyhydroxy component. The compositions described therein are suitable for producing high-quality coatings which are distinguished, inter alia, by improved easy-to-clean properties (owing to the highly functional hydroxy-polydimethylsiloxane units) without an improvement in hardness and ethanol resistance. The improvement in scratch resistance is not described and is not noticeable.

Thus, there remains an urgent need to provide water-based automotive clearcoats having improved scratch resistance and good optical properties.

It has now surprisingly been found that water-based copolymers comprising hydroxyl group-containing polyorganosiloxanes and modified with a specific class of silanes, in combination with inorganic nanoparticles, are suitable for producing coatings with significantly improved scratch resistance and with excellent gloss and very low haze.

It was therefore an object of the present invention to provide high-quality coating compositions, in particular automotive clearcoats, which have optimum gloss and haze and exhibit improved scratch resistance. The dispersion should also be sufficiently stable for storage.

Disclosure of Invention

One embodiment of the invention is an aqueous-based formulation comprising

A) Silane-modified copolymer a1) and hydroxyl-containing polyorganosiloxane a 2);

B) optionally surface-modified inorganic particles having an average particle size (z-average) of less than 200nm, as determined by dynamic light scattering in dispersion; and

C) and (3) water.

Another embodiment of the present invention is the above-mentioned water-based formulation, wherein the silane-modified copolymer a1) comprises a group of the general formula (1)

-Si(R¹O)₂R² (1)

Wherein

R¹Is C₂To C₈An alkyl group; and is

R²Is (R)¹O) or C₁To C₅An alkyl group.

Another embodiment of the present invention is the above-mentioned water-based formulation, wherein the silane-modified copolymer a1) is a copolymer (a copolymer white is build up from)

I) Hydroxy-functional hydrophobic polymers comprising as building monomers (build monomers)

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

ib) hydroxy-functional monomers; and

IS1) silane-functional monomers (silane-functional monomers) capable of polymerization;

and

II) hydroxy-functional hydrophilic polymers containing as building Components

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

IIb) a hydroxy-functional monomer; and

IIc) acid-functional monomers (acid-functional monomers).

Another embodiment of the present invention is the above-mentioned water-based formulation, wherein the silane-modified copolymer a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals; and

ib) a hydroxy-functional monomer;

and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

IIb) a hydroxy-functional monomer;

IIc) an acid functional monomer; and

IIS1) silane functional monomers capable of polymerization.

Another embodiment of the present invention IS the above-mentioned aqueous-based formulation, wherein the silane-functional monomer capable of polymerizing IS1) IS a compound of the general formula (2)

(R¹O)₂R²Si-(CH＝CH₂) (2)

Wherein

R¹Is C₂To C₈An alkyl group; and is

R²Is (R)¹O) or C₁To C₅An alkyl group;

and/or a compound of the general formula (3)

(R¹O)₂R²Si(CH₂)_m-O(CO)-(CR³＝CH₂) (3)

Wherein

R¹Is C₂To C₈An alkyl group;

R²is (R)¹O) or C₁To C₅An alkyl group;

R³is H or CH₃(ii) a And is

m is1 to 4.

Another embodiment of the present invention is the above water-based formulation, wherein the silane-functional monomer capable of polymerizing IIS1) is a compound of formula (2)

(R¹O)₂R²Si-(CH＝CH₂) (2)

Wherein

R¹Is C₂To C₈An alkyl group; and is

R²Is (R)¹O) or C₁To C₅An alkyl group;

and/or a compound of the general formula (3)

(R¹O)₂R²Si(CH₂)_m-O(CO)-(CR³＝CH₂) (3)

Wherein

R¹Is C₂To C₈An alkyl group;

R²is (R)¹O) or C₁To C₅An alkyl group;

R³is H or CH₃(ii) a And is

m is1 to 4.

Another embodiment of the present invention IS the above-described aqueous-based formulation, wherein the silane-functional monomer capable of polymerization IS1) IS selected from the group consisting of vinyltriethoxysilane, vinyltriisopropoxysilane, vinyl-tris- (2-methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldiisopropyloxysilane, vinylethyldiethoxysilane, 3- (triethoxysilyl) -propyl methacrylate or 3- (tri-isopropoxysilyl) -propyl methacrylate, vinylphenyldiethoxysilane, vinylphenylmethylethoxysilane or vinyltri-tert-butoxysilane.

Another embodiment of the present invention is the above-described aqueous-based formulation, wherein the silane-functional monomer capable of polymerization IIS1) is selected from the group consisting of vinyltriethoxysilane, vinyltriisopropoxysilane, vinyl-tris- (2-methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldiisopropyloxysilane, vinylethyldiethoxysilane, 3- (triethoxysilyl) -propyl methacrylate or 3- (tri-isopropoxysilyl) -propyl methacrylate, vinylphenyldiethoxysilane, vinylphenylmethylethoxysilane or vinyltri-tert-butoxysilane.

Another embodiment of the present invention is the above-mentioned water-based formulation, wherein the silane-modified copolymer a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals; and

ib) a hydroxy-functional monomer;

and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylic acid esters of hydrocarbon radicals and/or vinylaromatic compoundsAnd/or vinyl esters;

IIb) a hydroxy-functional monomer;

IIc) an acid functional monomer; and

IIS2) contain at least one epoxide functional (epoxyreaction) monomer in addition to silane groups.

Another embodiment of the present invention is the above water-based formulation, wherein the monomer IIS2) is selected from the group consisting of γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropyl-tri-isopropoxysilane, γ -glycidoxypropyl-diethoxy-methylsilane, β - (3, 4-epoxycyclohexyl) -triethoxysilane, and β - (3, 4-epoxycyclohexyl) -tri-isopropoxysilane.

Another embodiment of the present invention is the above-mentioned aqueous preparation, wherein the hydroxyl group-containing polyorganosiloxane a2) is a compound of the general formula (I)

Wherein

X is an aliphatic, optionally branched C₁To C₁₀A radical or [ -CH₂-O-(CH₂)_p-]Si unit, wherein r is an integer from 1 to 4;

r is a-CH (OH) Y group, wherein

Y is-CH₂-N(R²R³) Group (a) in which

R²Is H or methyl, ethyl, n-propyl, isopropyl or cyclohexyl, or 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl; and is

R³Is 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl,

R¹identical or different, is H or C optionally containing heteroatoms₁To C₁₀A hydrocarbyl group; and is

n is an integer from 1 to 40.

Another embodiment of the present invention is the above-mentioned aqueous preparation, wherein the hydroxyl group-containing polyorganosiloxane a2) is a compound of the formula (V)

Wherein

m is an integer of 5 to 15;

z is H or methyl; and is

n and o are integers from 1 to 12.

Another embodiment of the present invention is the above-mentioned aqueous preparation, wherein the hydroxyl group-containing polyorganosiloxane a2) is a compound of the formula (VI)

Wherein

m is an integer of 5 to 15; and is

y is an integer from 2 to 4.

Another embodiment of the present invention is the above-mentioned aqueous-based formulation, wherein said polyorganosiloxane a2) of the general formula (I) has a number average molecular weight of 200 to 3,000g/mol and an average OH functionality of at least 1.8.

Another embodiment of the present invention is the above-mentioned water-based formulation, wherein the number average molecular weight of said polyorganosiloxane a2) of the general formula (I) is 250 to 2,250 g/mol.

Another embodiment of the present invention is the above-described aqueous-based formulation, wherein the inorganic particles B) are selected from inorganic oxides, mixed oxides (mixed oxides), carbides, borides, and nitrides of elements of main groups II to IV and/or transition groups I to VIII of the periodic Table, including the lanthanides.

Another embodiment of the present invention is the above water-based formulation, wherein the inorganic particles B) are inorganic nanoparticles in a colloidally dispersed form (colloidally dispersed form) in an organic solvent or in water.

Another embodiment of the present invention is the above-mentioned aqueous-based formulation, wherein the inorganic particles B) are inorganic particles in the form of an aqueous-based formulation.

Another embodiment of the present invention is the above aqueous-based formulation, wherein the inorganic particles B) are surface-modified inorganic nanoparticles.

Yet another embodiment of the present invention is a water-based coating composition comprising the above-described water-based formulation and at least one crosslinker D).

Yet another embodiment of the present invention is a water-based two-component coating composition comprising the above-described water-based formulation and a polyisocyanate.

Yet another embodiment of the present invention is a clear paint comprising the above-described water-based formulation.

Detailed Description

The invention therefore provides an aqueous formulation comprising

A) Silane-modified copolymer a1) and hydroxyl-containing polyorganosiloxane a2),

B) inorganic particles which are optionally surface-modified and have an average particle size (z-average) of less than 200nm, determined in dispersion by dynamic light scattering, and

C) and (3) water.

The silane-modified copolymer a1) comprises groups of the general formula (1)

-Si(R¹O)₂R² (1)

Wherein

R¹Is C₂To C₈Alkyl, preferably C₃To C₆Alkyl radical, and

R²is (R)¹O) or C₁To C₅Alkyl, preferably (R)¹O) or C₁To C₃An alkyl group.

The hydroxyl-containing polyorganosiloxanes a2) are compounds according to the general formula (I)

Wherein

X is an aliphatic, optionally branched C₁To C₁₀The radical is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, particularly preferably methyl, or [ -CH₂-O-(CH₂)_p-]Si units, where r ═ 1 to 4, preferably where r ═ 3,

r is a-CH (OH) Y group, wherein

Y is-CH₂-N(R²R³) Group (a) in which

R²Can be H, methyl, ethyl, n-propyl, isopropyl or cyclohexyl or 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl, and

R³can be 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl,

R¹may be the same or different and is hydrogen or C optionally containing hetero atoms₁To C₁₀A hydrocarbon group, and

n is1 to 40.

In a first embodiment (. alpha.), component a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈Hydrocarbon-based (meth) acrylates and/or vinylaromatic and/or vinyl esters

Ib) hydroxy-functional monomers, and

IS1) silane-functional monomers capable of polymerization, and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals,

IIb) a hydroxy-functional monomer, and

IIc) acid functional monomers.

This embodiment (. alpha.) is preferred.

In a further embodiment (. beta.), component a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals,

ib) hydroxy-functional monomers, and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals,

IIb) a hydroxy-functional monomer,

IIc) an acid functional monomer, and

IIS1) silane functional monomers capable of polymerization.

The content of monomers Ia)/IIa) in the copolymers a1) in embodiments (α) and (β) IS from 34.3 to 89.3 parts by weight, preferably from 51.8 to 84.8 parts by weight, particularly preferably from 58 to 81 parts by weight, the content of monomers Ib)/IIb) in the copolymers a1) IS from 10 to 65 parts by weight, preferably from 13.5 to 46.5 parts by weight, particularly preferably from 17 to 40 parts by weight, the content of monomers IIc) in the copolymers a1) IS from 0.6 to 12 parts by weight, preferably from 1.2 to 5.5 parts by weight, particularly preferably from 1.25 to 3.5 parts by weight, and the content of monomers IS1)/IIS1) in the copolymers a1) IS from 0.1 to 12 parts by weight, preferably from 0.5 to 5 parts by weight, particularly preferably from 0.75 to 3.5 parts by weight.

Suitable silane-functional monomers IS1) and IIS1) which can be polymerized are, for example, compounds of the formula (2)

(R¹O)₂R²Si-(CH＝CH₂) (2)

Wherein

R¹Is C₂To C₈Alkyl, preferably C₃To C₆An alkyl group, a carboxyl group,

R²is (R)¹O) or C₁To C₅Alkyl, preferably (R)¹O) or C₁To C₃An alkyl group, a carboxyl group,

and/or a compound of the general formula (3)

(R¹O)₂R²Si(CH₂)_m-O(CO)-(CR³＝CH₂) (3)

Wherein

R¹Is C₂To C₈Alkyl, preferably C₃-C₆An alkyl group, a carboxyl group,

R²is (R)¹O) or C₁To C₅Alkyl, preferably (R)¹O) or C₁To C₃An alkyl group, a carboxyl group,

R³is H or CH₃And is and

m is1 to 4, preferably 3.

Examples of suitable silane-functional monomers IS1) and IIS1) which are capable of polymerization are vinyltriethoxysilane, vinyltriisopropoxysilane, vinyl-tris- (2-methoxy) silane, vinylmethyldiethoxysilane, vinylmethyldiisopropoxysilane, vinylethyldiethoxysilane, 3- (triethoxysilyl) -propyl methacrylate or 3- (tri-isopropoxysilyl) -propyl methacrylate, vinylphenyldiethoxysilane, vinylphenylmethylethoxysilane or vinyltri-tert-butoxysilane. Vinyl triisopropoxysilane is preferred.

It is likewise possible for component a1) (embodiment (. gamma.)) to be a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals,

ib) hydroxy-functional monomers, and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals,

IIb) a hydroxy-functional monomer,

IIc) an acid functional monomer, and

IIS2) contains at least one epoxy-functional monomer in addition to silane groups.

The content of monomers Ia)/IIa) in the copolymer a1) in embodiment (γ) is from 33.8 to 88.8 parts by weight, preferably from 49.1 to 83.9 parts by weight, particularly preferably from 56 to 79.5 parts by weight, the content of monomers Ib)/IIb) in copolymer a1) is from 10 to 65 parts by weight, preferably from 13.5 to 48.3 parts by weight, particularly preferably from 17 to 40.5 parts by weight, the content of monomers IIc) in copolymer a1) is from 1 to 15 parts by weight, preferably from 1.85 to 8 parts by weight, particularly preferably from 2.5 to 6.5 parts by weight, and the content of monomers IIS2) in copolymer a1) is from 0.2 to 12 parts by weight, preferably from 0.75 to 5.5 parts by weight, particularly preferably from 1 to 4.5 parts by weight.

Examples of suitable monomers IIS2) which, in addition to silane groups, also comprise at least one epoxy function are γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropyl-tri-isopropoxysilane, γ -glycidoxypropyl-diethoxy-methylsilane, glycidoxypropyl-di-isopropoxy-methylsilane, β - (3, 4-epoxycyclohexyl) -triethoxysilane, β - (3, 4-epoxycyclohexyl) -tri-isopropoxysilane, β - (3, 4-epoxycyclohexyl) -diethoxy-methylsilane, β - (3, 4-epoxycyclohexyl) -di-isopropoxy-methylsilane, β - (3, 4-epoxycyclohexyl) -diethoxy-ethylsilane or β - (3, 4-epoxycyclohexyl) -di-isopropoxy-ethylsilane. Gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltri-isopropoxysilane, gamma-glycidoxypropyl-diethoxy-methylsilane, beta- (3, 4-epoxycyclohexyl) -triethoxysilane or beta- (3, 4-epoxycyclohexyl) -tri-isopropoxysilane are preferred, and gamma-glycidoxypropyl-tri-isopropoxysilane, gamma-glycidoxypropyl-diethoxy-methylsilane and beta- (3, 4-epoxycyclohexyl) -tri-isopropoxysilane are particularly preferred.

Suitable monomers Ia)/IIa) are the esterification products of acrylic acid or methacrylic acid with simple alcohols, for example ethyl acrylate, ethyl methacrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl acrylate or cyclohexyl methacrylate, and vinylbenzenes (vinylbenzenes) such as styrene, vinyltoluene, alpha-methylstyrene or mixtures of these and other monomers.

Furthermore, compounds of the (meth) acrylate type suitable as monomers Ia)/IIa) are esters of acrylic acid or methacrylic acid with linear aliphatic monoalcohols having eight carbon atoms, such as the so-called fatty alcohols (monoalcohols), or with linear aliphatic saturated alcohols derived from natural fatty acids, such as lauryl (C)₁₂) Alcohol, Myristica fragrans Houtt (C)₁₄) Alcohol, palm (C)₁₆) Alcohols or stearates (C)₁₈) An alcohol. Likewise suitable aliphatic saturated alcohols are, for example, n-octanol, nonanol or n-decanol. Suitable monomers of the (meth) acrylate type comprising an aliphatic group having at least eight carbon atoms are, for example, n-octyl acrylate, nonyl acrylate, n-decyl acrylate, lauryl acrylate, myristyl acrylate, palmityl acrylate, stearyl acrylate and the corresponding methacrylic acid derivatives.

Suitable monomers of the above-mentioned type are, furthermore, esters of acrylic acid or methacrylic acid with cycloaliphatic alcohols (monoalcohols) having at least 10 carbon atoms, for example isobornyl acrylate, isobornyl methacrylate, dihydroxydicyclopentadienyl acrylate or 3, 3, 5-trimethylcyclohexyl methacrylate.

Suitable monomers Ia/IIa) are, furthermore, the esterification products of vinyl alcohol with linear or branched aliphatic carboxylic acids, for example vinyl acetate, vinyl propionate or vinyl butyrate. Preferred vinyl esters are esters of branched aliphatic carboxylic acids of the general formula (II)

Wherein R is¹And R²Are saturated alkyl radicals containing 6, 7 or 8C atoms in combination, corresponding to the compound VeoVa^TM9. 10 and 11.

For the monomers mentioned, their homopolymers differ in their glass transition temperature:

monomer	TG[℃]
		VeoVaTM9	+70
VeoVaTM10	-3
		VeoVaTM11	-40

Preferred monomers Ia)/IIa) are n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and styrene, and n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and styrene are particularly preferred.

In the preparation of the copolymers a1), further monomers capable of free-radical copolymerization can optionally also be used as compounds of components Ia/IIa). These may be, for example, derivatives of acrylic acid or methacrylic acid, such as acrylamide, methacrylamide, acrylonitrile or methacrylonitrile. Vinyl ethers or vinyl acetates are also optionally possible. Further possible components Ia/IIa) which are optionally used in small amounts are difunctional or more functional (meth) acrylate monomers and/or vinyl monomers, for example hexanediol di (meth) acrylate or divinylbenzene.

Suitable hydroxy-functional monomers Ib)/IIb) are, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate. Preferred monomers Ib)/IIb) are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 4-hydroxybutyl acrylate and also mixtures of these compounds.

Suitable ethylenically unsaturated acid-functional monomers IIc) are sulfonic acid-or carboxylic acid-functional monomers, preferably carboxylic acid-functional monomers, such as acrylic acid, methacrylic acid, β -carboxyethyl acrylate, crotonic acid, fumaric acid, maleic anhydride, itaconic acid or monoalkyl esters or anhydrides of dibasic acids, such as monoalkyl esters of maleic acid, acrylic acid or methacrylic acid being particularly preferred.

Furthermore, unsaturated compounds which are capable of undergoing free-radical polymerization and have phosphate or phosphonate, or sulfonic acid or sulfonate groups, as described, for example, in WO-A00/39181 (p.8, 1.13-p.9, 1.19), are also suitable as compounds of component IIc).

Suitable initiators for the polymerization are organic peroxides such as di-tert-butyl peroxide, di-tert-amyl peroxide or tert-butyl peroxy-2-ethylhexanoate and azo compounds such as Azobisisobutyronitrile (AIBN). The amount of initiator used depends on the desired molecular weight. For reasons of process reliability and ease of handling, peroxide initiators may also be used as solutions in suitable organic solvents of the type mentioned below.

The preparation of the copolymer a1) is carried out by free-radically initiated copolymerization of the monomer mixtures I) and II) in an organic solvent (mixture). The amount of organic solvent is chosen such that the resulting solution of copolymer a1) has a solids content of 95 to 60% by weight, preferably 92.5 to 80% by weight.

The polymerization procedures of unsaturated monomers are known per se to the person skilled in the art. Generally, for this purpose, a suitable solvent is initially introduced into the reaction vessel and the unsaturated monomer is polymerized during the addition using a free-radical initiator.

Suitable organic solvents which may be used are any of the desired solvents known in the lacquer art, preferably those which are usually used as co-solvents (co-solvents) in aqueous dispersions, for example alcohols, ethers, alcohols containing ether groups, esters, ketones or non-polar hydrocarbons, such as aliphatic or aromatic hydrocarbons, or mixtures of these solvents.

The preparation of component a1) in embodiment (. alpha.) or (. beta.) is carried out by two-stage addition and polymerization of the monomer mixtures I) and II) in the stated order. In this case, in a first step (I), a hydroxy-functional hydrophobic polymer I) is prepared from the monomers Ia) and Ib), the polymer I) having an OH number of from 12 to 250mg KOH/g solids, preferably from 50 to 200mg KOH/g solids. In a subsequent step (II), a hydroxy-functional hydrophilic polymer II) is prepared from the monomers IIa) to IIc) in the solution of the polymer I) obtained from step (I), which hydroxy-functional hydrophilic polymer II) has an OH number of from 20 to 250mg KOH/g solids, preferably from 120 to 220mg KOH/g solids, and an acid number of from 50 to 250mg KOH/g solids, preferably from 110 to 200mg KOH/g solids. Thus, silane-functional monomers IS1) are copolymerized with monomer mixtures Ia) and Ib) or IIS2) are copolymerized with monomer mixtures IIa), IIb) and IIc).

The preparation of component a1) in embodiment (. gamma.) is carried out by two-stage addition and polymerization of the monomer mixtures I) and II) in the stated order. In this case, in a first step (I), a hydroxy-functional hydrophobic polymer I) is prepared from the monomers Ia) and Ib), the polymer I) having an OH number of from 12 to 250mg KOH/g solids, preferably from 50 to 200mg KOH/g solids. In a subsequent step (II), a hydroxyl-functional hydrophilic polymer II) is prepared from the monomers IIa) to IIc) and IIS2) in the solution of the polymer I) obtained in step (I). In this step, the reaction of the epoxide groups of IIS2) with free carboxylic acid groups takes place simultaneously, according to the free-radical polymerization of components IIa) to IIc). The reaction may optionally be catalyzed by a suitable esterification catalyst, such as dibutyltin dilaurate or tin dioctoate. The hydroxyl-functional hydrophilic polymers II) have an OH number of from 20 to 250mg KOH/g solids, preferably from 120 to 220mg KOH/g solids, and an acid number of from 50 to 250mg KOH/g solids, preferably from 110 to 200mg KOH/g solids.

The copolymers a1) have a molecular weight of from 1,000 to 50,000Da, preferably from 1,200 to 20,000Da, particularly preferably from 1,500 to 12,500 Da.

The carboxyl groups copolymerized into the copolymer a1) can be neutralized using organic amines or water-soluble inorganic bases. N-methylmorpholine, triethylamine, dimethylethanolamine, dimethylisopropanolamine, methyldiethanolamine, triethanolamine or ethyldiisopropylamine are preferred. Diethylethanolamine, butanolamine, morpholine, 2-aminomethyl-2-methyl-propanol or isophoronediamine are likewise suitable.

The neutralizing agent is added in an amount such that the degree of neutralization of the carboxyl groups is from 70 to 130%, preferably from 90 to 105%, particularly preferably in an amount such that the free neutralizing agent is still present after all carboxyl groups have been converted into salt form. This corresponds to a degree of neutralization > 100%.

Suitable hydroxyl-containing polyorganosiloxanes a2) of the general formula (I) are characterized by a number-average molecular weight of 200 to 3,000g/mol and an average OH functionality of > 1.8.

The polyorganosiloxane a2) of the general formula (I) containing hydroxyl groups preferably has a number-average molecular weight of 250 to 2,250g/mol, particularly preferably 350 to 1,500 g/mol.

Polyorganosiloxane a2 of the general formula (I) containing hydroxyl groups can be obtained in this way: the epoxy group to amino function is preferably in stoichiometric ratio by reacting the corresponding epoxy-functional polyorganosiloxane with the hydroxyalkyl-functional amine.

The epoxy-functional siloxanes used for this purpose preferably contain 1 to 4, particularly preferably 2, epoxy groups per molecule. They furthermore have a number-average molecular weight of from 150 to 2,000g/mol, preferably from 250 to 1,500g/mol, very particularly preferably from 250 to 1,250 g/mol.

Preferred epoxy-functional siloxanes are alpha, omega-epoxysiloxanes corresponding to formula (III)

Wherein

X is an aliphatic, optionally branched C₁To C₁₀The radical is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, particularly preferably methyl, or [ -CH₂-O-(CH₂)_p]-Si units, wherein r-1 to 4, preferably wherein r-3,

R¹may be the same or different and is hydrogen or C optionally containing hetero atoms₁To C₁₀A hydrocarbon group, and

n is1 to 40.

R in the formulae (I) and (III)¹Preferably phenyl, alkyl, aralkyl, fluoroalkyl, alkyloxyethylene-co-oxypropylene groups or hydrogen, with phenyl or methyl being particularly preferred. R¹Very particular preference is given to methyl.

Suitable compounds corresponding to formula (III) are for example compounds of formulae IIIa) and IIIb):

wherein

n is an integer from 4 to 12, preferably from 6 to 9.

Examples of such a series of commercially available products are for example2810(momentivePerformance Materials, Leverkusen, Germany) or E-Si2330(TegoChemie Service GmbH，Essen，Germany)。

Suitable hydroxyalkyl-functional amines correspond to the general formula (IV)

Wherein

R²Can be H, methyl, ethyl, n-propyl, isopropyl or cyclohexyl or 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl, and

R³it may be 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl.

Preferred hydroxyalkylamines are ethanolamine, propanolamine, diethanolamine, diisopropanolamine, methylethanolamine, ethylethanolamine, propylethanolamine and cyclohexylethanolamine. Diethanolamine, diisopropanolamine or cyclohexylethanolamine are particularly preferred. Diethanolamine is very particularly preferred.

For the preparation of component a2), the epoxy-functional siloxanes of the general formula (III) are optionally initially introduced into a solvent and then reacted with the desired amount of hydroxyalkylamine (IV) or a mixture of several hydroxyalkylamines (IV). The reaction temperature is typically 20 to 150 ℃ and the reaction is continued until no further free epoxy groups are detectable.

Particular preference is given to using hydroxyalkyl-functional siloxanes a2) of the formula (I) obtained by the abovementioned reaction of epoxy-functional polyorganosiloxanes with hydroxyalkylamines.

Particularly preferred polyorganosiloxanes a2) are, for example, those of the formulae Ia) to Ih):

where n is 4 to 12, preferably 6 to 9.

Siloxanes which are likewise suitable as component a2) are, for example, hydroxyalkyl-functional siloxanes (. alpha.,. omega. -methanol) corresponding to the formula (V)

Wherein

m is a number of from 5 to 15,

z is H or methyl, preferably H, and

n and o are 1 to 12, preferably 1 to 5.

The hydroxyalkyl-functional siloxanes (. alpha.,. omega. -methanol) of the formula (V) preferably have a number average molecular weight of from 250 to 2,250g/mol, particularly preferably from 250 to 1,500g/mol, very particularly preferably from 250 to 1,250 g/mol. Examples of commercially available hydroxyalkyl-functional siloxanes of the type described areOF-OH 5023 and 6% concentration (GE-Bayer Silicones, Leverkusen, Germany).

Another route for preparing suitable hydroxy-functional polyorganosiloxanes corresponding to component a2) is the reaction of α, ω -carbinol-type hydroxyalkyl-functional siloxanes of the above-mentioned formula (V) with cyclic lactones. Suitable cyclic lactones are, for example,. epsilon. -caprolactone,. gamma. -butyrolactone or valerolactone.

This is carried out with a ratio of OH groups to lactone functions of from 1:2 to 2:1, the OH groups to lactone functions preferably being in a stoichiometric ratio. Hydroxyalkyl-functional siloxanes a2) obtained in this way are preferred. Examples of such compounds are polyorganosiloxanes of the general formula (VI) a2)

Wherein

m may be 5 to 15, and

y may be 2 to 4, preferably 4.

The hydroxyl-containing polyorganosiloxane a2) is preferably added to the resin melt of component a2) and homogeneously combined before it is dispersed in water. It is particularly preferred to incorporate the hydroxyl-containing polyorganosiloxane a2) into the resin melt of component a2) simultaneously with the components used for neutralizing the carboxyl groups incorporated in the copolymer a 1).

Possible particles B) are inorganic oxides, mixed oxides, hydroxides, sulfates, carbonates, carbides, borides and nitrides of elements of main groups II to IV and/or elements of transition groups I to VIII of the periodic Table of the elements, including the lanthanides. Preferred particles B) are silicon oxide, aluminum oxide, cerium oxide, zirconium oxide, niobium oxide and titanium oxide, silicon oxide nanoparticles being particularly preferred.

B) The particles used in (a) preferably have an average particle size of from 5 to 100nm, particularly preferably from 5 to 50nm, the average particle size being the z-average particle size determined by dynamic light scattering in the dispersion.

Preferably at least 75%, particularly preferably at least 90%, very particularly preferably at least 95%, of all the particles used have the abovementioned defined dimensions.

The optionally surface-modified nanoparticles B) are introduced during or after the preparation of the mixture of components a1) and a 2). This can be done simply by adding the particles with stirring. However, the use of increased dispersion energy is also conceivable, for example by ultrasound, jet dispersion (jet dispersion) or high-speed stirrers according to the rotor-stator principle. Simple mechanical stirring addition is preferred.

The particles B) can in principle be used in the form of powders and in the form of colloidal suspensions or dispersions in suitable solvents. The inorganic nanoparticles B) are preferably used in the form of a colloidal dispersion in an organic solvent (organosol) or in water.

Suitable solvents for the organosols are methanol, ethanol, isopropanol, acetone, 2-butanone, methyl isobutyl ketone, butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate, toluene, xylene, 1, 4-dioxane, diacetone alcohol, ethylene glycol n-propyl ether or any desired mixtures of these solvents. Suitable organosols have a solids content of from 10 to 60% by weight, preferably from 15 to 50% by weight. Suitable organosols are, for example, silica organosols, which may be described, for example, under the trade nameAnd(Nissan chem.am.Corp.) or by trade name(Clariant GmbH).

If the nanoparticles are used in an organic solvent (organosol), these are mixed with a mixture of components a1) and a2) before dispersion with water. The resulting mixture is then dispersed in water by adding water or by transferring to water. The mixing of the organosol with the mixture of components a1) and a2) can be carried out before or after neutralization of the carboxyl groups polymerized into the mixture of components a1) and a 2). If necessary, the organic solvent of the organosol can be removed by distillation before or after dispersion with water, preferably after dispersion with water.

For the purposes of the present invention, the inorganic particles B) are furthermore preferably used in the form of their aqueous preparations. The use of the inorganic particles B) in the form of aqueous preparations of surface-modified inorganic nanoparticles is particularly preferred. These may be modified by silanization, for example before or simultaneously with incorporation into the silane-modified polymeric organic binder or into the aqueous dispersion of the silane-modified polymeric organic binder. Such a process is known in principle from the literature and is described, for example, in DE-A19846660 or WO 03/44099.

Furthermore, the surface of the inorganic nanoparticles may be modified in an adsorptive/associative manner by surfactants or block copolymers, for example as described in WO 2006/008120.

Preferred surface modifications are silanization using alkoxysilanes and/or chlorosilanes. The partial modification with gamma-glycidoxypropyltrimethoxysilane corresponding to WO 2004/035474 is particularly preferred.

A preferred commercially available aqueous nanoparticle dispersion is(H.C. Starck GmbH, Goslar, Germany) and(EKA Chemical AB, Bohus, Sweden). Particular preference is given to using aqueous dispersions from EKA (EKA Chemical AB, Bohus, Sweden)CC 15、CC 30 andCC 40。

if the nanoparticles are used in aqueous form, they are added to an aqueous dispersion of copolymer a 1). In a further embodiment, the water-based nanoparticle colloid is added to the copolymer a1) after neutralization of the carboxyl groups polymerized into the mixture of components a1) and a2), and optionally the mixture is then further diluted with water.

The water-based formulations of the present invention can be processed into water-based coating compositions. In this case, one-component paints and two-component paints can be prepared by combining with the crosslinking agent D), depending on the reactivity or, where appropriate, the blocking of the crosslinking agent. A one-component lacquer in the context of the present invention is understood here to mean a coating composition in which the binder component and the crosslinking component can be stored together without crosslinking reactions taking place to a noticeable or disadvantageous extent for the subsequent application. The crosslinking reaction only takes place after activation of the crosslinking agent at the time of application. This activation can be carried out, for example, by increasing the temperature. Two-component paints are understood to mean coating compositions in which the binder component and the crosslinking component have to be stored in separate containers on account of their high reactivity. The two components are mixed only shortly before use and then the reaction is generally carried out without further activation. However, in order to accelerate the crosslinking reaction, it is also possible to use catalysts or to apply higher temperatures.

The present invention therefore also provides water-based coating compositions comprising a water-based formulation according to the invention and at least one crosslinker D).

Suitable crosslinkers D) are, for example, polyisocyanate crosslinkers, amide-and amine-formaldehyde resins (amide-and amine-formaldehyde resins), phenol-formaldehyde resins and aldehyde ketone resins (aldehyde and ketone resins).

Preferred crosslinkers D) are free or blocked polyisocyanates which may optionally be hydrophilically modified and/or unblocked polyisocyanates which are at least partially hydrophilically modified.

The invention also provides a water-based two-component (2C) coating composition comprising a water-based formulation according to the invention and a polyisocyanate. Preferably, at least a portion of the polyisocyanate is hydrophilically modified.

Suitable polyisocyanates are difunctional isocyanates, for example isophorone-diisocyanate, hexamethylene-diisocyanate, 2, 4-or 2, 6-tolylene-diisocyanate, 4' -diphenylmethane-diisocyanate and/or their higher molecular weight trimers, biurets, carbamates, iminooxadiazinediones and/or allophanates. The use of low-viscosity, optionally hydrophilicized polyisocyanates of the above-mentioned type based on aliphatic or cycloaliphatic isocyanates is particularly preferred.

For blocking, the above-mentioned polyisocyanates are reacted with blocking agents such as methanol, ethanol, butanol, hexanol, benzyl alcohol, acetoxime, butanone oxime, caprolactam, phenol, diethyl malonate, dimethyl malonate, dimethylpyrazole, triazole, dimethyltriazole, ethyl acetoacetate, diisopropylamine, dibutylamine, tert-butyl benzylamine, cyclopentanone carboxyethyl ester, dicyclohexylamine and/or tert-butyl isopropylamine.

Non-blocked and blocked polyisocyanates can also be converted to water-dispersible forms by the incorporation of hydrophilic groups, such as carboxylate, sulfonate and/or polyethylene oxide structures, and used in combination with the formulations of the present invention in this manner. The blocked polyisocyanates mentioned can also be prepared by jointly using hydroxy-or amino-functional, also higher molecular weight components, such as diols, triols, aminoalcohols, polyesters, polyethers, polycarbonates and mixtures of the starting materials mentioned and/or other starting materials.

The polyisocyanates used as crosslinkers D) generally have a viscosity of from 10 to 5,000mPas at 23 ℃ and can, if desired, also be used as a mixture with small amounts of inert solvents.

It is naturally also possible in principle to use mixtures of various crosslinkers D).

Auxiliary substances and additives customary in paint technology, such as defoamers, thickeners, pigments, dispersing aids, catalysts, antiskinning agents (skin preservation agents), antisettling agents or emulsifiers, can be added before, during or after the preparation of the water-based formulations according to the invention.

The water-based coating compositions comprising the formulations according to the invention are suitable for all fields of application in which water-based paints and coating systems having high requirements with regard to film resistance are used, for example for the coating of mineral building material surfaces, the painting and sealing of wood and timber, the coating of metal surfaces (metal coating), the coating and painting of coverings containing asphalt or bitumen, the painting and sealing of various plastic surfaces (plastic coating) and also as high-gloss paints.

The water-based coating compositions comprising the formulations of the invention are used for preparing base coats, fillers, pigmented or clear top coats, clearcoats and high-gloss coats, and one-coat lacquers, which can be used in individual or series applications, for example in the field of industrial lacquering and first-time and repair lacquering of automobiles.

In this context, the curing of water-based coating compositions comprising the formulations of the invention is generally carried out at temperatures of from 0 to 160 ℃ and preferably from 18 to 130 ℃.

These coatings not only have very good film optical properties, but also have a high level of scratch resistance, solvent and chemical resistance, good weatherability, high hardness and fast drying.

The coating can be produced by various spray methods, for example, pneumatic or airless or electrostatic spray methods, using one-component or optionally two-component spray devices. However, other methods of applying the paints and coating compositions comprising the water-based coating compositions of the invention are also possible, for example by brushing, rolling or knife coating.

All of the above references are incorporated by reference in their entirety for all useful purposes.

While certain specific structures embodying the invention have been shown and described, it will be apparent to those skilled in the art that various modifications and rearrangements of the parts may be made without departing from the spirit and scope of the underlying inventive concept and are not limited to the specific forms shown and described herein.

Examples

Unless otherwise indicated, percentage data are to be understood as percentages by weight.

The hydroxyl number (OH number) was determined in accordance with DIN 53240-2.

The viscosity was determined with the aid of a rotational viscometer "Paar Physica MCR 51" to DIN EN ISO 3219.

The acid number was determined in accordance with DIN EN ISO 2114.

Determination of particle size

Particle size was determined by dynamic light scattering using an HPPS particle size analyzer (Malvern, Worcestershire, UK). Evaluation was performed by Dispersion Technology software 4.10. To avoid multiple scattering, highly dilute nanoparticle dispersions were prepared. A drop of a dilute nanoparticle dispersion (about 0.1-10%) was introduced into a cell containing about 2ml of the same solvent as the dispersion, the cell was shaken and the measurements were performed in an HPPS analyzer at 20 to 25 ℃. The relevant parameters of the dispersion medium, temperature, viscosity and refractive index, are entered into the software beforehand, as is generally known to the person skilled in the art. In the case of organic solvents, glass baths are used. The intensity-and volume-particle size curves and the z-average of the particle size were obtained as results. It should be ensured that the polydispersity index is < 0.5.

XP 2655: hydrophilic aliphatic polyisocyanate based on hexamethylene-diisocyanate, isocyanate content: 21.2. + -. 0.5% (Bayer MaterialScienceAG/Leverkusen, Germany)

CC 40: 40% strength colloidal dispersed surface-modified silica in water, average particle size 12nm (EKA Chemical AB, Bohus, Sweden)

325: flow aids (Byk-Chemie GmbH, Wesel, Germany)

345: wetting additives (Byk-Chemie GmbH, Wesel, Germany)

XP 2410: aliphatic polyisocyanate, isocyanate content: 23.5. + -. 0.5% (Bayer Material Science AG/Leverkusen, Germany)

PnB: solvent (Dow chem.Corp., Horgen, Switzerland)

RPDE: solvent (Rhodia Syntech GmbH, Frankfurt a.M., Germany)

2810: epoxy functional polydimethylsiloxane, epoxy content 11.4% (Momentive Performance Materials, Leverkusen, DE)

1706: vinyl Triisopropoxysilane (Momentive Performance materials, Leverkusen, DE)

Example 1 hydroxy-functional polydimethylsiloxane

According to WO 2007/025670 (preparation of polyol I, page 14), 770g of an epoxy-functional polydimethylsiloxane were initially charged2810 is introduced into a reaction vessel and preheated to 80 ℃ and 231g of diethanolamine are added. The mixture was then stirred at 100 ℃ for 2 hours. Epoxy content of the product<0.01% and an OH number of about 365mg KOH/g (11.1%) and a viscosity of about 2,900mPas at 23 ℃.

Example 2 comparative example

Initially 220gPnB was introduced into 51 a reaction vessel with stirring, cooling and heating means and heated to 138 ℃.4g of di-tert-butyl peroxide in 4g were added dropwise over the course of 30 minutes at this temperatureMixture 1 in PnB). Immediately thereafter, a mixture 2) of 298.3g of isobornyl methacrylate, 292.0g of hydroxyethyl acrylate, 169.8g of butyl methacrylate, 139g of styrene and 90.4g of 2-ethylhexyl acrylate was metered in over the course of 3.5 hours, immediately thereafter a mixture 3) of 63.8g of styrene, 90g of hydroxyethyl acrylate, 50g of butyl acrylate and 28.7g of methacrylic acid was metered in over the course of 1.5 hours. In parallel with the mixtures 2) and 3), 14.5g of di-tert-butyl peroxide were metered in over a period of 5 hours in 14.5gMixture 4 in PnB). 4g of di-tert-butyl peroxide are then metered in over a period of 1 hour in 4gMixture 5 in PnB). The mixture was then cooled to 100 ℃ and 31.2g N, N-dimethylethanolamine was added. After homogenization for 30 minutes, dispersion was carried out at 80 ℃ for 2 hours with 1,245g of water. A copolymer dispersion was obtained with the following data:

OH content (calculated as solids) 4.5%

Acid value (solid) 18.6mg KOH/g

The solid content is 44.9 percent

Viscosity 2.050mPas_23℃

pH (10% strength in water) 8.0

The neutralization degree is 105 percent

Average particle size 105nm

Cosolvent 7.4% by weight

Example 3 according to the invention

Initially 220gPnB was introduced into 51 a reaction vessel with stirring, cooling and heating means and heated to 138 ℃.4g of di-tert-butyl peroxide in 4g were added dropwise over the course of 30 minutes at this temperatureMixture 1 in PnB). Immediately thereafter, 298.3g of isobornyl methacrylate, 292.0g of hydroxyethyl acrylate, 169.8g of butyl methacrylate, 126.5g of styrene, 90.4g of 2-ethylhexyl acrylate and 12.5g of alkenyltriisopropoxysilane ((III))1706) Mixture 2) of 63.8g of styrene, 90g of hydroxyethyl acrylate, 50g of butyl acrylate and 28.7g of methacrylic acid, mixture 3) were metered in immediately thereafter in the course of 1.5 hours. In parallel with the mixtures 2) and 3), 14.5g of di-tert-butyl peroxide were metered in over a period of 5 hours in 14.5gMixture 4 in PnB). 4g of di-tert-butyl peroxide are then metered in over a period of 1 hour in 4gMixture 5 in PnB). The mixture was then cooled to 100 ℃ and 31.2g N, N-dimethylethanolamine and 12.5g of example 1 were addedThe hydroxy-functional polydimethylsiloxane of (1). After homogenization for 30 minutes, dispersion was carried out at 80 ℃ for 2 hours with 1,260g of water. A copolymer dispersion was obtained with the following data:

OH content (calculated as solids) 4.6%

Acid value (solid) 20.1mg KOH/g

The solid content is 40.2 percent

Viscosity 1,800mPas_23℃

pH (10% strength in water) 8.0

The neutralization degree is 105 percent

Average particle size 160nm

Cosolvent 7.2% by weight

Example 4 according to the invention

Initially 220gPnB was introduced into 51 a reaction vessel with stirring, cooling and heating means and heated to 138 ℃.4g of di-tert-butyl peroxide in 4g were added dropwise over the course of 30 minutes at this temperatureMixture 1 in PnB). Immediately thereafter, 298.3g of isobornyl methacrylate, 292.0g of hydroxyethyl acrylate, 169.8g of butyl methacrylate, 126.5g of styrene, 90.4g of 2-ethylhexyl acrylate and 12.5g of vinyltriisopropoxysilane (II) ((III))1706) Mixture 2) of 63.8g of styrene, 90g of hydroxyethyl acrylate, 50g of butyl acrylate and 28.7g of methacrylic acid, mixture 3) were metered in immediately thereafter in the course of 1.5 hours. In parallel with the mixtures 2) and 3), 14.5g of di-tert-butyl peroxide were metered in over a period of 5 hours in 14.5gMixture 4 in PnB). 4g of di-tert-butyl peroxide are then metered in over a period of 1 hour in 4gMixture 5 in PnB). The mixture was then cooled to 100 ℃ and 31.2g N, N-dimethylethanolamine and 12.5g of the hydroxy-functional polydimethylsiloxane of example 1 were added. After homogenization for 30 minutes, 875g at 80 ℃The mixture of CC40 and 1,575g of water was dispersed over a period of 2 hours. A copolymer dispersion was obtained with the following data:

OH content (calculated as solids) 3.6%

Acid value (solid) 24.0mg KOH/g

The solid content is 40.4 percent

Viscosity 1,460mPas_23℃

pH (10% strength in water) 8.7

The neutralization degree is 105 percent

Average particle size 145nm

6.1% by weight of cosolvent

SiO₂8.8% by weight of nanoparticles

Example 5 use as clear lacquer

^*The invention

Gloss and haze

Gloss was measured according to DIN EN ISO 2813. The higher the gloss measurement, the better the gloss. Haze was measured according to DIN EN ISO 13803. The lower the haze value, the more transparent the paint.

Scratch resistance

The clear lacquers prepared were subjected to scratch resistance testing in accordance with DIN 55668.

The relative residual gloss (%) shows how high the gloss [20 ° ] is after scratching to DIN 5668 compared to the gloss before scratching. The higher the value, the better the scratch resistance.

Examples 5A to E clearly show that formulations D and E according to the invention are distinguished by a significantly higher scratch resistance while retaining good optical properties, in particular low haze.

Claims (22)

1. An aqueous-based formulation comprising

A) Silane-modified copolymer a1) and hydroxyl-containing polyorganosiloxane a 2);

B) optionally surface-modified inorganic particles having an average particle size (z-average) of less than 200nm, determined in dispersion by dynamic light scattering; and

C) and (3) water.

2. The water-based formulation according to claim 1, wherein the silane-modified copolymer a1) comprises groups of the general formula (1)

-Si(R¹O)₂R² (1)

Wherein

R¹Is C₂To C₈An alkyl group; and is

R²Is (R)¹O) or C₁To C₅An alkyl group.

3. The water-based formulation of claim 1, wherein the silane-modified copolymer a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

ib) a hydroxy-functional monomer; and

IS1) silane functional monomers capable of polymerization;

and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

IIb) a hydroxy-functional monomer; and

IIc) acid functional monomers.

4. The water-based formulation of claim 1, wherein the silane-modified copolymer a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals; and

ib) a hydroxy-functional monomer;

and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

IIb) a hydroxy-functional monomer;

IIc) an acid functional monomer; and

IIS1) silane functional monomers capable of polymerization.

5. The water-based formulation of claim 3, wherein the polymerizable silane-functional monomer IS1) IS a compound of the general formula (2)

(R¹O)₂R²Si-(CH＝CH₂) (2)

Wherein

R¹Is C₂To C₈An alkyl group; and is

R²Is (R)¹O) or C₁To C₅An alkyl group;

and/or a compound of the general formula (3)

(R¹O)₂R²Si(CH₂)_m-O(CO)-(CR³＝CH₂) (3)

Wherein

R¹Is C₂To C₈An alkyl group;

R²is (R)¹O) or C₁To C₅An alkyl group;

R³is H or CH₃(ii) a And is

m is1 to 4.

6. The aqueous-based formulation of claim 4, wherein the polymerizable silane-functional monomer IIS1) is a compound of the general formula (2)

(R¹O)₂R²Si-(CH＝CH₂) (2)

Wherein

R¹Is C₂To C₈An alkyl group; and is

R²Is (R)¹O) or C₁To C₅An alkyl group;

and/or a compound of the general formula (3)

(R¹O)₂R²Si(CH₂)_m-O(CO)-(CR³＝CH₂) (3)

Wherein

R¹Is C₂To C₈An alkyl group;

R²is (R)¹O) or C₁To C₅An alkyl group;

R³is H or CH 3; and is

m is1 to 4.

7. The water-based formulation according to claim 3, wherein the silane-functional monomer IS1) capable of polymerizing IS selected from the group consisting of vinyltriethoxysilane, vinyltriisopropoxysilane, vinyl-tris- (2-methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldiisopropyloxysilane, vinylethyldiethoxysilane, 3- (triethoxysilyl) -propyl methacrylate or 3- (tri-isopropoxysilyl) -propyl methacrylate, vinylphenyldiethoxysilane, vinylphenylmethylethoxysilane or vinyltri-tert-butoxysilane.

8. The water-based formulation according to claim 4, wherein the silane-functional monomer IIS1) capable of polymerizing is selected from the group consisting of vinyltriethoxysilane, vinyltriisopropoxysilane, vinyl-tris- (2-methoxyethoxy) silane, vinylmethyldiethoxysilane, vinylmethyldiisopropyloxysilane, vinylethyldiethoxysilane, 3- (triethoxysilyl) -propyl methacrylate or 3- (tri-isopropoxysilyl) -propyl methacrylate, vinylphenyldiethoxysilane, vinylphenylmethylethoxysilane or vinyltri-tert-butoxysilane.

9. The water-based formulation of claim 1, wherein the silane-modified copolymer a1) is a copolymer consisting of

I) A hydroxy-functional hydrophobic polymer comprising as a building monomer

Ia) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals; and

ib) a hydroxy-functional monomer;

and

II) a hydroxy-functional hydrophilic polymer, comprising as a building component

IIa) having C in the alcohol moiety₁To C₁₈(meth) acrylates and/or vinylaromatic and/or vinyl esters of hydrocarbon radicals;

IIb) a hydroxy-functional monomer;

IIc) an acid functional monomer; and

IIS2) contains at least one epoxy-functional monomer in addition to silane groups.

10. The aqueous-based formulation of claim 9, wherein said monomer IIS2) is selected from the group consisting of γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropyl-tri-isopropoxysilane, γ -glycidoxypropyl-diethoxy-methylsilane, β - (3, 4-epoxycyclohexyl) -triethoxysilane, and β - (3, 4-epoxycyclohexyl) -tri-isopropoxysilane.

11. The water-based formulation of claim 1, wherein the hydroxyl group-containing polyorganosiloxane a2) is a compound of the general formula (I)

Wherein

X is an aliphatic, optionally branched C₁To C₁₀A group, or [ -CH₂-O-(CH₂)_p-]Si unit, wherein r is an integer from 1 to 4;

r is a-CH (OH) Y group, wherein

Y is-CH₂-N(R²R³) Group (a) in which

R²Is H or methyl, ethyl, n-propyl, isopropyl or cyclohexyl, or 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxyPropyl; and is

R³Is 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl,

R¹identical or different, is H or C optionally containing heteroatoms₁To C₁₀A hydrocarbyl group; and is

n is an integer from 1 to 40.

12. The water-based formulation of claim 1, wherein the hydroxyl group-containing polyorganosiloxane a2) is a compound of the formula (V)

Wherein

m is an integer of 5 to 15;

z is H or methyl; and is

n and (b). Is an integer from 1 to 12.

13. The water-based formulation of claim 1, wherein the hydroxyl group-containing polyorganosiloxane a2) is a compound of the general formula (VI)

Wherein

m is an integer of 5 to 15; and is

y is an integer from 2 to 4.

14. The water-based formulation according to claim 11, wherein the polyorganosiloxane a2) having the general formula (I) has a number average molecular weight of 200 to 3,000g/mol and an average OH functionality of at least 1.8.

15. The water-based formulation according to claim 11, wherein the number average molecular weight of the polyorganosiloxane a2) having the general formula (I) is 250 to 2,250 g/mol.

16. The aqueous-based formulation of claim 1, wherein the inorganic particles B) are selected from inorganic oxides, mixed oxides, carbides, borides and nitrides of elements of main groups II to IV and/or elements of transition groups I to VIII of the periodic table, including the lanthanides.

17. The aqueous-based formulation of claim 1, wherein the inorganic particles B) are inorganic nanoparticles in the form of a colloidal dispersion in an organic solvent or in water.

18. The aqueous-based formulation of claim 1, wherein the inorganic particles B) are inorganic particles in the form of an aqueous-based formulation.

19. The aqueous-based formulation of claim 1, wherein the inorganic particles B) are surface-modified inorganic nanoparticles.

20. A water-based coating composition comprising the water-based formulation of claim 1 and at least one crosslinker D).

21. A water-based two-component coating composition comprising the water-based formulation of claim 1 and a polyisocyanate.

22. A clear paint comprising the aqueous-based formulation of claim 1.