Functionalized silica particles and their uses

Abstract

This invention provides functionalized silica particles that can simultaneously introduce the required hardness and anti-fouling / anti-fogging properties into coating formulations. [Solution] The present invention relates to silica particles functionalized with one or more silanes, each containing a terminal group that enables a condensation reaction with the surface of the silica particles and at least one further terminal group for modifying the properties of the silica particles. The present invention also relates to a method for functionalizing silica particles with silanes, silanes to be applied for the functionalization of silica particles according to the present invention, a method for functionalizing silica with silanes, silica particles containing functional groups, the use of silica particles according to the present invention, and a coating composition containing silica particles according to the present invention.

Description

[Technical Field]

[0001] This invention relates to silica particles functionalized with one or more silanes, their use in applications such as antifouling or anti-fogging coatings, methods for functionalizing silica particles, and specific silanes used for functionalizing silica particles. This invention also relates to coating compositions comprising such functionalized silica particles. The antifouling project is funded by the German Federal Ministry for Economic Affairs and Energy under Grant Agreement 03SX370H. [Background technology]

[0002] Coatings containing hydrophilic materials, such as polyether-functionalized silicone derivatives disclosed in EP3325540A1, have demonstrated a significant reduction in adhesion strength to marine organisms' surfaces. Furthermore, these additives, when incorporated into thermal acrylic clear coats, have been demonstrated to be effective as anti-fogging agents. [Overview of the project]

[0003] Problems to be solved However, adding functionalized, less branched, long-chain silicone derivatives or polyethers to coating formulations can gradually decrease the hardness of the coating, and therefore reduce its impact resistance and scratch resistance. Such properties are prerequisites for the successful application of coating formulations in fields such as marine antifouling and hard coats and clear coats for automotive headlights. To mitigate the hardness-reducing effect of additives, filler materials, such as surface-treated silica or other particle species, can be added, but this is undesirable as it can make the formulation mixture more complex.

[0004] The above problem is solved by providing silica particles functionalized with one or more silanes having specific structural characteristics, for example, by coating each silica particle with an antifouling additive or an anti-fogging additive.

[0005] The softening effect of the coating by the additive itself is directly offset by the hardness characteristics of the silica particles. Furthermore, the combination of the particles and the antifouling additive reduces the complexity of the final coating formulation, thus improving the overall applicability. Therefore, the necessary hardness and antifouling / anti-fogging properties can be introduced into the coating formulation simultaneously. Furthermore, in addition to the aforementioned advantages, the silica particles according to the present invention can be incorporated into the coating matrix, and at the same time have functional groups that make the silica particles hydrophobic or hydrophilic, and also bring specific properties to the coating, such as antifouling or antibacterial properties. According to the present invention, the silica particles can be functionalized as described in the following embodiments.

[0006] In one aspect, the present invention relates to silica particles functionalized with one or more silanes of the following formula, HN[-SiR 1 2-A]2(1) and / or R 1 x R 2 3-x Si-A (2) where R 1 is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R 1 is methyl, R 2 is independently selected from hydrolyzable residues, preferably hydrocarbylcarbonyloxy groups such as hydrogen, hydroxy, acyloxy groups, halogen groups, amino groups, hydrocarbyloxy groups such as alkoxy or aryloxy groups, and more preferably is selected from the group consisting of alkoxy groups, x is 0, 1, or 2, and A is a group of the following formula, -M-F, where M is selected from L or a group of the following formula, -{L-[SiR 1 2O] p -SiR 1 2} m -L-, where L is one or more -O-, -NR 3 -C(O)-, and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR 3 - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R 3 is hydrogen, Me 3 L is Si- or C1-C8-alkyl, preferably a divalent C2-C12-alkylene group, more preferably a divalent C2-C4 alkylene group, and most preferably L is -(CH2)2- and / or -(CH2)3-. R 1 This is defined as above, p=1 to about 9, preferably p=1 or 4, more preferably p=4, m=1 to about 20, preferably m=1, and F has up to approximately 100 carbon atoms, and also -O-, -S-, -NH-, -C(O)-, -C(S)-, and tertiary amino groups. [ka] or quaternary ammonium group [ka] Selected from the group consisting of optionally substituted, linear, cyclic, or branched, saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with an OH group, SH group, halide group, organosilyl group, or triorganosiloxy group, However, regarding the silane in formula (2), (i) A is the basis of the following equation, -{L-[SiR 1 20] p -SiR 1 2} m-LF, here L, R 1 p, m, and F are defined as above. or (ii) A is the basis of the following equation, -LF, where L contains at least one ether group (-O-) and optionally at least one hydroxy substituent (-OH), and where F is as defined above, provided that it contains at least one ester group (-OC(=O)- or -C(=O)-O-). These are the conditions. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 shows the change in the water droplet contact angle over time on the cured coating formulation 1. [Figure 2] Figure 2 shows the change in the water droplet contact angle over time on the cured coating formulation 2. [Figure 3] Figure 3 shows the change in the water droplet contact angle over time on the cured coating formulation 3. [Modes for carrying out the invention]

[0008] This invention generally relates to silica particles functionalized with one or more silanes. According to this invention, the term “silica particles” refers to silicon dioxide particles, including but not limited to colloidal silica particles or fumed silica particles. Generally, the silica particles according to the present invention have a diameter of about 1 to about 300 nm, preferably about 1 to about 150 nm, more preferably about 5 to about 50 nm. 50 It may have an average primary particle size, and when aggregates are formed, it is 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, and even more preferably about 5 to about 150 μm; most preferably about 5 to about 75 μm D 50The average aggregated particle size may be. The silica particles may include, but are not limited to, fumed (i.e., calcined) silica or precipitated silica, and may include crystalline or amorphous silica particles. In one embodiment, the silica particles are preferably fumed silica particles. According to the present invention, the particle size is determined in particular by laser dynamic light scattering using a Malvern zetasizer, a method also known as photon correlation spectroscopy or quasi-elastic light scattering, in accordance with ISO 13320-1 (see also http: / / en.wikipedia.org / wiki / Dynamic_light_scattering), to obtain an average particle size D 50 This can be determined by measuring the average particle size D. This method is particularly optimal for non-cured compositions, but in some cases, transmission electron microscopy (TEM) can be used to determine the average particle size D. 50 It is quite possible that this could be the decision.

[0009] According to the present invention, the term "functionalization" indicates that silica particles are modified by contact with one or more functionalized silanes, resulting in a change in the properties of the particles with respect to the properties of the particles before functionalization, due to the presence of other functional groups on the surface of the particles. Typically, the functionalization of silica particles with silanes is carried out by the formation of siloxane units through a condensation reaction between the silane or organosilyl ether and one or more OH groups present on the surface of the silica particles. According to this mode of functionalization, the silane contains one or more hydrolyzable groups, such as chloro groups, on the silicon atoms.

[0010] According to one embodiment of the present invention, several hydrolyzable groups R may be present in the silane of formula (2). 2These are defined as alkoxy or acyloxy groups that readily undergo condensation reactions with silanol-SiOH groups present on the silica surface, for example. Similarly, the proposed mechanism for the functionalization of silanol-SiOH groups on the silica surface with disilazane of formula (1) involves the initial hydrolysis of the silazane group by water present in the system or added to the reaction system, which leads to a silanol-functionalized silane. These silanol groups of the silane can condense with silanol groups present on the silica surface. The formation of terminalized silyl ethers by the silyl-based structures defined in formulas (1) and (2) allows for the attachment of various functional groups to the silica particle surface, making the particles hydrophobic, hydrophilic, coating matrix reactive, or providing other further properties required for the particles.

[0011] According to the present invention, R 1 The group is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R 1 Here, the term "non-hydrolyzable" indicates that the group cannot be easily cleaved by the addition of water, hydroxide anions, or, in exactly the same way, by the addition of alcohols or alkoxide anions, especially under acidic or basic conditions. The term "non-hydrolyzable" indicates that the group is preferably bonded to a silicon atom by a C-Si bond, and therefore, non-hydrolyzable groups are preferably organyl groups.

[0012] According to the present invention, non-hydrolyzable R 1 The group is preferably selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, alkaryl groups, aralkyl groups, and aryl groups, such as phenyl, benzyl, or tolyl groups, and in particular can be selected from such groups having 1 to about 22 carbon atoms, and is optionally a fluorinated hydrocarbyl group.

[0013] More preferably, non-hydrolyzable R 1The group can be selected from alkyl groups that can be unsubstituted linear, branched, and cyclic alkyl groups, or groups that combine linear and cyclic alkyl motifs, or structures that combine branched and cyclic structures, particularly 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 cyclic C3-C22 alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

[0014] More preferably, a non-hydrolyzable group R 1 The group is selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, or cyclohexyl groups, most preferably R 1 It is methyl.

[0015] According to the present invention, R 2 The group is selected independently of hydrolyzable residues and is preferably selected from the group consisting of hydrogen, hydroxy, hydrocarbylcarbonyloxy groups, such as acyloxy groups, halogen groups, amino groups, hydrocarbyloxy groups, such as alkoxy or aryloxy groups, and more preferably an alkoxy group.

[0016] Here, the term "hydrolyzable" means that it can be easily cleaved by the addition of water, a hydroxyl anion, or, in the case of water or alcohol, by the addition of an alcohol or alkoxyl anion, especially under acidic or basic conditions. The term "hydrolyzable" indicates that the group is bonded to the silicon atom by a Si-X bond rather than a C-Si bond, where X is Cl, Br, or I, or R 2 The bond is a Si-O bond, Si-N bond, Si-S bond, or Si-H bond, as is the case when selected from hydroxy, hydrocarbylcarbonyloxy, and hydrocarbyloxy groups.

[0017] According to the present invention, hydrolyzable group R 2 Preferably, the hydrocarbyl residue is independently selected from the group consisting of hydrogen, a hydroxyl group, and a hydrocarbyl carbonyloxy group, where the hydrocarbyl residue is an alkyl group, an alkenyl group, an alkynyl group, an alkaryl group, an aralkyl group, and an aryl group, particularly a linear C1-C22 alkyl group, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl group, a branched C1-C22 alkyl group, for example, isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl group, and a cyclic C3-C22 alkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl group, hydrocarbyl The hydrocarbyl group can represent an alkyl group, alkenyl group, alkynyl group, alkaryl group, aralkyl group and aryl group, in particular linear C1-C22 alkyl groups, e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl group, branched C1-C22 alkyl groups, e.g., isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl group, and cyclic C3-C22 alkyl groups, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl group, halogen group, and amino groups including primary, secondary and tertiary amino groups.

[0018] More preferably, hydrolyzable group R 2 The group is an alkoxy group, and more preferably a methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, iso-propoxy, iso-butoxy, tert-butoxy, neopentoxy, cyclopentoxy, or cyclohexoxy group, or more preferably a methoxy, ethoxy, or isopropoxy group, most preferably a methoxy group.

[0019] According to the present invention, in formula (2), x is 0, 1, or 2, preferably x is 0 or 1, and most preferably x is 0. Silanes having three hydrolyzable groups have been shown to be beneficially applicable to the functionalization of silica particles and can be conveniently prepared.

[0020] As defined above, according to the present invention, A is the base of the following formula, -MF, Here, M is selected from L or the base of the following formula, -{L-[SiR 1 20] p -SiR 1 2} m -L- L is one or more -O-, -NR 3 -C(O)-, and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR 3 - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R 3 These are hydrogen, Me3Si-, or C1-C8-alkyl.

[0021] According to the present invention, L is preferably independently selected from the group consisting of divalent C2-C12-alkylene groups, which includes linear divalent C2-C12 alkylenes, such as ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene; branched divalent C2-C12 alkylenes, such as isopropylene, isobutylene, tert-butylene, isopentylene, neopentylene, methylpentylene, methylhexylene, ethylhexylene, methylheptylene, ethylheptylene, methyloctylene, and ethyloctylene; and cyclic divalent C2-C12 alkylenes, such as cyclopentylene, cyclohexylene, and cycloheptylene.

[0022] More preferably, L is independently selected from the group consisting of 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 an n-propylene group.

[0023] According to the present invention, formula -{L-[SiR 1 20] p -SiR 1 2} m -L- Middle R 1 This is defined above, and preferably the following formula -{L-[SiR 1 20] p -SiR 1 2} m -L- Middle R 1 teeth, A saturated hydrocarbon substituent selected from the group consisting of monovalent C1-C22-alkyl, C6-C22-aryl, C8-C22-polycyclic aryl, C7-C22-alkylaryl, and C7-C22-arylalkyl groups, optionally substituted with one or more fluoro substituents, more preferably the following formula -{L-[SiR 1 20] p -SiR 1 2} m -L- Middle R 1 teeth, R is selected from the group consisting of methyl, 3,3,3-trifluoropropyl, phenyl, styryl, phenylpropyl, and naphthyl, and more preferably R is selected here. 1 is selected from methyl, phenyl, and 3,3,3-trifluoropropyl, and most preferably the following formula -{L-[SiR 1 20] p -SiR 1 2} m -L- Middle R 1 teeth, It is methyl.

[0024] According to the present invention, p=1 to about 9, preferably p=1 to 4, more preferably p=4. This should be understood in the sense that the mean of the silane subscript p of formulas (1) and / or (2) applied to the functionalization of silica particles is in the range of 1 to about 9, including these endpoints, where the mean is preferably in the range of 1 to 4, including these endpoints, and most preferably the mean of the subscript p is 4.

[0025] According to the present invention, it is more preferable that p is 1 to about 9, where the subscript p of all silanes of formula (1) and / or (2) applied to the functionalization of silica particles is an integer in 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 in the range of 1 to 4, i.e., 1, 2, 3 and 4, and most preferably p is 4.

[0026] This corresponds to the range from disiloxane block to decasiloxane block present in base M, which is represented by the following formula. -{L-[SiR 1 20] p -SiR 1 2} m -L-. Setting the parameter p to 4 corresponds to the presence of a pentasiloxane block at group M. The precursor of such a block is HMe2Si-O-[Me2SiO]3-SiMe2H, which can be readily synthesized in high purity by a non-equilibrium reaction of hexamethylcyclotrisiloxane and HMe2Si-O-SiMe2H (e.g., according to JP11158188B, the whole of which is incorporated herein by reference). After additional distillation, a pentasiloxane content of over 90% by weight can be achieved by gas chromatography. The above method for synthesizing non-equilibrium polyorganosiloxanes is also applicable to tetraorganodisiloxanes and hexaorganocyclotrisiloxanes other than hexamethylcyclotrisiloxane and HMe2Si-O-SiMe2H.

[0027] According to the present invention, m = 1 to about 20, preferably 1 to about 10, more preferably 1 to 5, and most preferably m = 1. This is understood to mean that the average of the silane subscript m in formulas (1) and / or (2) applied to the functionalization of silica particles is in the range of 1 to about 20, including these endpoints, where the average of m is preferably in the range of 1 to about 10, including these endpoints, more preferably in the range of 1 to 5, including these endpoints, and most preferably the average of the subscript m is 1.

[0028] According to the present invention, it is more preferable when m is 1 to about 20, where the subscript m of all silanes of formula (1) and / or (2) applied to the functionalization of silica particles is an integer in 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 in the range of 1 to 10, more preferably the subscript m is an integer in the range of 1 to 5, and most preferably m is 1. Polyorganosiloxanes having a single siloxane block, i.e., a group M with m=1, preferably bonded together via a divalent group L as defined above, and having up to about 20, particularly 2, 3, 4, or 5 siloxane blocks, i.e., up to about 20, particularly m=2, 3, 4, or 5, are synthesized by stepwise addition reactions of symmetrically substituted and asymmetrically substituted siloxane blocks, preferably di, penta, or decasiloxane blocks, most preferably pentasiloxane blocks.

[0029] According to the present invention, group A is terminated by group F which is bonded to group M as described above.

[0030] According to the present invention, F has up to about 100 carbon atoms, and -O-, -S-, -NH-, -C(O)-, -C(S)-, tertiary amino group, [ka] and quaternary ammonium groups [ka] Selected from the group consisting of optionally substituted, linear, cyclic, or branched, saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with OH groups, SH groups, halide groups, organosilyl groups, and triorganosiloxy groups. In the functionalization of silica particles, the properties of group F significantly influence the properties of the modified silica surface, as the terminal group F and its mode of functionalization determine whether the particles are hydrophobic or hydrophilic overall, or other properties the particles exhibit. In particular, the presence of reactive functional groups allows group F to interact and bond with other components of the composition, and thus bond to the polymer matrix of the cured composition.

[0031] In accordance with the above definition of F according to the present invention, F is preferably a 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, where all of these groups are C1-C8-alkyl, OH, Cl, or Br, and a silyl ether group R 1 3Si-O- is optionally substituted, and here R 1 The definitions for equations (1) and (2) above are as follows, and here R 1can be selected from the group consisting of, preferably a C1-C8 alkyl group, most preferably a methyl group, and F can preferably be an OH terminus or a C1-C8 oxyalkyl terminus or a C1-C8 oxycarbonylalkyl terminus, can be selected from the group consisting of poly(C2-C4 alkylene) oxide, F is vinyl, allyl, hexenyl, octenyl, allyloxypropyl, -CH2C≡CH, -C(O)C≡CH, -C(O)(CH2)8CH=CH2, cyclohexenylethyl, limonyl, norbornenylethyl, 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 -O-C(O)-C1-C4 alkyl, where a, b, c are from 0 to 20, and a + b + c = 1 to 20, -[Si(CH3)2OSi(CH3)2]CH=CH2, and

Chemical formula

Chemical formula

Chemical formula

[0032] According to the present invention, group F is preferably a C1-C24 unsubstituted alkyl group, specifically a linear C1-C24 alkyl group, a C2-C24 alkylene oxide, and a poly(alkylene oxide) group, where the alkylene oxide unit is an ethylene oxide unit, a propylene oxide unit, or a combination thereof, and represents a C2-C24 oxycarbonylhydrocarbyl group, particularly a C2-C24 oxycarbonyl alkyl group, a C1-C24 oxyalkyl group, a C1-C24 alkanoyl group, or a C1-C24 alkanoyl ester group, where the alkoxide group of the alkanoyl ester group is a C1-C12 alkoxide group. Here, 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, particularly methyl and ethyl groups. Unsubstituted hydrocarbon groups, especially unsubstituted alkyl groups, are highly nonpolar, i.e., hydrophobic functional groups, and thus functionalization of silica particles with silanes of formula (1) and / or (2), where group F is as described, makes the particles hydrophobic.

[0033] According to the present invention, when group F represents a C2-C24 poly(alkylene oxide) group, it preferably represents a poly(ethylene oxide) group having about 2 to about 12 ethylene oxide repeating units, or a poly(propylene oxide) group having about 2 to about 8 propylene oxide repeating units. Here, the poly(alkylene oxide) group is preferably terminated by an OH group, a methoxy group, or a trimethylsiloxy group. More preferably, the poly(alkylene oxide) group represented by F is structure-(O-CH2CH2) z1 -OH residues are selected, where z1 is in the range of about 3 to about 12, more preferably about 5 to about 11, and even more preferably about 6 to about 10.5. Here, z1 refers to the average number of repeating units (O-CH2CH2) contained in the silane base F of formula (1) and / or (2), which includes 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. More preferably, the poly(alkylene oxide) group represented by F is structure-(O-CH2CH2) z2 - Selected from OMe residues, where z2 is in the range of about 3 to about 12, more preferably about 5 to about 11, and even more preferably about 6 to about 10.5. Here, z2 refers to the average number of repeating units (O-CH2CH2) contained in the silane base F of formula (1) and / or (2), which includes 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. Similarly, more preferably, the poly(alkylene oxide) group represented by F is structure-(O-CH2CH2) z3 - Selected from OSiMe3 residues, where 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. Here, z3 refers to the average number of repeating units (O-CH2CH2) contained in the silane base F of formula (1) and / or (2), which includes 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. Most preferably, the poly(alkylene oxide) group represented by F is -(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-OSiMe3, -(O-CH2CH2)9-OSiMe3, -(O-CH2CH2) 10 -OSiMe3, -(O-CH2CH2) 11 -OSiMe3 and -(O-CH2CH2) 12 Selected from the group consisting of -SiMe3. The poly(alkylene oxide) group of F makes the silane residues bonded to the surface of the silica particles polar, i.e., hydrophilic, and therefore the surface of the silica particles becomes hydrophilic through such functionalization. It is particularly preferable that the poly(alkylene oxide) group is terminated with an OH group, a methoxy group, or a trimethylsiloxy group.

[0034] When group F represents a C2-C24 oxycarbonyl alkyl group, according to the present invention, it is preferable that the alkyl group of the oxycarbonyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, 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 cyclic C3-C22 alkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups. According to the present invention, it is also preferable that the alkyl group of the oxycarbonyl alkyl group is bonded to the oxycarbonyl group by carbon atoms substituted with three C1-C8 alkyl substituents. In this case, it is particularly preferable that the sum of the carbon atoms of all three alkyl substituents is about 10 or less, and it is even more preferable that one of the alkyl substituents is a methyl group and the sum of the carbon atoms of the two further alkyl substituents is about 8 or less.

[0035] When group F represents a C1-C24 oxyalkyl group, according to the present invention, the alkyl group of the C1-C24 oxyalkyl group is preferably selected from the group consisting of 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 cyclic C3-C22 alkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups.

[0036] When group F represents a C1-C24 alkanoyl group, according to the present invention, the C1-C24 alkanoyl group is preferably a carboxylic acid residue -COOH, -CH2CO2H, -(CH2)2CO2H, -(CH2)3CO2H, -(CH2)4CO2H, -(CH2)5CO2H, -(CH2)6CO2H, -(CH2)7CO2H, -(CH2)7CO2H, -(CH2)9CO2H, or (CH2) 10 Selected from the group consisting of CO2H.

[0037] When group F represents a C1-C24 alkanoyl ester group, the alkoxy group of the alkanoyl ester group is a C1-C12 alkoxy group, and according to the present invention, the alkanoyl group is preferably an alkanoyl residue -CO, -CH2CO, -(CH2)2CO, -(CH2)3CO, -(CH2)4CO, -(CH2)5CO, -(CH2)6CO, -(CH2)7CO, -(CH2)7CO, -(CH2)9CO, or (CH2) 10 The group is selected from the group consisting of CO, and the alkoxy group of the ester is preferably selected from methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy, or n-hexoxy. Particularly preferred alkanoyl ester groups according to the present invention are selected from the group consisting of -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.

[0038] According to the present invention, group F preferably comprises one or more coating matrix reactive groups which are functional groups that can interact with or bond to the polymer matrix of the coating matrix before, during, or after curing of the curable composition. These groups may be any type of group that can interact with the coating polymer matrix or its precursor, in particular functional groups selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxy, 1,3-dicarboxy, diester, 1,3-diester, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups for Michael addition reactions that are incorporated into the polymer matrix by the formation of covalent bonds.

[0039] According to the present invention, the definitions given above describe the present invention. However, regarding the silane in formula (2), (i) A is the basis of the following equation, -{L-[SiR 1 20] p -SiR 1 2} m -LF, here L, R 1 p, m, and F are defined as above. or (ii) A is the basis of the following equation, -LF, where L contains at least one ether group (-O-) and optionally has at least one hydroxy substituent (-OH), and F is as defined above, provided that it contains at least one ester group (-OC(=O)- or -C(=O)-O-). These are the conditions.

[0040] In a preferred embodiment of the present invention, silica particles are functionalized with one or more silanes of formula (1) and / or formula (2), where one or more silanes of formula (1) and / or (2) include one or two groups A comprising a group M of the following formula: -{L-[SiR 1 20] p -SiR 1 2} m -L- Here, L, R 1 p and m are as defined above, Here, the formula is -{L-[SiR 1 20] p -SiR 1 2} m One or more groups M of -L- essentially consist of one or more defined polysiloxane blocks, which consist of a disiloxane, a polyorganopentasiloxane, or a polyorganodecasiloxane block, where the term "essentially consists of" means that more than about 50% of the number of groups M in this embodiment have the same chain length, and the subscript p in the above formula is p = 1, 4, or about 9. In this specification, p cannot refer to the mean, but it is clear that it refers to a distinct value of p, which is an integer selected from 1, 4, or about 9.

[0041] In a more preferred embodiment of the present invention, the formula -{L-[SiR 1 20] p -SiR 1 2} m -L-(L, R here) 1 The base M of (where m is defined above) has subscripts p of exclusively 1, exclusively 4, or exclusively about 9. Particularly preferred is a formula with a number exceeding approximately 90% -{L-[SiR 1 20] p -SiR 1 2} m -L-(L, R here) 1The base M of (where m is defined above) has subscripts p of exclusively 1, exclusively 4, or exclusively about 9. Such a highly homogeneous group M with a polydispersity index close to 1 can be achieved by the precursor purification process according to the present invention. Therefore, it is said to have a group M having a unimodal chain length distribution. The precursors, i.e., compounds such as disubstituted tetraorganodisiloxanes, hexaorganocyclotrisiloxanes, and their reaction products in non-equilibrium reactions, have different boiling points and can be concentrated and purified, for example, by distillation or crystallization, in each of the subsequent steps of terminal group addition, thus enabling this feature to be achieved. For example, one preferred p=4 pentasiloxane unit can be derived from HMe2Si-O-[Me2SiO]3-SiMe2H, which is synthesized by a non-equilibrium reaction of hexamethylcyclotrisiloxane, which is already of high purity, with HMe2Si-O-SiMe2H (e.g., according to JP11158188B). After additional distillation, a pentasiloxane content of over 90% by weight can be achieved by gas chromatography.

[0042] The aforementioned process for synthesizing non-equilibrium polyorganosiloxanes is also applicable to other disubstituted tetraorganodisiloxanes and hexaorganocyclotrisiloxanes. M *H D3M *H Structure (here "M *HA purified pentasiloxane having (where ) represents a hydride-substituted siloxane monounit in its structure is subjected to the addition of further compounds containing reactive groups that can undergo hydrosilylation with terminal SiH units. Therefore, the reagent applied to the introduction of the L group needs to be appropriately functionalized to undergo the hydrosilylation step with a hydrogenated siloxane, for example by containing a terminal CC double bond. The reagent used for hydrosilylation may also already contain sufficient amounts of a silane structure bonded to A at the other end of group F and M. For example, by reacting one end of the precursor of formula (3a) with an allyl-terminated polyether in a hydrosilylation reaction, and then reacting the resulting intermediate with (MeO)3SiVi in a hydrosilylation reaction, a compound of formula (2) having three hydrolyzable methoxy groups at the silane end is obtained, where the first L group linking the silane portion to the polysiloxane portion is an ethylene group, the L group linking the polysiloxane group to group F is a propylene group, and F is a polyether group.

[0043] 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 provides symmetrically reactive substituents to the terminal groups. Particularly suitable polyorganosiloxanes include, but are not limited to, the following: [ka] Here L and R 1 The formula is -{L-[SiR 1 20] p -SiR 1 2} m -LF is defined as described above.

[0044] In a preferred embodiment, substituents on the polyorganosiloxane moiety of the precursor represented by formula (3a) are defined as follows: R is independently selected from methyl, 3,3,3-trifluoropropyl, phenyl, styryl, phenylpropyl, and naphthyl. 1is as defined above and is preferably methyl.

[0045] In yet another preferred embodiment according to the invention, less than 60% by number of the formula - {L - [SiR 1 2O] p -SiR 1 2} m -L- (L, R 1 , and m are as defined above) of the group M, and particularly preferably less than 50% by number of the formula - {L - [SiR 1 2O] p -SiR 1 2} m -L- (L, R 1 , and m are as defined above) of the group M have the same chain length, where the number average of the subscript p is in the range from about 2 to about 8, more preferably from about 3 to about 7, and most preferably from about 3.5 to about 6.5.

[0046] All subscripts indicating the range of the number of repeating units in the oligo- or poly(alkylene oxide) or oligo- or polysiloxane structural units generally refer to the average value obtained for the silanes of formula (1) and / or (2) applied to the functionalization of the silica particles containing at least one of each repeating unit. This is due to the fact that the starting materials for providing such structural motifs are often mixtures defined by the average chain length. However, in general, it is preferred that the subscript represents an integer within a given range, i.e., the number of repeating units is within the range indicated for all silanes of formula (1) and / or (2) applied to the functionalization of the silica particles containing one or more of each repeating unit shown.

[0047] In a preferred embodiment according to the invention, in formula (1), when M is L, silica particles are provided where 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. Preferably, in formula (1), M is L, and silica particles are provided in which the group F contains at least one heteroatom such as N, O, Si, or a halogen atom such as fluorine or chlorine. More preferably, in formula (1), M is L, the group F contains one or more oxygen atoms, and more preferably, F contains one or more oxygen atoms, where at least one oxygen atom is an oxygen atom of an ether or ester moiety, and still more preferably, the group F contains three or more oxygen atoms, where at least three oxygen atoms are oxygen atoms of an oligo or poly(alkylene oxide) group, and even more preferably, the group F contains five or more oxygen atoms, where at least five oxygen atoms are oxygen atoms of an oligo or poly(alkylene oxide) group, and still more preferably, the group F contains a poly(ethylene oxide) or poly(propylene oxide) unit containing five or more oxygen atoms. Most preferably, in the compound of formula (1), M is L, and F=-(O-CH2CH2) 4-12 -OH, or F=-(O-CH2CH2) 4-12 -OMe, or F=-(O-CH2CH2) 4-12 -OSiMe3.

[0048] The compound of formula (1) according to this embodiment of the present invention is, for example, the following formula HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2) 4-12 -OH)2, particularly HN(-SiMe2-(CH2)2-(O-CH2CH2) 10 -OH)2 and HN(-SiMe2-(CH2)3-(O-CH2CH2) 10 -OH)2, HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2) 4-12 -OMe)2, particularly HN(-SiMe2-(CH2)2-(O-CH2CH2) 7.5-OMe)2 and HN(-SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OMe)2, or HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2) 4-12 -OSiMe3)2, especially HN(-SiMe2-(CH2)2-(O-CH2CH2) 10 -OSiMe3)2, and HN(-SiMe2-(CH2)3-(O-CH2CH2) 10 -OSiMe3)2 It is a compound represented by [this symbol].

[0049] In this embodiment, M is L, and F preferably contains or is an oxycarbonylalkyl group of the following formula: -OC(O)-alkyl, Here, 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 from isopropyl, sec-butyl, tert-butyl, neopentyl, or formula-CR a R b R c From the alkyl group, Here, 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 the alkyl groups are alkyl groups, more preferably the alkyl groups are linear alkyl groups selected from ethyl or methyl, or formula -CR a R b R c , here R c R is hydrogen or methyl, a and R b It is a branched alkyl group selected from a linear alkyl group having a total of 3 to 11 carbon atoms.

[0050] Further compounds of formula (1) according to this embodiment of the present invention are, for example, compounds represented by the following formula: HN(-SiMe2-(CH2) 2-3 -(OC(O)alkyl))2, specifically HN(-SiMe2-(CH2)2-(OC(O)alkyl))2 and HN(-SiMe2-(CH2)3-(OC(O)alkyl))2, more specifically HN(-SiMe2-(CH2)2-(OC(O)-CMeR a R b ))2 and HN(-SiMe2-(CH2)3-(OC(O)-CMeR a R b ))2, here R a and R b It is a linear alkyl group with a total number of carbon atoms ranging from 3 to approximately 9.

[0051] In another preferred embodiment of the present invention, silica particles are provided, where in formula (1), M is L, and the group F comprises one or more silicon atoms, more preferably the group F comprises one or more silicon atoms, where one of the silicon atoms is a silicon atom of a terminal triorganosilyl group, for example -SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, -SitBuPh2, and more preferably the terminal of F The triorganosilyl group is selected from SiMe2CH=CH2, SiMe3, or SiEt3 and bonded to an oxygen atom, and 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 constitutes a terminal group of a C1-C12 linear alkyl group or a C1-C12 alkenyl group. Most preferably, in the compound of formula (1), M is L, and F = -(O-CH2CH2)4-12 -OSiMe3, or F = -(O - CH2CH2CH2) 4-12 -OSiMe3, or F = -(O-CH2CH2) 4-12 -OSiEt3, or F = -(O - CH2CH2CH2) 4-12 -OSiEt3.

[0052] The compound of formula (1) according to this embodiment of the present invention is, for example, a compound represented by the following formula: HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2CH2) 4-12 -OSiMe3)2, specifically HN(-SiMe2-(CH2)2-(O-CH2CH2CH2) 10 -OSiMe3)2 and HN(-SiMe2-(CH2)3-(O-CH2CH2CH2) 10 -OSiMe3)2, or HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2) 4-12 -OSiEt3)2, specifically HN(-SiMe2-(CH2)2-(O-CH2CH2) 7.5 -OSiEt3)2 and HN(-SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OSiEt3)2, or HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2CH2) 4-12 -OSiEt3)2, specifically HN(-SiMe2-(CH2)2-(O-CH2CH2CH2) 10 -OSiEt3)2 and HN(-SiMe2-(CH2)3-(O-CH2CH2CH2) 10 -OSiEt3)2.

[0053] Another preferred embodiment of the present invention provides silica particles, where in formula (1), the substituent of the hydrocarbyl radical F is selected from the group consisting of hydroxyl, thiol, alkoxy, siloxy, perfluoroalkyl, carboxyl, ester, aminoalkyl, thioalkyl, or polyether groups, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxy, 1,3-dicarboxy, diester, 1,3-diester, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0054] Preferably, the substituents of the hydrocarbyl radical F are hydroxyl groups, alkoxy groups, particularly methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butioxy, tert-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n-hexoxy, cyclopentoxy or cyclohexoxy groups, siloxy groups, particularly -SiMe2-O-SiMe2-CH=CH2, -OSiMe3, -OSiEt3, -OSi(iPr)3, -OSiPh3, -OSi(cyHex)3, -OSitBuMe2, -OSitBuPh2, perfluoroalkyl groups, particularly trifluoromethyl, and general formula -C x F 2x+1Linear perfluoroalkyl groups, where x=2 to approximately 24, pentafluorophenyl, ester groups, in particular ester groups having the following formulas: -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, and ester groups in which the alkoxy group is a tertiary C4-C25 alkoxy group, and 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 The polyether group is selected from the group of compounds represented by -O-SiR3, where R=C1-C8 alkyl, a, b, and c are from 0 to 20, and a+b+c=1 to 20; more preferably, the hydrocarbyl radical F comprises both a polyether group and a terminal hydroxyl group, both a polyether group and a terminal alkoxy group, or both a polyether group and a terminal siloxy group as defined above.

[0055] Preferably, the substituents of the hydrocarbyl radical F are selected from alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxy, 1,3-dicarboxy, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups for Michael addition reactions.

[0056] It is particularly preferable that the hydrocarbyl radical F contains one or more groups of the structure -(OC(O)-alkyl, where the alkyl group is of the formula CMeR a R b It is an alkyl group, and here R a and R b is an alkyl group containing a total of 7 carbon atoms, or here R a and R b The alkyl group contains a total of six carbon atoms, and it is particularly preferable that the hydrocarbyl radical F includes one or more polyether structures, preferably polyether structures terminated by an OCH3, OH, or OSiMe3 group, or that the hydrocarbyl radical F includes one or more butyl groups.

[0057] In yet another preferred embodiment of the present invention, silica particles are provided, where F comprises a polyether moiety, an ester moiety, and a coating matrix reactive moiety, for example, at least one moiety selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxy, 1,3-dicarboxy, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0058] It is preferred that F contains a polyether moiety that provides hydrophilicity to the functionalized silica particles, and it is also preferred that F contains one or more coating-reactive moieties.

[0059] Preferred polyether moieties included in group F are 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 -O-C(O)-C1-C4 alkyl, and -(OCH2CH2) a -(OCH2CH(CH3)) b -(OCH2CH2CH(CH3)) c -O-SiR3, where R = C1-C8 alkyl, and a, b, c are from 0 to about 20 and a + b + c = 1 to about 20, and are selected from the group of compounds represented by, and groups represented by the formula -(OCH2CH2) 3-10 -OCH3, -(OCH2CH2) 3-10 -OH, and (OCH2CH(CH3)) 3-10 -OCH3-, (OCH2CH(CH3)) 3-10 -OH are more preferred.

[0060] The term "coating matrix reactive moiety" according to the present invention relates to any functional group 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 formation of a covalent bond. In this context, the coating matrix is defined as the polymer scaffold formed by the polymerization and / or curing of the polymerizable and / or curable compounds present in the coating composition.

[0061] Therefore, the type of coating composition to which functionalized particles are applied depends on whether the functional portion is coating matrix reactive. For example, acrylate or methacrylate groups are coating matrix reactive compounds in coating compositions based on curable polyacrylate or polymethacrylate, and alkenyl groups can be coating matrix reactive in coating compositions containing systems suitable for the radical polymerization of olefins or polyolefins, or in compositions containing groups that can undergo ene reactions, i.e., ene-philic groups such as thiol or hydroxyl groups. Thus, various functional groups can be considered coating matrix reactive, and those skilled in the art are well aware of which functional groups are coating matrix reactive for certain types of coating compositions.

[0062] According to the present invention, the most preferred coating matrix reactive moieties are, for example, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate, ketone, diketone, CH-acidic group, for example, 1,3-diketone, 1,3-dicarboxyl group, 1,3-diester, methylenenitro(-NO2) group, methylenenitrile group, Michael donor and acceptor group.

[0063] The preferred coating matrix reactive moieties selected from the group of 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.

[0064] Preferred coating matrix reactive moieties selected from the group of epoxy groups are glycidyl groups and glycidyloxy groups, particularly propylene glycidyl ether, phenylene glycidyl ether, C3-C12-epoxyalkyl, C6-C12-epoxycycloalkyl, C7-C16-epoxybicycloalkyl, epoxylimonyl, epoxycyclohexanetyl, epoxynorbornyl, [ka] The group is a monoepoxy polyether group or an acetylene epoxy ether group, such as a propargyl glycidyl ether group or a 1,4-butynediol-di-glycidyl ether group, generally a group having a terminal epoxide group.

[0065] The preferred reactive portion of the coating matrix, selected from the group of amino groups, includes primary amino groups -NH2 and secondary amino groups -NHR. 1 and tertiary amino group-NR 1 2 is included, and here R 1 The C1-C8 linear, branched, or cyclic alkyl group is included, and heterocyclic amino compounds are more preferred, with -NH2, NHMe, NHEt, NHnBu, -NHcyHex, -NMe2, -NEt2, and NcyHex2 (where cyHex is cyclohexyl).

[0066] The preferred coating matrix reactive moiety selected from the group of diketones is any type of alkyl group including a 1,3-diketone or 1,4-diketone moiety, more preferably a 1,3-diketone moiety.

[0067] The preferred coating matrix reactive moieties selected from the group of diesters are all types of alkyl groups, including a 1,3-diester or 1,4-diester moiety, and more preferably a 1,3-diester moiety.

[0068] A more preferred reactive portion of the coating matrix is ​​a portion containing a CH bond at the α-position to a β-diketo group, β-ketoester group, β-diester group, or nitro or nitrile group.

[0069] The preferred coating matrix reactive moieties are selected from the group of Michael donors consisting of thioates, alkoxides, particularly phenolates, amines, and alkenyls, epoxys, acrylates, methacrylates, thiols, hydroxyls, alkoxys, carboxy(-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyls, 1,3-dicarboxyls, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), and alkylsulfonyl fluoride groups, as well as acceptor groups in the Michael addition reaction. Among these, thioates and alkoxides exist in the silane according to the present invention as the corresponding thiols and alcohols under neutral conditions. Similarly, carboxyl groups may also exist as the corresponding carboxylate groups.

[0070] Preferred coating matrix reactive moieties selected from the group 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, with α,β-unsaturated ester groups and amide groups, particularly 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 being more preferred. Even more preferred coating matrix reactive moieties are malonic acid esters, 1,3-diester moieties, and 1,4-diester moieties.

[0071] A more preferred embodiment of the present invention provides silica particles, where F is - Alkyl, - Alkenil, - Alkylcarbonyloxy, - Polyalkylene oxide group, preferably one of the following general formulas: [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 Here [-OC2H4] represents an ethylene oxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q+r+s>2, R 4 This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyl oxy groups, - Organosilyl group, e.g., -SiR 1 3. Here R 1 The group is independently selected from the groups defined above for formulas (1) and (2), and a siloxy group, for example, -OSi(R 1 )3, here R 1 This is selected independently of the bases defined above for equations (1) and (2), It is selected from the group consisting of the following.

[0072] According to this embodiment of the present invention, preferred alkyl groups from which group F is selected are selected from the group consisting of linear, branched, and cyclic alkyl groups, or groups combining linear and cyclic alkyl motifs, or structures combining branched and cyclic structures, particularly 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 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, and most preferably from methyl.

[0073] According to this embodiment of the present invention, the preferred alkenyl group from which group F is selected is selected from the group consisting of linear or branched alkenyl groups having at least one terminal CC double bond and cyclic C5- and C6-alkenyl groups, more preferably a linear or branched C2-C30 alkenyl group having at least one terminal CC double bond, even more preferably a C2-C30 linear or branched alkenyl group 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.

[0074] According to this embodiment of the present invention, the preferred alkylcarbonyloxy group from which group F is selected is selected from the group consisting of alkylcarbonyloxy groups, where alkyl represents linear C1-C22 alkyl groups, e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl groups, branched C1-C22 alkyl groups, e.g., isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, neopentyl and 2-ethylhexyl groups, and cyclic C3-C22 alkyl groups, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups, most preferably methyl, ethyl, tert-butyl groups, and further branched alkyl groups comprising tertiary carbon atoms bonded to three linear C1-C8 alkyl groups and bonded to a carbonyloxy group.

[0075] According to this embodiment of the present invention, it is preferable that F is selected from the polyalkylene oxide group of the following general formula. [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 . Here, it is preferable that q+r+s is in the range of 2 to about 15, and it is particularly preferable that 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.

[0076] R is selected from the group consisting of hydroxyl, hydroxymethyl, hydroxyethyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, methylcarbonyloxy, tert-butylcarbonyloxy, -OSiMe3, -SiMe2-O-SiMe2-CH=CH2, glycidoxy group, or -SiMe3, SiPh3, -SiEt3, -SitBuMe2, -SiMe2 vinyl, or -SiMe2 allyl. 4 It is also preferable if R is selected.4 When represents a glycidyl or glycidoxy group, the group is preferably selected from a glycidyl group, a glycidyl propyl ether, or an allyl glycidyl ether group. According to this embodiment of the present invention, the preferred glycidyl or glycidyloxy group from which group F is selected is selected from the group consisting of a glycidyl group, a propylene glycidyl ether, and a phenylene glycidyl ether group.

[0077] According to this embodiment of the present invention, F is an organosilyl group -SiR 1 3 or siloxy group -OSi(R 1 )It is also preferable that it be selected from 3, where R 1 R is in equation (1) or (2). 1 This refers to the hydrocarbyl group as defined above. Organosilyl group SiR 1 3 or siloxy group -OSi(R 1 )3 R 1 It is more preferable that F is independently selected from the group consisting of C1-C8 alkyl groups, C2-C8 alkenyl groups, C6-C20 aryl groups, C7-C20 aralkyl or alkylaryl groups. It is most preferable that F is a siloxy group selected from the group consisting of -SiMe3, SiPh3, -SiEt3, -Si(iPr)3, -SitBuMe2, -SiMe2 vinyl, or -SiMe2 allyl, -OSiMe3, -SiMe2-O-SiMe2-CH=CH2, or a siloxy group selected from the group consisting of -OSiPh3, -OSiEt3, -OSi(iPr)3, -OSitBuMe2, -OSiMe2 vinyl, or -OSiMe2 allyl.

[0078] In another preferred embodiment of the present invention, silica particles are provided, where one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophobic silanes.

[0079] According to the present invention, the partition coefficient P of a compound HLF containing the -LF- group of silane in a 50 / 50 mixture of water and octanol is defined as follows: oct / wat , MagP oct / wat = log((solute) nonionized octanol / (solute) nonionized water) If the logP value is approximately equal to or greater than 0.5, the silane in equation (1) or (2) is considered hydrophobic. According to the present invention, when group A of silane is of the following formula, -LF Furthermore, even if the silane group A is given by the following formula, -{L-[SiR 1 20] p -SiR 1 2} m -LF It should be noted that this definition applies. In the latter case, the terminal structural group "-LF" is considered as defined above. If the silane of formula (1) has two different groups -LF, it is considered hydrophobic if the logP value, determined from the average of the partition coefficients of the two compounds HLF, is approximately 0.5 or greater. Experimentally, the partition coefficient is determined using a water / n-octanol mixture (50 ml water, 50 ml octanol). To this mixture, 1 ml of the substance to be measured for HLF is added at 25°C. The concentration of HLF in each layer is determined by quantitative analytical spectroscopy or spectroscopic methods. These methods include, among others, nuclear magnetic resonance spectroscopy (NMR), gas chromatography-mass spectroscopy (GC / MS), high-performance liquid chromatography-mass spectroscopy (HPLC / MS), infrared spectroscopy (IR), ultraviolet-visible spectroscopy (UV-VIS), and titration.

[0080] Preferably, the logP values ​​of one or more silanes of formula (1) and / or (2) are 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, and 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.

[0081] According to this embodiment of the present invention, the hydrophobic silane of formula (1) and / or (2) is exclusively functionalized by one type of hydrophobic functional group selected from alkyl groups, halogenated alkyl groups, particularly perfluorinated alkyl groups, alkenyl groups, triorganosilyl-terminated alkyl groups, triorganosiloxy-terminated ester groups, and oxycarbonyl alkyl groups, particularly linear C1-C12 alkyl groups and oxycarbonyl alkyl groups, where the alkyl group of the oxycarbonyl alkyl group is a linear or branched alkyl group from C1 to C12.

[0082] A more preferred embodiment of the present invention provides silica particles in which one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophilic silanes.

[0083] According to the present invention, if the logP value of the partition coefficient Poct / wat (as defined above) of compound HLF containing the -LF- group of silane in a 50 / 50 mixture of water and octanol is less than about 0.5, then the silane of formula (1) or (2) is considered hydrophilic. If the silane of formula (1) has two different -LF groups, it is considered hydrophobic if the logP value, determined from the average of the partition coefficients of the two compounds HLF corresponding to the -LF groups of the silane, is less than approximately 0.5.

[0084] Preferably, according to the present invention, the logP value of one or more silanes of 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, and 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.

[0085] According to this embodiment of the present invention, it is also preferable that the hydrophilic silane of formula (1) and / or (2) is exclusively functionalized by one type of hydrophilic functional group selected from a polyether group, a CH3 end-capped polyether group, a SiMe3 end-capped polyether group or an OH-terminated polyether group, a hydroxylated alkyl residue, or a polyhydroxylated alkyl residue present in the -LF group.

[0086] In a preferred embodiment of the present invention, silica particles are functionalized with two or more different silanes of formula (1) and / or (2).

[0087] Silica particles according to this embodiment can be obtained by subjecting silica particles to a functionalization reaction with a mixture of two or more different silanes of formula (1) and / or (2), or by carrying out two or more subsequent steps (where in each step, the silica particles are subjected to a functionalization reaction with one or more silanes of formula (1) and / or (2)). Thus, silica particles according to this embodiment of the present invention have differently functionalized residues, thereby making it possible to provide the silica particles with new and highly specifically tuned properties. The tuning of properties can be achieved not only by selecting a silane of formula (1) or (2) containing a particular functional group, but also by a combination of two or more particular silanes, and by adjusting the ratio of different chains having the functional group introduced by the reaction of the silica particles with different silanes of formula (1) and / or (2). For example, silica particles can be made hydrophobic by functionalization using a silane of formula (1) or (2) in which group F is a linear alkyl chain having more than 10 carbon atoms or a perfluorinated alkyl chain having more than 10 carbon atoms, and at the same time, silica particles can be incorporated into a coating matrix by functionalization using a silane of formula (1) or (2) in which group F is one or more coating matrix reactive groups, for example, an acrylate group, a methacrylate group, or an isocyanate group, resulting in the silica particles being incorporated into the coating matrix during the curing process. According to the present invention, it is preferable that the difference in logP values ​​of at least two silanes of formula (1) and / or (2) used for functionalizing the silica particles is about 0.8 or more, more preferably about 1.5 or more, even more preferably about 2.5 or more, even more preferably about 3.5 or more, and most preferably about 5.0 or more. Here, it is preferable that the silane of formula (1) or (2) having a higher logP value is a hydrophobic silane (i.e., logP ≥ approximately 0.5), while the silane having a lower logP value is a hydrophilic silane (i.e., logP < approximately 0.5). Please note that the difference in logP values ​​for the different silanes defined above is obtained by subtracting the lower logP value from the higher logP value of the silane being considered.

[0088] In a more preferred embodiment of the present invention, each silica particle is functionalized with one or more hydrophobic silanes of formula (1) and / or (2), and with one or more hydrophilic silanes of formula (1) and / or (2).

[0089] Here, the definitions of "hydrophobic silane" and "hydrophilic silane" are the same as above. This definition is valid for all embodiments of the present invention.

[0090] In this embodiment, each silica particle is functionalized with one or more hydrophobic silanes of formula (1) and / or (2), for example, a silane in which group F is an unsubstituted alkyl group having more than six carbon atoms, a perfluoroalkyl group having more than three carbon atoms, or an alkyl group having only a triorganosilyl group as a substituent having more than six carbon atoms in the alkyl chain, and with one or more hydrophilic silanes, for example, a silane in which group F is a hydroxyl-terminated poly(alkoxyoxide), a hydroxylated or polyhydroxylated alkyl group, or an alkyl group substituted with one or more carboxylate groups. By appropriately selecting the amounts of group F and each silane used for functionalizing the silica particles, the surface properties of the coating containing the silica particles can be specifically adjusted. Similarly, various properties and requirements for the formulation of the coating composition, such as compatibility with other components and rheological properties, can be addressed by appropriately selecting the hydrophobic and hydrophilic silanes used for functionalizing the silica particles.

[0091] In another preferred embodiment of the present invention, silica particles are functionalized with two or more different silanes of formula (1) and / or (2), where in one or more silanes of formula (1) and / or (2), group F comprises one or more coating matrix reactive groups, and where one or more further silanes of formula (1) and / or (2) are exclusively hydrophilic silanes or exclusively hydrophobic silanes.

[0092] According to this embodiment, one or more coating matrix reactive groups contained in group F of the silane of formulas (1) and (2) are preferably selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxyl group, 1,3-dicarboxyl group, diester, 1,3-diester, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride group, and donor and acceptor groups in Michael addition reactions. Such selection of silanes for functionalization provides silica particles that can be incorporated into the coating matrix of a cured coating composition via the reaction of one or more coating matrix reactive groups, and that exhibit hydrophilicity or hydrophobicity due to the presence of one or more hydrophilic groups or one or more hydrophobic groups introduced by functionalization with each of the silanes of formula (1) and / or (2).

[0093] Preferably, one or more further hydrophilic silanes have a group F that exclusively comprises a hydrophilic functional group selected from the group consisting of carboxylic acids, hydroxyl groups, amino groups, polyether groups, and thiol groups, and otherwise a non-functionalized alkyl group having such a portion.

[0094] Similarly, preferably, one or more further hydrophobic silanes have a group F that exclusively comprises a hydrophobic functional group selected from the group consisting of ester groups, alkyl groups, alkenyl groups, halide groups and triorganosilyl groups, and otherwise a non-functionalized alkyl group having such a portion.

[0095] In a further preferred embodiment of the present invention, silica particles are functionalized with two or more different silanes of formula (1) and / or (2), where in one or more silanes of formula (1) and / or (2), group F comprises one or more coating matrix reactive groups, and one or more further silanes of formula (1) and / or (2) are exclusively hydrophilic silanes, where group F of one or more hydrophilic silanes comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups containing quaternary ammonium groups, hydrocarbon groups containing carboxylate groups, and hydrocarbon groups containing one or more amino groups.

[0096] Preferred combinations of coating matrix reactive groups and hydrophilic groups present in group F of the hydrophilic silane of formula (1) and / or (2) used for functionalizing silica particles according to this embodiment are polyether groups, particularly OH-terminated polyether groups, alkyl-endcapped polyether groups, specifically methoxy, ethoxy, propoxy, and butoxy-terminated polyether groups, and trialkylsiloxy-endcapped polyether groups, specifically -OSiMe3, -OSiEt3, and -OSi(iPr)3 groups, the polyether groups specified above in this embodiment in combination with isocyanate groups, and the polyether groups specified above in this embodiment in combination with epoxy or alkenyl groups.

[0097] In yet another preferred embodiment of the present invention, silica particles are functionalized with two or more different silanes of formula (1) and / or (2), where in one or more silanes of formula (1) and / or (2), group F comprises one or more coating matrix reactive groups, and one or more further silanes of formula (1) and / or (2) are exclusively hydrophobic silanes, where group F of 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 containing difluoromethylene and / or trifluoromethyl groups, particularly perfluorinated alkyl groups, alkyl groups having triorganosilyl groups, organosiloxy groups, alkenyl groups or substituent-free aromatic groups containing heteroatoms, particularly alkaryl groups and aralkyl groups.

[0098] Preferred combinations of coating matrix reactive groups and hydrophobic groups present in group F of the hydrophilic silane of formula (1) and / or (2) used for functionalizing silica particles according to this embodiment are isocyanate groups combined with unsubstituted alkyl groups or fluorinated alkyl groups, acrylate or methacrylate groups combined with unsubstituted alkyl groups or fluorinated alkyl groups, or epoxy groups combined with unsubstituted alkyl groups or fluorinated alkyl groups.

[0099] In another preferred embodiment of the present invention, the silica particles comprise at least two different silica particles functionalized with silanes of formula (1) and / or (2).

[0100] According to this embodiment, different types of silica particles are used as starting materials for functionalizing silica particles with one or more silanes of formula (1) and / or (2). For example, D of aggregates in the range of approximately 50 to 150 μm 50 Particles of fumed silica having an average particle size are functionalized with one or more silanes of formula (1) and / or (2), and D in the range of about 1 to about 150 nm. 50The present invention provides silica particles by individually functionalizing colloidal silica particles having an average particle size with one or more silanes of formula (1) and / or (2), and then mixing the functionalized silica particles thus obtained.

[0101] Preferably, two or more different types of silica particles are each functionalized with a different silane or a mixture of different silanes.

[0102] According to the present invention, a mixture of silica particles containing two or more different types of silica particles obtained by separately functionalizing them with different silanes is, - By mixing at least two different types of functionalized silica particles obtained by functionalizing one common type of silica particle used as a precursor, each separately functionalized with a specific silane or mixture of silanes of formulas (1) and / or (2) as defined in the above embodiments, which is different from at least one of the specific single or multiple silanes used for functionalizing other silica particle precursors, or alternatively, - By mixing at least two different types of functionalized silica particles obtained from different types of silica particles used as precursors, each separately functionalized with a specific silane or mixture of silanes of formulas (1) and / or (2) as defined in the above embodiments, which is different from at least one of the specific single or multiple silanes used for functionalizing other silica particle precursors, It is preferable that it be provided.

[0103] According to the present invention, it is generally preferred when the provided silica particles contain two different types of silica particles, obtained by separately functionalizing a general type of silica particle precursor with two different types of silane or a mixture of two different silanes, or by separately functionalizing two different types of silica particle precursors with two different types of silane or a mixture of two different silanes, and then mixing each of the different types of silica particles in a specific weight ratio.

[0104] According to the present invention, it is even more preferable that at least two different types of silica particles functionalized with different silanes have different silane groups F in formulas (1) and / or (2) applied to the functionalization of each type of silica particle. Preferably, the silica particles include one or more types of particles functionalized with one or more types of silanes of formula (1) and / or (2) in which group F represents a polyether group, and one or more other types of particles functionalized with one or more types of silanes of general formula (1) and / or (2) in which group represents an alkyl group. It is preferable that one or more types of silica are functionalized with silanes of formula (1) and / or (2) having a group F containing a polyether group, while one or more further types of silica particles are functionalized with silanes of formula (1) and / or (2) having a group F containing one or more coating matrix reactive groups, or that one or more types of silica particles are functionalized with silanes of formula (1) and / or (2) having a group F containing one or more ester groups, alkyl groups or fluorine-containing moieties, while one or more further types of silica particles are functionalized with silanes of formula (1) and / or (2) having a group F containing one or more coating matrix reactive groups. Functionalization of the silane group F of formula (1) and / or (2) with different types of functional groups results in different polarities of the silane used for functionalization, and therefore, different polarities of the functionalized silica particles thus obtained.

[0105] A more preferred embodiment of the present invention provides silica particles comprising at least two types of silica particles functionalized with different silanes having different polarities. The term "silanes with different polarities" refers to silanes having different logP values ​​for the partition coefficient P of the group HLF corresponding to the structural unit LF of the silane, as defined above for determining the hydrophilicity or hydrophobicity of silanes.

[0106] According to the present invention, it is preferable that the difference in logP values ​​of at least two silanes used for the functionalization of at least two types of silica is about 0.8 or more, more preferably about 1.5 or more, even more preferably about 2.5 or more, even more preferably about 3.5 or more, and most preferably about 5.0 or more. In this case, it is preferable that the silane of equation (1) or (2) having a higher logP value is a hydrophobic silane (i.e., logP ≥ approximately 0.5), while the silane having a lower logP value is a hydrophilic silane (i.e., logP < approximately 0.5). Generally, the difference is obtained by subtracting the lower logP value from the higher logP value obtained for the silane under consideration.

[0107] In a preferred embodiment of the present invention, silica particles are provided, where one or more silanes of formula (1) and / or (2) are, R 1 x R 2 3-x Si-L-[SiR 1 20] p -SiR 1 2-L-[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 R 1 x R 2 3-x Si-L-[SiR 1 20] p -SiR 1 2-LR 5 HN{-SiR 1 2-L-[SiR 1 20] p -SiR 1 2-L-[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4}2 HN{-SiR 1 2-L-[SiR 120] p -SiR 1 2-LR 5}2 R 1 x R 2 3-x Si-L-[SiR 1 20] p -SiR 1 2-LR 5 Here, R 1 , R 2 , R 4 L, p, q, r, and s are defined above, and R 5 The group is selected from alkyl, alkylcarbonyloxy, glycidyl, glycidyloxy, organosilyl, for example, -SiMe2-O-SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, and -SitBuPh2.

[0108] According to the present invention, it is preferable that q+r+s is in the range of about 2 to about 15, and it is particularly preferable that q is in the range of about 2 to about 15, while r and s=0, or r is in the range of about 2 to about 15, while q and s=0, or s is in the range of about 2 to about 15, while q and r=0.

[0109] According to the present invention, R 4 It is also preferable that R is selected from the group consisting of hydroxyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, methylcarbonyloxy, tert-butylcarbonyloxy, -OSiMe3, -SiMe2-O-SiMe2CH=CH2, glycidoxy group or -SiMe3, SiPh3, -SiEt3, -SitBuMe3, -SiMe2 vinyl, or -SiMe2 allyl, and R 5When selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methylcarbonyloxy, ethylcarbonyloxy, tert-butylcarbonyloxy, glycidyl, glycidyloxy, -SiMe2-O-SiMe2CH=CH2, SiMe3, SiEt3, -Si-(iPr)3, or SitBuMe2, most preferably R 5 It is preferable that the element is selected from methyl, glycidoxy, -SiMe3, or -SiMe2-O-SiMe2CH=CH2.

[0110] According to the present invention, 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-, and in either case, it is also preferable that it is optionally bonded to F via an oxygen atom.

[0111] In another preferred embodiment of the present invention, R 2 Silica particles that are alkoxy are provided.

[0112] base R 2 R is defined as a hydrolyzable group, and its presence in the silane of formula (2) is required to enable the bonding of group A to the surface of silica particles via silicon atoms by condensation of one, two, or three silanol OH groups on the silica surface with the silyl group of the silane to form a siloxane unit. Among these, one, two, or three hydrolyzable R 2 The group is cleaved. Therefore, the ability of silane to condense with the silica surface, and thus to bond for the functionalization of silica particles, and especially the rate of such a reaction, is due to the hydrolyzable group R 2 It depends on the type. Since the conditions under which these groups are hydrolyzed in the presence of an OH group are well known to those skilled in the art, the alkoxy group is a preferred hydrolyzable group according to the present invention R 2Furthermore, a silyl group having one, two, or three alkoxy groups can be easily introduced into the target compound by a hydrosilylation reaction between any hydridoalkoxysilane and any compound containing an unsaturated CC bond, particularly alkenyl polyorganosiloxane, alkenylcarbosilane, or alkenylcarbosiloxane, where the alkenyl group is preferably a vinyl group; or by a hydrosilylation reaction between an alkoxyalkenylsilane, preferably alkoxyvinylsilane, and a hydridosilyl compound, particularly hydridopolyorganosiloxane, hydridocarbosilane, or hydridocarbosiloxane. Since many hydridoalkoxysilanes and alkenylalkoxysilanes are commercially available, methods for producing and handling these compounds are well known to those skilled in the art.

[0113] According to this embodiment, the silane of formula (2) has two or three alkoxy groups R 2 Preferably, the silane of formula (2) is a hydrolyzable group R 2 It is more preferable to have three alkoxy groups.

[0114] Here, the alkoxy group is a linear C1-C22 alkoxy group, for example, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy or n-octyl group; a branched C1-C22 alkoxy group, for example, isopropoxy, isobutoxy, tert-butoxy, isopentoxy, tert-pentoxy, neopentoxy and 2-ethylhexyoxy group; and a cyclic C3-C22 alkoxy group, for example, cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclo The alkoxy group is independently selected from chlorohexoxy and cycloheptoxy groups, and preferably the alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, iso-propoxy, iso-butoxy, tert-butoxy, neo-pentoxy, cyclopentoxy, or cyclohexoxy groups, or more preferably the alkoxy group is selected from methoxy, ethoxy, or isopropoxy groups, and most preferably the alkoxy group is selected from methoxy groups.

[0115] The present invention also relates to specific silanes, particularly silanes of formula (1) as defined above, for the functionalization of silica particles. In preferred embodiments of the present invention, silane compounds of the following formula are provided: HN[-SiR 1 2-A]2(1) As defined above, where M is L, the group F includes at least one heteroatom, for example, N, O, P, S, Si, or a halogen atom, for example, fluorine, chlorine, bromine, or iodine. These silanes are particularly useful in the production of functionalized silica particles.

[0116] Preferably, a compound of formula (1) is provided, where M is L, and the group F comprises at least one heteroatom, for example, N, O, P, S, Si, or a halogen atom, for example, fluorine, chlorine, bromine, or iodine.

[0117] More preferably, in the compound of formula (1), M is L, group F comprises one or more oxygen atoms, more preferably F comprises one or more oxygen atoms, where at least one oxygen atom is an oxygen atom of the ether or ester moiety, more preferably F comprises three or more oxygen atoms, where at least three oxygen atoms are oxygen atoms of the oligo or poly(alkylene oxide) group, more preferably F comprises five or more oxygen atoms, where at least five oxygen atoms are oxygen atoms of the oligo or poly(alkylene oxide) group, and more preferably group F comprises a poly(ethylene oxide) or poly(propylene oxide) unit comprising five or more oxygen atoms.

[0118] Most preferably, in the compound of formula (1), M is L, and F = -(O-CH2CH2) 4-12 -OH, Specifically, the compound is represented by the following formula: HN(-SiMe2-(CH2) 2-4 -(O-CH2CH2) 4-12 -OH)2, More specifically, the compound is represented by the following formula: HN(-SiMe2-(CH2)2-(O-CH2CH2) 4-12 -OH)2, or HN(-SiMe2-(CH2)3-(O-CH2CH2) 4-12 -OH)2, most preferably the formula HN(-SiMe2-(CH2)3-(O-CH2CH2) 10 It is represented as -OH)2, or F = -(O-CH2CH2) 4-12 -OMe, and specifically, the compound is represented by the following formula: HN(-SiMe2-(CH2) 2-4 -(O-CH2CH2) 4-12 -OMe)2, more specifically, the compound is represented by the following formula: HN(-SiMe2-(CH2)2-(O-CH2CH2) 4-12 -OMe)2, or HN(-SiMe2-(CH2)3-(O-CH2CH2) 4-12-OMe)2, and most specifically, the formula HN(-SiMe2-(CH2)3-(O-CH2CH2) 7.5 - Represented by OMe)2, or F = -(O-CH2CH2) 4-12 -OSiMe3, and specifically the compound, is represented by the following formula: HN(-SiMe2-(CH2) 2-4 -(O-CH2CH2) 4-12 -OSiMe3)2, more specifically, the compound is represented by the following formula: HN(-SiMe2-(CH2)2-(O-CH2CH2) 4-12 -OSiMe3)2, or HN(-SiMe2-(CH2)3-(O-CH2CH2) 4-12 -OSiMe3)2, and most specifically the formula HN(-SiMe2-(CH2)3-(O-CH2CH2) 10 Represented by OSiMe3)2

[0119] According to the present invention, in the compound of formula (1) according to this embodiment, group F may also preferably include an oxycarbonylalkyl group having the following structure, F=-(OC(O)-alkyl, Here, 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 a branched alkyl group selected from iso-propyl, sec-butyl, tert-butyl, neo-pentyl, or formula-CR a R b R c Selected from alkyl groups, where 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 the alkyl groups are alkyl groups, more preferably the alkyl groups are linear alkyl groups selected from ethyl or methyl, or formula -CR aR b R c Selected from, here R c is hydrogen or methyl, and R a and R b It is a linear alkyl group having a total of about 3 to about 11 carbon atoms. Most preferably, formula -CR a R b R c In the alkyl group, R c R is a methyl group, a and R b It is a linear alkyl group having a total of 9 or 10 carbon atoms.

[0120] A more preferred compound of formula (1) according to this embodiment of the present invention is, for example, a compound represented by the following formula: HN(-SiMe2-(CH2) 2-3 -(OC(O)alkyl))2, specifically, HN(-SiMe2-(CH2)2-(OC(O)alkyl)2 and HN(-SiMe2-(CH2)3-(OC(O)alkyl)2, more specifically, HN(-SiMe2-(CH2)2-(OC(O)-CMeR a R b ))2 and HN(-SiMe2-(CH2)3-(OC(O)-CMeR a R b ))2, here R a and R b It is a linear alkyl group with a total number of carbon atoms ranging from approximately 3 to approximately 9.

[0121] In another preferred embodiment of the present invention, a compound of formula (1) is provided, where M is L, and the group F comprises one or more silicon atoms, more preferably the group F comprises one or more silicon atoms, where one of the silicon atoms is a terminal triorganosilyl group or a terminal triorganosiloxy group, for example, a silicon atom of -SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, -SitBuPh2, and even more preferably the terminal triorganosilyl group of F is -SiMe2CH=CH2, -SiMe3 The terminal triorganosiloxy group is selected from -OSiMe3, -OSiEt3, and -OSi(iPr)3 and bonded to an oxygen atom, and 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 constitutes a terminal group of a C1-C12 linear alkyl group or a C1-C12 alkenyl group. Most preferably, in the compound of formula (1), M is L, and F = -(O-CH2CH2) 4-12 -OSiMe3, or F = -(O - CH2CH2CH2) 4-12 -OSiMe3, or F = -(O-CH2CH2) 4-12 -OSiEt3, or F = -(O - CH2CH2CH2) 4-12 -OSiEt3.

[0122] A particularly preferred compound of formula (1) according to this embodiment is the compound of the following formula: HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2CH2) 4-12 -OSiMe3)2, specifically, HN(-SiMe2-(CH2)2-(O-CH2CH2CH2)10 -OSiMe3)2 and HN(-SiMe2-(CH2)3-(O-CH2CH2CH2) 10 -OSiMe3)2, or HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2) 4-12 -OSiEt3)2, specifically, HN(-SiMe2-(CH2)2-(O-CH2CH2) 7.5 -OSiEt3)2, and HN(-SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OSiEt3)2, or HN(-SiMe2-(CH2) 2-3 -(O-CH2CH2CH2) 4-12 -OSiEt3)2, specifically, HN(-SiMe2-(CH2)2-(O-CH2CH2CH2) 10 -OSiEt3)2, and HN(-SiMe2-(CH2)3-(O-CH2CH2CH2) 10 -OSiEt3)2.

[0123] In another preferred embodiment of the present invention, a silane of general formula (1) as defined above is provided, where an optional substituent of the hydrocarbyl radical F is selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxy, 1,3-dicarboxy, diester, 1,3-diester, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0124] The present invention also relates to a method for producing functionalized silica particles, and more particularly to the method for producing the above-mentioned functionalized silica particles. According to the present invention, the present invention is a method for producing functionalized silica particles, - Contact the silica particles with one or more silanes of formula (1) and / or (2). HN[-SiR 1 2-A]2(1), and / or R 1 x R 2 3-x Si-A (2) As defined above, A method including this is provided.

[0125] According to this embodiment, the D of the silica particles to be applied 50 The average particle size can be up to approximately 1000 μm, as determined by dynamic light scattering (DLS) or TEM (transmission electron microscopy). However, silica particles are less than approximately 800 μm. 50 The silica particles preferably have an average particle size, more preferably less than about 500 μm, and the silica particles are either fumed silica particles or colloidal silica particles, with colloidal silica particles in suspension being particularly preferred.

[0126] According to this embodiment, one or more silanes of formula (1) and / or (2) applied for the functionalization of silica particles are as defined in the above embodiment directed toward silica particles functionalized with one or more silanes of formula (1) and / or (2).

[0127] According to the present invention, the method of contacting silica particles with one or more silanes of formula (1) and / or (2) as defined above is not limited to a specific method, and such methods are known to those skilled in the art.

[0128] It is preferable to bring the silica particles into contact with one or more silanes used for functionalization in an open or closed reaction vessel, and if a mixing device is used, it is preferable to form a homogeneous reaction mixture, and depending on the one or more silanes applied, it is also preferable that the reaction vessel be cooled or heated. Such a mixing device may be a mixer or a stirrer, and all known types of industrial reactors, blenders, and mixers can be applied, such as ribbon mixers, twin-shaft mixers, vertical mixers, mixing reactors, or drum blenders, and the raw materials can also be brought into contact using a kneader, ball mill, or screw extruder. Depending on the one or more silanes applied, it is preferable to bring the starting materials into contact at a high temperature of at least about 40°C.

[0129] The reaction, carried out by contacting silica particles with one or more silanes of formula (1) and / or (2), can be carried out in the presence of one or more solvents and under reduced pressure or pressure, and an inert atmosphere can be applied when in contact with the aforementioned reaction partners.

[0130] Contact can be carried out in a batch or continuous process.

[0131] The time for contacting the silica particles with one or more silanes of formula (1) and / or (2) is not limited to any particular manner, however, preferably, when batch processing is applied, 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 less than about 4 hours, and even more preferably less than about 2 hours.

[0132] A preferred embodiment of the present invention provides a method for producing functionalized silica particles, wherein the silica particles are in contact with one or more silanes of formula (1) and / or (2) in the presence of a solvent.

[0133] In general, the method for producing functionalized silica particles can be carried out in or without the presence of one or more solvents, where the method is preferably carried out in the presence of one or more solvents, and more preferably in the presence of a single solvent which is a single compound rather than a mixture of compounds. According to the present invention, the term "solvent" refers to any compound or mixture thereof that is in a liquid state under reaction conditions and is suitable as a medium for functionalizing silica particles by contacting the silica particles with one or more compounds of formula (1) and / or (2). Preferably, the solvent is an organic compound or a mixture of organic compounds.

[0134] Therefore, the solvent is preferably inert to the silica particles used as starting materials and the silane compounds of formula (1) and / or (2) according to the present invention under the reaction conditions. Furthermore, the starting materials of formula (1) and (2) are preferably soluble in the solvent or completely miscible with the solvent. Preferably, the solvent is selected from the group of organic solvents consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, diorganocarbonates, ethers, ketones, alcohols, esters, and combinations thereof.

[0135] According to the present invention, preferred aliphatic hydrocarbons are selected from linear and branched C5-C24 alkyl groups, such as pentane, hexane, heptane, octane, and mixtures thereof, such as high-boiling or low-boiling petroleum ethers; Preferred alicyclic hydrocarbons are selected from C5-C24 cycloalkanes, such as cyclopentane, cyclohexane, or cycloheptane; Preferred aromatic hydrocarbons are alkyl-substituted aryl compounds based on benzene, such as toluene, xylene, mesitylene, tert-butylbenzene, and ethylbenzene; Preferred diorganocarbonates are dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; 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; Preferred ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, or methyl amyl ketone; Preferred alcohols are secondary or tertiary alcohols such as 1-methoxy-2-propanol or tert-butyl alcohol; 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, isoamyl acetate, hexyl acetate, or triacetin.

[0136] Among these, it is even more preferable that the solvent to be applied has a high boiling point, which according to the present invention is a boiling point above about 100°C under standard pressure, such as toluene, ortho-, meta-, para-xylene, dioxane, and 1-methoxy-2-propanol. According to this embodiment, it is preferable that one or more solvents are selected from the group consisting of toluene, xylene, dioxane, and 1-methoxy-2-propanol. To improve the homogeneity of the reaction mixture and the heat transport during the reaction, a solvent may be included to enhance the functionalization reaction.

[0137] In a more preferred embodiment of the present invention, the method for producing silica particles is carried out at a temperature above about 40°C, more preferably above about 50°C, and most preferably in the range of about 55°C to about 120°C.

[0138] By applying high temperatures, the reaction rate of the condensation reaction that occurs during the functionalization of 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 below about 120°C.

[0139] In another preferred embodiment of the present invention, the silica particles used as a starting material in the method for producing functionalized 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 measured by dynamic light scattering (DLS), or from fumed silica having an average particle size in the range of about 1 to about 600 μm, preferably about 20 to about 400 μm, as measured by DLS or transmission electron microscopy (TEM).

[0140] As described above, silica particles can be selected from silica particles that typically exist in a dispersion in colloidal form, i.e., as primary particles, or from silica particles that are aggregates of primary particles, typically corresponding to fumed silica particles. All types of silica particles can be subjected to the method for producing functionalized silica particles according to the present invention in order to obtain functionalized silica particles functionalized with one or more silanes of formula (1) and / or (2) according to the present invention, while the silica particles are measured by dynamic light scattering in the range of about 1 nm to about 800 μm. 50 It is preferable that the average particle size is such that the colloidal silica primary particles have a certain D 50 It is more preferable that the average particle size is in the range of about 1 to about 300 nm, even more preferably about 2 to about 150 nm, most preferably about 5 to about 50 nm, or where the D of silica aggregated particles 50 It is more preferable that the average particle size is in the range of about 1 to about 800 μm, even more preferable that it is about 10 to about 300 μm, and most preferable that it is about 50 to about 150 μm. Alternatively, the particle size can be determined by TEM, however DLS is D50 This is a preferred means for measuring particle size values.

[0141] In yet another preferred embodiment of the method for producing functionalized silica particles according to the present invention, contact between silica particles and one or more silanes of formula (1) and / or (2) is made 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.

[0142] Condensation catalysts can be used to increase the rate of a condensation reaction, particularly to achieve a suitable reaction rate at a moderate reaction temperature.

[0143] In a preferred embodiment of the present invention, the silane of formula (1) is L, where M is L.

[0144] According to this embodiment, the silane of formula (1) does not contain an oligo or polysiloxy moiety.

[0145] In another preferred embodiment of the method for producing functionalized silica particles according to the present invention, in the silane of formula (1) and / or (2), F is - Alkyl, - Alkenil, - Alkylcarbonyloxy, - Polyalkylene oxide group, preferably one of the following general formulas, [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 Here [-OC2H4] represents an ethylene oxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q+r+s>2, R 4 This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyl oxy groups, - Organosilyl group, e.g., -SiR 1 3. Here R 1 The group is independently selected from the groups defined above for formulas (1) and (2), and a siloxy group, for example, -OSi(R 1 )3, here R 1 This is selected independently of the bases defined above for equations (1) and (2), It is selected from the group consisting of the following.

[0146] In a more preferred embodiment of the method for producing functionalized silica particles according to the present invention, the group F of one or more silanes of formula (1) and / or (2) comprises at least one portion selected from the group consisting of a polyether portion, an ester portion, and a coating matrix reactive portion, such as alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxy, 1,3-dicarboxy, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions.

[0147] In general, all silanes of formula (1) or (2) described above as preferred for providing functionalized silica particles are similarly preferred in the method for producing functionalized silica particles according to the present invention.

[0148] In a further preferred embodiment of the present invention, in a method for producing functionalized silica particles, one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophobic silanes, or one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophilic silanes.

[0149] According to this embodiment, the same definitions of "hydrophobic silane" and "hydrophilic silane" provided above apply, and the partition coefficient P of compound HLF containing the -LF- group of silane in a 50 / 50 mixture of water and octanol oct / wat It is based on the logP value, which is defined as follows: MagP oct / wat = log((solute) nonionized octanol / (solute) nonionized water)

[0150] For one or more hydrophobic silanes, it is preferable that the logP value 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, and 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.

[0151] For one or more hydrophilic silanes, it is preferable that the logP value is in the range of 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, even 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.

[0152] According to this embodiment of the present invention, it is preferable that the hydrophobic silane of formula (1) and / or (2) is exclusively functionalized by one type of hydrophobic functional group, selected from alkyl groups, halogenated alkyl groups, particularly perfluorinated alkyl groups, alkenyl groups, triorganosilyl-terminated alkyl groups, ester groups, and oxycarbonyl alkyl groups, particularly linear C1-C12 alkyl groups and oxycarbonyl alkyl groups, wherein the alkyl group of the oxycarbonyl alkyl group is a linear or branched alkyl group from C1 to C12.

[0153] According to this embodiment of the present invention, it is also preferable that the hydrophilic silane of formula (1) and / or (2) is exclusively functionalized by one type of hydrophilic functional group selected from a polyether group, a CH3 end-capped polyether group, a SiMe3 end-capped polyether group or an OH-terminated polyether group, a hydroxylated alkyl residue, or a polyhydroxylated alkyl residue present on the -LF group.

[0154] In another preferred embodiment of the method for producing functionalized silica particles according to this embodiment, the silica particles are R 2 It is contacted with one or more silanes of formula (2) in which the alkoxy group is.

[0155] According to this embodiment, the silane of formula (2) has two or three alkoxy groups R 2 Preferably, the silane of formula (2) is a hydrolyzable group R 2 It is more preferable to have three alkoxy groups. There, the alkoxy groups include linear C1-C22 alkoxy groups, such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-hexoxy, n-heptoxy or n-octoxy groups, branched C1-C22 alkoxy groups, such as iso-propoxy, iso-butoxy, tert-butoxy, iso-pentoxy, tert-pentoxy, neo-pentoxy and 2-ethylhexyoxy groups, and cyclic C3-C22 alkoxy groups, such as cyclopropoxy, cyclobutoxy, cyclopentoxy, Preferably, the alkoxy group is selected independently from cyclohexoxy and cycloheptoxy groups, and more preferably, the alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, iso-propoxy, iso-butoxy, tert-butoxy, neo-pentoxy, cyclopentoxy, or cyclohexoxy groups, and more preferably, the alkoxy group is selected from methoxy, ethoxy, or isopropoxy groups, and most preferably, the alkoxy group is selected from methoxy groups.

[0156] In a preferred embodiment of the method for producing functionalized silica particles according to the present invention, two or more silanes of formula (1) and / or (2) as defined above are brought into contact with silica particles in one step, or two or more silanes of formula (1) and / or (2) are brought into contact with silica particles in two or more steps.

[0157] The process according to this embodiment yields silica particles having different functionalization residues, which allows for the imparting of novel and highly specific properties to the silica particles, as already described above. According to this embodiment, it is preferable to contact the silica particles with at least one or more silanes that are either hydrophobic or hydrophilic, providing surface properties corresponding to hydrophobic silica particles, and with at least one type of silane having coating matrix-reactive functional groups that allow for the incorporation of the silica particles into the coating matrix.

[0158] In a more preferred embodiment of the method for producing functionalized silica particles according to the present invention, silica particles are brought into contact with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and then brought into contact 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 Here, silica particles are brought into contact with one or more silanes of formula (1) and / or (2) containing one or more coating matrix reactive moieties, and then brought into contact with one or more hydrophilic silanes of formula (1) and / or (2) in the absence of hydrophobic silanes of formula (1) and / or (2).

[0159] Such a favorable selection of two or more silanes in contact with the silica particles can provide excellent surface properties for the silica particles.

[0160] In a more preferred embodiment of the method for producing functionalized silica particles according to the present invention, silica particles are brought into contact 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 one or more silanes of formula (1), preferably in the presence of at least about 1.0 equivalent, and most preferably in the presence of at least about 1.5 equivalents of water based on the molar amount of one or more silanes of formula (1).

[0161] Depending on the functionalization of hydrolyzable groups present in silanes and / or one or more silanes, the presence of water facilitates the condensation reaction of the silane with the silica particles being functionalized.

[0162] In another embodiment, the present invention relates to functionalized silica particles comprising one or more monovalent groups A, Here, A is the base of equation -MF, Here, M is selected from L or the base of the following formula, -{L-[SiR 1 20] p -SiR 1 2} m -L-, here L is one or more -O-, -NR 3 -C(O)-, and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR 3 - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R 3 L is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4 alkylene group, and most preferably L is -(CH2)2- and / or -(CH2)3-. R 1 is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R 1 It is methyl, p=1 to about 9, preferably p=1 or 4, more preferably p=4, m=1 to about 20, preferably m=1, and F has up to approximately 100 carbon atoms, and -O-, -S-, -NH-, -C(O)-, -C(S)-, tertiary amino groups, [ka] or quaternary ammonium group [ka] Selected from the group consisting of optionally substituted, linear, cyclic, or branched, saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with an OH group, SH group, halide group, organosilyl group, or triorganosiloxy group, Group A is bonded to the silica particles via silicon atoms linked to the silicon dioxide network of the silica particles via one or more oxygen atoms, where the valence of the silicon atoms not occupied by group A or oxygen atoms is determined by the substituent R as defined above. 1 It is occupied by.

[0163] As will be apparent to those skilled in the art, such silica particles correspond to the silica particles described in the above embodiments and are not limited to functionalization with silanes of general formula (1) and / or (2). Therefore, the above particular selected and preferred embodiments are as described in the above embodiments, with group A and its components -M-, -F, R 1 , and the formula that can represent M -{L-[SiR 1 20] p -SiR 1 2} m The parameters m and p present in -L- are also applicable and preferred for functionalized silica particles containing one or more monovalent groups A according to the present invention.

[0164] As defined above for the silanes of formulas (1) and (2) in a similar manner, the term "hydrophobic group A" refers to the partition coefficient P of compound HLF containing the terminal LF group of group A in a 50 / 50 mixture of water and octanol. oct / wat The term "hydrophilic group A" refers to a group A whose logP value is 0.5 or greater, while the term "hydrophilic group A" refers to a group A whose logP value of the partition coefficient of compound HLF containing the LF group of group A in a 50 / 50 mixture of water and octanol is less than 0.5.

[0165] The present invention further relates to the use of silica particles obtained by any of the embodiments described above or by the methods described herein for producing a coating composition.

[0166] There, the term “coating composition” is not particularly limited and refers to any composition used as a cover applied to the surface of an object, usually called a substrate. The purpose of applying a coating composition can be decorative, functional, or both. The coating obtained from the application of the coating composition itself may be a full-surface coating that completely covers the substrate, or it may cover only a portion of the substrate. Paints and lacquers are coatings that primarily serve two purposes: protection and decoration of the substrate, but they may also be used for decoration only, or for protective functions such as corrosion prevention.

[0167] By applying functional coating compositions, the surface properties of a substrate can be altered, such as adhesion, wettability, corrosion resistance, susceptibility to dirt, scratch resistance, gloss, and abrasion resistance. In other cases, for example, in the manufacture of semiconductor devices (when the substrate is a wafer), the coating obtained by applying a coating composition adds entirely new properties such as magnetic response and conductivity, forming an important part of the final product.

[0168] According to the present invention, the coating composition is preferably a protective coating composition, that is, its application yields a coating or paint that protects the substrate to at least some extent, such as a coating composition for sealing and waterproofing wood, a coating composition for sealing concrete surfaces, a film-forming sealer and floor paint, seamless polymer or resin flooring, a coating composition for waterproofing and moisture-proofing of embankment walls or containment linings, a coating composition for roofs, a coating composition for sealing and waterproofing masonry buildings, a coating composition for preserving machinery, equipment and structures, a maintenance coating composition and paint for metals, alloys and concrete, a chemical-resistant coating composition, a coating composition for improving abrasion resistance, in particular a friction-resistant, abrasion-resistant and scuff-resistant coating for rolling bearings. The following are selected from the group consisting of fine coating compositions, hard scratch-resistant coating compositions on plastics and other materials to reduce scratching and abrasion loss, barrier coating compositions on concrete, metals and alloys subjected to erosion / abrasion attack, anticorrosion coating compositions, in particular automotive underbody sealants, anticorrosion coating compositions for protecting equipment and structural steel from deterioration, coating compositions for thermal insulation and fire protection of structural steel, coatings for passive fire protection, coating compositions for insulation, coating compositions for waterproof paper and waterproof cloth, anti-graffiti coating compositions, anti-fogging coating compositions, anti-icing coating compositions, anti-dust coating compositions, easy-to-clean coating compositions, antimicrobial coating compositions for obtaining antimicrobial surfaces, and coating compositions for improving the fouling removal and antifouling properties of, for example, ship hull surfaces. The coating compositions that result in the formation of a coating are not particularly limited in terms of their formulation, as long as they contain the functionalized silica particles according to the present invention.

[0169] In a preferred embodiment of the present invention, the coating composition produced using the functionalized silica particles according to the present invention is a curable coating composition. The curable coating composition according to the present invention may be any curable coating composition, referring to the toughening or hardening of a polymer material by crosslinking polymer chains through a chemical process. The aforementioned hardening process may be influenced by heat, radiation, electron beams, or chemical additives, which also involve contact with moisture or oxygen from the ambient air and are characterized by an increase in viscosity or hardness. The term is also used when monomers present in the composition have multiple sites for polymerization, and polymerization and crosslinking of the monomer occur simultaneously. This is, for example, the case of a polyacrylate monomer containing several acrylate moieties that function as sites for polymerization and crosslinking.

[0170] Furthermore, the term "curable coating composition" according to the present invention refers to a variety of compositions, including various organic polymers, mixtures of organic polymers and organic monomers, or compositions containing organic monomers. The preferred type of curable coating composition in which silica particles according to the present invention are: - Epoxy / amine composition - Michael addition-curing composition - Radical polymerization curing composition - Condensation curing composition, and - It is an addition-curing composition.

[0171] According to the present invention, the term "epoxy / amine composition" refers to an epoxy coating composition in which an amine-based curing agent is used in the curing step, which is selected from aliphatic amines, polyamides and amide amines, alicyclic amines, aromatic amines, mercaptans, anhydrides, aromatic anhydrides, alicyclic anhydrides, and aliphatic anhydrides. Often, an additional curing catalyst is present in such a composition and is mainly selected from Lewis base catalysts, e.g., tertiary amines or Lewis acid catalysts, e.g., boron-based catalysts, quaternary ammonium salts, e.g., tetramethylammonium hydroxide, phosphines, e.g., triphenylphosphine, organozincs, organotin, organoboron, organotitanium compounds, compounds of group V elements, e.g., WCl6, metal oxides, and amines. Since such compositions can often react at ambient temperature, they are often chosen for any application sensitive to high temperatures. Amine-cured epoxy coatings are prepared by combining epoxy resin with a suitable amine curing agent. Primary or secondary amine groups attack carbon atoms in a three-membered epoxide ring, resulting in ring opening with an amine group and a hydroxyl group. Primary amines form secondary amines, which react again to form tertiary amines, but at a slower rate. Curing agent units have two or more amine functional groups, allowing the curing agent to crosslink across multiple epoxy resin molecules, increasing the crosslinking density and various resistances of the resulting epoxy. Aliphatic amines react more readily than alicyclic amines and far more readily than aromatic amines, although the less reactive amines of the latter tend to form epoxies with much higher temperature resistance. Aromatic amines are no longer used as much due to adverse health effects from handling the corresponding compounds. Each class of amine curing agents has its own unique advantages and disadvantages in terms of curing speed, chemical resistance, solvent resistance, temperature compatibility, flexibility, viscosity, mechanical strength, crosslinking density, color, and toxicity. Furthermore, each class encompasses an entire family of curing agents with various properties that further alter these characteristics.

[0172] According to the present invention, the term "Michael addition cured composition" refers to a coating composition whose curing involves a Michael addition reaction, i.e., the addition of various nucleophiles to an electron-withdrawing substituent (conjugated) unsaturated compound. This enables the synthesis of a wide range of very complex polymers in a highly efficient manner, often in quantitative yields, under relatively mild conditions. Basically, any monomer having an activated double bond, such as α,β-unsaturated aldehydes or ketones, vinyl esters, vinyl sulfones, imidazoles, and maleimides, undergoes Michael addition with a nucleophile such as a thiol, amine, or any stabilized carbanion. Michael addition reactions can also be used to prepare polymers of various structures. The monomers used in this type of step polymerization are typically conjugated bisdienes and bisdienophiles (AA-type and BB-type monomers or comonomers; in this respect, "A" refers to the reactive group present in the "AA-type monomer," for example, the conjugated bisdiene that reacts with the "BB-type monomer," for example, "(AABB)." n - This refers to a bisdienophile used to obtain a polymer, and is a molecule containing the group "A" present in the silanes of formulas (1) and (2).

[0173] The term "radical polymerization cured composition" according to the present invention refers to a composition cured by free radical polymerization. Free radical polymerization consists of three basic steps: initiation, growth, and termination. Initiation involves the formation of a radical and the subsequent reaction of the radical with a vinyl monomer; growth is the rapid and gradual addition of monomers to a growing polymer chain without change of the active site; and termination is the destruction of the growing active site, usually by the bonding or coupling of radicals in two growing polymer chains, or by disproportionation. In addition to these three processes, chain transfer may occur, which is the movement of a growing active site from the active chain to an inactive (resting) site, monomer, or solvent molecule (transfer agent).

[0174] According to the present invention, the term "condensation-curable composition" refers to a composition that is cured by condensation polymerization, a form of stepwise polymerization. Small molecules react with each other to form larger structural units, releasing small molecules as byproducts such as water and methanol. A well-known example of a condensation reaction is the esterification of carboxylic acids and alcohols. If both parts are difunctional, the condensation product is a linear polymer; if at least one of the parts is trifunctional or tetrafunctional, the resulting polymer is a crosslinked polymer (i.e., a three-dimensional network). Adding a monomer with only one reactive group stops the growing chain, resulting in a decrease in the (average) molecular weight. Therefore, the average molecular weight and crosslink density depend on the functional groups of each monomer involved in the condensation polymerization and their concentration in the mixture.

[0175] Finally, according to the present invention, the term "addition-curing composition" refers to a polyurethane-based composition formed from an organic diisocyanate or polyisocyanate and a diol or polyol compound, which results in urethane bonds (-NH-C(=O)-O-) in the main chain.

[0176] In a more preferred embodiment of 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 organic monomers selected from glycidyl-based epoxy resins, novolac-based epoxy resins, or aliphatic epoxy resins, as well as mixtures of various copolymers and polymer compounds, and corresponding monomers, namely mono(meth)acrylates, dimethyl carbonates and diols, particularly diphenylmethane derivatives, olefins and polyisocyanates, or mixtures thereof.

[0177] The coating composition according to the present invention, and in particular the curable coating composition according to the present invention, may also optionally contain further additives, such as further photoinitiators, photostabilizers, fillers, particularly carbon black, metal oxide particles and silica particles not according to the present invention, functionalized silica compounds other than those according to the present invention, flame retardants, solvents, curing catalysts, reactive surfactants, colorants, stabilizers, preservatives, photostabilizers, surfactants, leveling agents, and other rheological agents.

[0178] According to the present invention, the silica particles according to the present invention, as defined in the embodiments described above, are used in the manufacture of a coating composition, preferably a curable coating composition, by mixing the silica particles according to the present invention with other components of the coating composition, either by adding and mixing the silica particles to the final formulation, adding and mixing other components to the silica particles, or adding and mixing the silica particles at any point during the manufacture of the coating composition. Any appropriate mixing means can be applied depending on the type of coating composition to be manufactured and the apparatus used for manufacture.

[0179] In preferred embodiments of the present invention, the silica particles of the present invention are used as marine antifouling additives, general antifouling additives, anti-icing additives, anti-mud additives, anti-fogging additives, self-cleaning additives, anti-adhesion, anti-dust, anti-fingerprint, and anti-graffiti additives, particularly as general antifouling or anti-fogging additives in coating compositions.

[0180] Preferably, the silica particles according to the present invention are used as a general antifouling additive, and particularly as a marine antifouling additive. Coating compositions produced using the silica particles according to the present invention as defined in the embodiments above have been demonstrated to provide excellent antifouling properties to surfaces, particularly surfaces exposed to marine environments. Thus, the use of silica particles according to the present invention is highly desirable in the manufacture of curable coatings for ships, hulls, vessels, offshore concrete structures, underwater concrete structures, wooden offshore structures, underwater wooden structures, offshore plastic structures, underwater plastic structures, and all types of buildings, masonry buildings, structures, and equipment exposed to marine environments.

[0181] Preferably, the silica particles according to the present invention are used as an anti-fogging additive, more preferably as an anti-fogging additive for producing coating compositions for coating plastic substrates, particularly polycarbonate substrates or PMMA (polymethyl methacrylate) substrates. Coating compositions produced using the silica particles according to the present invention as defined in the above embodiments have been demonstrated to provide excellent anti-fogging properties to the surface, particularly when the coating composition is applied to the surface of polycarbonate or methacrylate or acrylate substrates, especially PMMA substrates. This makes the use of silica particles according to the present invention highly desirable in the production of curable coatings for optical devices, screens and shields or external lamps, particularly automotive headlamps.

[0182] The present invention also relates to a coating composition comprising silica particles according to the present invention as described in the above embodiments.

[0183] As described above, the coating composition according to the present invention is characterized by containing silica particles according to the present invention. The coating composition may be decorative, functional, or both, and may be applied as a full-surface coating that completely covers the substrate, or may cover only a portion of the substrate. Paints and lacquers are coatings that primarily serve two purposes: protection and decoration of the substrate, but may be used only for decoration, or only for protective functions such as corrosion prevention. Therefore, paints and lacquers containing silica particles according to the present invention are included in this embodiment of the present invention. The functional coating compositions according to the present invention can be applied to alter the surface properties of a substrate, such as adhesion, wettability, corrosion resistance, susceptibility to dirt, scratch resistance, gloss, and abrasion resistance. In other cases, for example, in the manufacture of semiconductor devices (when the substrate is a wafer), the coating obtained by applying the coating composition adds entirely new properties such as magnetic response and conductivity, forming an important part of the final product.

[0184] According to the present invention, the coating composition is preferably a protective coating composition as defined above, and most preferably a curable protective composition. The coating compositions that result in the formation of a coating are not particularly limited in terms of their formulation, as long as they contain functionalized silica particles according to the present invention.

[0185] According to the present invention, the coating composition produced using the functionalized silica particles according to the present invention is preferably a curable coating composition, particularly a curable epoxy / amine coating composition, a Michael addition-cured coating composition, a radical polymerization-cured coating composition, a condensation-cured coating composition, and an addition-cured coating composition.

[0186] The curable coating composition according to the present invention may be any curable coating composition, referring to the toughening or hardening of a polymer material by crosslinking polymer chains through a chemical process. The aforementioned hardening process may be influenced by heat, radiation, electron beams, or chemical additives, which also involve contact with moisture or oxygen from the ambient air and are characterized by an increase in viscosity or hardness. The term is also used when monomers present in the composition have multiple sites for polymerization, and polymerization and crosslinking of the monomer occur simultaneously. This is the case, for example, with polyacrylate monomers containing several acrylate moieties that function as sites for polymerization and crosslinking.

[0187] Furthermore, the curable coating compositions according to the present invention include a variety of compositions, preferably curable epoxy coating compositions, Michael addition curing coating compositions, radical polymerization curing coating compositions, condensation curing coating compositions, and various organic polymers, mixtures of organic polymers and monomers, or monomers, for example, all kinds of polycarbonates, poly(meth)acrylates, polyolefins, polyurethanes, polyethers, polyesters, polyorganosiloxanes, various kinds of epoxy resins, for example, glycidyl-based epoxy resins, novolac-based epoxy resins, or aliphatic epoxy resins, as well as mixtures of various copolymers and polymer compounds, and corresponding monomers, namely mono(meth)acrylates, dimethyl carbonates, and diols, particularly diphenylmethane derivatives, olefins, and polyisocyanates.

[0188] The coating composition according to the present invention, and in particular the curable coating composition according to the present invention, may also optionally contain further additives, such as further photoinitiators, photostabilizers, fillers, particularly carbon black, metal oxide particles and silica particles not according to the present invention, functionalized silica compounds other than those according to the present invention, flame retardants, solvents, curing catalysts, reactive surfactants, colorants, stabilizers, preservatives, photostabilizers, surfactants, leveling agents, and other rheological agents.

[0189] In preferred embodiments of the present invention, the coating composition containing silica particles according to the present invention is a condensation curable coating composition containing alkoxysilanes as a curable component, a radical polymerization curable coating composition containing poly(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 curing system.

[0190] In another preferred embodiment of the present invention, the coating composition comprising silica particles according to the present invention is a curable coating composition comprising, as a curable component, one or more combinations of acrylates, polyorganosiloxanes, alkoxysilanes, epoxides, amines, hydroxyacrylates, isocyanates, or such curable monomers, oligomers, or polymers. Preferably, the coating composition containing silica particles according to the present invention comprises an OH-terminated silicone oil, more preferably, the coating composition containing silica particles according to the present invention comprises an OH-terminated silicone oil and one or more silica particles according to the present invention having a polyether group in part F, and most preferably, the coating composition containing silica particles according to the present invention comprises an OH-terminated silicone oil having a chain length (number of silicon atoms in the main chain) in the range of 1 to about 400 and one or more silica particles according to the present invention having a polyether group in part F.

[0191] Preferably, the coating composition containing silica particles according to the present 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 present invention having a polyether group or an amino group in part F. Most preferably, the coating composition containing silica particles according to the present invention comprises two or more acrylate or methacrylate resins and at least one functionalized silica particle according to the present invention having a polyether group or an amino group in part F.

[0192] In yet another embodiment of the present invention, the coating composition comprising silica particles according to the present invention is - One or more curable components selected from curable polymers, oligomers or monomers or binders. - One or more types of functionalized silica particles according to the present invention - Optionally, one or more light stabilizers - Optionally, one or more solvents - Optionally, one or more colorants - Optionally, one or more surfactants or other rheological additives. - Optionally, one or more fillers - Optionally, one or more curing catalysts Includes.

[0193] Preferably, one or more curable components and / or binders are selected from the group consisting of acrylates, methacrylates, hydroxyacrylates, esters, aromatics, phenols, epoxides, siloxanes, or silanes, and constitute about 20.0 to about 99.9% by weight, preferably about 30.0 to about 99.5% by weight, and more preferably about 40.0 to about 99.0% by weight, of the total weight of the coating composition.

[0194] Preferably, one or more types of functionalized silica particles according to the present invention constitute up to about 90% by weight, more preferably about 0.1 to about 80% by weight, preferably about 0.5 to about 70% by weight, and more preferably about 1 to about 60% by weight of the total weight of the coating composition.

[0195] Preferably, the light stabilizer is selected from the group consisting of hindered amine light stabilizers (HALS), benzophenone derivatives, benzotriazole derivatives, triazine derivatives, resorcinol derivatives, and triorganophosphite compounds, and constitutes up to about 15% by weight of the coating composition, more preferably about 0.2 to about 10% by weight of the total weight of the coating composition, even more preferably about 0.5 to about 8% by weight, and most preferably about 1 to about 5% by weight.

[0196] Preferably, the solvent is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, diorganocarbonates, ethers, ketones, alcohols, esters and combinations thereof, and constitutes up to about 95% by weight of the coating composition, more preferably 0 to about 90% by weight of the total weight of the coating composition, and even more preferably 0 to about 80% by weight.

[0197] Preferably, the colorant constitutes up to about 5% by weight of the coating composition, more preferably about 0.01 to about 4.0% by weight of the total weight of the coating composition, even more preferably about 0.05 to about 2.0% by weight, and most preferably about 0.1 to about 1.5% by weight.

[0198] Preferably, the curing catalyst is selected from the group consisting of 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% by weight of the coating composition, more preferably about 0.1 to about 20.0% by weight of the total weight of the coating composition, even more preferably about 0.2 to about 5.0% by weight, and most preferably about 1.0 to about 2.0% by weight.

[0199] Preferably, the filler is selected from the group consisting of unmodified silica, modified silica other than that of the present invention, mica, talc, carbon black, titanium dioxide, calcium carbonate, barium sulfate, and 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 of the total weight of the coating composition, even more preferably about 1.0 to about 20.0% by weight, and most preferably about 2.0 to about 15.0% by weight.

[0200] Preferably, the surfactant or other rheological additive constitutes about 0.01 to about 5.0% by weight of the coating composition, more preferably about 0.05 to about 1.0% by weight of the total weight of the coating composition, and even more preferably about 0.1 to about 0.5% by weight.

[0201] In preferred embodiments of the present invention, the coating composition according to the present invention contains, based on the total weight of the coating composition, about 0.1 to about 80% by weight, preferably about 0.5 to about 70% by weight, more preferably about 1 to about 60% by weight, and more preferably about 20 to about 55% by weight, and most preferably about 25 to about 50% by weight, silica particles according to the present invention as defined in the above embodiments.

[0202] The coating composition according to the present invention preferably contains more than about 1% by weight of silica particles, because when a lower content of silica particles is applied, the desired effect is often not fully achieved. On the other hand, the coating composition preferably contains less than about 80% by weight of silica particles according to the present invention, because a high silica content may adversely affect crack and fatigue resistance, as described in the Handbook of Fillers (4th Edition) - 8. The Effect of Fillers on the Mechanical Properties of Filled Materials, by ChemTec Publishing, all of which are incorporated herein by reference. The coating composition more preferably contains 3 to 60% by weight of silica particles, and even more preferably contains 25 to 50% by weight of silica particles. It should be noted that the optimal content of 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.

[0203] List of preferred embodiments of the present invention The following summarizes preferred embodiments of the present invention. 1. Silica particles functionalized with one or more silanes of the following formula, HN[-SiR 1 2-A]2(1) and / or R 1 x R 2 3-x Si-A (2) Here R 1 is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R 1 It is methyl, R 2This is independently selected from hydrolyzable residues and is preferably selected from the group consisting of hydrogen, hydroxy, acyloxy groups and other hydrocarbylcarbonyloxy groups, halogen groups, amino groups, alkoxy or aryloxy groups and other hydrocarbyloxy groups, more preferably alkoxy groups. x is 0, 1, or 2, and A is the basis of the following equation, -MF, Here M is selected from L or the base of the following formula: -{L-[SiR 1 20] p -SiR 1 2} m -L-, here L is one or more -O-, -NR 3 -C(O)-, and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR 3 - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R 3 L is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4 alkylene group, and most preferably L is -(CH2)2- and / or -(CH2)3-. R 1 This is defined as above, p=1 to about 9, preferably p=1 or 4, more preferably p=4, m=1 to about 20, preferably m=1, and F has up to approximately 100 carbon atoms, and -O-, -S-, -NH-, -C(O)-, -C(S)-, tertiary amino groups, [ka] or quaternary ammonium group [ka] Selected from the group consisting of optionally substituted, linear, cyclic, or branched, saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with an OH group, SH group, halide group, organosilyl group, or triorganosiloxy group, However, regarding the silane in formula (2), (i) A is the basis of the following equation, -{L-[SiR 1 20] p -SiR 1 2} m -LF, here L, R 1 p, m, and F are defined as above. or (ii) A is the basis of the following equation, -LF, where L contains at least one ether group (-O-) and optionally at least one hydroxy substituent (-OH), and where F is as defined above, provided that it contains at least one ester group (-OC(=O)- or -C(=O)-O-). These are the conditions for silica particles. 2. Silica particles according to Embodiment 1, wherein in formula (1), when M is L, the group F comprises N, O, P, S, Si, or at least one heteroatom such as a halogen atom such as fluorine, chlorine, bromine, or iodine. 3. Silica particles according to Embodiment 1 or 2, wherein the substituent of the hydrocarbyl radical F in formula (1) is selected from the group consisting of hydroxyl, thiol, alkoxy, siloxy, perfluoroalkyl, carboxyl, ester, aminoalkyl, thioalkyl, or polyether groups, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxyl group, 1,3-dicarboxyl group, diester, 1,3-diester, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride group, and donor and acceptor groups in Michael addition reactions. 4.F comprises a polyether moiety, an ester moiety, and a coating matrix reactive moiety, for example, at least one moiety selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions, as described in any of the embodiments. 5.F is, - Alkyl, - Alkenil, - Alkylcarbonyloxy, - Polyalkylene oxide group, preferably one of the following general formulas, [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 Here [-OC2H4] represents an ethylene oxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q+r+s>2, R 4 This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyl oxy groups, - Organosilyl group, e.g., -SiR 1 3. Here R 1 The group is independently selected from the groups defined above for formulas (1) and (2), and a siloxy group, for example, -OSi(R 1 )3, here R 1 This is selected independently of the bases defined above for equations (1) and (2), Silica particles according to any of the embodiments, selected from the group consisting of the above. 6. One or more silanes of formula (1) and / or (2) are derived from hydrophobic silanes (i.e., the partition coefficient of the compound HLF containing the LF group of the silane in a 50 / 50 mixture of water and octanol P oct / wat Silica particles according to any of the embodiments, exclusively selected from silanes whose logP value is 0.5 or greater. 7. Silica particles according to any of the embodiments, wherein one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophilic silanes (i.e., from silanes whose logP value of the partition coefficient of compound HLF containing the LF group of the silane in a 50 / 50 mixture of water and octanol is less than 0.5). 8. Silica particles according to any of the embodiments, wherein the silica particles are functionalized with two or more different silanes of formula (1) and / or (2). 9. The silica particle according to Embodiment 8, wherein each silica particle is functionalized with one or more hydrophobic silanes of formula (1) and / or (2), and with one or more hydrophilic silanes of formula (1) and / or (2). 10. Silica particles according to Embodiment 8, wherein one or more silanes of formula (1) and / or (2) comprises one or more coating matrix reactive groups, and thereafter one or more further silanes of formula (1) and / or (2) are exclusively hydrophilic silanes or exclusively hydrophobic silanes. 11. Silica particles according to Embodiment 10, wherein one or more further silanes of formula (1) and / or (2) are exclusively hydrophilic silanes, and the group F of one or more hydrophilic silanes comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups containing quaternary ammonium groups, hydrocarbon groups containing carboxylate groups, and hydrocarbon groups containing one or more amino groups. 12. Silica particles according to Embodiment 10, wherein one or more further silanes of formula (1) and / or (2) are exclusively hydrophobic silanes, and the group F of 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 containing difluoromethylene and / or trifluoromethyl groups, particularly perfluorinated alkyl groups, alkyl groups having a triorganosilyl group, organosiloxy groups, alkenyl groups or heteroatoms, particularly alkaryl groups and aralkyl groups. 13. Silica particles according to any of the embodiments, comprising at least two different silica particles functionalized with silanes of formula (1) and / or (2). 14. Silica particles according to any of the embodiments, comprising at least two types of silica particles functionalized with different silanes having different polarities. 15. One or more silanes of formula (1) and / or (2) are R 1 x R 2 3-x Si-L-[SiR 1 20] p -SiR 1 2-L-[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 R 1 x R 2 3-x Si-L-[SiR 1 20] p -SiR 1 2-LR 5 HN{-SiR 1 2-L-[SiR 1 20] p -SiR 1 2-L-[-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4}2 HN{-SiR 1 2-L-[SiR 1 20] p -SiR 1 2-LR 5}2, and R 1 x R 2 3-x Si-L-[SiR 1 20] p -SiR 1 2-LR 5 Here, R 1 , R 2 , R 4 L, p, q, r, and s are as defined in the above embodiment, and R 5Silica particles according to any of the embodiments, selected from the group consisting of alkyl, alkylcarbonyloxy, glycidyl, glycidyloxy, organosilyl, for example, -SiMe2-O-SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, and -SitBuPh2. 16.R 2 Silica particles according to any of the above embodiments, wherein is an alkoxy. 17. A silane of formula (1) as defined in Embodiment 2. 18. A method for producing functionalized silica particles, - Contacting silica particles with one or more silanes of formula (1) and / or (2), HN[-SiR 1 2-A]2(1) and / or R 1 x R 2 3-x Si-A (2) As defined in Embodiment 1, A method that includes this. 19. The method according to Embodiment 18, wherein contact between silica particles and one or more silanes of formula (1) and / or (2) is made in the presence of a solvent. 20. The method according to Embodiment 18 or Embodiment 19, wherein silica particles and one or more silanes of formula (1) and / or (2) are brought into contact at a temperature above about 40°C, more preferably above about 50°C, and most preferably in the range of about 55°C to about 120°C. 21. The method according to any one of Embodiments 18 to 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 measured by dynamic light scattering (DLS), or fumed silica having an average particle size in the range of about 1 to about 600 μm, preferably about 20 to about 400 μm, as measured by DLS or transmission electron microscopy (TEM). 22. The method according to any one of Embodiments 18 to 21, wherein the contact of silica particles with 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. 23. The method according to any one of embodiments 18 to 22, wherein the silane of formula (1) has group M as L. 24. In the silane of formula (1) and / or (2), F is - Alkyl, - Alkenil, - Alkylcarbonyloxy, and - Polyalkylene oxide group, preferably one of the following general formulas, [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 Here [-OC2H4] represents an ethylene oxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q+r+s>2, R 4 This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyl oxy groups, - Organosilyl group, e.g., -SiR 1 3. Here R 1 The group is independently selected from the groups defined above for formulas (1) and (2), and a siloxy group, for example, -OSi(R 1 )3, here R 1 Silica particles according to any one of embodiments 18 to 23, selected from the group consisting of, independently selected from the groups defined above for formulas (1) and (2). 25. The method according to any one of embodiments 18 to 24, wherein the group F of one or more silanes of formula (1) and / or (2) comprises at least one part selected from the group consisting of a polyether moiety, an ester moiety, and a coating matrix reactive moiety, such as alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions. 26. The method according to any one of embodiments 18 to 25, wherein one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophobic silanes, or one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophilic silanes. 27. Silica particles are R 2The method according to any one of embodiments 18 to 26, wherein one or more silanes of formula (2), in which is an alkoxy group, are in contact with each other. 28. The method according to any one of embodiments 18 to 27, wherein two or more silanes of formula (1) and / or (2) as defined in the above embodiments are brought into contact with silica particles in one step, or wherein two or more silanes of formula (1) and / or (2) are brought into contact with silica particles in two or more steps. 29. Silica particles are brought into contact with one or more silanes of formula (1) and / or (2) containing one or more coating matrix reactive moieties, and are brought into contact 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 The method according to any one of embodiments 18 to 28, wherein the silica particles are in contact with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive moieties, and in the absence of hydrophobic silanes of formula (1) and / or (2), they are in contact with one or more hydrophilic silanes of formula (1) and / or (2). 30. The method according to any one of embodiments 18 to 28, wherein 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 one or more silanes of formula (1), preferably in the presence of at least about 1.0 equivalent, and most preferably in the presence of at least about 1.5 equivalents of water, based on the molar amount of one or more silanes of formula (1). 31. Functionalized silica particles containing one or more monovalent groups A, Here, A is the basis of the following equation, -MF, Here M is selected from L or the base of the following formula: -{L-[SiR 1 20] p -SiR 1 2} m -L-, here L is one or more -O-, -NR 3 -C(O)-, and / or -NR 3 -, -OC(O)NR 3 -, -NR 3 -C(O)-NR 3 - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R 3 L is hydrogen, Me3Si- or C1-C8-alkyl, preferably L is a divalent C2-C12-alkylene group, more preferably a divalent C2-C4 alkylene group, and most preferably L is -(CH2)2- and / or -(CH2)3-. R 1 is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R 1 It is methyl, p=1 to about 9, preferably p=1 or 4, more preferably p=4, m=1 to about 20, preferably m=1, and F has up to approximately 100 carbon atoms, and -O-, -S-, -NH-, -C(O)-, -C(S)-, tertiary amino groups, [ka] or quaternary ammonium group [ka] Selected from the group consisting of optionally substituted, linear, cyclic, or branched, saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with an OH group, SH group, halide group, organosilyl group, or triorganosiloxy group, Group A is bonded to the silica particles via silicon atoms linked to the silicon dioxide network of the silica particles via one or more oxygen atoms, where the valence of the silicon atoms not occupied by group A or oxygen atoms is determined by the substituent R as defined above. 1 Functionalized silica particles, which are occupied by this material. 32. Functionalized silica particles according to Embodiment 31, wherein M is L, and group F comprises N, O, P, S, Si, or at least one heteroatom such as a halogen atom such as fluorine, chlorine, bromine, or iodine. 33. Silica particles according to Embodiment 31 or 32, wherein the substituent of the hydrocarbyl radical F is selected from the group consisting of hydroxyl, thiol, alkoxy, siloxy, perfluoroalkyl, carboxyl, ester, aminoalkyl, thioalkyl, or polyether groups, alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketone, diketone, 1,3-diketone, dicarboxyl group, 1,3-dicarboxyl group, diester, 1,3-diester, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride group, and donor and acceptor groups in Michael addition reactions. Silica particles according to any one of embodiments 31 to 33, wherein 34.F comprises a polyether moiety, an ester moiety, and a coating matrix reactive moiety, for example, at least one moiety selected from the group consisting of alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diesters, nitro(-NO2), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions. 35.F is, - Alkyl, - Alkenil, - Alkylcarbonyloxy, and - Polyalkylene oxide group, preferably one of the following general formulas, [-OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 Here [-OC2H4] represents an ethylene oxy unit, [-OC3H6] represents a propyleneoxy unit, and [-OC4H8] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q+r+s>2, R 4 This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyl oxy groups, - Organosilyl group, e.g., -SiR 1 3. Here R 1 The group is selected independently of the groups defined above, and also includes siloxy groups, such as -OSi(R 1 )3, here R 1 Silica particles according to any one of embodiments 31 to 34, which are selected from the group consisting of, independently of the groups defined above. 36.1 or more groups A are hydrophobic (i.e., the partition coefficient P of compound HLF containing the LF-group of group A in a 50 / 50 mixture of water and octanol) oct / wat Silica particles according to any one of embodiments 31 to 35, which are exclusively selected from base A, the logP value of which is 0.5 or greater. 37. Silica particles according to any one of embodiments 31 to 36, wherein one or more groups A of formula (1) and / or (2) are exclusively selected from hydrophilic groups (i.e., from groups A whose logP value of the partition coefficient of compound HLF containing the LF-group of group A in a 50 / 50 mixture of water and octanol is less than 0.5). 38. Silica particles according to any one of embodiments 31 to 37, wherein the silica particles are functionalized with two or more different groups A. 39. The silica particle according to Embodiment 38, wherein each silica particle is functionalized with one or more hydrophobic groups A and one or more hydrophilic groups A. 40. Silica particles according to Embodiment 38, wherein in one or more groups A, group F comprises one or more coating matrix reactive groups, and thereafter one or more further groups A are exclusively hydrophilic groups A or exclusively hydrophobic groups A. 41. Silica particles according to Embodiment 40, wherein one or more further groups A are exclusively hydrophilic groups A, and thereafter, the group F of 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 containing quaternary ammonium groups, hydrocarbon groups containing carboxylate groups, and hydrocarbon groups containing one or more amino groups. 42. Silica particles according to Embodiment 40, wherein one or more further groups A are exclusively hydrophobic silanes, and thereafter, one or more groups F of hydrophobic group A comprises one or more hydrophilic groups selected from the group consisting of linear or branched unsubstituted alkyl groups, alkyl groups containing difluoromethylene and / or trifluoromethyl groups, particularly perfluorinated alkyl groups, alkyl groups having triorganosilyl groups, organosiloxy groups, alkenyl groups, or non-substituted aromatic groups containing heteroatoms, particularly alkaryl groups and aralkyl groups. 43. Silica particles according to any one of embodiments 31 to 42, comprising at least two different silica particles functionalized with group A. 44. 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. 45. One or more silanes of formula (1) and / or (2) are -L-[SiR 1 20] p -SiR 1 2-L-[OC2H4] q [-OC3H6] r [-OC4H8] s -R 4 -L-[SiR 1 20] p -SiR 1 2-LR 5 Selected from the group consisting of, Here R 1 , R 4 L, p, q, r, and s are as defined in the above embodiment, and R 5 Silica particles according to any one of embodiments 31 to 44, selected from the group consisting of alkyl, alkylcarbonyloxy, glycidyl, glycidyloxy, organosilyl, for example -SiMe2-O-SiMe2-CH=CH2, -SiMe3, -SiEt3, -Si(iPr)3, -SiPh3, -Si(cyHex)3, -SitBuMe2, and -SitBuPh2. 46. ​​Use of silica particles described in any of Embodiments 1 to 16, 31 to 45, or silica particles produced by the method described in any of Embodiments 18 to 30, for the production of a coating composition. 47. Use of silica particles described in any of Embodiments 1 to 16, 31 to 45, or silica particles produced by the method described in any of Embodiments 18 to 30, as marine antifouling additives, general antifouling additives, anti-icing additives, anti-mud additives, anti-fogging additives, self-cleaning additives, anti-adhesion, anti-dust, anti-fingerprint, and anti-graffiti additives, particularly as general antifouling additives or anti-fogging additives, in coating compositions. 48. A coating composition comprising silica particles according to any one of embodiments 1 to 16, 31 to 45, or silica particles produced by the method described in any one of embodiments 18 to 30. 49. The coating composition according to Embodiment 48, comprising, based on the total weight of the coating composition, about 0.1 to about 80% by weight, preferably about 0.5 to about 70% by weight, more preferably about 1 to about 60% by weight, and more preferably about 20 to about 55% by weight, and most preferably about 25 to about 50% by weight, silica particles. [Examples]

[0204] example The following abbreviations and product names are used in the Examples section. Me = methyl(-CH3) Aerosil300 (BET270-330m) 2 / g;SiO2 content >99.8%;Particle size: 5-50nm primary particle size, 100μm average aggregate size);Breox AA E450H (BASF), Lamoreaux catalyst (abcr) VeoVa9 (Vinyl ester of Versatic® acid 9, synthetic saturated monocarboxylic acid with a highly branched structure containing 10 carbon atoms, Hexion);Levasil EXP 310 (Dispersion of silica in water;Silica content: 30 wt%;Particle size: 10nm;BET of silica: 200m 2 g -1);Epikote 828EL (epoxy resin prepared from bisphenol A and epichlorohydrin, Hexion);Silopren E0.5 (dihydroxy-terminated linear polysiloxane-based polymer with a viscosity of 0.5 Pa.s at 20°C; Momentive Performance Materials);Silopren E2 (dihydroxy-terminated linear polysiloxane-based polymer with a viscosity of 2 Pa.s at 20°C; Momentive Performance Materials).

[0205] Example 1 (Starting material) Preparation of NH(SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me)2 150.5 g of n-butylhydrogen pentasiloxane (HSiMe2(OSiMe2)3-SiMe2-(CH2)3Me) and 58.5 g of dimethyl vinyl chlorosilane were reacted under N2 conditions at 100°C for 3 hours with the addition of 0.06 g of Lamoreaux catalyst (3 wt% Pt solution). The reaction mixture was further heated to 80°C, and the reaction flask was degassed. A stream of NH3 was slowly added to the reactants until a pressure increase, measured using a digital pressure sensor, indicated completion of the reaction due to the release of HCl. The reaction mixture was further stirred at 50°C and under high pressure of NH3 at 100 mbar for 1.5 hours. The reaction flask was then degassed at 50°C for 1 hour (<30 mbar). PALL Seitz® K series grade EK filter pad (1400 mass / unit area g / m²) 2 The product was filtered using a filter (3.8 mm thick).

[0206] Example 2 (Starting material) NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 Preparation of -OMe)2 900g allylmethyl-capped polyether (CH2=CH-CH2-(O-CH2CH2) 7.5-OCH3) was dissolved in 270 mL of xylene and heated to 80°C. Approximately 0.5 g of platinum catalyst (Lamoreaux) was added (totaling 10 ppm Pt), 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, and the remaining dimethylchlorosilane was removed under vacuum at 40°C. 170 g of the obtained hydrosilylation product was dissolved in 100 mL of xylene. The reaction flask was degassed, and a stream of NH3 was slowly added until the completion of the substitution reaction, in which the chloro atom was replaced by an amino group, was indicated by a pressure increase. The reaction mixture was further stirred at 50°C and under high pressure of NH3 at 100 mbar for 1.5 hours. The reaction flask was then degassed at 50°C for 1 hour (<30 mbar). PALL Seitz® K series grade EK filter pad (1400 mass / unit area g / m²) 2 The product was filtered using a filter (3.8 mm thick).

[0207] Example 3 (Starting Material) NH(SiMe2-(CH2)3-(OCH2CH2) 10 - OSiMe3)2 preparation 200g of allyl polyether Breox AA E450H(CH2=CH-CH2-(O-CH2CH2) 10 -OH) was dissolved in 400 mL of xylene. A mixture of 14.3 g of trimethylchlorosilane and 21.3 g of hexamethylenedisilazane (both used as OH capping agents for allyl polyether) 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. 58 g of the obtained product was heated to 80°C and approximately 64 mg of platinum catalyst (Lamoreaux, total 10 ppm Pt) was added. 11.4 g of dimethylchlorosilane (HSi(Me2)Cl) was added dropwise. The reaction mixture was then heated to 120°C and stirred for 4 hours. 220 g of the resulting product was dissolved in 100 mL of xylene. The reaction flask was degassed, and a stream of NH3 was slowly added until the pressure rise indicated completion of the reaction. The reaction mixture was further stirred at 50°C and under high pressure of NH3 at 100 mbar for 1.5 hours. The reaction flask was then degassed at 50°C for 1 hour (<30 mbar). PALL Seitz® K series grade EK filter pad (1400 mass / unit area g / m²) 2 The product was filtered using a filter (3.8 mm thick).

[0208] Example 4 Functionalization of silica using NH(SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me)2 (Example 1) 20 g of Aerosil® 300 was dispersed in 200 ml of dioxane, and then 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) were added. 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 a surface functionalization reaction of the SiOH surface groups by SiMe2-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)3Me had occurred. The dispersion was used without further purification and contained approximately 8 wt% silica.

[0209] Example 5 Preparation of polyetherpentasiloxane-functionalized silica Monodisperse polyetherpentasiloxane (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)3-(OCH2CH2) 10-OH) was prepared according to Example 6 of WO2017 / 012714A1. 10 g of Aerosil® 300 was dispersed in 250 g of toluene, followed by the addition of 0.12 g of diisopropoxybis(ethyl acetate) titanate. The mixture was heated to 80°C, and 2.0 g of (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)3-(OCH2CH2) 10 -OH) was slowly added. The slurry was then heated under reflux for 6 hours. The solvent was removed under vacuum (50°C / <1 mbar) to obtain a pale yellow powder (approximately 12 g).

[0210] Example 6 Preparation of polyether-functionalized silica 20g of Aerosil® 300 was dispersed in 200ml of dioxane, followed by 4.31g of deionized water and 36.9g of NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OMe)2 (Example 2) was added. 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 a surface functionalization reaction. The dispersion was used without further purification and contained approximately 8% by weight of silica.

[0211] Example 7 Preparation of VeoVa9 pentasiloxane-functionalized silica This example is monodisperse (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-O-SiMe2-(CH2)2-OC(O)-C(Me)R a R b , here R a , R b This relates to the functionalization of Aerosil® 300 by alkyl groups, each having a total of six carbon atoms. R a and R b =alkyl, where R a and R bThis monodisperse VeoVa9 pentasiloxane (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)2-OC(O)-C(CH3)R has a total of 6 carbon atoms. a R b According to example 7 of WO2017 / 012714A1, VeoVa9 [manufactured by Hexion] is M H -D3-M H It was prepared by reacting it with vinyltrimethoxysilane, followed by a reaction with vinyltrimethoxysilane. 10 g of Aerosil® 300 was dispersed in 250 g of toluene, followed by the addition of 0.12 g of diisopropoxybis(ethyl acetate) titanate. The mixture was heated to 80°C, and 2.0 g of monodisperse (MeO)3Si-(CH2)2-SiMe2(OSiMe2)3-SiMe2-(CH2)2-OC(O)-C(CH3)R was added. a R b (R here) a +R b An alkyl group (containing a total of 6 carbon atoms) was slowly added. The slurry was then heated under reflux for 6 hours. The solvent was removed under vacuum (50°C / <1 mbar) to obtain a pale yellow powder (10.5 g).

[0212] Example 8 Colloidal silica nanoparticles dispersed in 1-methoxy-2-propanol 100 g of a dispersion of silica nanoparticles in water (AkzoNobel Levasil EXP310, 30 wt% silica) was mixed with 44 g of 1-methoxy-2-propanol (Dowanol PM). Approximately 20–25 wt% of the solvent mixture was removed using a rotary evaporator. This procedure was repeated twice to obtain silica nanoparticles dispersed in 1-methoxy-2-propanol. The mixture still contained 10–15 wt% water, as measured by the KarlFischer method.

[0213] Example 9 NH(SiMe2-(CH2)3-(O-CH2CH2) 7.5 -OMe)2- Functionalized Colloidal Silica Nanoparticles 60 g of a dispersion of silica nanoparticles in 1-methoxy-2-propanol (Example 8) was mixed with approximately 517 g of 1-methoxy-2-propanol (Dowanol PM) (final SiO2 content: 3 wt%) and heated to 80°C under reflux and an inert N2 atmosphere. Then, 15 g of NH(SiMe2-(CH2)3-(O-CH2CH2)) was added to 15 mL of 1-methoxy-2-propanol. 7.5 A solution of -OMe)2 (Example 2) was added dropwise through a funnel. The mixture was stirred under reflux for 8 hours. Then, part of the solvent was removed under vacuum to obtain a liquid product with a silica content of 40% by weight.

[0214] Example 10 NH(SiMe2-(CH2)3-(OCH2CH2) 10 -OSiMe3)2-functionalized colloidal silica nanoparticles 60 g of a dispersion of silica nanoparticles in 1-methoxy-2-propanol (Example 8) was mixed with approximately 517 g of 1-methoxy-2-propanol (final SiO2 content: 3 wt%) and heated to 80°C. Then, 15 g of NH(SiMe2-(CH2)3-(OCH2CH2)) was added to 15 mL of 1-methoxy-2-propanol. 10 A solution of -OSiMe3)2 (Example 3) was added dropwise. The mixture was stirred under reflux for 8 hours. Then, part of the solvent was removed under vacuum to obtain a liquid product with a silica content of 15% by weight.

[0215] Application examples Preparation of antifouling coating formulations To test the activity of functionalized silica particles, coating formulations were prepared, and coated test panels were immersed in the sea (North Sea, Nordaney Port). Representative examples of the prepared coating formulations are as follows:

[0216] Application Example 1 (Anti-fouling test) The following coating compositions were prepared using functionalized Aerosil300® particles according to Examples 4, 5, 6, and 7 of the present invention. An adduct was prepared by reacting Epikote828EL (an epoxy resin prepared from bisphenol A and epichlorohydrin of Hexion) with silane A-1100 in a weight ratio of 34 / 47. 34.0 g of Epikote82EL and 47.0 g of silane A-1100 were dissolved in 70 g of xylene and heated at 80°C for 6 hours. Silane A-1100 is gamma-aminotriethoxysilane. [ka] *SiPEG is prepared as described in WO2014 / 126599A1 and is represented by the following formula. [ka] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] Primer-treated (50 μm coating thickness) PVC test (Simona) panels were prepared using the following primer compositions. - Component A: A mixture of Epikure3292-FX-60 (aliphatic amine curing agent for epoxy coatings), xylene, and SF1706 (a curable polymer containing amine functional groups and dimethylpolysiloxane units in a silicone fluid) in a weight ratio of 60:19:0.95. - Component B: Epon Resin 828 (liquid epoxy resin derived from bifunctional bisphenol A / epichlorohydrin) Here, component A and component B are mixed in a weight ratio of 10:7.2. The primer-treated panels were cured at room temperature for 24 hours. Next, coating formulations 990-G to 1103-G, as described above, were applied to the primer-treated PVC test panels (purchased from Simona AG) using a coating knife (coating thickness 300 μm). After curing the coatings at room temperature for one day, they were immersed in the North Sea at Nordaney Port (by Dr. Brill + Partner GmbH). Fouling and defouling evaluations were performed in accordance with the international ASTM standard ASTM D6990-05 (2011) (Standard test method for evaluating marine biofouling on coated test panels).

[0217] The following results were observed (dirt grade 100 = no dirt, 0 = surface covered with dirt): [Table 6] PVC-4 was used as the standard (PVC without surface treatment). Compared to the reference PVC panel, antifouling / defouling-resistant effects were observed in Examples 4, 5, 6, and 7, and these effects were shown to last for almost two years, even in the case of a mixture of Example 5 and Example 7 (50 / 50 by weight).

[0218] Application Example 2 (Anti-fogging test) Preparation of anti-fogging compounds To test the anti-fogging performance of functionalized particles, the particles were added to a UV-curing coating formulation. Contact angle was measured and evaluated in addition to anti-fogging performance.

[0219] Description of the coating composition The coating formulation consists of (i) a (meth)acrylate resin with a total molecular weight Mw of 30,000 based on 30 parts by mass of 2-acetoacetoxyethyl methacrylate (AAEM), 50 parts by mass of dimethylacrylamide (DMAA), 10 parts by mass of methyl methacrylate (MMA), and 10 parts by mass of butyl methacrylate (BMA); (ii) acrylate oligomerge pentaerythritol 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 the solvent. The coating formulation was prepared by mixing all components at room temperature and flow-coated onto polycarbonate test plates to obtain a coating thickness of 2–8 μm. After a flash-off period of approximately 5 minutes at room temperature, the coated panels were placed in a 120°C oven for approximately 20 minutes. [Table 7] *Anti-fog test acc. GMW 16508; 3.3.6 (This specification covers the certification requirements for transparent anti-condensation coatings used on the inner surface of the outer lens of the external lamp assembly). Formulation 1 (containing the functionalized silica particles of Example 9 according to the present invention) and Formulation 2 (containing the functionalized silica particles of Example 10 according to the present invention) showed improved anti-fogging properties compared to a standard without surface-treated silica particles.

[0220] Anti-fog performance evaluation contact angle measurement Water contact angle measurements were performed using the static droplet method with a Kruess DAS100 droplet shape analyzer. Deionized and filtered (0.2 μm filter) water was used. The volume of the analyzed droplet was 3.5 μL. The table below shows the results of water contact angle measurements after 60 seconds for formulations 1, 2, and 3. [Table 8]

[0221] Figures 1 to 3 show the results of contact angle measurements for formulations 1 to 3. Lower contact angles, particularly for formulation 1, indicate increased surface hydrophilicity, which is supported by improved anti-fogging performance.

[0222] Anti-fogging test The test plates were placed 15 cm apart on a water bath heated to 60°C, and their anti-fogging performance was evaluated for 90 seconds according to the GMW16508 specification, section 3.3.6.

[0223] [Table 9]

Claims

1. Silica particles functionalized with one or more silanes of the following formula, HN[-SiR １ ２ -A] ２ (1) and / or R １ ｘ R ２ ３－ｘ Si-A (2) Here R １ is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R １ is methyl, R ２ This is independently selected from hydrolyzable residues and is preferably selected from the group consisting of hydrogen, hydroxy, acyloxy groups and other hydrocarbylcarbonyloxy groups, halogen groups, amino groups, alkoxy or aryloxy groups and other hydrocarbyloxy groups, more preferably alkoxy groups. x is 0, 1, or 2, and A is the basis of the following equation, -M-F, Here M is selected from L or the base of the following formula: -{L-[SiR １ ２ O] ｐ -SiR １ ２ } ｍ -L-, here L is one or more -O-, -NR ３ -C(O)-, and / or -NR ３ -, -OC(O)NR ３ -, -NR ３ -C(O)-NR ３ - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R ３ is hydrogen, Me ３ L is Si- or C1-C8-alkyl, preferably a divalent C2-C12-alkylene group, more preferably a divalent C2-C4 alkylene group, and most preferably L is -(CH ２ ) ２ - and / or - (CH ２ ) ３ - and R １ This is defined as described above, p = 1 to about 9, preferably p = 1 or 4, more preferably p = 4, m = 1 to about 20, preferably m = 1, and F has up to approximately 100 carbon atoms, and -O-, -S-, -NH-, -C(O)-, -C(S)-, tertiary amino group, 【Chemistry 1】 or quaternary ammonium group 【Chemistry 2】 Selected from the group consisting of optionally substituted, linear, cyclic, or branched saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with an OH group, SH group, halide group, organosilyl group, or triorganosiloxy group, However, regarding the silane in formula (2), (i) A is the base of the following equation, -{L-[SiR １ ２ O] ｐ -SiR １ ２ } ｍ -L-F, here L, R １ p, m, and F are as defined above. or (ii) A is the base of the following equation, -L-F, where L comprises at least one ether group (-O-) and optionally at least one hydroxy substituent (-OH), and where F is as defined above, provided that it comprises at least one ester group (-OC(=O)- or -C(=O)-O-). These are the conditions for silica particles.

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

3. F consists of a polyether moiety, an ester moiety, and a coating matrix reactive moiety, such as alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diesters, and nitro(-NO). ２ It comprises at least one moiety selected from the group consisting of ), cyano(-CN), alkylsulfonyl fluoride groups, and donor and acceptor groups in Michael addition reactions, Or, here F is, - Alkyl, - Alkenil, - Alkylcarbonyloxy, - Polyalkylene oxide group, preferably one of the following general formulas, [-OC ２ H ４ ] ｑ [-OC ３ H ６ ] ｒ [-OC ４ H ８ ] ｓ -R ４ Here [-OC ２ H ４ ] represents an ethylene oxy unit, [-OC ３ H ６ ] represents a propyleneoxy unit, and [-OC ４ H ８ ] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q + r + s > 2, R ４ This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyloxy groups, - -SiR １ ３ organosilyl groups such as, where R １ is selected independently of the bases defined above for formulas (1) and (2), and -OSi(R １ ) ３ Siloxy groups such as, here R １ The silica particle according to claim 1 or 2, wherein is selected from the group consisting of, which is independently selected from the groups defined above for formulas (1) and (2).

4. One or more silanes of formula (1) and / or (2) are hydrophobic silanes (i.e., the partition coefficient of the compound H-L-F containing the L-F group of the silane in a 50 / 50 mixture of water and octanol P ｏｃｔ／ｗａｔ Silica particles according to any one of the claims, which are exclusively selected from silanes having a logP value of 0.5 or greater.

5. Silica particles according to any one of the claims, wherein one or more silanes of formula (1) and / or (2) are exclusively selected from hydrophilic silanes (i.e., silanes whose logP value of the partition coefficient of the compound H-L-F containing the L-F group of the silane in a 50 / 50 mixture of water and octanol is less than 0.5).

6. The silica particles according to any one of the claims, wherein the silica particles are functionalized with two or more different silanes of formula (1) and / or (2).

7. The silica particle according to claim 6, wherein each silica particle is functionalized with one or more hydrophobic silanes of formula (1) and / or (2), and with one or more hydrophilic silanes of formula (1) and / or (2).

8. In one or more silanes of formula (1) and / or (2), group F comprises one or more coating matrix reactive groups, wherein one or more further silanes of formula (1) and / or (2) are exclusively hydrophilic silanes or exclusively hydrophobic silanes, where preferably Silica particles according to claim 6, wherein one or more hydrophilic silane groups F comprises one or more hydrophilic groups selected from the group consisting of polyhydroxylated alkyl groups, polyether groups, hydrocarbon groups containing quaternary ammonium groups, hydrocarbon groups containing carboxylate groups, and hydrocarbon groups containing one or more amino groups, or, preferably, one or more hydrophobic silane groups F comprises one or more hydrophilic groups selected from the group consisting of linear or branched unsubstituted alkyl groups, alkyl groups containing difluoromethylene and / or trifluoromethyl groups, particularly perfluorinated alkyl groups, alkyl groups having triorganosilyl groups, organosiloxy groups, alkenyl groups, or aromatic groups without substituents containing heteroatoms, particularly alkaryl groups and aralkyl groups.

9. A silane of formula (1) as defined in claim 2.

10. A method for producing functionalized silica particles, - This involves contacting silica particles with one or more silanes of formula (1) and / or (2), HN[-SiR １ ２ -A] ２ (1) and / or R １ ｘ R ２ ３－ｘ Si-A (2) As defined in claim 1, Here, preferably, the silica particles are R ２ It is in contact with one or more silanes of formula (2) which are alkoxy groups, and Here, optionally, contact between silica particles and one or more silanes of formula (1) and / or (2) is made in the presence of a solvent, and Optionally, silica particles are brought into contact with one or more silanes of formula (1) and / or (2) at a temperature above about 40°C, more preferably above about 50°C, and most preferably in the range of about 55°C to about 120°C. Furthermore, optionally, contact between silica particles and one or more silanes of formula (1) and / or (2) is performed 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, and A further method wherein the silica particles are brought into contact 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 one or more silanes of formula (1), preferably in the presence of at least about 1.0 equivalent, and most preferably in the presence of at least about 1.5 equivalents of water, based on the molar amount of one or more silanes of formula (1).

11. In the silane of formula (1) and / or (2), F is - Alkyl, - Alkenil, - Alkylcarbonyloxy, and - Polyalkylene oxide group, preferably one of the following general formulas, [-OC ２ H ４ ] ｑ [-OC ３ H ６ ] ｒ [-OC ４ H ８ ] ｓ -R ４ Here [-OC ２ H ４ ] represents an ethylene oxy unit, [-OC ３ H ６ ] represents a propyleneoxy unit, and [-OC ４ H ８ ] represents the butylene oxy unit, q = 0 to about 40, preferably 0 to about 20, more preferably 1 to about 15. r = 0 to about 30, preferably 0 to about 20, more preferably 0 to about 10. s = 0 to about 20, preferably 0 to about 15, more preferably 0 to about 10, Here, q + r + s > 2, R ４ This is selected from the group consisting of hydroxyl, alkoxy, alkylcarbonyloxy, hydroxyalkyl, and siloxy groups, such as triorganosiloxy, organosilyl, glycidyl, and glycidyloxy groups. - Glycidyl and glycidyloxy groups, - -SiR １ ３ such as an organosilyl group, where R １ is independently selected from the groups defined above for formulas (1) and (2), and -OSi(R １ ) ３ such as a siloxy group, where R １ is independently selected from the groups defined above for formulas (1) and (2), and is selected from the group consisting of, Or, here, one or more silane groups F of formula (1) and / or (2) are a polyether moiety, an ester moiety, and a coating matrix reactive moiety, e.g., alkenyl, epoxy, acrylate, methacrylate, thiol, hydroxyl, alkoxy, carboxy(-COOH), amino, alkoxysilyl and isocyanate groups, ketones, diketones, 1,3-diketones, dicarboxyl groups, 1,3-dicarboxyl groups, diesters, 1,3-diesters, nitro(-NO) ２ The method according to claim 10, comprising at least one part selected from the group consisting of ), cyano(-CN), alkylsulfonyl fluoride group, and donor and acceptor groups in a Michael addition reaction.

12. Contacting silica particles with two or more silanes of formula (1) and / or (2) as defined in claim 1 in one step, or contacting silica particles with two or more silanes of formula (1) and / or (2) in two or more steps, wherein the silica particles are preferably contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive portions, and are contacted 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 The method according to claim 10 or 11, wherein the silica particles are preferably contacted with one or more silanes of formula (1) and / or (2) comprising one or more coating matrix reactive portions, and in the absence of the hydrophobic silanes of formula (1) and / or (2), they are contacted with one or more hydrophilic silanes of formula (1) and / or (2).

13. Functionalized silica particles containing one or more monovalent groups A, Here, A is the basis of the following equation, -M-F, Here M is selected from L or the base of the following formula: -{L-[SiR １ ２ O] ｐ -SiR １ ２} ｍ -L-, where L is one or more -O-, -NR ３ -C(O)-, and / or -NR ３ -, -OC(O)NR ３ -, -NR ３ -C(O)-NR ３ - Independently selected from the group consisting of divalent alkylene groups having at least two carbon atoms, which can be interrupted by a portion and can be substituted with one or more OH groups, where R ３ is hydrogen, Me ３ L is Si- or C1-C8-alkyl, preferably a divalent C2-C12-alkylene group, more preferably a divalent C2-C4 alkylene group, and most preferably L is -(CH ２ ) ２ - and / or - (CH ２ ) ３ - and R １ is independently selected from non-hydrolyzable residues, preferably hydrocarbyl groups, more preferably alkyl groups, and most preferably R １ It is methyl, p = 1 to about 9, preferably p = 1 or 4, more preferably p = 4, m = 1 to about 20, preferably m = 1, and F has up to approximately 100 carbon atoms, and -O-, -S-, -NH-, -C(O)-, -C(S)-, tertiary amino group, 【Transformation 3】 or quaternary ammonium group 【Chemistry 4】 Selected from the group consisting of optionally substituted, linear, cyclic, or branched saturated, unsaturated, or aromatic hydrocarbyl groups, which optionally contain one or more groups selected from and may be substituted with an OH group, SH group, halide group, organosilyl group, or triorganosiloxy group, Group A is bonded to the silica particles via silicon atoms linked to the silicon dioxide network of the silica particles via one or more oxygen atoms, and the valence of the silicon atoms not occupied by group A or oxygen atoms is determined by the substituent R defined above. １ Functionalized silica particles, which are occupied by this material.

14. Preferably, for the manufacture of a coating composition, use of silica particles according to any one of claims 1 to 8, silica particles according to claim 13, or silica particles manufactured by the method according to any one of claims 10 to 12 as a marine antifouling additive, general antifouling additive, anti-de-icing additive, anti-mud additive, anti-fogging additive, self-cleaning additive, anti-adhesion, anti-dust, anti-fingerprint, and anti-graffiti additive, particularly as a general antifouling additive or anti-fogging additive, in the coating composition.

15. A coating composition comprising silica particles according to any one of claims 1 to 8, silica particles according to claim 13, or silica particles produced by the method according to any one of claims 10 to 12, preferably comprising silica particles in an amount of about 0.1 to about 80% by weight, more preferably about 0.5 to about 70% by weight, even more preferably about 1 to about 60% by weight, and even more preferably about 20 to about 55% by weight, most preferably about 25 to about 50% by weight, based on the total weight of the coating composition.

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