Functionalized silica particles and their uses

Abstract

The invention relates to silica particles functionalized with one or more silanes comprising terminal groups enabling condensation reactions with the surface of the silica particles and at least one other terminal group for modifying the properties of the silica particles. The invention also relates to a process for functionalizing silica particles by means of silanes, silanes such as are used for the functionalization of silica particles according to the invention, a process for functionalizing silica by means of silanes, silica particles comprising functional groups, uses of the silica particles according to the invention, and coating compositions comprising the silica particles according to the invention.

Description

Technical Field

[0001] The present invention relates to silica particles functionalized with one or more silanes and their use in applications such as antifouling or antifogging coatings, processes for functionalizing silica particles, and to specific silanes such as for functionalizing silica particles. The invention also relates to coating compositions comprising such functionalized silica particles. The antifouling project received funding from the Federal Ministry of Economic Affairs and Energy Germany under Grant Agreement 03SX370H. Background Art

[0002] Coatings containing hydrophilic materials such as polyether functionalized silicone derivatives (such as disclosed in EP3325540 A1) have demonstrated a significant reduction in the adhesion strength of marine organisms on the surface. In addition, these additives formulated into thermal acrylic clearcoats have been shown to be effective as anti-fogging agents.

[0003] Problem to be solved

[0004] However, adding functionalized less branched, long chain silicone derivatives or polyethers to coating formulations can gradually reduce the hardness of the coating and thus reduce impact and scratch resistance. Such properties are a prerequisite for the successful application of coating formulation products in fields like marine antifouling or hard coatings and clear coatings for automotive headlamps. In order to mitigate the hardness reducing effect of the additives, filler materials such as surface treated silica or other particulate species can be added, but this can lead to a more complex formulation mixture and is therefore undesirable. Summary of the invention

[0005] The above problems are solved by providing silica particles functionalized with one or more silanes having specific structural features, for example coating the silica particles with an antifouling additive or an antifogging additive, respectively.

[0006] The softening effect on the coating caused by the additive itself is directly offset by the hardness properties of the silica particles. In addition, by the combination of the particles and the antifouling additive, the overall applicability is improved because the complexity of the final coating formulation is reduced. Therefore, the necessary hardness and antifouling / antifogging properties can be introduced into the coating formulation at the same time. Further, in addition to the aforementioned benefits, the silica particles according to the present invention can be integrated into the coating matrix and simultaneously carry functional groups that make the silica particles hydrophobic, hydrophilic or provide specific properties such as antifouling or antimicrobial properties for the coating. According to the present invention, the silica particles can be functionalized as described in the following embodiments.

[0007] In one aspect, the present invention relates to silica particles functionalized with one or more silanes having formula (1) and / or (2):

[0008] HN[–SiR 1 2–A]2 (1),

[0009] R 1 x R 2 3-x Si–A (2)

[0010] in

[0011] R 1 are independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, most preferably R 1 Methyl,

[0012] R 2 independently selected from hydrolyzable residues, preferably selected from hydrogen, hydroxyl, hydrocarbylcarbonyloxy groups such as acyloxy groups, halogen groups, amino groups, hydrocarbyloxy groups such as alkoxy or aryloxy groups, more preferably alkoxy groups,

[0013] x is 0, 1, or 2, and

[0014] A is a group of the formula

[0015] –M–F,

[0016] in

[0017] M is selected from L or a group of the formula:

[0018] –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where

[0019] L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4-alkylene group, most preferably L is -(CH2)2- and / or -(CH2)3-,

[0020] R 1 As defined above,

[0021] p=1 to about 9, preferably p=1 or 4, more preferably p=4,

[0022] m=1 to about 20, preferably m=1,

[0023] and

[0024] F is selected from an optionally substituted linear, cyclic or branched saturated, unsaturated or aromatic hydrocarbon group having up to about 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted by an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group,

[0025] The condition is that for the silane of formula (2)

[0026] (i) A is a group of the formula

[0027] –{L–[SiR 1 2O] p –SiR 1 2} m –L–F, where L, R 1 , p, m and F are as defined above, or

[0028] (ii) A is a group of the formula

[0029] -LF, wherein L contains at least one ether group (—O—) and optionally has at least one hydroxyl substituent (—OH), and wherein F is as defined above, with the proviso that it includes at least one ester group (—O—C(═O)— or —C(═O)—O—). DETAILED DESCRIPTION

[0030] The present invention generally relates to silica particles functionalized with one or more silanes. According to the present invention, the term "silica particles" refers to particles of silicon dioxide, including but not limited to particles of colloidal silica or particles of pyrogenic silica. Generally, the silica particles according to the present invention may have a D of about 1 to about 300 nm, preferably about 1 to about 150 nm, and more preferably about 5 to about 50 nm. 50 The average primary particle size, and if agglomerates are formed, is as follows: 50 Average agglomerate particle size: about 1 to about 800 μm, preferably about 5 to about 600 μm, more preferably about 5 to about 400 μm; even more preferably about 5 to about 200 μm, still more preferably about 5 to about 150 μm; and most preferably about 5 to about 75 μm. The silica particles may include pyrogenic (i.e., igneous) silica or precipitated silica without limitation, and include crystalline or amorphous silica particles. In one embodiment, the silica particles are preferably particles of pyrogenic silica.

[0031] According to the present invention, the particle size can be determined by measuring the average particle size D 50 , in particular by laser dynamic light scattering (also known as photon correlation spectroscopy or quasi-elastic light scattering) with a Malvern Zetasizer in accordance with ISO 13320-1 (see also http: / / en.wikipedia.org / wiki / Dynamic_light_scattering) to measure the average particle size D 50 Although this method is the preferred method of determination, especially in uncured compositions, in some cases the average particle size D is determined by transmission electron microscopy (TEM). 50 It may also be sufficient.

[0032] According to the invention, the term "functionalized" means that the silica particles are modified by contacting them with one or more functionalized silanes, resulting in a change in the properties of the particles relative to the properties of the particles before functionalization due to the presence of further functional groups on the surface of the particles. Typically, the functionalization of the silica particles by silanes takes place by forming siloxane units via a condensation reaction of silanes or organosilyl ethers and one or more OH groups present on the surface of the silica particles. According to this functionalization mode, the silanes include one or more hydrolyzable groups, such as chlorine groups, on the silicon atom.

[0033] According to one embodiment of the present invention, the hydrolyzable group R that can be present in the silane of formula (2) and that is susceptible to condensation reaction with the silanol SiOH groups present on the silica surface is 2For example, the number of alkoxy groups or acyloxy groups is limited. In a similar manner, the mechanism of functionalizing the silanol SiOH groups on the silica surface by the disilazane of formula (1) is assumed to involve the initial hydrolysis of the silazane groups by water present in the system or added to the reaction system to obtain silanol functionalized silanes. Those silanol groups of the silane can condense with the silanol groups present at the silica surface. By forming silyl ethers terminated by silyl-based structures as defined in formulas (1) and (2), a variety of functional groups can be placed at the silica particle surface, thereby making the particles hydrophobic, hydrophilic, coating matrix reactive or providing the particles with other desired further properties.

[0034] According to the invention, the group R 1 are independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, most preferably R 1 Here, the term "non-hydrolyzable" means that the group cannot be easily cut off by adding water, hydroxide anions, or completely analogously thereto, by adding alcohol or alkoxide anions, especially under acidic or basic conditions. The term "non-hydrolyzable" means that the group is preferably bonded to the silicon atom via a C-Si bond and therefore, the non-hydrolyzable group is preferably an organic group.

[0035] According to the present invention, the non-hydrolyzable R 1 The radical is preferably an optionally fluorinated hydrocarbon radical which may be chosen from alkyl, alkenyl, alkynyl, alkaryl, aralkyl and aryl radicals, such as phenyl, benzyl or tolyl radicals, in particular from such radicals having 1 to about 22 carbon atoms.

[0036] More preferably, the non-hydrolyzable R 1 The radical is selected from alkyl radicals which may be selected from unsubstituted linear, branched and cyclic alkyl radicals or radicals combining linear and cyclic alkyl moieties or structures combining branched and cyclic structures, in particular from linear C1-C22 alkyl radicals such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl radicals, branched C1-C22 alkyl radicals such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl radicals, and cyclic C3-C22 alkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl radicals.

[0037] Even more preferably, the non-hydrolyzable group R 1 is selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl or cyclohexyl groups, most preferably R 1 It is methyl.

[0038] According to the invention, the group R 2Independently selected from hydrolyzable residues, preferably selected from hydrogen, hydroxyl, hydrocarbylcarbonyloxy groups such as acyloxy groups, halogen groups, amino groups, hydrocarbyloxy groups such as alkoxy or aryloxy groups, more preferably alkoxy groups.

[0039] Here, the term "hydrolyzable" means that the group can be easily cleaved by adding water, hydroxide anions or by adding alcohol or alkoxide anions, in the case of water or alcohol, especially under acidic or basic conditions. The term "hydrolyzable" shall mean that the group is not bonded to the silicon atom via a C-Si bond, but via a Si-X bond, wherein X is Cl, Br or I; a Si-O bond, in the case of R 2 This is the case when it is selected from hydroxy, hydrocarbylcarbonyloxy and hydrocarbyloxy groups; Si-N bonds; Si-S bonds or Si-H bonds.

[0040] According to the present invention, the hydrolyzable group R 2 Preferably, the alkyl radicals are independently selected from: hydrogen; hydroxyl radicals; hydrocarbylcarbonyloxy radicals, wherein the hydrocarbyl radicals may represent alkyl radicals, alkenyl radicals, alkynyl radicals, alkaryl radicals, aralkyl radicals and aryl radicals, in particular linear C1-C22 alkyl radicals such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl radicals, branched C1-C22 alkyl radicals such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl radicals, and cyclic C3-C22 alkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl radicals; hydrocarbyloxy radicals; The hydrocarbon radical may represent an alkyl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group and an aryl group, in particular a linear C1-C22 alkyl group such as a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl group, a branched C1-C22 alkyl group such as an isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl group, and a cyclic C3-C22 alkyl group such as a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl group; a halogen group; and an amino group, which includes primary, secondary and tertiary amino groups.

[0041] More preferably, the hydrolyzable group R 2 It is an alkoxy group, even more preferably a group selected from the following: methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, isopropoxy, isobutoxy, tert-butoxy, neopentoxy, cyclopentoxy or cyclohexyloxy group, still more preferably a methoxy, ethoxy or isopropoxy group, most preferably a methoxy group.

[0042] According to the present invention, in formula (2), x is 0, 1 or 2, preferably x is 0 or 1, most preferably x 0. Silanes with three hydrolyzable groups have been shown to be advantageously applied to the functionalization of silica particles and can be prepared conveniently.

[0043] As defined above, according to the present invention, A is a radical of the formula

[0044] –M–F,

[0045] Wherein M is selected from L or a group of the formula:

[0046] –{L–[SiR 1 2O] p –SiR 1 2} m –L–.

[0047] L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl.

[0048] According to the present invention, L is preferably independently selected from divalent C2-C12-alkylene groups, which include linear divalent C2-C12 alkylene groups such as ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene and n-decylene, branched divalent C2-C12 alkylene groups such as isopropylene, isobutylene, tert-butylene, isopentylene, neopentylene, methylpentylene, methylhexylene, ethylhexylene, methylheptylene, ethylheptylene, methyloctylene and ethyloctylene, and cyclic divalent C2-C12 alkylene groups such as cyclopentylene, cyclohexylene and cycloheptylene.

[0049] More preferably, L is independently selected from divalent C2-C4 alkylene groups such as ethylene, n-propylene, n-butylene, isopropylene, isobutylene and tert-butylene, and most preferably L is independently selected from -(CH2)2- and / or -(CH2)3-, i.e. an ethylene group or a n-propylene group.

[0050] According to the present invention, the formula -{L-[SiR 1 2O] p –SiR 1 2} m The R in –L– 1As defined above,

[0051] and preferably the formula –{L–[SiR 1 2O] p –SiR 1 2} m The R in –L– 1 is a saturated hydrocarbon substituent selected from the group consisting of a monovalent C1-C22-alkyl group (optionally substituted with one or more fluorine substituents), a C6-C22-aryl group, a C8-C22-polycyclic aryl group, a C7-C22-alkylaryl group, and a C7-C22-arylalkyl group; more preferably a group of formula -{L-[SiR 1 2O] p –SiR 1 2} m The R in –L– 1 is selected from methyl, 3,3,3-trifluoropropyl, phenyl, styryl, phenylpropyl, and naphthyl, and even more preferably wherein R 1 is selected from methyl, phenyl, 3,3,3-trifluoropropyl; the most preferred formula is -{L-[SiR 1 2O] p –SiR 1 2} m The R in –L– 1 It is methyl.

[0052] According to the present invention, p = 1 to about 9, and preferably p = 1 to 4, more preferably p = 4. This is to be understood as follows: the average value of the subscript p of the silane of formula (1) and / or (2) used for functionalizing the silica particles is in the range of 1 to about 9, including these endpoints, wherein preferably the average value is in the range of 1 to 4, including these endpoints, and most preferably the average value of the subscript p is 4.

[0053] According to the present invention, it is further preferred when p is 1 to about 9, wherein the subscript p of all silanes of formula (1) and / or (2) used to functionalize the silica particles is an integer from the range of 1 to 9, i.e. 1, 2, 3, 4, 5, 6, 7, 8 or 9, more preferably the subscript p is an integer from the range of 1 to 4, i.e. 1, 2, 3 and 4, and most preferably p is 4.

[0054] This corresponds to the range from disiloxane blocks to decasiloxane blocks present in the group M represented by the formula

[0055] –{L–[SiR 1 2O] p –SiR 1 2} m –L–.

[0056] Setting the parameter p to 4 corresponds to the presence of a pentasiloxane block in the group M. The precursor of such a block is HMe2Si-O-[Me2SiO]3-SiMe2H, which can be conveniently (for example, according to JP11158188B, which is fully incorporated herein by reference) already synthesized in high purity by a non-equilibrium reaction of hexamethylcyclotrisiloxane and HMe2Si-O-SiMe2H. After an additional distillation, a pentasiloxane content of more than 90% by weight according to gas chromatography is achievable. The aforementioned process for the synthesis of non-equilibrium polyorganosiloxanes is also applicable to other tetraorganodisiloxanes and hexaorganocyclotrisiloxanes besides hexamethylcyclotrisiloxane and HMe2Si-O-SiMe2H.

[0057] According to the present invention, m=1 to about 20, preferably 1 to about 10, even more preferably 1 to 5, most preferably m=1.

[0058] This is to be understood in the following manner: the average value of the subscript m of the silane of formula (1) and / or (2) used to functionalize the silica particles is in the range of 1 to about 20, including these endpoints, wherein preferably, the average value of m is in the range of 1 to about 10, including these endpoints, even more preferably, the average value of m is in the range of 1 to 5, including these endpoints, and most preferably the average value of the subscript m is 1.

[0059] According to the present invention, it is further preferred when m is 1 to about 20, wherein the subscript m of all silanes of formula (1) and / or (2) used for functionalizing the silica particles is an integer from the range of 1 to 20, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20, more preferably the subscript m is an integer from the range of 1 to 10, more preferably the subscript m is an integer from the range of 1 to 5, and most preferably m is 1.

[0060] Although groups M with a single siloxane block, i.e. m=1, are preferred according to the invention, polyorganosiloxanes with up to about 20, in particular with 2, 3, 4 or 5, which are linked together via divalent radicals L as defined above, i.e. m=up to about 20, in particular m=2, 3, 4 or 5, are synthesized by stepwise addition reaction of symmetrically substituted and asymmetrically substituted siloxane blocks, preferably di-, penta- or deca-siloxane blocks, most preferably pentasiloxane blocks.

[0061] According to the invention, the group A is terminated by a group —F, which is bonded to a group M as described above.

[0062] According to the invention, F is selected from optionally substituted linear, cyclic or branched saturated, unsaturated or aromatic hydrocarbon radicals having up to about 100 carbon atoms and which optionally contain a radical selected from -O-, -S-, -NH-, -C(O)-, -C(S)-, a tertiary amino group ( and quaternary ammonium groups and may be substituted with an OH group, an SH group, a halogen group, an organosilyl group, and a triorganosiloxy group.

[0063] In the functionalization of silica particles, the nature of the group F has a significant influence on the properties of the modified silica surface, since the terminal group F and its functionalization pattern determine whether the particles as a whole are hydrophobic, hydrophilic or which other properties they exhibit. In particular, through the presence of the reactive functional group, the group F can interact and bond with other components of the composition and can thus be attached to the polymer matrix of the cured composition.

[0064] According to the above definition of F according to the invention, F can preferably be selected from C8-C22-alkylarylalkyl, C6-C22-aryl ether, C6-C22-cycloalkyl, C7-C22-cycloalkylalkylene, C7-C22-bicycloalkyl, C5-C12-hetero-N,-O,-aryl, C1-C20-alkylaldehyde and C7-C20-alkylarylaldehyde, all of which are optionally replaced by C1-C8-alkyl, OH, Cl, or Br, and silyl ether groups R 1 3Si–O-substituted, where R 1 As defined above for formula (1) and (2), and wherein R 1 Preferably it is a C1-C8 alkyl group, most preferably a methyl group, and F may preferably be selected from polyoxy(C2-C4-alkylene) groups, which may be terminated by OH- or C1-C8 oxyalkyl- or C1-C8 oxycarbonylalkyl groups, and F may preferably be selected from vinyl, allyl, hexenyl, octenyl, allyloxypropyl, -CH2C≡CH, -C(O)C≡CH, -C(O)(CH2)8CH=CH2, cyclohexenylethyl, citronyl, norborneneethyl, vinylphenylethyl, allyloxyphenyloxypropyl, -(OCH2CH2O) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OCH=CH2, or -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3))b -(OCH2CH2CH(CH3)) c -O-C1-C4 alkyl, or -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)-C1-C4 alkyl, wherein a, b, c are 0-20 and a+b+c=1-20,

[0065] -[Si(CH3)2OSi(CH3)2]CH=CH2, and

[0066]

[0067] In formula (2), F can be (X) x R 1 3-x Si-, where R 1 As defined above for formula (1) and (2), x = 1-3, and X is = OH, OR 1 、-NR 1 2. R 1 -C(O)-O-;

[0068] F in formula (1) and formula (2) may further preferably be selected from unsubstituted or substituted oxyphenyl moieties of the following formula:

[0069]

[0070] Where R 10 , R 14 is hydrogen or R as defined for formula (1) or (2) 1 , and R 11 , R 12 , R 13 Selected from -OR, where R = H or C1-C8 alkyl,

[0071] The group R 11 -R 13 At least one of them is OH, and F may preferably be selected from a eugenol group, a bisphenol ether, a cumylphenol ether, or a glycidyl propyl ether group, an epoxy citronyl group, an epoxy cyclohexane ethyl group, an epoxy norbornane group,

[0072]

[0073] and carbonate derivatives of these epoxides, tetrahydro-2H-thiananthracene, carbazole, indole,

[0074] triphenylsilyl, and R 6 Me2Si-, where R6 = C6-C10-aryl, C7-C12-arylalkyl, C6-C12-cycloalkyl, C7-C16-bicycloalkyl, C6-C12-epithioalkyl, C5-C12-N- or C5-C12-O-aryl, optionally substituted by C1-C8-alkyl, OH, Cl, CN, and silyl ether groups R3Si-O-,

[0075] F may preferably be selected from phenyl, phenylpropyl, styryl, naphthyl, eugenol, bisphenol ether, cumylphenol ether, norbornyl, vinyl, allyl, allyloxypropyl, hexenyl, norbornenyl, cyclohexenylethyl, citronyl, and glycidyl propyl ether, epoxycitronyl, epoxycyclohexaneethyl, epoxynorbornyl, and carbonate derivatives of these epoxides,

[0076] (X) x R 1 3-x Si- or R 6 x R 1 3-x Si-, where x = 1-3, where X = OH, OR 1 、-NR 1 2-, R 1 -C(O)-O- and wherein R6 = phenyl, naphthyl, phenylethyl, phenylpropyl, eugenol, limonyl, epoxylimonyl, glycidyl propyl ether, epoxycyclohexylethyl, norbornenylethyl, epoxynorbornenylethyl, carbazole, indole. The above-mentioned alkyloxysilyl group and alkylcarbonyloxysilyl group cannot constitute F in the compound of formula (1).

[0077] According to the invention, the group F preferably represents a C1-C24 unsubstituted alkyl group, in particular a linear C1-C24 alkyl group; an oxyC2-C24 alkylene and poly(oxyalkylene) group, wherein the oxyalkylene unit is an oxyethylene unit, an oxypropylene unit or a combination of these units; a C2-C24 oxycarbonyl hydrocarbon group, in particular a C2-C24 oxycarbonylalkyl group; a C1-C24 oxyalkyl group; a C1-C24 alkanoyl group; or a C1-C24 alkanoyl ester group, wherein the alkoxy group of the alkanoyl ester group is a C1-C12 alkoxy group.

[0078] In this case, F preferably represents a C1-C24 unsubstituted alkyl group selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl groups, in particular methyl and ethyl groups. Unsubstituted hydrocarbon groups, in particular unsubstituted alkyl groups, are highly nonpolar, i.e. hydrophobic functional groups and therefore the silica particles are functionalized with silanes of formula (1) and / or (2) in which the groups F are as described, so that the particles are hydrophobic.

[0079] According to the invention, when the group F represents a C2-C24 poly(oxyalkylene) group, it preferably represents a poly(oxyethylene) group having about 2 to about 12 oxyethylene repeating units, or a poly(oxypropylene) group having about 2 to about 8 oxypropylene repeating units. The poly(oxyalkylene) group is preferably terminated by an OH group, by a methoxy group, or by a trimethylsiloxy group.

[0080] More preferably, the poly(oxyalkylene) group represented by F is selected from the structure -(O-CH2CH2) z1 The residue of -OH, wherein z1 is in the range of about 3 to about 12, even more preferably in the range of about 5 to about 11, and even further preferably in the range of about 6 to about 10.5.

[0081] wherein z1 refers to the average number of repeating units (O—CH2CH2) contained in the group F of the silane of formula (1) and / or (2) containing at least one of these repeating units; however, most preferably z1 is an integer in the range of about 3 to about 12, more preferably in the range of about 5 to about 11, and even more preferably in the range of about 6 to about 10.

[0082] Still more preferably, the poly(oxyalkylene) group represented by F is selected from the structure -(O-CH2CH2) z2 -OMe residue, wherein z2 is in the range of about 3 to about 12, even more preferably in the range of about 5 to about 11, and even further preferably in the range of about 6 to about 10.5.

[0083] wherein z2 refers to the average number of repeating units (O—CH2CH2) contained in the group F of the silane of formula (1) and / or (2) containing at least one of these repeating units; however, most preferably z2 is an integer in the range of about 3 to about 12, more preferably in the range of about 5 to about 11, and even more preferably in the range of about 6 to about 10.

[0084] Similarly more preferably, the poly(oxyalkylene) group represented by F is selected from the structure -(O-CH2CH2) z3- a residue of OSiMe3, wherein z3 is in the range of about 3 to about 12, more preferably in the range of about 5 to about 11, and even more preferably in the range of about 6 to about 10.5.

[0085] Wherein, z3 refers to the average number of repeating units (O—CH2CH2) contained in the group F of the silane of formula (1) and / or (2) containing at least one of these repeating units; however, most preferably z3 is an integer in the range of about 3 to about 12, more preferably in the range of about 5 to about 11, and even more preferably in the range of about 6 to about 10.

[0086] Most preferably, the poly(oxyalkylene) group represented by F is selected from -(O-CH2CH2)7-OH, -(O-CH2CH2)8-OH, -(O-CH2CH2)9-OH, -(O-CH2CH2) 10 –OH, –(O–CH2CH2) 11 –OH, –(O–CH2CH2) 12 –OH, –(O–CH2CH2)7–OMe, –(O–CH2CH2)8–OMe, –(O–CH2CH2)9–OMe, –(O–CH2CH2) 10 –OMe, –(O–CH2CH2) 11 –OMe, –(O–CH2CH2) 12 –OMe, –(O–CH2CH2)7–OSiMe3, –(O–CH2CH2)8–O SiMe3, –(O–CH2CH2)9–O SiMe3, –(O–CH2CH2) 10 –O SiMe3, –(O–CH2CH2) 11 –O SiMe3, and –(O–CH2CH2) 12 –SiMe3.

[0087] The poly(oxyalkylene) groups in F make the silane residues attached to the surface of the silica particles polar, i.e. hydrophilic, and thus the surface of the silica particles is rendered hydrophilic by such functionalization. It is particularly preferred when the poly(oxyalkylene) groups are terminated by OH groups, methoxy groups or trimethylsiloxy groups.

[0088] When group F represents C2-C24oxycarbonylalkyl group, according to the present invention, it is preferred when the alkyl group of the oxycarbonyl group is selected from: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-hexyl, n-heptyl or n-octyl group, branched C1-C22 alkyl group such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl group, and cyclic C3-C22 alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl group. According to the present invention, it is also preferred when the alkyl group of the oxycarbonylalkyl group is bonded to the oxycarbonyl group by the carbon atom substituted by three C1-C8 alkyl substituents. Wherein, it is particularly preferred when the sum of the carbon atoms of all three alkyl substituents is about 10 or less, and it is even more preferred when one of the alkyl substituents is a methyl group and the sum of the carbon atoms of the other two alkyl substituents is about 8 or less.

[0089] When the radical F represents a C1-C24oxyalkyl group, according to the invention, the alkyl radical of the C1-C24oxyalkyl group is preferably selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl radicals, branched C1-C22alkyl radicals such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl radicals, and cyclic C3-C22alkyl radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl radicals.

[0090] When the radical F represents a C1-C24-alkanoyl group, according to the invention, the C1-C24-alkanoyl group is preferably selected from the carboxylic acid residues -COOH, -CH2CO2H, -(CH2)2CO2H, -(CH2)3CO2H, -(CH2)4CO2H, -(CH2)5CO2H, -(CH2)6CO2H, -(CH2)7CO2H, -(CH2)7CO2H, -(CH2)9CO2H, or (CH2) 10 CO2H.

[0091] When the group F represents a C1-C24 alkanoyl ester group, wherein the alkoxy group of the alkanoyl ester group is a C1-C12 alkoxy group, according to the invention, the alkanoyl group is preferably selected from the alkanoyl residues -CO, -CH2CO, -(CH2)2CO, -(CH2)3CO, -(CH2)4CO, -(CH2)5CO, -(CH2)6CO, -(CH2)7CO, -(CH2)7CO, -(CH2)9CO, or (CH2) 10 CO, and the alkoxy radical of the ester is preferably selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy or n-hexoxy radicals.

[0092] Particularly preferred alkanoyl ester groups according to the invention are selected from -COOMe, -COOEt, -COOtBu, -CH2CO2Me, -CH2CO2Et, -CH2CO2tBu, -(CH2)2CO2Me, -(CH2)2CO2Et, -(CH2)2CO2tBu, -(CH2)3CO2Me, -(CH2)3CO2Et, -(CH2)3CO2tBu, -(CH2)4CO2Me, -(CH2)4CO2Et, -(CH2)4CO2tBu, -(CH2)5CO2Me, -(CH2)5CO2Et, -(CH2)5CO2tBu, -(CH2)6CO2Me, -(CH2)6CO2Et and -(CH2)6CO2tBu, where Bu=butyl, tBu=tert-butyl, Me=methyl and Et=ethyl.

[0093] According to the invention, the group F preferably contains one or more coating matrix reactive groups, which are functional groups capable of interacting or bonding with the polymer matrix of the coating matrix before, during or after curing of the curable composition. These groups can be any kind of groups capable of interacting with the coating polymer matrix or its precursors, in particular functional groups selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxyl, 1,3-dicarboxyl, diester, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions, which are incorporated into the polymer matrix by forming a covalent bond.

[0094] According to the invention, the definitions given above describe the invention, provided that for the silane of formula (2) (i) A is a radical of the formula

[0095] –{L–[SiR 1 2O] p –SiR 1 2} m –L–F, where L, R 1 , p, m and F are as defined above, or (ii) A is a group of the formula

[0096] -LF, wherein L contains at least one ether group (—O—) and optionally has at least one hydroxyl substituent (—OH), and wherein F is as defined above, with the proviso that it includes at least one ester group (—O—C(═O)— or —C(═O)—O—).

[0097] In a preferred embodiment according to the invention, the silica particles are functionalized with one or more silanes of formula (1) and / or formula (2), wherein one or more of the silanes of formula (1) and / or (2) contain one or two groups A, wherein group A comprises a group M having the formula

[0098] –{L–[SiR 1 2O] p –SiR 1 2} m –L–

[0099] Among them, L, R 1 , p, and m are as defined above,

[0100] wherein the one or more of the formula -{L-[SiR 1 2O] p –SiR 1 2} m The group M of -L- consists of one or more defined polysiloxane blocks consisting essentially of any of disiloxane, polyorganopentasiloxane, or polyorganodecasiloxane blocks, wherein the term "consisting essentially of..." means that greater than about 50% of the groups M according to this embodiment have the same chain length, wherein the subscript p in the above formula is p=1, 4, or about 9.

[0101] It is clear that p here does not refer to an average value but to different p values ​​which are integers selected from 1, 4 or about 9.

[0102] In a further preferred embodiment according to the present invention, the formula -{L-[SiR 1 2O] p –SiR 1 2} m –L–(where L, R 1 Greater than about 80% of the number of groups M having only 1, or only 4, or only about 9 p subscripts (wherein m is as defined above) have only 1, or only 4, or only about 9 p subscripts.

[0103] Particularly preferred, the formula -{L-[SiR 1 2O] p –SiR 1 2} m –L–(where L, R 1 Greater than about 90% of the number of groups M having only 1, or only 4, or only about 9 p subscripts (wherein m is as defined above) have only 1, or only 4, or only about 9 p subscripts.

[0104] Such highly homogeneous groups M with a polydispersity index close to about 1 can be achieved by the purification process of the precursor according to the invention. It is thus said that the groups M have a monomodal chain length distribution.

[0105] This feature can be achieved because the precursors, i.e. compounds like disubstituted tetraorganodisiloxane, hexaorganocyclotrisiloxane and the reaction products of non-equilibrium reactions thereof, have different boiling points and can be enriched and purified, for example, by distillation or crystallization in each of the subsequent steps of adding (addition) terminal groups, respectively.

[0106] For example, one of the preferred pentasiloxane units in which p=4 can be derived from HMe2Si-O-[Me2SiO]3-SiMe2H, which has been synthesized in high purity by nonequilibrium reaction of hexamethylcyclotrisiloxane and HMe2Si-O-SiMe2H (for example according to JP 11158188 B). After additional distillation, pentasiloxane contents of more than about 90% by weight according to gas chromatography can be achieved.

[0107] The foregoing process for the synthesis of non-equilibrium polyorganosiloxanes is also applicable to other disubstituted tetraorganodisiloxanes, and hexaorganocyclotrisiloxanes.

[0108] The purified protein with structure M* H D3M* H The pentasiloxane (wherein "M*H" represents a siloxane mono-unit substituted with a hydride of the structure) is subjected to the addition of other compounds including reactive groups that can undergo a hydrosilylation reaction with the terminal SiH unit. The reagent for introducing the L group therefore needs to be appropriately functionalized to undergo a hydrosilylation step with the hydrosiloxane (for example by including a terminal CC double bond). The reagent for hydrosilylation may further include a group F, and a silane structure bonded to A at the other end of M. For example, by reacting one end of the precursor of formula (3a) with an allyl-terminated polyether in a hydrosilylation reaction, and reacting the intermediate obtained therefrom with (MeO)3SiVi in a hydrosilylation reaction, a compound of formula (2) is obtained as follows: wherein the silane terminal carries three hydrolyzable methoxy groups, the first L group connecting the silane portion to the polysiloxane portion is an ethylene group, the L group connecting the polysiloxane group to the group F is a propylene group, and F is a polyether group.

[0109] The compounds of formula (1) and / or (2) used for functionalizing silica particles according to the present invention can be derived from any suitable polyorganosiloxane as a starting material that symmetrically provides reactive substituents at the terminal groups. Particularly suitable polyorganosiloxanes include, but are not limited to:

[0110]

[0111] Where L and R 1 As mentioned above for the formula –{L–[SiR 12O] p –SiR 1 2} m –L–F defined.

[0112] In a preferred embodiment, the substituents of the polyorganosiloxane portion of the precursor represented by formula (3a) are defined as follows:

[0113] R is independently selected from methyl, 3,3,3-trifluoropropyl, phenyl, styryl, phenylpropyl, naphthyl, and R 1 As defined above, methyl is preferred.

[0114] In a further preferred embodiment according to the present invention, the formula -{L-[SiR 1 2O] p –SiR 1 2} m –L–(where L, R 1 , and m is as defined above) and less than 60% of the number of groups M, and particularly preferably the formula -{L-[SiR 1 2O] p –SiR 1 2} m –L–(where L, R 1 , and m are as defined above) have the same chain length, wherein the number average of the subscript p is in the range of about 2 to about 8, more preferably about 3 to about 7, and most preferably about 3.5 to about 6.5.

[0115] All subscripts indicating ranges for the number of repetitions of a repeating unit in an oligo- or poly(oxyalkylene) or oligo- or polysiloxane structural unit generally refer to average values ​​obtained for the silanes of formula (1) and / or (2) used for functionalizing silica particles containing at least one of the respective repeating units. This is due to the fact that the starting materials used to provide such structural moieties are often mixtures defined by their average chain length; however, it is generally preferred that in all silanes of formula (1) and / or (2) used for functionalizing silica particles containing one or more of the respective repeating units as indicated, the subscript refers to an integer from the given range, i.e. the number of repeating units is within the indicated range.

[0116] In a preferred embodiment according to the present invention, silica particles are provided, wherein in formula (1), when M is L, the group F contains at least one heteroatom, such as N, O, P, S, Si, or a halogen atom such as fluorine, chlorine, bromine or iodine.

[0117] Preferably, silica particles are provided wherein in formula (1), M is L and the group F contains at least one heteroatom, such as N, O, Si, or a halogen atom such as fluorine or chlorine.

[0118] More preferably, in formula (1), M is L and group F contains one or more oxygen atoms, more preferably F contains one or more oxygen atoms, wherein at least one oxygen atom is an oxygen atom of an ether or ester moiety, even more preferably group F contains three or four oxygen atoms, wherein at least three oxygen atoms are oxygen atoms of an oligo- or poly(oxyalkylene) group, still more preferably group F contains five or more oxygen atoms, wherein at least five oxygen atoms are oxygen atoms of an oligo- or poly(oxyalkylene) group, and even more preferably group F contains a poly(oxyethylene) or poly(oxypropylene) unit comprising five or more oxygen atoms.

[0119] Most preferably, in the compound of formula (1), M is L, and

[0120] F=-(O–CH2CH2) 4-12 –OH, or

[0121] F=–(O–CH2CH2) 4-12 –OMe, or

[0122] F=–(O–CH2CH2) 4-12 – OSiMe3.

[0123] The compound of formula (1) according to this embodiment of the present invention is, for example, a compound represented by the following formula

[0124] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2) 4-12 –OH)2, especially

[0125] HN(–SiMe2–(CH2)2–(O–CH2CH2) 10 –OH)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2) 10 –OH)2,

[0126] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2) 4-12 –OMe)2, especially

[0127] HN(–SiMe2–(CH2)2–(O–CH2CH2) 7.5 –OMe)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2) 7.5 –OMe)2, or

[0128] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2)4-12 –OSiMe3)2, especially

[0129] HN(–SiMe2–(CH2)2–(O–CH2CH2) 10 – OSiMe3)2 and

[0130] HN(–SiMe2–(CH2)3–(O–CH2CH2) 10 –OSiMe3)2.

[0131] It is also preferred according to this embodiment that M is L and F contains or is an oxycarbonylalkyl group of the formula

[0132] -OC(O)-alkyl,

[0133] The alkyl group is a linear, branched or cyclic C1-C12 alkyl group, preferably a linear alkyl group selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl groups, or selected from isopropyl, sec-butyl, tert-butyl, neopentyl or selected from the formula -CR a R b R c The alkyl group of the branched alkyl group,

[0134] The residue R a , R b and R c is selected from linear alkyl groups and hydrogen and R a , R b and R c Two or more of are alkyl groups, more preferably the alkyl groups are linear alkyl groups selected from ethyl or methyl, or from the formula -CR a R b R c , where R c is hydrogen or methyl, and R a and R b is a linear alkyl group having a total of 3 to about 11 carbon atoms.

[0135] The other compound of formula (1) according to this embodiment of the present invention is, for example, a compound represented by the following formula

[0136] HN(–SiMe2–(CH2) 2-3 –(O–C(O)alkyl))2, especially

[0137] HN(–SiMe2–(CH2)2–(O–C(O)alkyl))2 and HN(–SiMe2–(CH2)3–(OC(O)alkyl))2, even more particularly HN(–SiMe2–(CH2)2–(O–C(O)-CMeRa R b ))2 and HN(–SiMe2–(CH2)3–(OC(O)-CMeR a R b ))2, where R a and R b is a linear alkyl group and has a total of 3 to about 9 C atoms.

[0138] In a preferred embodiment according to the present invention, silica particles are provided, wherein in formula (1), M is L, and the group F contains one or more silicon atoms, more preferably the group F contains one or more silicon atoms, wherein one of the silicon atoms is a terminal triorganosilyl group such as -SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, -SitBuPh2-, or even More preferably, the terminal triorganosilyl group of F is selected from -SiMe2-CH=CH2, -SiMe3 or -SiEt3 and is bonded to an oxygen atom, and still more preferably, the terminal triorganosilyl group is selected from -SiEt3 or -SiMe3 and constitutes a capping group of a group selected from a poly(ethylene oxide) group, a poly(propylene oxide) group, or a mixed poly(propylene oxide)-poly(ethylene oxide) group, or constitutes a terminal group of a C1-C12 linear alkyl group or a C1-C12 alkenyl group.

[0139] Most preferably, in the compound of formula (1), M is L, and

[0140] F=-(O–CH2CH2) 4-12 – OSiMe3, or

[0141] F=-(O–CH2CH2CH2) 4-12 – OSiMe3, or

[0142] F=-(O–CH2CH2) 4-12 – OSiEt3, or

[0143] F=-(O–CH2CH2CH2) 4-12 –OSiEt3.

[0144] The compound of formula (1) according to this embodiment of the present invention is, for example, a compound represented by the following formula

[0145] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2CH2) 4-12 –OSiMe3)2, especially

[0146] HN(–SiMe2–(CH2)2–(O–CH2CH2CH2) 10 –OSiMe3)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2CH2) 10 – OSiMe3)2, or

[0147] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2) 4-12 –OSiEt3)2, especially

[0148] HN(–SiMe2–(CH2)2–(O–CH2CH2) 7.5 –OSiEt3)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2) 7.5 – OSiEt3)2, or

[0149] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2CH2) 4-12 –OSiEt3)2, especially

[0150] HN(–SiMe2–(CH2)2–(O–CH2CH2CH2) 10 –OSiEt3)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2CH2) 10 –OSiEt3)2.

[0151] In another preferred embodiment according to the present invention, silica particles are provided, wherein in formula (1), the substituents of the hydrocarbon group F are selected from hydroxyl, thiol, alkoxy, siloxy, perfluoroalkyl, carboxyl, ester, aminoalkyl, thioalkyl, or polyether groups, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate groups, ketone, dione, 1,3-diketone, dicarboxyl, 1,3-dicarboxyl, diester, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0152] Preferably, the substituents of the hydrocarbon radical F are selected from hydroxyl groups, alkoxy groups, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, n-hexyloxy, cyclopentyloxy or cyclohexyloxy groups, siloxy groups, in particular -SiMe2-O-, SiMe2-CH=CH2, -OSiMe3, -OSiEt3, -OSi(iPr)3, -OSiPh3, -OSi(cyHex)3, -OSitBuMe2, -OSitBuPh2, perfluoroalkyl groups, in particular trifluoromethyl, compounds of the general formula -C in which x=2 to about 24 x F 2x+1 Linear perfluoroalkyl groups, pentafluorophenyl groups, ester groups, especially those of the formula -COOMe, -COOEt, -COOtBu, -CH2CO2Me, -CH2CO2Et, -CH2CO2tBu, -(CH2)2CO2Me, -(CH2)2CO2Et, -(CH2)2CO2tBu, -(CH2)3CO2Me, -(CH2)3CO2Et, -(CH2)3CO2tBu, -(C -(CH2)4CO2Me, -(CH2)4CO2Et, -(CH2)4CO2tBu, -(CH2)5CO2Me, -(CH2)5CO2Et, -(CH2)5CO2tBu, -(CH2)6CO2Me, -(CH2)6CO2Et and -(CH2)6CO2tBu, and ester groups in which the alkoxy group is a tertiary C4-C25 alkoxy group, and ester groups selected from the formula -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OH, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-C1-C4 alkyl, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)-C1-C4 alkyl and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c-O-SiR3 represents a polyether group of a compound, wherein R = C1-C8 alkyl, a, b, c are 0-20 and a+b+c=1-20; more preferably, the hydrocarbon group F includes both a polyether group and a terminal hydroxyl group, a polyether group and a terminal alkoxy group, or a polyether group and a terminal siloxy group as defined above.

[0153] Also preferably, the substituents of the hydrocarbon radical F are selected from alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxyl, 1,3-dicarboxyl, diester, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0154] It is particularly preferred when the hydrocarbyl group F comprises one or more groups having the structure -(OC(O)-alkyl, wherein the alkyl group is of the formula CMeR a R b An alkyl group, and wherein R a and R b is an alkyl group containing a total of 7 carbon atoms, or wherein R a and R b is an alkyl group containing a total of 6 carbon atoms; it is also particularly preferred when the hydrocarbon group F comprises one or more polyether structures, preferably a polyether structure terminated by an OCH3, OH or OSiMe3 group, or when the hydrocarbon group F comprises one or more butyl groups.

[0155] In another preferred embodiment according to the present invention, silica particles are provided, wherein F comprises at least one moiety selected from the group consisting of a polyether moiety, an ester moiety, and a coating matrix reactive moiety, such as an olefinic, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (—COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyls, 1,3-dicarboxyls, diesters, 1,3-diester, nitro (—NO2), cyano (—CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0156] Preferably, F includes a polyether moiety that provides hydrophilic properties to the functionalized silica particles, and it is also preferred that F includes one or more coating reactive moieties.

[0157] The preferred polyether moiety included in group F is selected from the group consisting of the formula -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c-OH, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-C1-C4 alkyl, -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -OC(O)-C1-C4 alkyl and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-SiR3, wherein R = C1-C8 alkyl, a, b, c are 0 to about 20 and a + b + c = 1 to about 20, more preferably a compound represented by the formula -(OCH2CH2) 3-10 -OCH3, -(OCH2CH2) 3-10 -OH and (OCH2CH(CH3)) 3-10 -OCH3-, (OCH2CH(CH3)) 3-10 A group represented by -OH.

[0158] The term "coating matrix reactive moiety" according to the present invention relates to any functional moiety that interacts with the coating matrix by a reaction that results in incorporation into the coating matrix during the polymerization or curing reaction of the coating composition, i.e. by forming a covalent bond. Therein, the coating matrix is ​​defined as a polymeric scaffold formed by polymerization and / or curing of polymerizable and / or curing compounds present in the coating composition.

[0159] The type of coating composition to which the functionalized particles are applied therefore depends on whether the functional moiety is coating matrix reactive. For example, acrylate or methacrylate groups are coating matrix reactive compounds in coating compositions based on curable multiacrylates or multimethacrylates, and alkenyl groups will be coating matrix reactive in coating compositions comprising systems suitable for free radical polymerization of olefins or polyolefins, or in compositions comprising ene-reactive groups, i.e., containing enophilic groups such as thiol or hydroxyl groups. Thus, a wide variety of functional groups may be considered coating matrix reactive, and the skilled person is fully aware of which functional groups are coating matrix reactive for a certain type of coating composition.

[0160] Most preferred according to the present invention are coating matrix reactive moieties such as alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate, ketone, dione, CH-acidic groups such as 1,3-diketone, 1,3-dicarboxyl groups, 1,3-diester, methylene nitro (-NO2) groups, methylene nitrile groups, Michael donors and acceptor groups.

[0161] Preferred coating matrix reactive moieties selected from alkenyl groups are linear or branched alkenyl groups having at least one terminal CC double bond and cyclic C5 and C6 alkenyl groups, more preferably linear or branched C2-C30 alkenyl groups having at least one terminal CC double bond, even more preferably C2-C30 linear or branched alkenyl groups having a single CC double bond which is a terminal CC double bond, and most preferably vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups.

[0162] Preferred coating matrix reactive moieties selected from epoxy groups are glycidyl groups and glycidyloxy groups, in particular propylene glycidyl ether, phenylene glycidyl ether, C3-C12-epoxyalkylene, C6-C12-epoxycycloalkylene, C7-C16-epoxybicycloalkylene, epoxycitylene, epoxycyclohexylethylene, epoxynorbornylene,

[0163]

[0164] Monoepoxy polyether groups or acetylenic-epoxy ether groups, such as propargyl glycidyl ether groups, 1,4-butanediol diglycidyl ether groups, which are usually groups with terminal epoxy groups.

[0165] Preferred coating matrix reactive moieties selected from amino groups include primary amino groups -NH2, secondary amino groups -NHR 1 and tertiary amino group -NR 1 2, where R 1 is a C1-C8 linear, branched or cyclic alkyl group, and a heterocyclic amino compound, more preferably -NH2, NHMe, NHEt, NHnBu, -NHcyHex, -NMe2, -NEt2, and -NcyHex2 (wherein cyHex is cyclohexyl).

[0166] Preferred coating matrix reactive moieties selected from diketones are all kinds of alkyl groups containing 1,3-diketone or 1,4-diketone moieties, more preferably 1,3-diketone moieties.

[0167] Preferred coating matrix reactive moieties selected from diesters are all kinds of alkyl groups containing 1,3-diester or 1,4-diester moieties, more preferably 1,3-diester moieties.

[0168] Other preferred coating matrix reactive moieties are moieties containing a β-diketonyl group, a β-ketoester group, a β-diester group, or a CH bond in the alpha position to a nitro group or a nitrile group.

[0169] Preferred coating matrix reactive moieties are selected from Michael donors consisting of thiolates, alkoxylates, in particular phenolates, amines, and alkenyls, epoxides, acrylates, methacrylates, thiols, hydroxyls, alkoxyls, carboxyls (-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyls, 1,3-dicarboxyls, diesters, 1,3-diesters, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and acceptor groups in the Michael addition reaction. Thiols and alkoxylates are present in the silanes according to the invention as corresponding thiols and alcohols under neutral conditions. Similarly, carboxyl groups can also be present as corresponding carboxylate groups.

[0170] Preferred coating matrix reactive moieties selected from the group consisting of Michael acceptor groups are α,β-unsaturated aldehyde groups, α,β-unsaturated keto groups, α,β-unsaturated ester groups, α,β-unsaturated amide groups and α,β-unsaturated nitrile groups, more preferably α,β-unsaturated ester groups and amide groups, especially α,β-unsaturated methyl ester groups and α,β-unsaturated ethyl ester groups, and α,β-unsaturated -C(O)NH2, -C(O)NMe2 and -C(O)NEt2 groups. Further preferred coating matrix reactive moieties are esters, 1,3-diester moieties and 1,4-diester moieties of malonic acid.

[0171] In a further preferred embodiment according to the present invention, silica particles are provided, wherein F is selected from:

[0172] -alkyl,

[0173] -alkenyl,

[0174] -alkylcarbonyloxy,

[0175] - a polyoxyalkylene group, which preferably has the following general formula:

[0176] [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0177] in

[0178] [-OC2H4] represents an ethyleneoxy unit,

[0179] [-OC3H6] represents a propyleneoxy unit, and

[0180] [-OC4H8] represents a butyleneoxy unit,

[0181] q=0 to about 40, preferably 0 to about 20, more preferably 1 to about 15,

[0182] r=0 to about 30, preferably 0 to about 20, more preferably 0 to about 10,

[0183] s=0 to about 20, preferably 0 to about 15, more preferably 0 to about 10,

[0184] And q+r+s>2,

[0185] R 4 is selected from hydroxy, alkoxy, alkylcarbonyloxy, hydroxyalkyl, siloxy groups such as triorganosiloxy groups, organosilyl groups, glycidyl groups and glycidyloxy groups,

[0186] - glycidyl and glycidyloxy groups,

[0187] -Organosilyl groups, such as –SiR 1 3, where R 1 independently selected from the groups defined above for formulae (1) and (2); and siloxy groups such as -OSi(R 1 )3, where R 1 are independently selected from the groups defined above for formulae (1) and (2).

[0188] According to this embodiment of the invention, the preferred alkyl group from which group F is selected is selected from linear, branched and cyclic alkyl groups or groups combining linear and cyclic alkyl moieties, or structures combining branched and cyclic structures, in particular selected from linear C1-C22 alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl groups, branched C1-C22 alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl groups, and selected from cyclic C3-C22 alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups. Most preferably, the alkyl group from which group F is selected is selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl or cyclohexyl groups, most preferably selected from methyl.

[0189] According to this embodiment of the invention, the preferred alkenyl groups from which the group F is selected are selected from linear or branched alkenyl groups having at least one terminal CC double bond and cyclic C5 and C6 alkenyl groups, more preferably linear or branched C2-C30 alkenyl groups having at least one terminal CC double bond, even more preferably C2-C30 linear or branched alkenyl groups having a single CC double bond (which is a terminal CC double bond), and most preferably vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups.

[0190] According to this embodiment of the invention, the preferred alkylcarbonyloxy groups from which the group F is selected are selected from alkylcarbonyloxy groups, wherein the alkyl group represents a linear C1-C22 alkyl group such as a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl group, a branched C1-C22 alkyl group such as an isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl group, and a cyclic C3-C22 alkyl group such as a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl group, and most preferably a methyl, ethyl, tert-butyl group and further, a branched alkyl group comprising tertiary carbon atoms bonded to three linear C1-C8 alkyl groups.

[0191] According to this embodiment of the invention, it is preferred when F is selected from polyoxyalkylene groups of the following general formula:

[0192] [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 .

[0193] Among them, it is preferred when q+r+s is in the range of 2 to about 15, and it is particularly preferred when: q is in the range of 2 to about 15, and r and s=0, or r is in the range of 2 to about 15, and q and s=0, or s is in the range of 2 to about 15, and q and r=0.

[0194] It is also preferred when: R 4Selected from hydroxyl, hydroxymethyl, hydroxyethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, methylcarbonyloxy, tert-butylcarbonyloxy, -OSiMe3, -SiMe2-O-SiMe2-CH=CH2, glycidyloxy group or -SiMe3, SiPh3, -SiEt3, -SitBuMe2, -SiMe2 vinyl or -SiMe2 allyl. Wherein, it is also preferred that if R4 represents a glycidyl or glycidyloxy group, the group is preferably selected from a glycidyl group, a glycidyl propyl ether, or an aryl glycidyl ether group. According to this embodiment of the present invention, the preferred glycidyl or glycidyloxy group selected from group F is selected from a glycidyl group, a propylene glycidyl ether and a phenylene glycidyl ether group.

[0195] According to this embodiment of the invention, it is also preferred when: F is selected from the group consisting of an organosilyl group -SiR 1 3 or siloxy groups –OSi(R 1 )3, where R 1 As for R in formula (1) or (2) above 1 More preferably, the organosilyl group SiR 1 3 or siloxy groups –OSi(R 1 )3 in R 1 Independently selected from C1-C8 alkyl groups, C2-C8 alkenyl groups, C6-C20 aryl groups, C7-C20 aralkyl groups or alkylaryl groups. Most preferably, F is an organosilyl group selected from -SiMe3, SiPh3, -SiEt3, -Si(iPr)3, -SitBuMe2, -SiMe2 vinyl, or -SiMe2 allyl, -OSiMe3, -SiMe2-O-SiMe2-CH=CH2, or a siloxy group selected from -OSiPh3, -OSiEt3, -OSi(iPr)3, -OSitBuMe2, -OSiMe2 vinyl, or -OSiMe2 allyl.

[0196] In another preferred embodiment according to the present invention, silica particles are provided, wherein the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophobic silanes.

[0197] According to the invention, the partition coefficient P of a silane of formula (1) or (2) in a 50 / 50 mixture of water and octanol of a compound HLF comprising a -LF- group of said silane is defined as follows: 辛醇 / 水 LogP values ​​at or above about 0.5 are considered hydrophobic:

[0198]

[0199] It is noted that according to the present invention, this definition applies in the following cases: when the group A of the silane has the formula

[0200] –LF,

[0201] And when the silane group A has the following formula

[0202] –{L–[SiR 1 2O] p –SiR 1 2} m –L–F.

[0203] In the latter case, the terminal structural group "-LF" as defined above is considered.

[0204] In the case of a silane of formula (1) carrying two different groups -LF, it is considered hydrophobic when the logP value determined by the average of the partition coefficients of the two compounds HLF is equal to or higher than about 0.5.

[0205] In the experiment, the partition coefficient is measured in a water / n-octanol mixture (water: 50 ml, octanol: 50 ml). 1 mL of the substance to be measured HLF is added to such a mixture at 25°C. The concentration of HLB in each layer is determined by quantitative analytical spectrometry or spectroscopic methods. The method includes, for example, nuclear magnetic resonance spectroscopy (NMR), gas chromatography mass spectrometry (GC / MS), high performance liquid chromatography mass spectrometry (HPLC / MS), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-VIS) and titration techniques.

[0206] Preferably, the logP value of the one or more silanes having formula (1) and / or (2) is in the range of about 0.5 to about 10, more preferably in the range of about 1.0 to about 7, even more preferably in the range of about 1.5 to about 6, still more preferably in the range of about 2.0 to about 5.0, and most preferably in the range of about 2.5 to about 4.5.

[0207] According to this embodiment of the invention, it is also preferred that the hydrophobic silane of formula (1) and / or (2) is functionalized with only one type of hydrophobic functional group selected from the following: an alkyl group, a halogenated alkyl group, in particular a perfluorinated alkyl group, an alkenyl group, a triorganosilyl-terminated alkyl group, a triorganosiloxy-terminated ester group, and an oxycarbonyl alkyl group, in particular a linear C1-C12 alkyl group and an oxycarbonyl alkyl group, wherein the alkyl group of the oxycarbonyl alkyl group is a C1-C12 linear or branched alkyl group.

[0208] In a further preferred embodiment according to the present invention, silica particles are provided in which the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophilic silanes.

[0209] According to the invention, the partition coefficient P as defined above of a silane of formula (1) or (2) in a 50 / 50 mixture of water and octanol of a compound HLF comprising a -LF- group of said silane is 辛醇 / 水 LogP values ​​below about 0.5 are considered hydrophilic.

[0210] In case the silane of formula (1) carries two different groups -LF, it is considered hydrophobic when the logP value determined by the average of the partition coefficients of the two compounds HLF corresponding to the -LF groups of the silane is below about 0.5.

[0211] Preferably, according to the present invention, the logP value of the one or more silanes having formula (1) and / or (2) is in the range of less than about 0.5 to about -10, more preferably in the range of about 0.0 to about -5, even more preferably in the range of about -0.5 to about -3.0, still more preferably in the range of about -1.0 to about -2.5, and most preferably in the range of about -1.0 to about -2.0.

[0212] According to this embodiment of the invention, it is also preferred that the hydrophilic silane of formula (1) and / or (2) is functionalized only with one type of hydrophilic functional group present in the -LF group selected from the following: a polyether group, a CH3-terminated polyether group, a SiMe3-terminated polyether group or an OH-terminated polyether group, a hydroxylated alkyl residue, or a polyhydroxylated alkyl residue.

[0213] In a preferred embodiment according to the invention, the silica particles are functionalized with two or more different silanes of the formula (1) and / or (2).

[0214] The silica particles according to this embodiment can be obtained by functionalizing the silica particles with a mixture of two or more different silanes of formula (1) and / or (2), or by carrying out two or more successive steps, wherein in each step the silica particles are functionalized with one or more silanes of formula (1) and / or (2). The silica particles according to this embodiment of the invention thus carry residues functionalized in different ways, which allows providing the silica particles with unprecedented and very specifically tuned properties. The tuning of the properties can be achieved not only by the choice of the silane of formula (1) or (2) comprising a specific functional group, but also by the combination of two or more specific silanes, and by adjusting the ratio of different chains carrying said functional groups introduced by the reaction of the silica particles with different silanes of formula (1) and / or (2). For example, the silica particles can be rendered hydrophobic by functionalization with silanes of formula (1) or (2) in which the radical F is a linear alkyl chain with more than 10 C atoms or a perfluorinated alkyl chain with more than 10 C atoms, and at the same time the silica particles can be incorporated into the coating matrix by functionalization with silanes of formula (1) or (2) in which the radical F carries one or more coating matrix reactive groups, such as acrylate groups, methacrylate groups or isocyanate groups, which lead to the incorporation of the silica particles into the coating matrix during curing. According to the invention, it is preferred when the difference in logP values ​​of the at least two silanes of formula (1) and / or (2) used for functionalizing the silica particles is about 0.8 or more, more preferably the difference in logP values ​​is about 1.5 or more, even more preferably about 2.5 or more, still further preferably about 3.5 or more, and most preferably about 5.0 or more.

[0215] Among them, it is preferred when the silane of formula (1) or (2) with a higher logP value is a hydrophobic silane (ie, logP ≥ about 0.5), and the silane with a lower logP value is a hydrophilic silane (ie, logP < about 0.5).

[0216] Note that the difference in logP values ​​for different silanes as defined above is obtained by subtracting the lower logP value from the higher logP value for the silane in question.

[0217] In a further preferred embodiment of the invention, the individual silica particles are functionalized by one or more hydrophobic silanes of the formula (1) and / or (2) and by one or more hydrophilic silanes of the formula (1) and / or (2).

[0218] Here, the definitions of "hydrophobic silane" and "hydrophilic silane" are the same as above, and this definition is valid for all embodiments according to the present invention.

[0219] In this embodiment, each silica particle is functionalized by one or more hydrophobic silanes of formula (1) and / or (2), for example silanes in which the group F is an unsubstituted alkyl group with more than 6 C atoms, a perfluorinated alkyl group with more than 3 C atoms, or an alkyl group carrying only triorganosilyl groups with more than 6 C atoms as substituents in the alkyl chain; and one or more hydrophilic silanes, for example silanes in which the group F is a hydroxyl-terminated poly(alkoxy oxide), a hydroxylated or polyhydroxylated alkyl group, or an alkyl group substituted by one or more carboxylate groups. By appropriately selecting the group F and the amount of the respective silanes used to functionalize the silica particles, the surface properties of the coating comprising the silica particles can be adjusted in a remarkable manner. Similarly, by appropriately selecting the hydrophobic and hydrophilic silanes used to functionalize the silica particles, different properties and requirements of the formulation of the coating composition, such as compatibility with other components and rheological properties, can be addressed.

[0220] In another preferred embodiment according to the invention, the silica particles are functionalized with two or more different silanes of formula (1) and / or (2), wherein in one or more of the silanes of formula (1) and / or (2), the group F comprises one or more coating matrix reactive groups, and wherein the one or more other silanes of formula (1) and / or (2) are exclusively hydrophilic silanes or exclusively hydrophobic silanes.

[0221] According to this embodiment, the one or more coating matrix reactive groups included in the group F of the silane of formula (1) and (2) are preferably selected from alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0222] By selecting the silane for functionalization in this way, silica particles are provided which can be incorporated into the coating matrix of a cured coating composition via reaction of the one or more coating matrix reactive groups and which can simultaneously exhibit hydrophilic or hydrophobic properties due to the presence of one or more hydrophilic groups or one or more hydrophobic groups introduced, for example, by functionalization with a silane having formula (1) and / or (2), respectively.

[0223] Preferably, the one or more further hydrophilic silanes have a group F which contains only hydrophilic functional groups selected from carboxylic acids, hydroxyl groups, phosphine groups, amino groups, polyether groups and thiol groups, and otherwise unfunctionalized alkyl groups carrying such moieties.

[0224] Similarly, preferably, the one or more other hydrophilic silanes have a group F containing only hydrophobic functional groups selected from ester groups, alkyl groups, alkenyl groups, halogen groups and triorganosilyl groups, and otherwise unfunctionalized alkyl groups carrying such moieties.

[0225] In a further preferred embodiment according to the present invention, the silica particles are functionalized with two or more different silanes of formula (1) and / or (2), wherein in one or more of the silanes of formula (1) and / or (2), the group F comprises one or more coating matrix reactive groups, and the one or more other silanes of formula (1) and / or (2) are exclusively hydrophilic silanes, wherein the group F of the one or more hydrophilic silanes comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups comprising quaternary ammonium groups, hydrocarbon groups comprising carboxylate groups, and hydrocarbon groups comprising one or more amino groups.

[0226] Preferred combinations of coating matrix reactive groups and hydrophilic groups present in group F of the hydrophilic silane of formula (1) and / or (2) for functionalizing silica particles according to this embodiment are: polyether groups, in particular OH-terminated polyether groups, alkyl-terminated polyether groups, in particular methoxy-, ethoxy-, propoxy- and butoxy-terminated polyether groups, and trialkylsiloxy-terminated polyether groups, in particular -OSiMe3, -OSiEt3, -OSi(iPr)3 groups, in combination with methacrylate or acrylate groups; polyether groups as described in detail above in this embodiment in combination with isocyanate groups; and polyether groups as described in detail above in this embodiment in combination with epoxy groups or alkenyl groups.

[0227] In a further preferred embodiment according to the invention, the silica particles are functionalized with two or more different silanes of formula (1) and / or (2), wherein in one or more of the silanes of formula (1) and / or (2), the group F comprises one or more coating matrix reactive groups and the one or more other silanes of formula (1) and / or (2) are exclusively hydrophobic silanes, and wherein the group F of the one or more hydrophobic silanes comprises one or more hydrophilic groups selected from the group consisting of linear or branched unsubstituted alkyl groups, alkyl groups including difluoromethylene and / or trifluoromethyl groups, in particular perfluorinated alkyl groups, alkyl groups carrying triorganosilyl groups, organosiloxy groups, alkenyl groups without heteroatom-containing substituents or aromatic groups, in particular alkaryl groups and aralkyl groups.

[0228] Preferred combinations of coating matrix reactive groups and hydrophobic groups present in group F of the hydrophilic silane of formula (1) and / or (2) for functionalizing silica particles according to this embodiment are: isocyanate groups in combination with unsubstituted alkyl groups or fluorinated alkyl groups, acrylate or methacrylate groups in combination with unsubstituted alkyl groups or fluorinated alkyl groups, or epoxy groups in combination with unsubstituted alkyl groups or fluorinated alkyl groups.

[0229] In another preferred embodiment according to the invention, the silica particles comprise at least two different types of silica particles functionalized with silanes of the formula (1) and / or (2).

[0230] According to this embodiment, different types of silica particles are used as starting material to functionalize the silica particles with one or more silanes of formula (1) and / or (2).

[0231] For example, this embodiment is met if silica particles are provided by: having agglomerates D in the range of about 50 to about 150 μm 50 The fumed silica particles having an average particle size of D in the range of about 1 to about 150 nm are functionalized with one or more silanes having formula (1) and / or (2). 50 Colloidal silica particles of average particle size are individually functionalized with one or more silanes having formula (1) and / or (2), and the functionalized silica particles thus obtained are then mixed.

[0232] Preferably, the two or more different kinds of silica particles are each functionalized by a different silane or a different mixture of silanes.

[0233] According to the present invention, it is preferred that a silica particle mixture comprising two or more kinds of different types of silica particles obtained by separate functionalization with different silanes is provided as follows:

[0234] - mixing at least two different types of functionalized silica particles obtained by functionalizing one common type of silica particles used as precursors, which are individually each functionalized with a specific silane or a mixture of silanes of formula (1) and / or (2) as defined in the preceding embodiments, said silane being different from at least one of the specific silane(s) used to functionalize the other silica particle precursors; or alternatively

[0235] - by mixing at least two different types of functionalized silica particles obtained from different types of silica particles used as precursors, which are each individually functionalized with a specific silane or a mixture of silanes of formula (1) and / or (2) as defined in the preceding embodiments, said silane being different from at least one of the specific silane(s) used to functionalize the other silica particle precursors.

[0236] According to this embodiment, it is generally preferred when the silica particles provided include two different types of silica particles, which can be obtained as follows: by separately functionalizing a common type of silica particle precursor with two different types of silanes or two different silane mixtures, or by separately functionalizing two different types of silica particle precursors with two different types of silanes or two different silane mixtures, each followed by mixing the different types of silica particles in a specific weight ratio.

[0237] According to the invention, it is further preferred that the at least two different types of silica particles functionalized with different silanes differ in the radical F of the silane of the formula (1) and / or (2) used to functionalize the respective type of silica particles.

[0238] It is preferred when the silica particles comprise: one or more types of particles functionalized by one or more types of silanes of formula (1) and / or (2) in which the group F represents a polyether group; and one or more other types of particles functionalized by one or more types of silanes of formula (1) and / or (2) in which the group represents an alkyl group.

[0239] It is also preferred when one or more types of silica are functionalized with silanes of formula (1) and / or (2) having a group F comprising a polyether group, while one or more other types of silica particles are functionalized with silanes of formula (1) and / or (2) having a group F comprising one or more coating matrix reactive groups, or when one or more types of silica particles are functionalized with silanes of formula (1) and / or (2) having a group F comprising one or more ester groups, alkyl groups or fluorine-containing moieties, while one or more other types of silica particles are functionalized with silanes of formula (1) and / or (2) having a group F comprising one or more coating matrix reactive groups.

[0240] The functionalization of the radicals F of the silanes of the formula (1) and / or (2) by different types of functional groups leads to different polarities of the silanes used for the functionalization, and

[0241] This results in different polarities of the functionalized silica particles thus obtained.

[0242] In a further preferred embodiment according to the present invention, silica particles are provided which comprise at least two types of silica particles functionalized with different silanes having different polarities.

[0243] The term "silanes having different polarities" refers to silanes having a different logP value of the partition coefficient P of the group HLF corresponding to the structural unit -LF of the silane, as defined above for the determination of the hydrophilicity or hydrophobicity of the silane.

[0244] According to the present invention, it is preferred when the difference in logP values ​​of the at least two silanes used to functionalize the at least two types of silica is about 0.8 or more, more preferably the difference in logP values ​​is about 1.5 or more, even more preferably about 2.5 or more, still further preferably about 3.5 or more, and most preferably about 5.0 or more.

[0245] Among them, it is preferred when the silane of formula (1) or (2) with the higher logP value is a hydrophobic silane (i.e. logP ≥ about 0.5), while the silane with the lower logP value is a hydrophilic silane (i.e. logP < about 0.5). Typically, the difference is obtained by subtracting the lower logP value from the higher logP value obtained for the silane in question.

[0246] In a preferred embodiment according to the present invention, silica particles are provided, wherein the one or more silanes having formula (1) and / or (2) are selected from:

[0247] R 1 x R 2 3-x Si–L–[SiR 1 2O] p –SiR 1 2–L–[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0248] R 1 x R 2 3-x Si–L–[SiR 1 2O] p –SiR 1 2–L–R 5

[0249] HN{–SiR 1 2–L–[SiR 1 2O] p–SiR 1 2–L–[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4}2

[0250] HN{–SiR 1 2–L–[SiR 1 2O] p –SiR 1 2–L–R 5}2

[0251] R 1 x R 2 3-x Si–L–[SiR 1 2O] p –SiR 1 2–L–R 5

[0252] Where R 1 , R 2 , R 4 , L, p, q, r, s are each as defined above, and R 5 Selected from alkyl, alkylcarbonyloxy, glycidyl, glycidyloxy, organosilyl such as

[0253] -SiMe2-O-SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, and -SitBuPh2.

[0254] According to the present invention, it is preferred when q+r+s is in the range of about 2 to about 15, and it is particularly preferred when q is in the range of about 2 to about 15, and r and s=0, or r is in the range of about 2 to about 15, and q and s=0, or s is in the range of about 2 to about 15, and q and r=0.

[0255] According to the present invention, when R 4 It is also preferred if R is selected from hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, methylcarbonyloxy, tert-butylcarbonyloxy, -OSiMe3, -SiMe2-O-SiMe2-CH=CH2, a glycidyloxy group or -SiMe3, SiPh3, -SiEt3, -SitBuMe3, -SiMe2 vinyl, or -SiMe2 allyl. 5is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methylcarbonyloxy, ethylcarbonyloxy, tert-butylcarbonyloxy, glycidyl, glycidyloxy, -SiMe2-O-SiMe2-CH=CH2, -SiMe3, SiEt3, -Si(iPr)3 or -SitBuMe2 is preferred, and most preferably R 5 Selected from methyl, glycidyloxy, -SiMe3 or -SiMe2-O-SiMe2-CH=CH2.

[0256] It is also preferred according to the invention when L here is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4-alkylene group, most preferably L is -(CH2)2- and / or -(CH2)3-, in each case optionally bonded to F via an oxygen atom.

[0257] In another preferred embodiment according to the present invention, silica particles are provided, wherein R 2 It is an alkoxy group.

[0258] Group R 2 is defined as a hydrolyzable group, and its presence in the silane of formula (2) is required to enable the group A to be attached to the surface of the silica particles via the silicon atom by condensation of one, two or three silanol OH-groups on the silica surface with the silyl groups of the silane to form siloxane units. 2 The ability of the silane to condense with the silica surface and thus become attached to functionalize the silica particles, and in particular the rate of such reaction, depends on the hydrolyzable group R 2 According to the present invention, alkoxy groups are preferred hydrolyzable groups R 2 , so the conditions for the hydrolysis of these groups in the presence of OH groups are well known to the skilled person. Further, silyl groups with one, two or three alkoxy groups can be easily introduced into the target compound as follows: by hydrosilylation reaction of hydroalkoxysilane with any compound containing unsaturated CC bonds, in particular alkenylpolyorganosiloxane, alkenylcarbosilane or alkenylcarbosiloxane, wherein the alkenyl group is preferably a vinyl group; or by hydrosilylation reaction of alkoxyalkenylsilane, preferably alkoxyvinylsilane with hydrosilyl compounds, in particular with hydropolyorganosiloxane, hydrocarbosilane or hydrocarbosiloxane. Since many hydroalkoxysilanes and alkenylalkoxysilanes are commercially available, the production and processing methods of these compounds are well known to the skilled person.

[0259] According to this embodiment, it is preferred that the silane of formula (2) carries two or three alkoxy groups R2, and more preferably that the silane of formula (2) carries three alkoxy groups as hydrolyzable groups R2.

[0260] Wherein, the alkoxy group is independently selected from a linear C1-C22 alkoxy group such as a methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy or n-octyl group, a branched C1-C22 alkoxy group such as an isopropoxy, isobutoxy, tert-butoxy, isopentyloxy, tert-pentyloxy, neopentyloxy and 2-ethylhexyloxy group, and a cyclic C3-C22 alkoxy group such as a cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and cycloheptyloxy group, preferably the alkoxy group is selected from a methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, isopropoxy, isobutoxy, tert-butoxy, neopentyloxy, cyclopentyloxy or cyclohexyloxy group, still more preferably the alkoxy group is selected from a methoxy, ethoxy or isopropoxy group, and most preferably the alkoxy group is selected from a methoxy group.

[0261] The present invention also relates to specific silanes, in particular silanes of formula (1) as defined above for the functionalization of silica particles. In a preferred embodiment according to the present invention, there is provided a silane compound of the formula

[0262] HN[–SiR 1 2–A]2 (1),

[0263] When M is L, the group F contains at least one heteroatom, such as N, O, P, S, Si, or a halogen atom such as fluorine, chlorine, bromine or iodine.

[0264] These silanes are particularly useful for the production of functionalized silica particles.

[0265] Preferably, compounds of formula (1) are provided wherein M is L and the group F contains at least one heteroatom, such as N, O, P, S, Si, or a halogen atom such as fluorine, chlorine, bromine or iodine.

[0266] More preferably, in the compound of formula (1), M is L and group F contains one or more oxygen atoms; more preferably F contains one or more oxygen atoms, wherein at least one oxygen atom is an oxygen atom of an ether or ester moiety; even more preferably group F contains three or four oxygen atoms, wherein at least three oxygen atoms are oxygen atoms of an oligo- or poly(oxyalkylene) group; still more preferably group F contains five or more oxygen atoms, wherein at least five oxygen atoms are oxygen atoms of an oligo- or poly(oxyalkylene) group; and even more preferably group F contains a poly(oxyethylene) or poly(oxypropylene) unit comprising five or more oxygen atoms.

[0267] Most preferably, in the compound of formula (1), M is L, and

[0268] F=-(O–CH2CH2) 4-12 -OH, and in particular the compound is represented by the formula

[0269] HN(–SiMe2–(CH2) 2-4 –(O–CH2CH2) 4-12 –OH)2,

[0270] More specifically, the compound is represented by the formula

[0271] HN(–SiMe2–(CH2)2–(O–CH2CH2) 4-12 –OH)2 or HN(–SiMe2–(CH2)3–(O–CH2CH2) 4-12 –OH)2, and most particularly, of the formula HN(–SiMe2–(CH2)3–(O–CH2CH2) 10 –OH)2, or

[0272] F=–(O–CH2CH2) 4-12 -OMe, and in particular the compound is represented by the formula

[0273] HN(–SiMe2–(CH2) 2-4 –(O–CH2CH2) 4-12 -OMe)2, more particularly the compound is represented by the formula

[0274] HN(–SiMe2–(CH2)2–(O–CH2CH2) 4-12 –OMe)2 or HN(–SiMe2–(CH2)3–(O–CH2CH2) 4-12 –OMe)2, and most particularly of the formula HN(–SiMe2–(CH2)3–(O–CH2CH2) 7.5 –OMe)2, or

[0275] F=–(O–CH2CH2) 4-12 -OSiMe3, and in particular the compound is represented by the formula

[0276] HN(–SiMe2–(CH2) 2-4 –(O–CH2CH2) 4-12 -OSiMe3)2, more particularly the compound is represented by the formula

[0277] HN(–SiMe2–(CH2)2–(O–CH2CH2) 4-12 – OSiMe3)2 or

[0278] HN(–SiMe2–(CH2)3–(O–CH2CH2) 4-12 –OSiMe3)2, and most particularly represented by

[0279] HN(–SiMe2–(CH2)3–(O–CH2CH2) 10 OSiMe3)2.

[0280] According to the invention, it is also preferred that, in the compounds of formula (1) according to this embodiment, group F contains an oxycarbonylalkyl group of the structure

[0281] F=-(OC(O)-alkyl,

[0282] wherein the alkyl group is a linear, branched or cyclic C1-C12 alkyl group, preferably a linear alkyl group selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl group, or a branched alkyl group selected from isopropyl, sec-butyl, tert-butyl, neopentyl or from the formula -CR a R b R c An alkyl group, wherein the residue R a , R b and R c is selected from linear alkyl groups and hydrogen and R a , R b and R c Two or more of are alkyl groups, more preferably the alkyl groups are linear alkyl groups selected from ethyl or methyl, or from the formula -CR a R b R c , where R c is hydrogen or methyl, and R a and R b is a linear alkyl group having a total of about 3 to about 11 carbon atoms. Most preferably, in the formula -CR a R b R c In the alkyl group, R c is methyl, and R a and R b is a linear alkyl group having a total of 9 or 10 carbon atoms.

[0283] Further preferred compounds having formula (1) according to this embodiment of the present invention are, for example, compounds represented by the following formula

[0284] HN(–SiMe2–(CH2) 2-3 –(O–C(O)alkyl))2, especially

[0285] HN(–SiMe2–(CH2)2–(O–C(O)alkyl)2 and HN(–SiMe2–(CH2)3–(OC(O)alkyl)2, even more particularly HN(–SiMe2–(CH2)2–(O–C(O)-CMeR a R b ))2 and HN(–SiMe2–(CH2)3–(OC(O)-CMeR a R b ))2, where R a and R b is a linear alkyl group and has a total of about 3 to about 9 C atoms.

[0286] In a further preferred embodiment according to the present invention, a compound of formula (1) is provided, wherein M is L, and the group F contains one or more silicon atoms, more preferably the group F contains one or more silicon atoms, wherein one of the silicon atoms is a terminal triorganosilyl group or a terminal triorganosiloxy group such as a silicon atom of -SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, -SitBuPh2, even more preferably the terminal triorganosilyl group of F is selected from -SiM e2-CH=CH2, -SiMe3, or -SiEt3 and is bonded to an oxygen atom, or the terminal triorganosiloxy group is selected from -OSiMe3, -OSiEt3, and -OSi(iPr)3 and is bonded to a carbon atom, and still more preferably the terminal triorganosilyl group is selected from -SiEt3 or -SiMe3 and constitutes an end capping group of a group selected from a poly(ethylene oxide) group, a poly(propylene oxide) group, or a mixed poly(propylene oxide)-poly(ethylene oxide) group, or it constitutes an end group of a C1-C12 linear alkyl group or a C1-C12 alkenyl group.

[0287] Most preferably, in the compound of formula (1), M is L, and

[0288] F=-(O–CH2CH2) 4-12 – OSiMe3, or

[0289] F=-(O–CH2CH2CH2) 4-12 – OSiMe3, or

[0290] F=-(O–CH2CH2) 4-12 – OSiEt3, or

[0291] F=-(O–CH2CH2CH2) 4-12 –OSiEt3.

[0292] Particularly preferred compounds of formula (1) according to this embodiment are compounds of the formula

[0293] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2CH2) 4-12 –OSiMe3)2, especially

[0294] HN(–SiMe2–(CH2)2–(O–CH2CH2CH2) 10 –OSiMe3)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2CH2) 10 – OSiMe3)2, or

[0295] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2) 4-12 –OSiEt3)2, especially

[0296] HN(–SiMe2–(CH2)2–(O–CH2CH2) 7.5 –OSiEt3)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2) 7.5 – OSiEt3)2, or

[0297] HN(–SiMe2–(CH2) 2-3 –(O–CH2CH2CH2) 4-12 –OSiEt3)2, especially

[0298] HN(–SiMe2–(CH2)2–(O–CH2CH2CH2) 10 –OSiEt3)2 and HN(–SiMe2–(CH2)3–(O–CH2CH2CH2) 10 –OSiEt3)2.

[0299] In another preferred embodiment according to the present invention, a silane of the general formula (1) as defined above is provided, wherein the optional substituents of the hydrocarbon group F are selected from alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate groups, ketone, dione, 1,3-diketone, dicarboxyl, 1,3-dicarboxyl, diester, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0300] The present invention also relates to a process for producing functionalized silica particles, in particular to a process for producing functionalized silica particles as described above.

[0301] According to the present invention, the present invention provides a process for producing functionalized silica particles, which comprises

[0302] - contacting the silica particles with one or more silanes of formula (1) and / or (2) as defined above:

[0303] HN[–SiR 1 2–A]2 (1),

[0304] and / or

[0305] R 1 x R 2 3-x Si–A (2).

[0306] According to this embodiment, the silica particles used have a D 50 The average particle size may be up to about 1000 μm, as measured by dynamic light scattering (DLS) or TEM (transmission electron microscopy). However, it is preferred that the silica particles have a D value of less than about 800 μm, and even more preferably less than about 500 μm. 50 The average particle size, and preferably, the silica particles are fumed silica particles or colloidal silica particles, especially colloidal silica particles in suspension.

[0307] According to this embodiment, the one or more silanes of formula (1) and / or (2) used to functionalize the silica particles are as defined in the above embodiment involving silica particles functionalized with one or more silanes of formula (1) and / or (2).

[0308] According to the present invention, the method of contacting the silica particles with one or more silanes of formula (1) and / or (2) as defined above is not limited to any particular method and such methods will be known to those of ordinary skill in the art.

[0309] It is preferred that the silica particles and the one or more silanes used for functionalization are contacted in an open or closed reaction vessel; further, it is preferred that when a mixing device is used, a homogeneous reaction mixture is formed; and it is also preferred that, depending on the one or more silanes used, the reaction vessel can be cooled or heated. Such a mixing device can be a mixer or a stirrer, wherein all known types of industrial reactors, blenders and mixers can be used, such as ribbon mixers, twin-shaft mixers, vertical mixers, mixing reactors, or drum blenders; the starting materials can also be contacted by using a kneader, a ball mill or a screw-type extruder. Depending on the one or more silanes used, the starting materials are preferably contacted at an elevated temperature of at least about 40°C.

[0310] The reaction carried out by contacting the silica particles with the one or more silanes of formula (1) and / or (2) can be carried out in the presence of one or more solvents and it can be carried out under reduced or elevated pressure, wherein an inert atmosphere can be applied when contacting the aforementioned reaction partners.

[0311] The contacting can be performed as a batch process or as a continuous process.

[0312] The time for contacting the silica particles with one or more silanes of formula (1) and / or (2) is not limited in a particular way, however, preferably, in the case of applying a batch process, the conditions are selected to obtain the desired degree of functionalization of the surface of the silica particles within a reaction time of less than about 6 hours, more preferably within less than about 4 hours, and even more preferably within less than about 2 hours.

[0313] In a preferred embodiment according to the present invention, a process for producing functionalized silica particles is provided, wherein the contacting of the silica particles with the one or more silanes of formula (1) and / or (2) is in the presence of a solvent.

[0314] Generally, the process for producing functionalized silica particles can be carried out in the presence or absence of one or more solvents, wherein preferably the process is carried out in the presence of one or more solvents, even more preferably in the presence of one solvent for a single compound rather than a mixture of compounds.

[0315] According to the present invention, the term "solvent" refers to any compound or mixture thereof which is in liquid state under the reaction conditions and which is suitable as a medium for functionalizing silica particles by contacting them with one or more compounds of formula (1) and / or (2). Preferably, the solvent is an organic compound or a mixture of organic compounds.

[0316] Therefore, the solvent is preferably inert to the silica particles used as starting materials and the compound silane of formula (1) and / or (2) according to the invention under the reaction conditions. In addition, the starting materials of formula (1) and (2) are preferably soluble in the solvent or completely miscible with the solvent.

[0317] Preferably, the solvent is selected from the group of organic solvents consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, diorganic carbonates, ethers, ketones, alcohols, esters and combinations thereof.

[0318] According to the invention, preferred aliphatic hydrocarbons are selected from linear and branched C5-C24-alkyl groups, for example pentane, hexane, heptane, octane and mixtures thereof such as, for example, high-boiling or low-boiling petroleum ether;

[0319] Preferred alicyclic hydrocarbons are selected from C5-C24 cycloalkanes, such as cyclopentane, cyclohexane or cycloheptane;

[0320] Preferred aromatic hydrocarbons are alkyl-substituted benzene-based aromatic compounds such as toluene, xylene, mesitylene, tert-butylbenzene and ethylbenzene;

[0321] Preferred diorganocarbonates are dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate;

[0322] Preferred ethers are tert-amyl ethyl ether, cyclopentyl ethyl methyl ether, di-tert-butyl ether, di(propylene glycol) methyl ether, dibutyl ether, diisopropyl ether, dimethoxyethane, 1,4-dioxane, 2-(2-methoxyethoxy)ethanol, methyl tert-butyl ether, 2-methyltetrahydrofuran, morpholine, polyethylene glycol, propylene glycol methyl ether, tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydropyran, and 2,2,5,5-tetramethyltetrahydrofuran;

[0323] Preferred ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, or methyl amyl ketone;

[0324] Preferred alcohols are secondary or tertiary alcohols, such as 1-methoxy-2-propanol or tert-butanol; preferred esters are acetates of linear or branched C2-C24 alcohols, such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, tert-butyl acetate, isopentyl acetate, hexyl acetate or triacetin.

[0325] It is further preferred that the solvent used has a high boiling point, which according to the invention is a boiling point above about 100° C. at standard pressure, as is the case, for example, with toluene, o-, m- and p-xylene, dioxane and 1-methoxy-2-propanol.

[0326] According to this embodiment, it is preferred when the one or more solvents are selected from toluene, xylene, dioxane and 1-methoxy-2-propanol.

[0327] A solvent may be included to improve the functionalization reaction in terms of homogeneity of the reaction mixture and heat transfer during the reaction.

[0328] In a further preferred embodiment according to the present invention, the process for producing silica particles is carried out at a temperature above about 40°C, more preferably at a temperature above about 50°C, most preferably at a temperature in the range of about 55°C to about 120°C.

[0329] By applying elevated temperatures, the reaction rate of the condensation reaction occurring in the functionalization of the silica particles can be increased. However, to prevent undesirable side reactions, the temperature is preferably maintained below about 250° C., more preferably below about 180° C., even more preferably below about 150° C., and most preferably at or below about 120° C.

[0330] In another preferred embodiment according to the present invention, the silica particles used as starting material in the process for producing functionalized silica particles are chosen from colloidal silica particles having an average particle size in the range of about 1 to about 300 nm, preferably about 1 to about 150 nm, as determined by dynamic light scattering (DLS), or from pyrogenic silica having an average particle size in the range of about 1 to about 600 μm, preferably about 20 to about 400 μm, as determined by DLS or transmission electron microscopy (TEM).

[0331] As mentioned above, the silica particles can be selected from silica particles in colloidal form, i.e. as primary particles, typically in dispersion, or from silica particles as agglomerates of primary particles, which are typically suitable, for example, for pyrogenic silica particles. Although the process for producing functionalized silica particles according to the invention can be carried out on all types of silica particles to obtain functionalized silica particles functionalized by one or more silanes of formula (1) and / or (2) according to the invention, it is preferred that the silica particles have a D in the range of about 1 nm to about 800 μm as determined by dynamic light scattering. 50 Average particle size particle size, where D of colloidal silica primary particles 50 The average particle size is more preferably in the range of about 1 to about 300 nm, even more preferably in the range of about 2 to about 150 nm, and most preferably in the range of about 5 to about 50 nm, or wherein the silica agglomerate particles have a D 50 The average particle size is more preferably in the range of about 1 to about 800 μm, even more preferably about 10 to about 300 μm, and most preferably about 50 to about 150 μm. Particle size can alternatively be determined by TEM; however, DLS is a useful tool for measuring D 50 Preferred means of particle size value.

[0332] In a further preferred embodiment of the process for producing functionalized silica particles according to the present invention, the contacting of the silica particles with the one or more silanes of formula (1) and / or (2) is in the presence of a condensation catalyst selected from the group consisting of organotin, organozinc, organotitanium and organoboron compounds, primary amines, secondary amines, tertiary amines, ammonium compounds, cyclic amines, aliphatic amines, metal oxides, metal hydroxides, metal carbonates, ammonia and combinations thereof, preferably organotin and organotitanium compounds.

[0333] A condensation catalyst may be used to increase the rate of the condensation reaction, particularly to achieve a suitable reaction rate at a moderate reaction temperature.

[0334] In a preferred embodiment according to the invention, in the silane of formula (1), the group M is L.

[0335] According to this embodiment, the silane of formula (1) contains no oligo- or polysiloxy moieties.

[0336] In another preferred embodiment of the process for producing functionalized silica particles according to the invention, in the silane of formula (1) and / or (2), F is selected from:

[0337] -alkyl,

[0338] -alkenyl,

[0339] -alkylcarbonyloxy,

[0340] - a polyoxyalkylene group, which preferably has the following general formula:

[0341] [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0342] in

[0343] [-OC2H4] represents an ethyleneoxy unit,

[0344] [-OC3H6] represents a propyleneoxy unit, and

[0345] [-OC4H8] represents a butyleneoxy unit,

[0346] q=0 to about 40, preferably 0 to about 20, more preferably 1 to about 15,

[0347] r=0 to about 30, preferably 0 to about 20, more preferably 0 to about 10,

[0348] s=0 to about 20, preferably 0 to about 15, more preferably 0 to about 10,

[0349] And q+r+s>2,

[0350] R 4 is selected from hydroxy, alkoxy, alkylcarbonyloxy, hydroxyalkyl, siloxy groups such as triorganosiloxy groups, organosilyl groups, glycidyl groups and glycidyloxy groups,

[0351] - glycidyl and glycidyloxy groups,

[0352] -Organosilyl groups, such as –SiR 1 3, where R 1 independently selected from the groups defined above for formulae (1) and (2), and siloxy groups such as -OSi(R 1 )3, where R 1 are independently selected from the groups defined above for formulae (1) and (2).

[0353] In a further preferred embodiment of the process for producing functionalized silica particles according to the invention, the group F of the one or more silanes of formula (1) and / or (2) comprises at least one moiety selected from the group consisting of a polyether moiety, an ester moiety and a coating matrix reactive moiety, such as an olefinic, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (—COOH), amino, alkoxysilyl and isocyanate group, ketone, dione, 1,3-diketone, dicarboxyl, 1,3-dicarboxyl, diester, 1,3-diester, nitro (—NO2), cyano (—CN), alkylsulfonyl fluoride group, and donor and acceptor groups in Michael addition reactions.

[0354] In general, all silanes of the formula (1) or (2) which are described above as being preferred for providing functionalized silica particles are likewise preferred in the process according to the invention for producing functionalized silica particles.

[0355] In a further preferred embodiment of the invention, in the process for producing functionalized silica particles, the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophobic silanes, or the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophilic silanes.

[0356] According to this embodiment, the partition coefficient P of the compound HLF based on the -LF- group including silane in a 50 / 50 mixture of water and octanol is 辛醇 / 水 The same definitions of "hydrophobic silane" and "hydrophilic silane" apply, with logP values ​​being defined as follows:

[0357]

[0358] For hydrophobic silanes, logP values ​​in the range of about 0.5 to about 10 are preferred, more preferably in the range of about 1.0 to about 7, even more preferably in the range of about 1.5 to about 6, still more preferably in the range of 2.0 to about 5.0, and most preferably in the range of about 2.5 to about 4.5.

[0359] For hydrophilic silanes, logP values ​​in the range of about 0.5 to about -10 are preferred, more preferably in the range of about 0.0 to about -5, even more preferably in the range of about -0.5 to about -3.0, still more preferably in the range of about -1.0 to about -2.5, and most preferably in the range of about -1.0 to about -2.0.

[0360] According to this embodiment of the invention, it is preferred that the hydrophobic silane of formula (1) and / or (2) is functionalized by only one type of hydrophobic functional group selected from the following: alkyl groups, halogenated alkyl groups, in particular perfluorinated alkyl groups, alkenyl groups, triorganosilyl-terminated alkyl groups, ester groups, and oxycarbonyl alkyl groups, in particular linear C1-C12 alkyl groups and oxycarbonyl alkyl groups, wherein the alkyl group of the oxycarbonyl alkyl group is a C1-C12 linear or branched alkyl group.

[0361] According to this embodiment of the invention, it is also preferred that the hydrophilic silane of formula (1) and / or (2) is functionalized only by the presence of one type of hydrophilic functional group in the -LF group selected from the following: a polyether group, a CH3-terminated polyether group, a SiMe3-terminated polyether group or an OH-terminated polyether group, a hydroxylated alkyl residue or a polyhydroxylated alkyl residue.

[0362] In another preferred embodiment of the process for producing functionalized silica particles according to this embodiment, the silica particles are contacted with one or more silanes of formula (2), wherein R 2 is an alkoxy group.

[0363] According to this embodiment, it is preferred that the silane of formula (2) carries two or three alkoxy groups R 2 , and more preferably the silane of formula (2) has three alkoxy groups as the hydrolyzable groups R 2 .

[0364] Among them, it is preferred when the alkoxy group is independently selected from a linear C1-C22 alkoxy group such as a methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-hexoxy, n-heptyloxy or n-octyloxy group, a branched C1-C22 alkoxy group such as an isopropoxy, isobutoxy, tert-butoxy, isopentyloxy, tert-pentyloxy, neopentyloxy and 2-ethylhexyloxy group, and a cyclic C3-C22 alkoxy group such as a cyclopropoxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and cycloheptyloxy group, more preferably the alkoxy group is selected from a methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, isopropoxy, isobutoxy, tert-butoxy, neopentyloxy, cyclopentyloxy or cyclohexyloxy group, still more preferably the alkoxy group is selected from a methoxy, ethoxy or isopropoxy group, and most preferably the alkoxy group is selected from a methoxy group.

[0365] In a preferred embodiment of the process for producing functionalized silica particles according to the invention, two or more silanes of formula (1) and / or (2) as defined above are contacted with the silica particles in one step, or wherein two or more silanes of formula (1) and / or (2) are contacted with the silica particles in two or more steps.

[0366] By means of the process according to this embodiment, silica particles are obtained which carry residues functionalized in different ways, which allow to provide the silica particles with unprecedented and very specifically adjusted properties, as already explained above. According to this embodiment, it is preferred to contact the silica particles with at least one or more silanes, hydrophobic or hydrophilic, which provide the silica particles with corresponding surface properties and, in the case of at least one type of silane carrying coating matrix-reactive functional groups, which enables the silica particles to be incorporated into the coating matrix.

[0367] In a further preferred embodiment of the process according to the invention for producing functionalized silica particles, the silica particles are contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix-reactive moieties and with one or more hydrophobic silanes of formula (1) and / or (2) in the absence of hydrophilic silanes of formula (1) and / or (2), or

[0368] wherein silica particles are contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and with one or more hydrophilic silanes of formula (1) and / or (2) in the absence of a hydrophobic silane of formula (1) and / or (2).

[0369] By such preferred selection of the two or more silanes to be contacted with the silica particles, excellent surface properties of the silica particles can be provided.

[0370] In a still further preferred embodiment of the process for producing functionalized silica particles according to the present invention, the silica particles are contacted with one or more silanes of formula (1) in the presence of at least about 0.5 equivalents of water based on the molar amount of the one or more silanes of formula (1), preferably in the presence of at least about 1.0 equivalents of water, most preferably in the presence of at least about 1.5 equivalents of water based on the molar amount of the one or more silanes of formula (1).

[0371] Depending on the functionalization of the silane and / or the hydrolyzable groups present in the one or more silanes, the presence of water promotes the condensation reaction of the silane with the silica particles to be functionalized.

[0372] In another aspect, the present invention relates to functionalized silica particles comprising one or more monovalent groups A,

[0373] wherein A is a group of formula –M–F,

[0374] Wherein M is selected from L or a group of the formula:

[0375] –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where

[0376] L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4-alkylene group, most preferably L is -(CH2)2- and / or -(CH2)3-,

[0377] R 1 are independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, most preferably R 1 Methyl,

[0378] p=1 to about 9, preferably p=1 or 4, more preferably p=4,

[0379] m=1 to about 20, preferably m=1, and

[0380] F is selected from an optionally substituted linear, cyclic or branched saturated, unsaturated or aromatic hydrocarbon group having up to about 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted by an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group,

[0381] and the group A is bonded to the silica particle via a silicon atom which is connected to the silicon dioxide network of the silica particle via one or more oxygen atoms, wherein the valences of the silicon atom not occupied by a group -A or an oxygen atom are replaced by a substituent R as defined above 1 occupy.

[0382] It is clear to the skilled person that such silica particles correspond to the silica particles as described in the above embodiments, without being limited to silane functionalization by the general formula (1) and / or (2). 1 and in the formula -{L-[SiR 1 2O] p –SiR 1 2} m The specific selection and preferred embodiments of the parameters m and p in —L— are also applicable and preferred for the functionalized silica particles comprising one or more monovalent groups A according to the invention.

[0383] It is expressly pointed out that, in a similar manner as defined above for the silanes of formulae (1) and (2), the term "hydrophobic group A" refers to a group A for which the partition coefficient P of the compound HLF comprising a terminal LF-group of the group A in a 50 / 50 mixture of water and octanol is 辛醇 / 水 The term "hydrophilic group A" refers to a group A for which the logP value of the partition coefficient of the compound HLF comprising the LF-group of group A in a 50 / 50 mixture of water and octanol is lower than 0.5.

[0384] The present invention further relates to the use of the silica particles according to any of the preceding embodiments or obtained by the process described therein for the manufacture of a coating composition.

[0385] Wherein, the term "coating composition" is not particularly limited and refers to any composition used as a covering applied to the surface of an object (commonly referred to as a substrate). The purpose of applying the coating composition may be decorative, functional, or both. The coating obtained by applying the coating composition itself may be a full coverage coating that completely covers the substrate, or it may only cover part of the substrate. Paints and lacquers are such coatings: most of them have the dual purpose of protecting the substrate and being decorative, but may be used only for decoration, or only for the function of protection (e.g., by preventing corrosion).

[0386] Functional coating compositions can be applied to modify the surface properties of a substrate, such as adhesion, wettability, corrosion resistance, sensitivity to dirt, scratch resistance, gloss, wear resistance. In other cases, such as semiconductor device manufacturing (where the substrate is a wafer), the coating resulting from the application of the coating composition adds entirely new properties, such as magnetic response or electrical conductivity, and forms an integral part of the finished product.

[0387] According to the invention, the coating composition is preferably a protective coating composition, i.e. a coating or paint the application of which results in at least some protection of the substrate, selected from coating compositions for sealing and waterproofing wood, coating compositions for sealing surfaces of concrete, film-forming sealants and floor paints, seamless polymer or resin floors, wainscot walls or containment linings, coating compositions for waterproofing and moisture-proofing concrete walls, roof coating compositions, coating compositions for sealing and waterproofing masonry, coating compositions for protecting machinery, equipment and structures, maintenance coating compositions and paints for metals, alloys and concrete, chemical-resistant coating compositions, coating compositions for improving wear resistance, in particular anti-friction, wear and abrasion-resistant coating compositions for rolling bearings, Hard anti-scratch coating compositions on plastics and other materials for reducing scratches and wear losses, barrier coating compositions on concrete, metals and alloys subjected to erosive / abrasive attack, anti-corrosion coating compositions, in particular chassis sealants for automobiles, anti-corrosion coating compositions for protecting equipment and structural steel from degradation, coating compositions for thermal insulation (thermal insulation) and protective fire protection of structural steel, coatings for passive fire protection, coating compositions for insulation, coating compositions for waterproofing paper and waterproofing fabrics, anti-graffiti coating compositions, anti-fog coating compositions, anti-icing coating compositions, anti-fouling coating compositions, easy-to-clean coating compositions, anti-microbial coating compositions for obtaining an antimicrobial surface, and coating compositions for improving the fouling release and anti-fouling properties of surfaces (such as ship hulls).

[0388] The coating compositions leading to the formation of the coating are not particularly restricted with regard to their formulation, as long as they contain the functionalized silica particles according to the invention.

[0389] In a preferred embodiment according to the present invention, the coating composition produced using the functionalized silica particles according to the present invention is a curable coating composition.

[0390] The curable coating composition according to the present invention can be any coating composition that can be cured (it refers to toughening or hardening the polymer material by crosslinking the polymer chain via a chemical process). As mentioned before, the curing process can be achieved by heat, radiation, electron beam or chemical additives, which also includes contact with moisture or oxygen from ambient air, and characteristically causes an increase in viscosity or hardness. The term is also used in the case where the monomer present in the composition has more than one polymerization site and the polymerization and crosslinking of the monomer occur simultaneously. For example, this is the case in the multi-acrylate monomers including several acrylate parts that serve as polymerization and crosslinking sites.

[0391] Further, the term "curable coating composition" according to the present invention refers to a diversified type of composition containing various organic polymers, a mixture of an organic polymer and an organic monomer, or an organic monomer.

[0392] Preferred types of curable coating compositions in which the silica particles according to the invention are used are

[0393] - Epoxy / amine combinations

[0394] -Michael addition curable composition

[0395] - Radical polymerization curable composition

[0396] - a condensation curable composition, and

[0397] - Addition curable compositions.

[0398] According to the present invention, the term "epoxy / amine composition" refers to an epoxy coating composition in which an amine-based hardener is used in the curing process, the amine-based hardener being selected from aliphatic amines, polyamides and amidoamines, alicyclic amines, aromatic amines, thiols, anhydrides, aromatic anhydrides, alicyclic anhydrides, aliphatic anhydrides. In many cases, an additional curing catalyst is present in such a composition, which is mainly selected from Lewis base catalysts such as tertiary amines or Lewis acid catalysts such as boron-based catalysts, quaternary ammonium salts such as tetramethylammonium hydroxide, phosphines such as triphenylphosphine, selected from organozinc, organotin, organoboron, organotitanium compounds, compounds of group V elements such as WCl6, metal oxides, and amines. Such compositions are often able to react at ambient temperatures and are therefore often selected for any application that is sensitive to high temperatures.

[0399] Amine-cured epoxy coatings are prepared by combining an epoxy resin with an appropriate amine hardener. Primary or secondary amine groups attack the carbon atoms of the three-membered epoxy ring, resulting in a ring opening with an amine group and a hydroxyl group. Primary amines form secondary amines, which can react again to form tertiary amines, although at a slower rate. The hardener unit may have two or more amine functional groups, thereby enabling the hardener to crosslink across multiple epoxy resin molecules, thereby increasing the crosslink density and various tolerances of the resulting epoxy. Aliphatic amines react more easily than alicyclic amines and react much more easily than aromatic amines, but the latter less reactive amines tend to form epoxies with much higher temperature resistance. Aromatic amines are no longer frequently used due to the negative health effects of handling these corresponding compounds.

[0400] Each class of amine hardeners has its own advantages and disadvantages in terms of cure speed, chemical resistance, solvent resistance, temperature compatibility, flexibility, viscosity, mechanical strength, crosslink density, color, and toxicity. In addition, each class contains a whole range of individual hardeners that further modify these properties.

[0401] According to the present invention, the term "Michael addition curable composition" refers to a coating composition whose curing involves Michael addition reaction, i.e., the addition of various nucleophiles to (conjugated) unsaturated compounds with electron withdrawing substituents. It allows the synthesis of a wide range of highly complex macromolecules under relatively mild conditions and in a very efficient manner and in often quantitative yields. Basically, any monomer with an activated double bond, such as α,β-unsaturated aldehydes or ketones, vinyl esters, vinyl sulfones, imidazoles, and maleimides, undergo Michael addition with nucleophiles such as thiols, amines or any stabilized carbanions.

[0402] Michael addition reactions can also be used to prepare polymers of various structures. This type of monomer for step-growth polymerization is typically a molecule containing a conjugated bisdiene and a bisdienophile (AA-type and BB-type monomers or comonomers; in this case, the term "A" refers to the "AA-type monomer" such as the conjugated bisdiene present in the reaction with the "BB-type monomer" such as the bisdienophile to obtain "(AABB) n -polymer" other than the group "A" present in the silanes of formula (1) and (2)).

[0403] The term "free radical polymerization curable composition" according to the present invention refers to a composition that is cured by free radical polymerization. Free radical polymerization consists of three basic steps, namely initiation, propagation, and termination. Initiation involves the formation of free radicals, followed by the reaction of free radicals with vinyl monomers, propagation is the rapid and gradual addition of monomers to the growing polymer chain without change of the active center, and termination is the destruction of the growing active center, usually by the combination or coupling of free radicals of two growing polymer chains or by disproportionation. In addition to these three processes, chain transfer may also occur, which is the transfer of the growing active site from the active chain to an inactive (dormant) site, a monomer or a solvent molecule (transfer agent).

[0404] According to the present invention, the term "condensation curable composition" refers to a composition that is cured by polycondensation, which is a form of step-growth polymerization. Small molecules react with each other to form larger structural units, while releasing smaller molecules such as water or methanol as by-products. A well-known example of a condensation reaction is the esterification of carboxylic acids with alcohols. If both parts are difunctional, the condensation product is a linear polymer, and if at least one of the parts is tri- or tetrafunctional, the resulting polymer is a cross-linked polymer (i.e., a three-dimensional network). Adding a monomer with only one reactive group will terminate the growing chain and thus reduce the (average) molecular weight. Therefore, the average molecular weight and the cross-linking density will depend on the functionality of each monomer involved in the polycondensation and its concentration in the mixture.

[0405] Finally, according to the invention, the term "addition curing composition" refers to a polyurethane-based composition which is formed from an organic diisocyanate or polyisocyanate and a diol or polyol compound, which results in urethane bonds (-NH-C(=O)-O-) in the backbone.

[0406] In a further preferred embodiment according to the present invention, the curable coating composition according to the present invention comprises an organic polymer, a mixture of an organic polymer and an organic monomer, or an organic monomer selected from polycarbonates, poly(meth)acrylates, polyolefins, polyurethanes, polyethers, polyesters, polyorganosiloxanes, various types of epoxy resins such as glycidyl-based epoxy resins, novolac-based epoxy resins or aliphatic epoxy resins, and various copolymers and mixtures of polymer compounds, and corresponding monomers, i.e. mono(meth)acrylates, dimethyl carbonates and diols, in particular diphenylmethane derivatives, olefins, and polyisocyanates, or mixtures thereof.

[0407] It is also preferred that the coating composition according to the invention, in particular the curable coating composition according to the invention, optionally comprises further additives such as other photoinitiators, light stabilizers, fillers, in particular carbon black, metal oxide particles and silica particles not according to the invention, functionalized silica compounds other than according to the invention, flame retardants, solvents, curing catalysts, reactive surface agents, colorants, stabilizers, preservatives, light stabilizers, surfactants, leveling agents and other rheological agents.

[0408] According to the invention, the silica particles according to the invention as defined in the above embodiments are used to manufacture a coating composition, preferably a curable coating composition, by mixing the silica particles according to the invention with other components of the coating composition, by adding the silica particles to the finished formulation and mixing, by adding the other components to the silica particles and mixing, or by adding the silica particles at any point during the manufacture of the coating composition and mixing. Any mixing means suitable depending on the type of coating composition manufactured and the equipment used for manufacture can be applied.

[0409] In a preferred embodiment according to the invention, the silica particles according to the invention are used in coating compositions as marine antifouling additives, general antifouling additives, anti-icing additives, antifouling additives, antifogging additives, self-cleaning additives, anti-adhesion, anti-dust, anti-fingerprint, and anti-graffiti additives, in particular as general antifouling additives or antifogging additives.

[0410] Preferably, the silica particles according to the invention are used as a general antifouling additive, in particular as a marine antifouling additive. It has been demonstrated that coating compositions manufactured using the silica particles according to the invention as defined in the above embodiments provide excellent antifouling properties for surfaces, in particular for such surfaces exposed to a marine environment. This makes it highly desirable to use the silica particles according to the invention in the manufacture of curable coatings for ships, hulls, ships, marine concrete structures, underwater concrete structures, wooden marine structures, underwater wooden structures, plastic marine structures and underwater plastic structures, as well as all kinds of buildings, masonry, constructions and equipment exposed to a marine environment.

[0411] Moreover, preferably, the silica particles according to the invention are used as an anti-fog additive, more preferably as an anti-fog additive for coating compositions for the manufacture of coatings for plastic substrates, in particular polycarbonate substrates or PMMA (polymethyl methacrylate) substrates. It has been demonstrated that the coating compositions manufactured using the silica particles according to the invention as defined in the above embodiments provide excellent anti-fog properties to surfaces, in particular when the coating compositions are applied to surfaces of polycarbonate or methacrylate or acrylate substrates, in particular PMMA substrates. This makes it highly desirable to use the silica particles according to the invention in the manufacture of curable coatings for optics, screens and shields or exterior lamps, in particular automotive headlamps.

[0412] The present invention also relates to a coating composition comprising the silica particles according to the present invention as described in the above embodiments.

[0413] As mentioned above, the coating composition according to the present invention is characterized in that it includes the silica particles according to the present invention. The coating composition can be decorative, functional or both, and can be used as a full-cover coating that completely covers the substrate, or it can only cover part of the substrate. Paints and lacquers are such coatings: most of them have the dual purpose of protecting the substrate and being decorative, but can be used only for decoration, or only for the function of protection (for example by preventing corrosion). Therefore, paints and lacquers comprising silica particles according to the present invention are included by this embodiment of the present invention.

[0414] The functional coating composition according to the present invention can be applied to change the surface properties of the substrate, such as adhesion, wettability, corrosion resistance, sensitivity to dirt, scratch resistance, gloss, and wear resistance. In other cases such as semiconductor device manufacturing (where the substrate is a wafer), the coating resulting from the application of the coating composition adds completely new properties, such as magnetic response or conductivity, and forms an essential part of the finished product.

[0415] According to the invention, the coating composition is preferably a protective coating composition as defined above, most preferably a curable protective composition.The coating compositions resulting in the formation of the coating are not particularly limited as far as their formulation is concerned, as long as they contain the functionalized silica particles according to the invention.

[0416] According to the present invention, it is preferred that the coating composition made using the functionalized silica particles according to the present invention is a curable coating composition, in particular a curable epoxy / amine coating composition, a Michael addition curable coating composition, a free radical polymerization curable coating composition, a condensation curable coating composition, and an addition curable coating composition.

[0417] The curable coating composition according to the present invention can be any coating composition that can be cured (it refers to toughening or hardening the polymer material by crosslinking the polymer chain via a chemical process). As mentioned before, the curing process can be achieved by heat, radiation, electron beam or chemical additives, which also includes contact with moisture or oxygen from ambient air, and characteristically causes an increase in viscosity or hardness. The term is also used in the case where the monomer present in the composition has more than one polymerization site and the polymerization and crosslinking of the monomer occur simultaneously. For example, this is the case in the multi-acrylate monomers including several acrylate parts that serve as polymerization and crosslinking sites.

[0418] Further, the curable coating composition according to the present invention includes diversified types of compositions, preferably curable epoxy coating compositions, Michael addition curable coating compositions, free radical polymerization curable coating compositions, condensation curable coating compositions, and addition curable coating compositions, which contain various organic polymers, mixtures of organic polymers and monomers, or monomers, such as all kinds of polycarbonates, poly(meth)acrylates, polyolefins, polyurethanes, polyethers, polyesters, polyorganosiloxanes, various types of epoxy resins such as glycidyl-based epoxy resins, novolac-based epoxy resins or aliphatic epoxy resins, as well as various copolymers and mixtures of polymer compounds, and corresponding monomers, namely mono(meth)acrylates, dimethyl carbonates and diols, especially diphenylmethane derivatives, olefins, and polyisocyanates.

[0419] It is also preferred that the coating composition according to the invention, in particular the curable coating composition according to the invention, optionally comprises further additives, such as other photoinitiators, light stabilizers, fillers, in particular carbon black, metal oxide particles and silica particles not according to the invention, functionalized silica compounds other than according to the invention, flame retardants, solvents, curing catalysts, reactive surface agents, colorants, stabilizers, preservatives, light stabilizers, surfactants, leveling agents, and other rheological agents.

[0420] In a preferred embodiment according to the present invention, the coating composition comprising the silica particles according to the present invention is a condensation-curable coating composition comprising alkoxysilane as a curable component, a free radical polymerization-curable coating composition comprising multi(meth)acrylate as a curable component, or a curable epoxy coating composition containing one or more epoxy compounds and one or more amine compounds as a curable system.

[0421] In another preferred embodiment of the present invention, the coating composition comprising the silica particles according to the present invention is a curable coating composition comprising as a curable component: acrylate, polyorganosiloxane, alkoxysilane, epoxide, amine, hydroxyacrylate, isocyanate, or a combination of one or more of such curable monomers, oligomers or polymers.

[0422] Preferably, the coating composition comprising the silica particles according to the invention comprises an OH-terminated silicone oil, more preferably the coating composition comprising the silica particles according to the invention comprises an OH-terminated silicone oil and one or more silica particles according to the invention containing polyether groups in part F, and most preferably the coating composition comprising the silica particles according to the invention comprises an OH-terminated silicone oil having a chain length (number of silicon atoms in the backbone) in the range of 1 to about 400 and one or more silica particles according to the invention containing polyether groups in part F.

[0423] Also preferably, the coating composition comprising the silica particles according to the invention comprises one or more acrylate or methacrylate resins, more preferably one or more acrylate or methacrylate resins and at least one functionalized silica particle according to the invention containing polyether groups or amino groups in part F, most preferably the coating composition comprising the silica particles according to the invention comprises two or more acrylate or methacrylate resins and at least one functionalized silica particle according to the invention containing polyether groups or amino groups in part F.

[0424] In yet another embodiment according to the present invention, the coating composition comprising the silica particles according to the present invention comprises

[0425] - one or more curable components or binders selected from curable polymers, oligomers or monomers

[0426] - one or more types of functionalized silica particles according to the invention

[0427] - Optionally, one or more light stabilizers

[0428] - Optionally, one or more solvents

[0429] - Optionally, one or more colorants

[0430] - Optionally, one or more surfactants or other rheological additives

[0431] - Optionally, one or more fillers

[0432] - Optionally, one or more curing catalysts

[0433] Preferably, the one or more curative components and / or binders are selected from acrylates, methacrylates, hydroxyacrylates, esters, aromatic compounds, phenols, epoxides, siloxanes or silanes and constitute about 20.0 to about 99.9 weight %, preferably about 30.0 to about 99.5 weight %, more preferably about 40.0 to about 99.0 weight % of the total weight of the coating composition.

[0434] Preferably, the one or more types of functionalized silica particles according to the present invention constitute up to about 90 wt %, more preferably about 0.1 to about 80 wt %, preferably about 0.5 to about 70 wt %, more preferably about 1 to about 60 wt % of the total weight of the coating composition.

[0435] Preferably, the light stabilizer is selected from hindered amine light stabilizers (HALS), benzophenone derivatives, benzotriazole derivatives, triazine derivatives, resorcinol derivatives, and triorganophosphite compounds and constitutes up to about 15 weight % of the coating composition, more preferably about 0.2 to about 10 weight %, even more preferably about 0.5 to about 8 weight %, and most preferably about 1 to about 5 weight % of the total weight of the coating composition.

[0436] Preferably, the solvent is selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, diorganocarbonates, ethers, ketones, alcohols, esters, and combinations thereof, and constitutes up to about 95 weight % of the coating composition, more preferably 0 to about 90 weight %, even more preferably 0 to about 80 weight % of the total weight of the coating composition.

[0437] Preferably, the colorant comprises up to about 5 weight percent of the coating composition, more preferably constituting about 0.01 to about 4.0 weight percent, even more preferably about 0.05 to about 2.0 weight percent, most preferably about 0.1 to about 1.5 weight percent of the total weight of the coating composition.

[0438] Preferably, the curing catalyst is selected from organotin, organozinc, organotitanium and organoboron compounds, primary amines, secondary amines, tertiary amines, ammonium, cyclic amines, aliphatic amines, metal oxides, metal hydroxides, metal carbonates, ammonia and combinations thereof and constitutes up to about 20 weight % of the coating composition, more preferably about 0.1 to about 20.0 weight %, even more preferably about 0.2 to about 5.0 weight %, and most preferably about 1.0 to about 2.0 weight % of the total weight of the coating composition.

[0439] Preferably, the filler is selected from the group selected from unmodified silica, modified silica other than according to the present invention, mica, talc, carbon black, titanium dioxide, calcium carbonate, barium sulfate, calcium carbonate and constitutes up to about 50% by weight of the coating composition, more preferably about 0.5 to about 30.0% by weight, even more preferably about 1.0 to about 20.0% by weight, and most preferably about 2.0 to about 15.0% by weight of the total weight of the coating composition.

[0440] Preferably, the surfactant or other rheological additive comprises about 0.01 to about 5.0 weight percent of the coating composition, more preferably about 0.05 to about 1.0 weight percent, even more preferably about 0.1 to about 0.5 weight percent of the total weight of the coating composition.

[0441] In a preferred embodiment according to the present invention, the coating composition according to the present invention comprises about 0.1 to about 80 wt. %, preferably about 0.5 to about 70 wt. %, more preferably about 1 to about 60 wt. %, still more preferably about 20 to about 55 wt. %, and most preferably about 25 to about 50 wt. % of silica particles according to the present invention as defined in the above embodiments, based on the total weight of the coating composition.

[0442] It is preferred that the coating composition according to the present invention comprises greater than about 1% by weight of the silica particles, because in many cases, if a lower content of the silica particles is applied, the desired effect cannot be fully achieved, and on the other hand, it is preferred that the coating composition comprises less than about 80% by weight of the silica particles according to the present invention, because higher contents of the silica can have a negative impact on crack resistance and fatigue resistance, such as described in: Handbook of Fillers (4th Edition) - 8. The Effect of Fillers on the Mechanical Properties of Filled Materials, by ChemTec Publishing, which is fully incorporated herein by reference. More preferably, the coating composition comprises 3-60% by weight of the silica particles, and even more preferably, the coating composition comprises 25-50% by weight of the silica particles. Note that the optimal content of the silica particles according to the present invention in the coating composition also depends on the specific type of coating composition and the specific application of the coating.

[0443] List of preferred embodiments according to the present invention

[0444] In the following, preferred embodiments according to the present invention are summarized:

[0445] 1. Silica particles functionalized with one or more silanes of formula (1) and / or (2):

[0446] HN[–SiR 1 2–A]2 (1),

[0447] R 1 x R 2 3-x Si–A (2)

[0448] in

[0449] R 1 are independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, most preferably R 1 Methyl,

[0450] R 2 independently selected from hydrolyzable residues, preferably selected from hydrogen, hydroxyl, hydrocarbylcarbonyloxy groups such as acyloxy groups, halogen groups, amino groups, hydrocarbyloxy groups such as alkoxy or aryloxy groups, more preferably alkoxy groups,

[0451] x is 0, 1, or 2, and

[0452] A is a group of the formula

[0453] –M–F,

[0454] in

[0455] M is selected from L or a group of the formula:

[0456] –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where

[0457] L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4-alkylene group, most preferably L is -(CH2)2- and / or -(CH2)3-,

[0458] R 1 As defined above,

[0459] p=1 to about 9, preferably p=1 or 4, more preferably p=4,

[0460] m=1 to about 20, preferably m=1,

[0461] and

[0462] F is selected from an optionally substituted linear, cyclic or branched saturated, unsaturated or aromatic hydrocarbon group having up to about 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted by an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group,

[0463] The condition is that for the silane of formula (2)

[0464] (i) A is a group of the formula

[0465] –{L–[SiR 1 2O] p –SiR 1 2} m –L–F, where L, R 1 , p, m and F are as defined above, or

[0466] (ii) A is a group of the formula

[0467] -LF, wherein L contains at least one ether group (—O—) and optionally has at least one hydroxyl substituent (—OH), and wherein F is as defined above, with the proviso that it includes at least one ester group (—O—C(═O)— or —C(═O)—O—).

[0468] 2. The silica particles according to embodiment 1, wherein in formula (1), when M is L, the group F contains at least one heteroatom, such as N, O, P, S, Si, or a halogen atom such as fluorine, chlorine, bromine or iodine.

[0469] 3. Silica particles according to embodiment 1 or 2, wherein in formula (1), the substituents of the hydrocarbon group F are selected from hydroxyl, thiol, alkoxy, siloxy, perfluoroalkyl, carboxyl, ester, aminoalkyl, thioalkyl, or polyether groups, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0470] 4. The silica particles according to any of the preceding embodiments, wherein F comprises at least one moiety selected from the group consisting of a polyether moiety, an ester moiety, and a coating matrix reactive moiety, such as an olefinic group, an epoxy group, an acrylate group, a methacrylate group, a thiol group, a hydroxyl group, an alkoxy group, a carboxyl group (—COOH), an amino group, and an isocyanate group, a ketone group, a diketone group, a 1,3-diketone group, a dicarboxyl group, a 1,3-dicarboxyl group, a diester group, a 1,3-diester group, a nitro group (—NO2), a cyano group (—CN), an alkylsulfonyl fluoride group, and donor and acceptor groups in a Michael addition reaction.

[0471] 5. The silica particles according to any one of the preceding embodiments, wherein F is selected from:

[0472] -alkyl,

[0473] -alkenyl,

[0474] -alkylcarbonyloxy,

[0475] - a polyoxyalkylene group, which preferably has the following general formula:

[0476] [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0477] in

[0478] [-OC2H4] represents an ethyleneoxy unit,

[0479] [-OC3H6] represents a propyleneoxy unit, and

[0480] [-OC4H8] represents a butyleneoxy unit,

[0481] q=0 to about 40, preferably 0 to about 20, more preferably 1 to about 15,

[0482] r=0 to about 30, preferably 0 to about 20, more preferably 0 to about 10,

[0483] s=0 to about 20, preferably 0 to about 15, more preferably 0 to about 10,

[0484] And q+r+s>2,

[0485] R 4 is selected from hydroxy, alkoxy, alkylcarbonyloxy, hydroxyalkyl, siloxy groups such as triorganosiloxy groups, organosilyl groups, glycidyl groups and glycidyloxy groups,

[0486] - glycidyl and glycidyloxy groups,

[0487] -Organosilyl groups, such as –SiR 1 3, where R 1 independently selected from the groups defined above for formulae (1) and (2), and siloxy groups such as -OSi(R 1 )3, where R 1 are independently selected from the groups defined above for formulae (1) and (2).

[0488] 6. Silica particles according to any of the preceding embodiments, wherein the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophobic silanes (i.e. from silanes having a partition coefficient P of the compound HLF in a 50 / 50 mixture of water and octanol of which the LF-group of the silane is included). 辛醇 / 水 logP value equal to or higher than 0.5).

[0489] 7. Silica particles according to any of the preceding embodiments, wherein the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophilic silanes (i.e. from silanes wherein the compound HLF, including the LF group of the silane, has a partition coefficient in a 50 / 50 mixture of water and octanol with a logP value of less than 0.5).

[0490] 8. The silica particles according to any of the preceding embodiments, wherein the silica particles are functionalized with two or more different silanes of formula (1) and / or (2).

[0491] 9. The silica particles according to embodiment 8, wherein each silica particle is functionalized by one or more hydrophobic silanes of formula (1) and / or (2) and by one or more hydrophilic silanes of formula (1) and / or (2).

[0492] 10. Silica particles according to embodiment 8, wherein in one or more of the silanes of formula (1) and / or (2), group F comprises one or more coating matrix reactive groups, and wherein the one or more other silanes of formula (1) and / or (2) are exclusively hydrophilic silanes or exclusively hydrophobic silanes.

[0493] 11. Silica particles according to embodiment 10, wherein the one or more other silanes of formula (1) and / or (2) are exclusively hydrophilic silanes, and wherein the group F of the one or more hydrophilic silanes comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups comprising quaternary ammonium groups, hydrocarbon groups comprising carboxylate groups, and hydrocarbon groups comprising one or more amino groups.

[0494] 12. Silica particles according to embodiment 10, wherein the one or more other silanes of formula (1) and / or (2) are exclusively hydrophobic silanes, and wherein the radical F of the one or more hydrophobic silanes comprises one or more hydrophilic groups selected from the group consisting of linear or branched unsubstituted alkyl groups, alkyl groups including difluoromethylene and / or trifluoromethyl groups, in particular perfluorinated alkyl groups, alkyl groups carrying triorganosilyl groups, organosiloxy groups, alkenyl groups without substituents containing heteroatoms or aromatic groups, in particular alkaryl groups and aralkyl groups.

[0495] 13. The silica particles according to any of the preceding embodiments, comprising at least two types of different silica particles functionalized with silanes of formula (1) and / or (2).

[0496] 14. The silica particles according to any one of the preceding embodiments, comprising at least two species of silica particles functionalized with different silanes having different polarities.

[0497] 15. The silica particles according to any one of the preceding embodiments, wherein the one or more silanes having formula (1) and / or (2) are selected from:

[0498] R 1 x R 2 3-x Si–L–[SiR 1 2O] p –SiR 1 2–L–[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0499] R 1 x R 2 3-x Si–L–[SiR 1 2O] p –SiR 1 2–L–R 5

[0500] HN{–SiR 1 2–L–[SiR 1 2O] p –SiR 1 2–L–[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4}2

[0501] HN{–SiR 1 2–L–[SiR 1 2O] p –SiR 1 2–L–R 5}2 and

[0502] R 1 x R 2 3-x Si–L–[SiR 1 2O] p –SiR 1 2–L–R 5

[0503] Where R 1 , R 2 , R 4 , L, p, q, r, s are each as defined in the above embodiment, and R 5 Selected from alkyl, alkylcarbonyloxy, glycidyl, glycidyloxy, organosilyl such as -SiMe2-O-SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, and -SitBuPh2.

[0504] 16. The silica particles according to any one of the preceding embodiments, wherein R 2 It is an alkoxy group.

[0505] 17. A silane having the formula (1) as defined in embodiment 2.

[0506] 18. A process for producing functionalized silica particles comprising

[0507] - contacting the silica particles with one or more silanes of formula (1) and / or (2) as defined in embodiment 1:

[0508] HN[–SiR 1 2–A]2 (1),

[0509] and / or

[0510] R 1 x R 2 3-x Si–A (2).

[0511] 19. The process according to embodiment 18, wherein the contacting of the silica particles with the one or more silanes of formula (1) and / or (2) is in the presence of a solvent.

[0512] 20. A process according to embodiment 18 or embodiment 19, wherein the silica particles and the one or more silanes having formula (1) and / or (2) are contacted at a temperature above about 40°C, more preferably above about 50°C, and most preferably at a temperature in the range of about 55°C to about 120°C.

[0513] 21. A process according to any one of embodiments 18-20, wherein the silica particles are selected from colloidal silica particles having an average particle size in the range of about 1 to about 300 nm, preferably about 1 to about 150 nm, as determined by dynamic light scattering (DLS), or pyrogenic silica having an average particle size in the range of about 1 to about 600 μm, preferably about 20 to about 400 μm, as determined by DLS or transmission electron microscopy (TEM).

[0514] 22. A process according to any one of embodiments 18 to 21, wherein the contacting of the silica particles and the one or more silanes having formula (1) and / or (2) is in the presence of a condensation catalyst selected from the group consisting of organotin, organozinc, organotitanium and organoboron compounds, primary amines, secondary amines, tertiary amines, ammonium compounds, cyclic amines, aliphatic amines, metal oxides, metal hydroxides, metal carbonates, ammonia and combinations thereof, preferably organotin and organotitanium compounds.

[0515] 23. The process according to any one of embodiments 18 to 22, wherein in the silane of formula (1), the group M is L.

[0516] 24. The process according to any one of embodiments 18 to 23, wherein in the silane of formula (1) and / or (2), F is selected from:

[0517] -alkyl,

[0518] -alkenyl,

[0519] -alkylcarbonyloxy, and

[0520] - a polyoxyalkylene group, which preferably has the following general formula:

[0521] [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0522] in

[0523] [-OC2H4] represents an ethyleneoxy unit,

[0524] [-OC3H6] represents a propyleneoxy unit, and

[0525] [-OC4H8] represents a butyleneoxy unit,

[0526] q=0 to about 40, preferably 0 to about 20, more preferably 1 to about 15,

[0527] r=0 to about 30, preferably 0 to about 20, more preferably 0 to about 10,

[0528] s=0 to about 20, preferably 0 to about 15, more preferably 0 to about 10,

[0529] And q+r+s>2,

[0530] R 4 selected from hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, siloxy groups such as triorganosiloxy groups, organosilyl groups, glycidyl and glycidyloxy groups,

[0531] - glycidyl and glycidyloxy groups,

[0532] -Organosilyl groups, such as –SiR 1 3, where R 1 independently selected from the groups defined above for formulae (1) and (2), and siloxy groups such as -OSi(R 1 )3,

[0533] Where R 1 are independently selected from the groups defined above for formulae (1) and (2).

[0534] 25. A process according to any one of embodiments 18-24, wherein the group F of the one or more silanes having formula (1) and / or (2) comprises at least one moiety selected from the group consisting of a polyether moiety, an ester moiety and a coating matrix reactive moiety, such as an olefinic, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (—COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diester, nitro (—NO2), cyano (—CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0535] 26. A process according to any one of embodiments 18 to 25, wherein the one or more silanes having formula (1) and / or (2) are selected only from hydrophobic silanes, or wherein the one or more silanes having formula (1) and / or (2) are selected only from hydrophilic silanes.

[0536] 27. The process according to any one of embodiments 18 to 26, wherein the silica particles are contacted with one or more silanes having formula (2), wherein R 2 is an alkoxy group.

[0537] 28. A process according to any one of embodiments 18 to 27, wherein two or more silanes of formula (1) and / or (2) as defined in the preceding embodiments are contacted with the silica particles in one step, or wherein two or more silanes of formula (1) and / or (2) are contacted with the silica particles in two or more steps.

[0538] 29. A process according to any of the preceding embodiments 18 to 28, wherein the silica particles are contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and with one or more hydrophobic silanes of formula (1) and / or (2) in the absence of a hydrophilic silane of formula (1) and / or (2), or

[0539] wherein silica particles are contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and with one or more hydrophilic silanes of formula (1) and / or (2) in the absence of a hydrophobic silane of formula (1) or (2).

[0540] 30. A process according to any one of embodiments 18-28, wherein the silica particles are contacted with one or more silanes having formula (1) in the presence of at least about 0.5 equivalents of water based on the molar amount of the one or more silanes having formula (1), preferably in the presence of at least about 1.0 equivalents of water, and most preferably in the presence of at least about 1.5 equivalents of water based on the molar amount of the one or more silanes having formula (1).

[0541] 31. Functionalized silica particles comprising one or more monovalent groups A,

[0542] wherein A is a group of the formula

[0543] –M–F,

[0544] in

[0545] M is selected from L or a group of the formula:

[0546] –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where

[0547] L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4-alkylene group, most preferably L is -(CH2)2- and / or -(CH2)3-,

[0548] R 1 are independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, most preferably R 1 Methyl,

[0549] p=1 to about 9, preferably p=1 or 4, more preferably p=4,

[0550] m=1 to about 20, preferably m=1,

[0551] and

[0552] F is selected from an optionally substituted linear, cyclic or branched saturated, unsaturated or aromatic hydrocarbon group having up to about 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted by an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group,

[0553] and the group A is bonded to the silica particle via a silicon atom which is connected to the silicon dioxide network of the silica particle via one or more oxygen atoms, wherein the valences of the silicon atom not occupied by a group -A or an oxygen atom are replaced by a substituent R as defined above 1 occupy.

[0554] 32. Functionalized silica particles according to embodiment 31, wherein M is L and the group F contains at least one heteroatom, such as N, O, P, S, Si, or a halogen atom such as fluorine, chlorine, bromine or iodine.

[0555] 33. Silica particles according to embodiment 31 or 32, wherein the substituents of the hydrocarbon group F are selected from hydroxyl, thiol, alkoxy, siloxy, perfluoroalkyl, carboxyl, ester, aminoalkyl, thioalkyl, or polyether groups, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxyl (-COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diester, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0556] 34. Silica particles according to any one of embodiments 31-33, wherein F comprises at least one moiety selected from the group consisting of a polyether moiety, an ester moiety, and a coating matrix reactive moiety, such as an olefinic group, an epoxy group, an acrylate group, a methacrylate group, a thiol group, a hydroxyl group, an alkoxy group, a carboxyl group (—COOH), an amino group, and an isocyanate group, a ketone group, a diketone group, a 1,3-diketone group, a dicarboxyl group, a 1,3-dicarboxyl group, a diester group, a 1,3-diester group, a nitro group (—NO2), a cyano group (—CN), an alkylsulfonyl fluoride group, and donor and acceptor groups in a Michael addition reaction.

[0557] 35. The silica particles according to any one of embodiments 31 to 34, wherein F is selected from:

[0558] -alkyl,

[0559] -alkenyl,

[0560] -alkylcarbonyloxy,

[0561] - a polyoxyalkylene group, which preferably has the following general formula:

[0562] [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0563] in

[0564] [-OC2H4] represents an ethyleneoxy unit,

[0565] [-OC3H6] represents a propyleneoxy unit, and

[0566] [-OC4H8] represents a butyleneoxy unit,

[0567] q=0 to about 40, preferably 0 to about 20, more preferably 1 to about 15,

[0568] r=0 to about 30, preferably 0 to about 20, more preferably 0 to about 10,

[0569] s=0 to about 20, preferably 0 to about 15, more preferably 0 to about 10,

[0570] And q+r+s>2,

[0571] R 4 is selected from hydroxy, alkoxy, alkylcarbonyloxy, hydroxyalkyl, siloxy groups such as triorganosiloxy groups, organosilyl groups, glycidyl groups and glycidyloxy groups,

[0572] - glycidyl and glycidyloxy groups,

[0573] -Organosilyl groups, such as –SiR 1 3, where R 1 are independently selected from the groups defined above, and siloxy groups such as -OSi(R 1 )3, where R 1 are independently selected from the groups defined above.

[0574] 36. Silica particles according to any one of embodiments 31 to 35, wherein the one or more groups A are selected only from hydrophobic groups (i.e. selected from the following groups A: the compound HLF including the LF-group of the group A has a partition coefficient P in a 50 / 50 mixture of water and octanol 辛醇 / 水 logP value equal to or higher than 0.5).

[0575] 37. Silica particles according to any one of embodiments 31 to 36, wherein the one or more groups A having formula (1) and / or (2) are selected only from hydrophilic groups (i.e. selected from the following groups A: the logP value of the distribution coefficient of the compound HLF including the LF group of the group A in a 50 / 50 mixture of water and octanol is lower than 0.5).

[0576] 38. The silica particles according to any one of embodiments 31 to 37, wherein the silica particles are functionalized with two or more different groups A.

[0577] 39. The silica particles according to embodiment 38, wherein each silica particle is functionalized by one or more hydrophobic groups A and by one or more hydrophilic groups A.

[0578] 40. The silica particles according to embodiment 38, wherein in one or more of the groups A, the group F comprises one or more coating matrix reactive groups, and wherein the one or more other groups A are only hydrophilic groups A or only hydrophobic groups A.

[0579] 41. Silica particles according to embodiment 40, wherein the one or more other groups A are only hydrophilic groups A, and wherein the group F of the one or more hydrophilic groups A comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups including quaternary ammonium groups, hydrocarbon groups including carboxylate groups, and hydrocarbon groups including one or more amino groups.

[0580] 42. Silica particles according to embodiment 40, wherein the one or more other groups A are only hydrophobic silanes, and wherein the group F of the one or more hydrophobic groups A comprises one or more hydrophilic groups selected from the following: linear or branched unsubstituted alkyl groups, alkyl groups including difluoromethylene and / or trifluoromethyl groups, in particular perfluorinated alkyl groups, alkyl groups with triorganosilyl groups, organosiloxy groups, alkenyl groups without heteroatom-containing substituents or aromatic groups, in particular alkaryl groups and aralkyl groups.

[0581] 43. The silica particles according to any one of embodiments 31 to 42, comprising at least two types of different silica particles functionalized with groups A.

[0582] 44. The silica particles according to any one of embodiments 31 to 43, comprising at least two types of silica particles functionalized with different groups A having different polarities.

[0583] 45. The silica particles according to any one of embodiments 31 to 44, wherein the one or more silanes having formula (1) and / or (2) are selected from:

[0584] –L–[SiR 1 2O] p –SiR 1 2–L–[OC2H4] q [-OC3H6] r [-OC4H8] s -R 4

[0585] –L–[SiR 1 2O] p –SiR 1 2–L–R 5

[0586] Where R 1 , R 4 , L, p, q, r, s are each as defined in the above embodiment, and R 5Selected from alkyl, alkylcarbonyloxy, glycidyl, glycidyloxy, organosilyl such as -SiMe2-O-SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, and -SitBuPh2.

[0587] 46. ​​Use of the silica particles according to any one of embodiments 1-16, 31-45 or produced by the process according to any one of embodiments 18-30 for the manufacture of a coating composition.

[0588] 47. Use of the silica particles according to any one of embodiments 1-16, 31-45 or produced by the process according to any one of embodiments 18-30 in a coating composition as a marine antifouling additive, a general antifouling additive, an anti-icing additive, an antifouling additive, an antifouling additive, an antifogging additive, a self-cleaning additive, an anti-adhesion, an anti-dust, an anti-fingerprint, and an anti-graffiti additive, in particular as a general antifouling additive or an antifogging additive.

[0589] 48. A coating composition comprising silica particles according to any of embodiments 1-16, 31-45 or produced by the process according to any of embodiments 18-30.

[0590] 49. A coating composition according to the aforementioned embodiment 48, comprising about 0.1 to about 80 weight %, preferably about 0.5 to about 70 weight %, more preferably about 1 to about 60 weight %, still more preferably about 20 to about 55 weight %, and most preferably about 25 to about 50 weight % of the silica particles based on the total weight of the coating composition.

[0591] Example

[0592] The following abbreviations and trade names are used in the Examples section:

[0593] Me=methyl (-CH3)

[0594] Aerosil 300(BET 270-330m 2 / g; SiO2 content> 99.8%; particle size: 5-50nm primary particle size, 100μm average agglomerate size); Breox AA E 450H (BASF), Lamoreaux catalyst (abcr) VeoVa9 (Versatic TMVinyl ester of Acid 9 (synthetic saturated monocarboxylic acid with a highly branched structure containing 10 carbon atoms, Hexion); Levasil EXP 310 from AkzoNobel (dispersion of silica in water; silica content: 30% by weight; particle size: 10 nm; BET of silica: 200 nm 2 g -1 ); Epikote 828EL (epoxy resin prepared from bisphenol A and epichlorohydrin, Hexion); Silopren E0.5 (a dihydroxy-terminated linear polysiloxane base polymer having a viscosity of 0.5 Pa.s at 20°C; Momentive Performance Materials); Silopren E2 (a dihydroxy-terminated linear polysiloxane base polymer having a viscosity of 2 Pa.s at 20°C; Momentive Performance Materials).

[0595] Example 1 (Starting Materials)

[0596] Preparation of NH(SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me)2

[0597] 150.5 g of n-butylhydrogenpentasiloxane (HSiMe2(OSiMe2)3-SiMe2-(CH2)3Me), and 58.5 g of dimethylvinylchlorosilane were reacted at 100° C. under N2 for 3 hours upon addition of 0.06 g of Lamoreaux catalyst (3 wt % Pt solution).

[0598] The reaction mixture was further heated to 80°C and the reaction flask was degassed. A stream of NH3 was slowly added to the reaction until the reaction was complete as indicated by the pressure increase using a digital pressure sensor due to the release of HCl. The reaction mixture was further stirred at 50°C and 100 mbar NH3 elevated pressure for 1.5 hours. Afterwards, the reaction flask was degassed (to <30 mbar) at 50°C for 1 hour. The product was purified by using a HPLC-MS / MS from PALL. K series grade EK filter pad (1400 mass / unit area g / m 2 , thickness 3.8mm) filtration.

[0599] Example 2 (Starting Materials)

[0600] NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 Preparation of -OMe)2

[0601] 900 g of allyl methyl terminated polyether (CH2=CH-CH2-(O-CH2CH2) 7.5 -OCH3) was dissolved in 270 mL of xylene and heated to 80°C. About 0.5 g of platinum catalyst (Lamoreaux) (total 10 ppm Pt) was added and a mixture of 261 g of dimethylchlorosilane in 450 mL of xylene was added dropwise. The reaction mixture was stirred at 100°C for 12 hours, after which the remaining dimethylchlorosilane was removed under vacuum at 40°C.

[0602] 170 g of the obtained hydrosilation product was dissolved in 100 mL of dimethylbenzene. The reaction flask was degassed and NH3 stream was slowly added until the pressure increase indicated the completion of the substitution reaction of the chlorine atom by the amino group. The reaction mixture was further stirred for 1.5 hours at 50 ° C and 100 mbar NH3 elevated pressure. Afterwards, the reaction flask was degassed (to <30 mbar) at 50 ° C for 1 hour. The product was purified by using a 1% NH3 column from PALL. K series grade EK filter pad (1400 mass / unit area g / m 2 , thickness 3.8mm) for filtration.

[0603] Example 3 (Starting Materials)

[0604] NH(SiMe2-(CH2)3-(OCH2CH2) 10 Preparation of -OSiMe3)2

[0605] 200 g of allyl polyether Breox AA E 450H (CH2=CH-CH2-(O-CH2CH2) 10 -OH) was dissolved in 400mL of dimethylbenzene. A mixture of 14.3g trimethylchlorosilane and 21.3g hexamethylenedisilazane (both used as OH end-capping agents for allyl polyethers) was added dropwise at room temperature. The reaction mixture was then stirred at room temperature for 3 hours. The precipitated NH4Cl was removed by filtration. The solvent was removed under vacuum at 60°C. 58g of the obtained product was heated to 80°C and about 64mg of a platinum catalyst (Lamoreaux, 10ppm Pt in total) was added. 11.4g dimethylchlorosilane (HSi(Me2)Cl) was added dropwise. The reaction mixture was then heated to 120°C and stirred for 4 hours.

[0606] 220 g of the product thus obtained were dissolved in 100 mL of xylene. The reaction flask was degassed and a stream of NH3 was slowly added until the pressure increase indicated the completion of the reaction. The reaction mixture was further stirred at 50°C and 100 mbar NH3 elevated pressure for 1.5 hours. Afterwards, the reaction flask was degassed (to <30 mbar) at 50°C for 1 hour. The product was purified by using a 100 mL NH3 column from PALL. K series grade EK filter pad (1400 mass / unit area g / m 2 , thickness 3.8mm) for filtration.

[0607] Example 4

[0608] Silica was functionalized using NH(SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me)2 (Example 1)

[0609] 20g 300 was dispersed in 200 ml of dioxane, followed by the addition of 4.31 g of deionized water and 36.9 g of NH(SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me)2 (Example 1). The mixture was heated to 100° C. under an argon atmosphere. After a reaction time of 1 hour, the reaction slurry became less viscous and less turbid, indicating that surface functionalization reaction of SiOH surface groups with SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me occurred. The dispersion was used without further purification and contained about 8% by weight of silica.

[0610] Example 5

[0611] Preparation of polyether pentasiloxane functionalized silica

[0612] Preparation of monodisperse polyether pentasiloxane (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)3-(OCH2CH2) according to Example 6 of WO 2017 / 012714 A1 10 -OH). 10g 300 was dispersed in 250 g of toluene, followed by the addition of 0.12 g of diisopropoxy-bis(ethyl acetoacetate) titanate. The mixture was heated to 80°C and 2.0 g of (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)3-(OCH2CH2) was slowly added. 10-OH). Afterwards, the slurry was heated at reflux for 6 hours. The solvent was removed under vacuum (50°C / <1 mbar) to give a light yellow powder (-12 g).

[0613] Example 6

[0614] Preparation of polyether functionalized silica

[0615] 20g 300 was dispersed in 200 ml of dioxane, followed by the addition of 4.31 g of deionized water and 36.9 g of NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OMe)2 (Example 2). The mixture was heated to 100°C under an argon atmosphere. After 1 hour of reaction time, the reaction slurry became less viscous and less turbid, indicating a surface functionalization reaction. The dispersion was used without further purification and contained about 8% by weight of silica.

[0616] Example 7

[0617] Preparation of VeoVa9 Pentasiloxane-Functionalized Silica

[0618] This embodiment involves 300 monodispersed (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)2-OC(O)-C(Me)R a R b Functionalization, where R a , R b Each is an alkyl radical having a total of 6 C atoms.

[0619] According to Example 7 of WO 2017 / 012714 A1, VeoVa 9 [from Hexion] was mixed with M H -D3-M H The monodispersed VeoVa9 pentasiloxane (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)2-OC(O)-C(CH3)R a R b , where R a and R b = alkyl, and R a and R b There are 6 C atoms in total.

[0620] 10g 300 was dispersed in 250 g of toluene, followed by the addition of 0.12 g of diisopropoxy-bis(ethyl acetoacetate) titanate. The mixture was heated to 80°C and 2.0 g of monodispersed (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)2-OC(O)-C(CH3)R a R b (where R a +R b = alkyl group with a total of 6 C atoms). Thereafter, the slurry was heated under reflux for 6 hours. The solvent was removed under vacuum (50° C. / <1 mbar) to give a light yellow powder (10.5 g).

[0621] Example 8

[0622] Colloidal silica nanoparticles dispersed in 1-methoxy-2-propanol

[0623] 44 g of 1-methoxy-2-propanol (Dowanol PM) are added to 100 g of a silica nanoparticle dispersion in water (Levasil EXP 310 from AkzoNobel, 30% by weight silica). About 20-25% by weight of the solvent mixture is removed using a rotary evaporator. The procedure is repeated twice to obtain dispersed silica nanoparticles in 1-methoxy-2-propanol. The mixture still contains 10-15% by weight of water, as measured by the Karl Fischer method.

[0624] Example 9

[0625] NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OMe)2 functionalized colloidal silica nanoparticles

[0626] 60 g of silica nanoparticle dispersion in 1-methoxy-2-propanol (Example 8) were mixed with about 517 g of 1-methoxy-2-propanol (Dowanol PM) (final SiO2 content: 3 wt. %) and heated to 80° C. under reflux and N2 inert atmosphere. 15 g NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OMe)2 (Example 2) in 15 mL of 1-methoxy-2-propanol. The mixture was stirred under reflux for 8 hours. A portion of the solvent was then removed under vacuum to obtain a liquid product having a silica content of 40% by weight.

[0627] Example 10

[0628] NH(SiMe2-(CH2)3-(OCH2CH2) 10 -OSiMe3)2 functionalized colloidal silica nanoparticles

[0629] 60 g of the silica nanoparticle dispersion in 1-methoxy-2-propanol (Example 8) were mixed with about 517 g of 1-methoxy-2-propanol (final SiO2 content: 3 wt. %) and heated to 80° C. 15 g of NH(SiMe2-(CH2)3-(OCH2CH2) 10 -OSiMe3)2 (Example 3) in 15 mL of 1-methoxy-2-propanol. The mixture was stirred under reflux for 8 hours. A portion of the solvent was then removed under vacuum to obtain a liquid product having a silica content of 15% by weight.

[0630] Application Examples

[0631] Preparation of antifouling coating formulations

[0632] To test the activity of the functionalized silica particles, coating formulations were prepared and the coated test panels were immersed in the ocean (North Sea, Norderney Harbor). A representative example of the prepared coating formulation was made as follows:

[0633] Application Example 1 (Anti-fouling Test)

[0634] Using the functionalized Aerosil according to Examples 4, 5, 6 and 7 of the present invention The following coating compositions were prepared.

[0635] The adduct was prepared by reaction of Epikote 828EL (epoxy resin prepared from bisphenol A and epichlorohydrin, from Hexion), and Silane A-1100 in a weight ratio of 34 / 47 and is described as follows:

[0636] 34.0 g of Epikote 828EL and 47.0 g of Silane A-1100 were dissolved in 70 g of xylene and heated to 80° C. for 6 h.

[0637] Silane A-1100 is γ-aminotriethoxysilane:

[0638]

[0639] *SiPEG was prepared as described in WO 2014 / 126599 A1 and is represented by the following formula:

[0640]

[0641] Composition 990-G

[0642] Table 1

[0643] SiPEG* 72.6g Adduct Epikote 828EL + A-1100 (Application Example 1) 47.6g Tetrapropyl orthosilicate 7.3g Momentive Silopren E 0.5 246.0g Momentive Silopren E2 288.8g Dibutyltin dilaurate (DBTL) 5.4g Polyether Pentasiloxane Functionalized Silica Particles (Example 5) 290.1g

[0644] Composition 993-G

[0645] Table 2

[0646] SiPEG* 72.7g Adduct Epikote 828EL + A-1100 (Application Example 1) 47.7g Tetrapropyl orthosilicate 7.3g Momentive Silopren E2 535.4g Dibutyltin dilaurate (DBTL) 5.4g VeoVa9 Pentasiloxane Functionalized Silica Particles (Example 7) 290.4g

[0647] Composition 994-G

[0648] Table 3

[0649] Momentive Silopren E 0.5 257.4g Momentive Silopren E2 302.1g VeoVa9 Pentasiloxane Functionalized Silica Particles (Example 7) 220.4g Polyether Pentasiloxane Functionalized Silica Particles (Example 5) 220.4g

[0650] Composition 1101-G

[0651] Table 4

[0652] SiPEG* 60.0g Adduct Epikote 828EL + A-1100 (Application Example 1) 39.3g Tetrapropyl orthosilicate 7.3g Momentive Silopren E 0.5 203.3g Momentive Silopren E2 238.7g Dibutyltin dilaurate (DBTL) 4.5g Polyether functionalized silica particles (Example 6) 239.7g

[0653] Composition 1103-G

[0654] Table 5

[0655] SiPEG* 63.2g Adduct Epikote 828EL + A-1100 (Application Example 11) 41.4g Tetrapropyl orthosilicate 6.3g Momentive Silopren E 0.5 214.2g Momentive Silopren E2 251.4g Dibutyltin dilaurate (DBTL) 4.7g Butyl Pentasiloxane Functionalized Silica Particles (Example 4) 252.5g

[0656] Primed (50 μm coating thickness) PVC test panels (Simona) were prepared using the following primer composition.

[0657] - Component A: a mixture of Epikure 3292-FX-60 (aliphatic amine curing agent for epoxy coatings), xylene, and SF1706 (silicone fluid, a curable polymer containing amine functions and dimethylpolysiloxane units) in a weight ratio of 60:19:0.95.

[0658] - Component B: Epon Resin 828 (bifunctional bisphenol A / epichlorohydrin derived liquid epoxy resin)

[0659] Component A and component B are mixed in a weight ratio of 10:7.2.

[0660] The primed panels were cured at room temperature for 24 hours.

[0661] The coating formulations 990-G to 1103-G shown above were then applied with a doctor blade on the above primed PVC test panels (available from Simona AG) (300 μm coating thickness). The coatings were then cured at room temperature for 1 day and subsequently immersed in the ocean in the North Sea, Norderney Harbor (by Dr. Brill + Partner GmbH). Fouling release evaluation was performed according to the international ASTM standard ASTM D6990-05 (2011) (Standard Test Method for Evaluating Marine Biofouling on Coated Test Panels).

[0662] The following results were observed (fouling scale 100 = no dirt, 0 = surface covered with dirt):

[0663] Marine antifouling evaluation of the test panels:

[0664] Table 6

[0665]

[0666]

[0667] PVC-4 was used as a reference (PVC without surface treatment).

[0668] The results show that, compared to the reference PVC sheet, an antifouling / fouling release effect can be observed for Examples 4, 5, 6 and 7 which is persistent, even for almost 2 years in the case of the mixture of Examples 5 and 7 (50 / 50 by weight).

[0669] Application Example 2 (Anti-fog Test)

[0670] Preparation of anti-fog formulations

[0671] To test the anti-fog properties of the functionalized particles, the particles have been added to UV curable coating formulations. The contact angle as well as the anti-fog properties have been measured and evaluated.

[0672] Description of the coating composition

[0673] The coating formulation is composed of: (i) (meth) acrylate resin, which has a total molecular weight of Mw 30,000 based on 30 parts by mass of 2-acetoacetoxyethyl methacrylate (AAEM), 50 parts by mass of dimethyl acrylamide (DMAA), 10 parts by mass of methyl methacrylate (MMA), and 10 parts by mass of butyl methacrylate (BMA); (ii) acrylate oligomer dipentaerythritol penta / hexaacrylate (DPHA); (iii) 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst; and (iv) a polyether-siloxane copolymer as a leveling agent. Methoxypropanol is used as a solvent.

[0674] The coating formulation was prepared by mixing all components at room temperature and flow coated on polycarbonate test panels to give a coating thickness of 2-8 μm. After a drying period of approximately 5 minutes at room temperature, the coated panels were placed in an oven at 120° C. for approximately 20 minutes.

[0675] Table 7

[0676]

[0677] *Anti-fog test acc. GMW 16508; 3.3.6 (This specification covers the qualification requirements for transparent anti-condensation coatings to be used on the inner surface of the outer lens of exterior lamp assemblies).

[0678] Formulation 1 (containing functionalized silica particles according to Example 9 of the invention) and Formulation 2 (containing functionalized silica particles according to Example 10 of the invention) show an improvement in anti-fog properties compared to the reference without surface treated silica particles.

[0679] Anti-fog performance evaluation

[0680] Contact angle measurement

[0681] Water contact angle measurements were performed using the sessile drop method with a drop shape analyzer Krüss DAS 100. Deionized and filtered (0.2 μm filter) water was used.

[0682] The analyzed droplet volume was 3.5 μL.

[0683] The results of the water contact angle measurements after 60 seconds for formulations 1, 2 and 3 are given in the table below.

[0684] Table 8

[0685]

[0686] exist Figure 1-3 , contact angle measurements for Formulations 1 to 3 are shown. Lower contact angles, especially for Formulation 1, indicate an increased hydrophilicity of the surface, which is evidenced by the enhanced anti-fog properties.

[0687] Anti-fog test

[0688] The test panel was placed at a distance of 15 cm above a water bath heated to 60°C and the anti-fog performance was evaluated over a period of 90 seconds according to GMW16508 specification section 3.3.6.

[0689] Anti-fog test results

[0690] Table 9

[0691] sample Observations Formulation 1 No fogging for at least 90 seconds Formulation 2 Fogging occurs after 38 seconds Formulation 3 Fogging occurred after 3 seconds.

Claims

1. An antifouling or antifog coating comprising silica particles functionalized with one or more silanes of formula (1) and / or (2): HN[–SiR 1 2–A]2(1), R 1 x R 2 3-x Si–A(2) in In formula (1) A is a group of the formula –M–F, in M is selected from L or a group of the formula: –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, Provided that when M is selected from L, L is independently selected from a divalent alkylene group having at least two carbon atoms, which is separated by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, R 1 are independently selected from non-hydrolyzable residues, p＝1-9， m = 1-20, and F is selected from an optionally substituted linear, cyclic or branched, saturated or unsaturated, or aromatic hydrocarbon group having up to 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted with an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group; And in formula (2) R 1 are independently selected from non-hydrolyzable residues, R 2 are independently selected from hydrolyzable residues, x is 0, 1, or 2, and A is a group of the formula –M–F, in M is selected from L or a group of the formula: –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, p=1-9, m＝1-20， and F is selected from an optionally substituted linear, cyclic or branched, saturated or unsaturated, or aromatic hydrocarbon group having up to 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted by an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group, The condition is that for the silane of formula (2) (i) When A is a group of the formula -LF, then L contains at least one ether group (-O-), and optionally has at least one hydroxyl substituent (-OH), and F is as defined above, provided that it includes at least one ester group (-O-C(=O)- or -C(=O)-O-), or (ii) When A is a group of the formula –{L–[SiR 1 2O] p –SiR 1 2} m –L–F, then L, R 1 , p, m are as defined above, and F further comprises at least one moiety selected from the group consisting of acrylate, methacrylate, thiol, alkoxy, amino and isocyanate groups, ketones, dicarboxyl groups, diesters, nitro, cyano, alkylsulfonyl fluoride groups, oxycarbonylalkyl groups, wherein the alkyl groups are selected from branched or cyclic C3-C22 alkyl groups, or polyoxyalkylene groups of the following formula: [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 in [-OC2H4] represents an ethyleneoxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents a butyleneoxy unit, q＝0-40， r＝0-30， s＝0-20， And q+r+s>2, R 4 Selected from hydroxyl, alkoxy, hydroxyalkyl, siloxy, glycidyl and glycidyloxy groups, and organosilyl groups SiR 1’ 3, where R 1’ are independently selected from alkyl groups.

2. The antifouling or antifogging coating according to claim 1, wherein (ii) when A is of the formula -{L-[SiR 1 2O] p –SiR 1 2} m When the group is -L-F, F further includes a diketone.

3. The antifouling or antifogging coating according to claim 1, wherein L is a divalent C2-C12-alkylene group.

4. The antifouling or antifogging coating according to claim 1, wherein L is a divalent C2-C4 alkylene group.

5. The antifouling or antifogging coating according to claim 1, wherein L is -(CH2)2- and / or -(CH2)3-.

6. The antifouling or antifogging coating according to claim 1, wherein R 1 are independently selected from hydrocarbyl groups.

7. The antifouling or antifogging coating according to claim 1, wherein R 1 are independently selected from alkyl groups.

8. The antifouling or antifogging coating according to claim 1, wherein R 1 It is methyl.

9. The antifouling or antifogging coating according to claim 1, wherein p=1 or 4.

10. The antifouling or antifogging coating according to claim 1, wherein p=4.

11. The antifouling or antifogging coating according to claim 1, wherein m=1.

12. The antifouling or antifogging coating according to claim 1, wherein in formula (2), R 2 Independently selected from hydrogen, hydroxyl, hydrocarbylcarbonyloxy group, halogen group, amino group, hydrocarbyloxy group.

13. The antifouling or antifog coating according to claim 12, wherein the hydrocarbylcarbonyloxy group is an acyloxy group.

14. The antifouling or antifogging coating according to claim 12, wherein the hydrocarbyloxy group is an alkoxy or aryloxy group.

15. The antifouling or antifogging coating according to claim 1, wherein in formula (2), R 2 Independently selected from alkoxy groups.

16. The antifouling or antifogging coating according to claim 1, wherein q = 0-20.

17. The antifouling or antifogging coating according to claim 1, wherein q = 1-15.

18. The antifouling or antifogging coating according to claim 1, wherein r = 0-20.

19. The antifouling or antifogging coating according to claim 1, wherein r = 0-10.

20. The antifouling or antifog coating according to claim 1, wherein s = 0-15.

21. The antifouling or antifog coating according to claim 1, wherein s = 0-10.

22. An antifouling or antifog coating according to claim 1, wherein in formula (1), when M is L, the group F contains at least one additional heteroatom selected from N, O, P, S, Si, or a halogen atom.

23. The antifouling or antifog coating according to any one of claims 1 to 22, wherein F further comprises at least one moiety selected from the group consisting of polyether moieties, ester moieties and alkenyl groups, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, amino and isocyanate groups, ketones, diketones, dicarboxyl groups, diesters, nitro groups (-NO2), cyano groups (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

24. The antifouling or antifog coating according to claim 1, wherein the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophobic silanes, wherein the partition coefficient HLF of the compound including the LF-group of the silane in a 50 / 50 mixture of water and octanol is 辛醇 / 水 The logP value is equal to or higher than 0.

5.

25. The antifouling or antifog coating according to claim 1, wherein the one or more silanes of formula (1) and / or (2) are selected exclusively from hydrophilic silanes, wherein the partition coefficient of the compound HLF comprising the LF-group of the silane in a 50 / 50 mixture of water and octanol has a logP value of less than 0.

5.

26. The antifouling or antifog coating of claim 1, wherein the silica particles are functionalized with two or more different silanes of formula (1) and / or (2).

27. An antifouling or antifog coating according to claim 26, wherein each silica particle is functionalized by one or more hydrophobic silanes of formula (1) and / or (2) and by one or more hydrophilic silanes of formula (1) and / or (2).

28. An antifouling or antifog coating according to claim 26, wherein in one or more of the silanes of formula (1) and / or (2), group F comprises one or more coating matrix reactive groups, and wherein the one or more other silanes of formula (1) and / or (2) are exclusively hydrophilic silanes or exclusively hydrophobic silanes.

29. The antifouling or antifog coating according to claim 28, wherein the radical F of the one or more hydrophilic silanes comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups comprising quaternary ammonium groups, hydrocarbon groups comprising carboxylate groups, and hydrocarbon groups comprising one or more amino groups, or wherein the radical F of the one or more hydrophobic silanes comprises one or more hydrophilic groups selected from the group consisting of linear or branched unsubstituted alkyl groups, alkyl groups comprising difluoromethylene and / or trifluoromethyl groups, alkyl groups carrying triorganosilyl groups, organosiloxy groups, alkenyl groups without substituents containing heteroatoms or aromatic groups.

30. The antifouling or antifog coating according to claim 29, wherein the group F of the one or more hydrophobic silanes is a perfluorinated alkyl group.

31. The antifouling or antifogging coating according to claim 29, wherein the group F of the one or more hydrophobic silanes is an alkylaryl group and an aralkyl group.

32. The antifouling or antifog coating of claim 1 wherein the silica particles are functionalized with a silane of formula (1).

33. The antifouling or antifogging coating of claim 1, wherein the silica particles are produced by a process comprising - contacting the silica particles with one or more silanes of formula (1) and / or (2) as defined in claim 1: HN[–SiR 1 2–A]2(1), and / or R 1 x R 2 3-x Si–A(2), wherein optionally, the contacting of the silica particles with the one or more silanes of formula (1) and / or (2) is in the presence of a solvent, and Optionally, the silica particles are contacted with the one or more silanes of formula (1) and / or (2) at a temperature above 40° C., Further optionally, the contacting of the silica particles and the one or more silanes of formula (1) and / or (2) is in the presence of a condensation catalyst selected from the group consisting of organotin, organozinc, organotitanium and organoboron compounds, primary amines, secondary amines, tertiary amines, ammonium compounds, cyclic amines, aliphatic amines, metal oxides, metal hydroxides, metal carbonates, ammonia and combinations thereof, and Further optionally, the silica particles are contacted with one or more silanes having formula (1) in the presence of at least 0.5 equivalents of water based on the molar amount of the one or more silanes having formula (1).

34. An antifouling or antifogging coating according to claim 33, wherein the silica particles are contacted with one or more silanes having the formula (2) wherein R 2 is an alkoxy group.

35. An antifouling or antifog coating according to claim 33, wherein the silica particles are contacted with the one or more silanes of formula (1) and / or (2) at a temperature above 50°C.

36. The antifouling or antifog coating of claim 33, wherein the silica particles are contacted with the one or more silanes of formula (1) and / or (2) at a temperature in the range of 55°C to 120°C.

37. The antifouling or antifogging coating of claim 33, wherein the condensation catalyst is an organotin or organotitanium compound.

38. The antifouling or antifog coating of claim 33, wherein the silica particles are contacted with one or more silanes of formula (1) in the presence of at least 1.0 equivalent of water based on the molar amount of the one or more silanes of formula (1).

39. The antifouling or antifog coating of claim 33, wherein the silica particles are contacted with one or more silanes of formula (1) in the presence of at least 1.5 equivalents of water based on the molar amount of the one or more silanes of formula (1).

40. The antifouling or antifogging coating according to claim 33, wherein in the silane of formula (1) and / or (2), F is selected from: -alkyl, -alkenyl, -alkylcarbonyloxy, and - polyoxyalkylene groups, Alternatively, the group F of one or more silanes of formula (1) and / or (2) comprises at least one moiety selected from the group consisting of a polyether moiety, an ester moiety and a coating matrix reactive moiety.

41. The antifouling or antifog coating of claim 40, wherein the polyoxyalkylene group has the general formula: [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 in [-OC2H4] represents an ethyleneoxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents a butyleneoxy unit, q＝0-40， r＝0-30， s＝0-20， And q+r+s>2, R 4 is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, siloxy, organosilyl, glycidyl and glycidyloxy groups, -Organosilyl group –SiR 1 3, where R 1 independently selected from the groups defined above for formulae (1) and (2), and a siloxy group -OSi(R 1 )3, Where R 1 are independently selected from the groups defined above for formulae (1) and (2).

42. An antifouling or antifog coating according to claim 41, wherein q = 0-20.

43. The antifouling or antifog coating according to claim 41, wherein q = 1-15.

44. The antifouling or antifogging coating according to claim 41, wherein r = 0-20.

45. The antifouling or antifog coating according to claim 41, wherein r = 0-10.

46. ​​The antifouling or antifog coating of claim 41, wherein s = 0-15.

47. The antifouling or antifog coating of claim 41, wherein s = 0-10.

48. The antifouling or antifog coating of claim 41, wherein the siloxy groups are triorganosiloxy groups.

49. An antifouling or antifog coating according to claim 1, wherein the group F of the one or more silanes having formula (1) and / or (2) comprises alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, amino, alkoxysilyl and isocyanate groups, ketones, dicarboxyl groups, diesters, nitro (-NO2), cyano (-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

50. The antifouling or antifog coating of claim 49, wherein the ketone is a diketone.

51. The antifouling or antifog coating of claim 49, wherein the ketone is a 1,3-diketone.

52. The antifouling or antifog coating of claim 49, wherein the dicarboxyl groups are 1,3-dicarboxyl groups.

53. The antifouling or antifog coating of claim 49, wherein the diester is a 1,3-diester.

54. An antifouling or antifog coating according to any one of claims 33 to 53, wherein two or more silanes of formula (1) and / or (2) as defined in claim 1 are contacted with the silica particles in one step, or wherein two or more silanes of formula (1) and / or (2) are contacted with the silica particles in two or more steps.

55. An antifouling or antifog coating according to claim 54, wherein the silica particles are contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and with one or more hydrophobic silanes of formula (1) and / or (2) in the absence of a hydrophilic silane of formula (1) and / or (2), or wherein silica particles are contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and with one or more hydrophilic silanes of formula (1) and / or (2) in the absence of a hydrophobic silane of formula (1) or (2).

56. An antifouling or antifogging coating comprising functionalized silica particles comprising one or more monovalent groups A, wherein A is a group of the formula –M–F, in M is selected from L or a group of the formula: –{L–[SiR 1 2O] p –SiR 1 2} m –L–, where R 1 are independently selected from non-hydrolyzable residues, L is independently selected from a divalent alkylene group having at least two carbon atoms, which may be replaced by one or more of -O-, -NR 3 –C(O)–, and / or –NR 3 –, –OC(O)NR 3 –、–NR 3 –C(O)–NR 3 -part and may be substituted by one or more OH groups, wherein R 3 is hydrogen, Me3Si- or C1-C8-alkyl, p＝1-9， m＝1-20， and F is selected from an optionally substituted linear, cyclic or branched, saturated or unsaturated or aromatic hydrocarbon group having up to 100 carbon atoms and which optionally contains a tertiary amino group selected from -O-, -S-, -NH-, -C(O)-, -C(S)- or quaternary ammonium group and may be substituted by an OH group, an SH group, a halogen group, an organosilyl group or a triorganosiloxy group, in (ii) When A is a group of the formula -LF, then L contains at least one ether group (-O-), and optionally has at least one hydroxyl substituent (-OH), and F is as defined above, provided that it includes at least one ester group (-O-C(=O)- or -C(=O)-O-), or (i) When A is a group of the formula –{L–[SiR 1 2O] p –SiR 1 2} m –L–F, then L, R 1 , p, m are as defined above in the claim, and F further comprises at least one moiety selected from the group consisting of acrylate, methacrylate, thiol, alkoxy, amino and isocyanate groups, ketones, diketones, dicarboxyl groups, diesters, nitro, cyano, alkylsulfonyl fluoride groups, oxycarbonylalkyl groups, wherein the alkyl groups are selected from branched or cyclic C3-C22 alkyl groups, or polyoxyalkylene groups of the following formula: [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 in [-OC2H4] represents an ethyleneoxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents a butyleneoxy unit, q＝0-40， r＝0-30， s＝0-20， And q+r+s>2, R 4 Selected from hydroxyl, alkoxy, hydroxyalkyl, siloxy, glycidyl and glycidyloxy groups, and organosilyl groups SiR 1’ 3, where R 1’ are independently selected from alkyl groups, and the group A is bonded to the silica particle via a silicon atom which is connected to the silicon dioxide network of the silica particle via one or more oxygen atoms, wherein the valences of the silicon atom not occupied by a group -A or an oxygen atom are replaced by a substituent R as defined above 1 occupy.

57. The antifouling or antifogging coating of claim 56, wherein R 1 are independently selected from hydrocarbyl groups.

58. The antifouling or antifogging coating of claim 56, wherein R 1 are independently selected from alkyl groups.

59. The antifouling or antifogging coating of claim 56, wherein R 1 It is methyl.

60. The antifouling or antifog coating according to claim 56, wherein L is a divalent C2-C12-alkylene group.

61. The antifouling or antifog coating of claim 56, wherein L is a divalent C2-C4 alkylene group.

62. The antifouling or antifog coating of claim 56, wherein L is -(CH2)2- and / or -(CH2)3-.

63. The antifouling or antifog coating of claim 56, wherein p=1 or 4.

64. The antifouling or antifog coating of claim 56, wherein p=4.

65. The antifouling or antifog coating of claim 56, wherein m=1.

66. The antifouling or antifog coating of claim 56, wherein q = 0-20.

67. The antifouling or antifog coating of claim 56, wherein q = 1-15.

68. The antifouling or antifog coating of claim 56, wherein r = 0-20.

69. The antifouling or antifog coating of claim 56, wherein r = 0-10.

70. The antifouling or antifog coating of claim 56, wherein s = 0-15.

71. The antifouling or antifog coating of claim 56, wherein s = 0-10.

72. Use of an antifouling or antifog coating according to any one of claims 1 to 71 for the manufacture of a coating composition for an antifouling or antifog coating.

73. Use according to claim 72, wherein the use is as a marine antifouling additive, an anti-icing additive, a self-cleaning additive, an anti-adhesion additive in a coating composition.

74. The use according to claim 72, wherein the use is as a general antifouling additive or antifogging additive in a coating composition.

75. Use according to claim 72, wherein the use is as an antifouling additive in a coating composition.

76. The use according to claim 75, wherein the use is as an anti-dust, anti-fingerprint, and anti-graffiti additive in a coating composition.

77. The use according to claim 72, wherein the coating composition comprises 0.1 to 80 wt% of the silica particles, based on the total weight of the coating composition.

78. The use according to claim 72, wherein the coating composition comprises 0.5-70 wt% of the silica particles based on the total weight of the coating composition.

79. The use according to claim 72, wherein the coating composition comprises 1 to 60 wt% of the silica particles based on the total weight of the coating composition.

80. The use according to claim 72, wherein the coating composition comprises 20-55 wt% of the silica particles based on the total weight of the coating composition.

81. The use according to claim 72, wherein the coating composition comprises 25-50 wt% of the silica particles based on the total weight of the coating composition.

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