Curable composition, cured product, and coated substrate

Abstract

To provide a curable composition capable of forming a cured film in which the resulting film exhibits high water repellency derived from an amino-modified silicone.SOLUTION: There is provided a curable composition comprising an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (1) and a hydrolyzable group-containing organosilicon compound [wherein, R1 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R2 and R3 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R4 represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a sulfur atom, a silicon atom, an ester bond or a urea bond, p is an integer of 1 to 1000, q is 0 or 1, r is 0, 1 or 2, and X represents R13Si or the like].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a cured product, and a coated substrate, and more specifically to a curable composition, a cured product, and a coated substrate, which contain an alkoxysilylalkylaminopropyl-modified polysiloxane compound and a hydrolyzable group-containing organosilicon compound. [Background technology]

[0002] Aminoalkyl-modified polysiloxane compounds (hereinafter also referred to as "amino-modified silicones") are used in a variety of applications, such as resin modifiers, fiber treatment agents, cosmetic raw materials, and paint additives, taking advantage of the reactivity of the amino group.

[0003] Amino-modified silicones have a polysiloxane structure, which allows them to exhibit water repellency and flexibility. For example, when used as a resin modifier, a modified resin can be obtained by reacting the amino-modified silicone with an epoxy resin or an isocyanate resin, which are resins that have functional groups that can react with amino groups. This allows the resin to be endowed with the water repellency and flexibility that come from the polysiloxane structure of the amino-modified silicone.

[0004] In addition, a coating agent for vehicles has been developed that consists of a silicone oligomer, a silicone modified at both ends with amino groups, a curing catalyst, and a solvent. This coating agent is said to be able to impart high water repellency to the object to which it is applied due to the effect of the silicone modified at both ends (Patent Document 1). Furthermore, a coating agent consisting of a polysilazane compound, a silicone modified at both ends with amino groups, and a solvent has also been developed. This coating agent is also said to be able to impart high water repellency to the object to be coated due to the effect of the silicone modified at both ends (Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-075021 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-139301 Summary of the Invention [Problem to be solved by the invention]

[0006] In the coating agents described in Patent Documents 1 and 2, the amino-modified silicone that provides water repellency does not contain a hydrolyzable silyl group in the molecule. Therefore, when attempting to form a cured coating by mixing it with a hydrolyzable group-containing organosilicon compound such as a silicone oligomer or a polysilazane compound, there are problems in that the coating cannot be formed or it takes a long time to form the coating.

[0007] The present invention has been made in view of the above circumstances, and has an object to provide a curable composition that can form a cured coating, the resulting coating exhibiting high water repellency derived from the amino-modified silicone, a cured product obtained by curing the cured composition, and a coated substrate having a coating formed from the curable composition. [Means for solving the problem]

[0008] The present inventors conducted extensive research to solve the above problems and discovered that a curable composition containing an alkoxysilylaminoalkyl-modified polysiloxane compound and a hydrolyzable group-containing organosilicon compound such as a silicone oligomer or a polysilazane compound can form a cured coating in a short period of time, and that the resulting coating exhibits good water repellency, thereby completing the present invention.

[0009] That is, the present invention provides: 1. A curable composition comprising an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (1) and a hydrolyzable group-containing organosilicon compound: [ka] [In the formula, R 1 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R3 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 4 represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a sulfur atom, a silicon atom, an ester bond or a urea bond, p is an integer of 1 to 1000, q is 0 or 1, r is 0, 1 or 2, X is a group represented by the following general formula (2) or R 1 Represents 3Si. [ka] (In the formula, R 2 ~R 4 , q and r have the same meanings as above.)] 2. The curable composition of 1, wherein the hydrolyzable group-containing organosilicon compound is at least one selected from the group consisting of alkoxysilanes, partial hydrolysis condensates of alkoxysilanes, polysilazanes, and polysiloxazanes. 3. The curable composition of 1 or 2 containing a solvent; 4. The curable composition according to any one of 1 to 3, which contains at least one metal compound selected from the group consisting of titanium compounds, aluminum compounds, zinc compounds, and tin compounds. 5. A cured product of the curable composition according to any one of 1 to 4. 6. A coated substrate having a substrate and a coating formed thereon, wherein the coating is formed from a curable composition according to any one of 1 to 4. to provide. [Effects of the Invention]

[0010] The curable composition of the present invention can undergo co-hydrolytic condensation with the hydrolyzable group-containing organosilicon compound, allowing rapid formation of a cured coating. The resulting cured coating also exhibits high water repellency due to the polysiloxane structure. [Brief explanation of the drawings]

[0011] [Figure 1]FIG. 1 is a diagram showing an IR spectrum of 2,2-dimethoxy-N-(trimethoxysilyl octyl)-1-aza-2-silacyclopentane obtained in Production Example 1. [Figure 2] FIG. 1 is a diagram showing the 1H-NMR spectrum of 2,2-dimethoxy-N-(trimethoxysilyl octyl)-1-aza-2-silacyclopentane obtained in Production Example 1. [Figure 3] FIG. 2 is a diagram showing an IR spectrum of 2-ethoxy-2-methyl-N-(triethoxysilyl octyl)-1-aza-2-silacyclopentane obtained in Production Example 2. [Figure 4] FIG. 1 is a diagram showing the 1H-NMR spectrum of 2-ethoxy-2-methyl-N-(triethoxysilyloctyl)-1-aza-2-silacyclopentane obtained in Production Example 2. [Figure 5] FIG. 2 is a diagram showing an IR spectrum of 2-methoxy-2-methyl-N-(trimethoxysilylpropylthioethyl)-1-aza-2-silacyclopentane obtained in Production Example 3. [Figure 6] FIG. 1 is a diagram showing the 1H-NMR spectrum of 2-methoxy-2-methyl-N-(trimethoxysilylpropylthioethyl)-1-aza-2-silacyclopentane obtained in Production Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be specifically described below. [1] Curable composition The curable composition of the present invention contains an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (1) (hereinafter referred to as "compound (1)") and a hydrolyzable group-containing organosilicon compound.

[0013] [ka]

[0014] In general formula (1), R 1are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. R 1 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, thexyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Among these, methyl, ethyl, propyl, vinyl and phenyl groups are preferred from the viewpoint of ease of procurement of raw materials.

[0015] Also, R 1 In the monovalent hydrocarbon group, some or all of the hydrogen atoms may be substituted with fluorine atoms or chlorine atoms. Specific examples of such substituted monovalent hydrocarbon groups include fluoroalkyl groups such as a (3,3,3-trifluoro)propyl group; and chloroalkyl groups such as a chloromethyl group and a chloropropyl group.

[0016] In general formula (1), R 2 and R 3 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. R 2 and R 3 The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and pentenyl; and aryl groups such as phenyl. Among these, methyl and ethyl groups are preferred because of the ease of procurement of raw materials.

[0017] In general formula (1), R 4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms, which may contain a sulfur atom, a silicon atom, an ester bond, or a urea bond. R 4 The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as methylethylene and methyltrimethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as propenylene, butenylene, hexenylene, and octenylene; branched alkenylene groups such as isopropenylene and isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene, methylenephenylenemethylene, and methylenephenyleneethylene. Among these, from the viewpoint of ease of procurement of raw materials, a linear alkylene group is preferred, and a linear alkylene group having 1 to 6 carbon atoms is more preferred.

[0018] R 4 When the divalent hydrocarbon group contains a sulfur atom, specific examples thereof include a thioalkylene group and an alkylenethioalkylene group. R 4 Specific examples of the divalent hydrocarbon group when contains a silicon atom include an alkylenedialkylsilylalkylene group and a group represented by the following general formula (3).

[0019] [ka] (In the formula, R 1 has the same meaning as above.)

[0020] In general formula (3), R 4’are each independently an oxygen atom or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. 4’ The total number of carbon atoms in 4 Specific examples of this divalent hydrocarbon group include the above-mentioned R 4 Examples of the groups include the same as those exemplified in the above.

[0021] R 4 When R contains an ester bond, examples of the divalent hydrocarbon group include a substituent represented by the following general formula (4): 4 When the divalent hydrocarbon group contains a urea bond, examples of the divalent hydrocarbon group include substituents represented by the following general formula (5).

[0022] [ka]

[0023] In general formulas (4) and (5), R 4 " are each independently a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6, and more preferably 1 to 3 carbon atoms, and two R 4 The total number of carbon atoms in 4 is the same as R 4 As the divalent hydrocarbon group of ", R 4 Among the groups exemplified above, those having 1 to 10 carbon atoms are exemplified. In general formula (5), R 5 R is a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6, and more preferably 1 to 3 carbon atoms. 5 As the monovalent hydrocarbon group, R 1 In particular, a hydrogen atom is preferred from the viewpoint of ease of procurement of raw materials.

[0024] In general formula (1), p is an integer of 1 to 1000, preferably 4 to 300, and more preferably 12 to 100, from the viewpoints of ease of handling and ability to impart sufficient water repellency. q is 0 or 1, and r is 0, 1, or 2.

[0025] In the general formula (1), X is a group represented by the following general formula (2) or R 1 Represents 3Si.

[0026] [ka] (In the formula, R 2 ~R 4 , q and r have the same meanings as above.)

[0027] Compound (1) can be obtained, for example, by reacting a silanol-modified polysiloxane compound represented by the following general formula (6) (hereinafter referred to as "compound (6)") with a cyclic silazane compound having an alkoxysilyl group represented by the following general formula (7) (hereinafter referred to as "compound (7)"). Compound (7) can also be produced by known methods such as those described in JP-A-2011-102267.

[0028] [ka] (In the formula, R 1 ~R 4 , X, p, q and r have the same meanings as above.)

[0029] Specific examples of compound (6) include 1-hydroxy-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octamethyl-7-vinyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octamethyl-7-chloromethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7-octamethyl-7-chloropropyltetrasiloxane, and 1-hydroxy-1,1,3,3,5,5-hexavinyl-7,7,7-trimethyltetrasiloxane. tetrasiloxane, 1-hydroxy-1,1,3,3,5,5-hexaphenyl-7,7,7-trimethyltetrasiloxane, 1-hydroxy-1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5,7,7,7-hexamethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7-heptavinyl-7,7-dimethyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7-heptamethyl-7,7-diphenyltetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7- 1-Hydroxypolysiloxane compounds such as octaphenyl-7-methyl-tetrasiloxane, 1-hydroxy-1,1,3,3,5,5,7,7,7-nonaphenyltetrasiloxane, α-hydroxy-ω-methylpolydimethylpolysiloxane, α-hydroxy-ω-vinylpolydimethylpolysiloxane, α-hydroxy-ω-chloromethyldimethylpolysiloxane, α-hydroxy-ω-chloropropyldimethylpolysiloxane, and α-hydroxy-ω-phenyldimethylpolysiloxane; 1,7-dihydroxy-1,1,3 dihydroxypolysiloxane compounds such as 1,3,5,5,7,7-octamethyltetrasiloxane, 1,7-dihydroxy-1,1,3,3,5,5,7-heptamethyl-7-vinyltetrasiloxane, 1,7-dihydroxy-1,3,5-tris(3,3,3-trifluoropropyl)-1,3,5,7,7-pentamethyltetrasiloxane, and α,ω-dihydroxydimethylpolysiloxane; and dialkylsilanediols such as dibutylsilanediol, diphenylsilanediol, and dicyclopentylsilanediol.

[0030] Specific examples of compound (7) include 2,2-dimethoxy-N-(trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylpropyl)- 1-Aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(trimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilylhexyl)-1-aza-2-silacyclopentane 2-ethoxy-2-methyl-N-(triethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(triethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(triethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(triethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(triethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(triethoxysilylhexyl)-1-aza-2-silacyclopentane 2,2-Dimethoxy-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(trimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(trimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-[(trimethoxysilyl)ethyldimethylsiloxydimethylsilyl(methyl)propyl]-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-[(trimethoxysilyl)ethyldimethylsiloxydimethylsilyl(methyl)propyl]-1-aza-2-silacyclopentane 2,2-Dimethoxy-N-(3-trimethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-N-(3-triethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(3-trimethoxysilylpropoxycarbonyl(methyl)ethyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-N-(3-trimethoxysilylpropoxycarbonyl(methyl)ethyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-N-(3-triethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane 2,2-Dimethoxy-N-(3-trimethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(3-trimethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy-N-(3-triethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane, 2-Ethoxy-2-methyl-N-(3-triethoxysilylpropylureidoethyl)-1-aza-2-silacyclopentane Cyclic silazane compounds having trialkoxysilylalkyl groups such as aza-2-silacyclopentane, 2,2-dimethoxy-N-(trimethoxysilylethyldimethylsiloxydimethylsilylpropyl(methyl))-1-aza-2-silacyclopentane, and 2,2-dimethoxy-N-(1,1,1-trimethoxy-3,3,5,5,7,7-hexamethyltetrasiloxydimethylsilylpropyl)-1-aza-2-silacyclopentane; 2,2-dimethoxy-N-(methyldimethoxysilylpropyl)-1-aza-2-silacyclopentane,2-Dimethoxy-N-(methyldimethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(methyldimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(methyldimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-Diethoxy Si-N-(methyldiethoxysilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilylmethyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-N-(methyldiethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(methyldiethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-N-(methyldiethoxysilylhexyl)-1-aza-2-silacyclopentane 2,2-Dimethoxy-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylthioethyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(methyl 2,2-Dimethoxy-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(methyldimethoxysilylthiopropyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(3-methyldimethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,Cyclic silazane compounds having alkyldialkoxysilylalkyl groups such as 2-diethoxy-N-(3-methyldiethoxysilylpropoxycarbonylethyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(3-methyldimethoxysilylpropoxycarbonyl(methyl)ethyl)-1-aza-2-silacyclopentane, and 2,2-diethoxy-N-(3-methyldiethoxysilylpropoxycarbonyl(methyl)ethyl)-1-aza-2-silacyclopentane; 2,2-Dimethoxy-N-(dimethylmethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N-(dimethylmethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(dimethylmethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-Methoxy-2-methyl-N-(dimethylmethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-Dimethoxy-N -(Diethylmethoxysilylhexyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(diethylmethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(diethylmethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(diethylmethoxysilyloctyl)-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-(diphenylmethoxysilylhexyl)-1-aza-2-silacyclopentane, 2, Examples include cyclic silazane compounds having a dialkylalkoxysilylalkyl group, such as 2-dimethoxy-N-(diphenylmethoxysilyloctyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(diphenylmethoxysilylhexyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-N-(diphenylmethoxysilyloctyl)-1-aza-2-silacyclopentane, and 2,2-diethoxy-N-(dimethylethoxysilylmethyl)-1-aza-2-silacyclopentane.

[0031] Specific examples of compound (1) include 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(3-triethoxysilylpropylaminopropyl)-1,1-diethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(8-trimethoxysilylpropylaminooctyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(8-triethoxysilylpropylaminooctyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(8-triethoxysilylpropylaminopropyl)-1-ethoxy-1,3,3,5,5,7,7,9,9,9-decamethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9 -Octamethyl-9-vinylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octamethyl-9-chloromethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octamethyl-9-chloropropylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octamethyl-9-chloropropylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7-hexavinyl-9,9,9-tri Methylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7-hexaphenyl-9,9,9-trimethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,5,7-tris(3,3,3-trifluoropropyl)-3,5,7,9,9,9-hexamethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9-heptavinyl-9,9-Dimethylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9-heptamethyl-9,9-diphenylpentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9-octaphenyl-7-methyl-pentasiloxane, 1-(3-trimethoxysilylpropylaminopropyl)-1,1-dimethoxy-3,3,5,5,7,7,9,9,9-nonaphenylpentasiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-methylpolydimethylpolysiloxane X is R, such as α-(3-triethoxysilylpropylaminopropyl)-α,α-diethoxy-ω-methylpolydimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-vinylpolydimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-chloromethyldimethylpolysiloxane, α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-chloropropyldimethylpolysiloxane, and α-(3-trimethoxysilylpropylaminopropyl)-α,α-dimethoxy-ω-phenyldimethylpolysiloxane. 11-(alkoxysilylalkylaminopropyl)polysiloxane compounds in the case of 3Si: 1,11-bis(3-trimethoxysilylpropylaminopropyl)-1,1,11,11-tetramethoxy-3,3,5,5,7,7,9,9-octamethylhexasiloxane, 1,11-bis(3-triethoxysilylpropylaminopropyl)-1,1,11,11-tetraethoxy-3,3,5,5,7,7,9,9-octamethylhexasiloxane, 1,11-bis(3-trimethoxysilylpropyl 1,11-bis(3-trimethoxysilylpropylaminopropyl)-1,1,11,11-tetramethoxy-3,5,7-tris(3,3,3-trifluoropropyl)-3,5,7,9,9-pentamethylhexasiloxane, α,ω-bis(3-trimethoxysilylpropylaminopropyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, α,ω -bis(3-triethoxysilylpropylaminopropyl)-α,α,ω,ω-tetraethoxydimethylpolysiloxane, α,ω-bis(8-trimethoxysilylpropylaminooctyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, α,ω-bis(8-triethoxysilylpropylaminooctyl)-α,α,ω,ω-tetraethoxydimethylpolysiloxane, α,ω-bis(trimethoxysilylpropylaminomethyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, Examples of such α,ω-bis(alkoxysilylalkylaminopropyl)polysiloxane compounds in which X is represented by general formula (2) include α,ω-bis(triethoxysilylpropylaminomethyl)-α,α,ω,ω-tetraethoxydimethylpolysiloxane, α,ω-bis(dimethylmethoxysilylpropylaminomethyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane, and α,ω-bis(dimethylethoxysilylpropylaminomethyl)-α,α,ω,ω-tetramethoxydimethylpolysiloxane.

[0032] Next, the hydrolyzable group-containing organosilicon compound will be described. The hydrolyzable group-containing organosilicon compound used in the present invention is not particularly limited as long as it has a functional group capable of hydrolysis and condensation, but is preferably at least one selected from the group consisting of alkoxysilanes, partial hydrolysis and condensation products of alkoxysilanes, polysilazanes, and polysiloxazanes.

[0033] The alkoxysilane compound is, for example, a compound represented by the following general formula (8) (hereinafter referred to as "compound (8)").

[0034] [ka]

[0035] In general formula (8), R 6 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may contain an oxygen atom; R 7 is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and x is an integer of 0 to 2. R 6 and R 7 Specific examples of the monovalent hydrocarbon group include R 1 The same substituents as those mentioned above can be mentioned. R 6 Specific examples of the monovalent hydrocarbon group containing an oxygen atom include alkyloxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxypropyl groups.

[0036] Specific examples of compound (8) include dialkyldialkoxysilane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and dicyclopentyldimethoxysilane; alkyltrialkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, methoxymethyltrimethoxysilane, ethoxymethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; and tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane.

[0037] The partial hydrolysis condensate of compound (8) can be obtained by adding water to compound (8) in the presence of a catalyst as needed, and then heating and stirring as needed. In this case, the alkoxysilane compound used can be used alone or in combination of two or more kinds.

[0038] The polysilazane compound is a polycondensation product of a chlorosilane compound and ammonia, and is, for example, a compound having a repeating unit represented by the following general formula (9) (hereinafter referred to as "compound (9)").

[0039] [ka]

[0040] In general formula (9), R 8 R are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain an organosiloxane group at its terminal, and which is represented by the following general formula (9A): 8 As the monovalent hydrocarbon group, R 1 The same substituents as those mentioned above can be mentioned. and y is 0, 1, 2, or 3.

[0041] [ka]

[0042] In formula (9A), R 9 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and some or all of the hydrogen atoms of this monovalent hydrocarbon group may be substituted with halogen atoms such as chlorine atoms, bromine atoms, or iodine atoms. In formula (9A), a is 0, 1, 2, or 3. When a is 0 or 1, a plurality of OSiR 9 Three groups may be condensed together to form a cyclic siloxane. Furthermore, b represents an integer of 0 to 30, preferably 0 to 20, and more preferably 5 to 15. R 9 The combination of a and b is arbitrary and there is no restriction.

[0043] Such an R 9 Specific examples of the organosiloxane group represented by general formula (9A) defined by a and b include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, and tert-butyldiphenylsilyl groups; polyalkylpolysiloxanyl groups such as pentamethyldisiloxanyl, heptamethyltrisiloxanyl, nonamethyltetrasiloxanyl, α-trimethylsilyl-polydimethylsiloxanyl, and α-butyldimethylsilyl-polydimethylsiloxanyl; and polyalkylcyclopolysiloxanyl groups such as pentamethylcyclotrisiloxanyl, heptamethylcyclotetrasiloxanyl, and nonamethylcyclopentasiloxanyl groups.

[0044] The polysilazane compound may be composed of only one structural unit as represented by general formula (9), or may be composed of two or more structural units, except for the case where y=3 only, i.e., hexaalkyldisilazane.

[0045] Compound (9) can be obtained by reacting the above chlorosilane compound with ammonia, optionally in the presence of a solvent, and removing the ammonium chloride produced as the reaction proceeds.

[0046] The polysiloxazane compound contains a siloxane structure and a silazane structure in the molecule, and is, for example, a compound represented by the following general formula (10) (hereinafter referred to as "compound (10)").

[0047] [ka] (In the formula, R 6 has the same meaning as above.)

[0048] In general formula (10), R 10 R are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom or a silicon atom. 10 As the monovalent hydrocarbon group, R 1 The same substituents as those mentioned above can be mentioned.

[0049] Also, R 10 When contains a sulfur atom, specific examples of the monovalent hydrocarbon group include alkylenethioalkyl groups. R 10 Specific examples of the monovalent hydrocarbon group when contains a silicon atom include a trialkylsilylalkyl group, a dialkylmonoalkoxysilylalkyl group, an alkyldialkoxysilylalkyl group, and a trialkoxysilylalkyl group, and the monovalent hydrocarbon group may contain an organosiloxane group represented by general formula (9A) at the end.

[0050] Furthermore, R 10 may contain both a sulfur atom and a silicon atom. Specific examples of the monovalent hydrocarbon group containing both a sulfur atom and a silicon atom include an alkylenethioalkylenedialkylmonoalkoxysilyl group, an alkylenethioalkylenealkyldialkoxysilyl group, and an alkylenethioalkylenetrialkoxysilyl group.

[0051] In general formula (10), each A independently represents R 6 , an oxygen atom, or NH-SiA2, or represents an oxygen atom to which A's are bonded. e and f are each independently 0, 1, or 2, except when both e and f are 0. m represents an integer from 0 to 300, preferably from 2 to 100, more preferably from 2 to 40. c and d are numbers that satisfy 0 < c ≤ 1, 0 ≤ d < 1, and c + d = 1. Further, when the number of NH-SiA2 is g, c is a number that satisfies 0 ≤ g / (2m + 4) ≤ 0.5.

[0052] Compound (10) can be obtained by reacting a chlorosiloxane compound represented by the following general formula (12) and a both-end silanol-modified polysiloxane represented by the following general formula (13) with ammonia in the presence of a solvent as needed, and removing ammonium chloride generated as the reaction proceeds, similar to the polysilazane compound.

[0053] [Chemical formula] (In the formula, R 6 and m have the same meanings as described above.)

[0054] In general formula (12), each E independently represents R 6 , a chlorine atom, or an oxygen atom, or represents an oxygen atom to which E's are bonded. In general formula (12), when the number of chlorine atoms is h, h is a number that satisfies 0 ≤ h / (2m + 2) ≤ 0.5.

[0055] In the curable composition of the present invention, the hydrolyzable group-containing organosilicon compound may be used alone or in combination with a plurality of components. Examples of the use of a plurality of components in combination include a mixture of compound (8) and its partial hydrolyzed condensate, a mixture of a partial hydrolyzed condensate of compound (8) and compound (9), and a mixture of a partial hydrolyzed condensate of compound (8) and compound (10).

[0056] The compounding ratio of compound (1) to the hydrolyzable group-containing organosilicon compound in the curable composition is not particularly limited, but the amount of compound (1) is preferably 0.1 to 90 mass%, more preferably 0.5 to 75 mass%, and even more preferably 1 to 60 mass%, based on the total mass of compound (1) and the hydrolyzable group-containing organosilicon compound.

[0057] The curable composition can be used without a solvent, but a solvent may be used as long as it does not affect the compound (1) or the hydrolyzable group-containing organosilicon compound. Specific examples of solvents include aliphatic hydrocarbon compounds having 5 to 20 carbon atoms, such as pentane, hexane, cyclohexane, octane, isooctane, nonane, decane, dodecane, and isododecane; aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as benzene, toluene, and xylene; ether compounds, such as diethyl ether, tetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, and dioxane; ester compounds, such as ethyl acetate, isopropyl acetate, and butyl acetate; and aprotic polarizing compounds, such as acetonitrile and N,N-dimethylformamide. alcohol compounds such as methanol, ethanol, propanol, 2-propanol, and butanol; chlorinated hydrocarbon compounds such as dichloromethane and chloroform; and siloxane compounds having 2 to 10 silicon atoms such as hexamethyldisiloxane, octamethyltrisiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylpentasiloxane. These solvents may be used alone or in combination of two or more. Among these, aliphatic hydrocarbon compounds having 8 to 12 carbon atoms and siloxane compounds having 2 to 8 silicon atoms are particularly preferred from the standpoint of safety.

[0058] The amount of solvent used is not particularly limited, but is preferably an amount such that the concentration of compound (1) and the hydrolyzable group-containing organosilicon compound becomes 0.1 to 90 mass %, more preferably 1 to 90 mass %, and even more preferably 5 to 80 mass %.

[0059] The curable composition may also contain, as a curing catalyst, at least one metal compound selected from titanium compounds, aluminum compounds, zinc compounds, and tin compounds. Specific examples of titanium compounds include tetraalkyl orthotitanates such as tetrabutyl orthotitanate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, and tetraisopropyl orthotitanate, partial hydrolysis condensates thereof, and titanium acylate. Specific examples of aluminum compounds include aluminum trihydroxide, aluminum alcoholates, aluminum acylates, salts of aluminum acylates, aluminosiloxy compounds, and aluminum metal chelate compounds. Specific examples of zinc compounds include zinc octoate and zinc 2-ethylhexanoate. Specific examples of tin compounds include dioctyltin dioctate and dioctyltin dilaurate. The amount of the curing catalyst used is not particularly limited, but from the viewpoint of exerting the effect of the catalyst, it is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, based on the mass of the curable composition.

[0060] The curing catalyst may be added to the curable composition later, or may be dissolved in a hydrolyzable group-containing organosilicon compound or a solvent and then added.

[0061] The curable composition may contain one or more other additives selected from pigments, antifoaming agents, lubricants, preservatives, pH adjusters, film-forming agents, antistatic agents, antibacterial agents, dyes, etc., as long as the effects of the curable composition are not impaired.

[0062] The curable composition can be prepared by mixing compound (1) and a hydrolyzable group-containing organosilicon compound with a solvent, a curing catalyst, and other additives, if necessary, while taking care to avoid moisture, to obtain a homogeneous solution. Specifically, the components can be handled under an inert gas atmosphere such as nitrogen or argon to prevent moisture contamination. There is no restriction on the order in which the components are added, but from the viewpoint of minimizing the progress of hydrolysis, it is preferable to add the curing catalyst last.

[0063] Next, the cured product obtained by curing the curable composition will be described. The cured product of the present invention is obtained by curing the above-mentioned curable composition. Specifically, the curable composition is cured by hydrolysis and condensation of the alkoxysilyl group in compound (1) and the hydrolyzable group in the hydrolyzable-group-containing organosilicon compound. When the curable composition contains a solvent, the solvent may or may not be evaporated before curing, or the composition may be cured while evaporating the solvent. The curing temperature can be from room temperature to heated conditions. There are no particular restrictions on the temperature as long as it does not adversely affect the substrate, but to maintain reactivity, the temperature is preferably 0 to 250°C, more preferably 20 to 180°C, and even more preferably 20 to 150°C. Since the reaction occurs with moisture in the air, the reaction is preferably carried out in an atmosphere with a relative humidity of preferably 15 to 100%, more preferably 25 to 80%.

[0064] Furthermore, the curable composition of the present invention can be coated on the surface of a substrate made of an inorganic or organic material, and then cured by reacting with moisture in the air to obtain a coated substrate.

[0065] Specific examples of inorganic materials include metals, glass, silica, alumina, talc, calcium carbonate, and carbon. The glass may be any commonly used type of glass such as E glass, C glass, or quartz glass, or may be glass fiber. The glass fiber may be an aggregate thereof, such as a glass-based (filament) fiber bundle, twisted yarn, or woven fabric having a fiber diameter of 3 to 30 μm.

[0066] Specific examples of organic materials include resin materials such as polyethylene, polypropylene, polystyrene, poly(meth)acrylic, polyvinyl chloride, polycarbonate, nylon, polyurethane, polybutylene terephthalate, polyethylene terephthalate, ABS (polymer of acrylonitrile, butadiene, and styrene), melamine, phenol, epoxy, and polyimide; elastomers such as polybutadiene rubber, polyisopropylene rubber, nitrile rubber, neoprene rubber, polysulfide, and urethane rubber; and rubber materials, with poly(meth)acrylic being particularly preferred. The shape of the substrate is not particularly limited, and may be any of a plate, sheet, fiber, and powder.

[0067] Examples of a method for applying the curable composition to a substrate include known application methods, such as brush coating, sponge coating, cloth coating, spray coating, wire bar coating, blade coating, roll coating, dipping, and spin coating. In addition, for powdery materials such as silica, alumina, talc, and calcium carbonate, a mixing method may be employed in which the curable composition is directly mixed with the base material in a mixer or mill. [Example]

[0068] The present invention will be explained in more detail below with reference to Production Examples, Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0069] [Production Example 1] Synthesis of 2,2-dimethoxy-N-(trimethoxysilyl octyl)-1-aza-2-silacyclopentane [ka] (In the formula, Me represents a methyl group. The same applies hereinafter.)

[0070] The inside of a four-necked glass flask equipped with a stirrer, thermometer, distillation column, and reflux condenser was purged with nitrogen, and 122 g (0.296 mol) of (trimethoxysilylpropyl)-(trimethoxysilyloctyl)amine, 132 g of toluene, and 0.75 g (0.0050 mol) of trifluoromethanesulfonic acid were added and refluxed. 58.4 g (0.311 mol) of N-trimethylsilyl-N-methylaniline was added to this mixture and stirred, and the generated trimethylmethoxysilane was extracted together with toluene using the distillation column until the reaction temperature reached 150°C. The resulting reaction solution was distilled to obtain 66 g of a fraction having a boiling point of 170°C / 0.5 kPa (yield: 58%). 1 H-NMR analysis was performed, and the results are shown in Figures 1 and 2.

[0071] [Production Example 2] Synthesis of 2-ethoxy-2-methyl-N-(triethoxysilyl octyl)-1-aza-2-silacyclopentane [ka] (In the formula, Et represents an ethyl group. The same applies hereinafter.)

[0072] The inside of a four-necked glass flask equipped with a stirrer, thermometer, distillation column, and reflux condenser was purged with nitrogen, and 162 g (0.348 mol) of (methyldiethoxysilylpropyl)-(triethoxysilyloctyl)amine, 114 g of toluene, and 1.0 g (0.0067 mol) of trifluoromethanesulfonic acid were added and refluxed. 68.5 g (0.382 mol) of N-trimethylsilyl-N-methylaniline was added to this mixture and stirred, and the generated trimethylethoxysilane was withdrawn together with toluene using the distillation column until the reaction temperature reached 150°C. The resulting reaction solution was distilled to obtain 110 g of a fraction having a boiling point of 177°C / 0.2 kPa (yield: 75%). 1 H-NMR analysis was performed, and the results are shown in Figures 3 and 4.

[0073] [Production Example 3] Synthesis of 2-methoxy-2-methyl-N-(trimethoxysilylpropylthioethyl)-1-aza-2-silacyclopentane [ka]

[0074] The inside of a four-necked glass flask equipped with a stirrer, thermometer, distillation column, and reflux condenser was purged with nitrogen, and 86.0 g (0.221 mol) of (methyldimethoxysilylpropyl)-(trimethoxysilylpropylthioethyl)amine, 110 g of toluene, and 0.4 g (0.003 mol) of trifluoromethanesulfonic acid were added and refluxed. 44.0 g (0.245 mol) of N-trimethylsilyl-N-methylaniline was added to this mixture and stirred, and the generated trimethylmethoxysilane was withdrawn together with toluene using the distillation column until the reaction temperature reached 140°C. The resulting reaction solution was distilled to obtain 54 g of a fraction having a boiling point of 140-150°C / 0.4 kPa (yield: 69%). 1 H-NMR analysis was performed, and the results are shown in Figures 5 and 6.

[0075] [Synthesis Example 1-1] Synthesis of both-terminal alkoxysilylalkylaminopropyl-modified polysiloxane compound 1 [ka]

[0076] A four-neck glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 225 g (0.15 mol of silanol) of silanol-modified polydimethylsiloxane with a number-average molecular weight of 3000 as determined by gel permeation chromatography (GPC) was added and stirred. 51.0 g (0.165 mol) of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was added via a dropping funnel and stirred at room temperature for 1 hour. Gas chromatography (GC) analysis of the reaction mixture confirmed the disappearance of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane, marking the end of the reaction. IR analysis of the product revealed the disappearance of the silanol-related peaks. From the above, 268.5 g of a polysiloxane compound 1 modified at both ends with alkoxysilylpropylaminopropyl was obtained as a colorless, transparent liquid.

[0077] [Synthesis Example 1-2] Synthesis of both-end alkoxysilylalkylaminopropyl-modified polysiloxane compound 2 [ka]

[0078] The reaction was carried out in the same manner as in Synthesis Example 1-1, except that 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was replaced with 63.0 g (0.165 mol) of 2,2-diethoxy-N-triethoxysilylpropyl-1-aza-2-silacyclopentane. When the product was subjected to IR analysis, the peaks derived from silanol had disappeared, and 286.5 g of a polysiloxane compound 2 modified at both ends with alkoxysilylpropylaminopropyl was obtained as a colorless, transparent liquid.

[0079] [Synthesis Example 1-3] Synthesis of both-end alkoxysilylalkylaminopropyl-modified polysiloxane compound 3 [ka]

[0080] The reaction was carried out in the same manner as in Synthesis Example 1-1, except that the amount of silanol-modified polydimethylsiloxane used was changed to 15.0 g (0.0100 mol as silanol) and 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was changed to 4.1 g (0.011 mol) of 2,2-dimethoxy-N-trimethoxysilyloctyl-1-aza-2-silacyclopentane. When the product was subjected to IR analysis, the peaks derived from silanol had disappeared, and 18 g of a polysiloxane compound 3 modified at both ends with alkoxysilylalkylaminopropyl was obtained as a colorless, transparent liquid.

[0081] [Synthesis Example 1-4] Synthesis of both-end alkoxysilylalkylaminopropyl-modified polysiloxane compound 4 [ka]

[0082] The reaction was carried out in the same manner as in Synthesis Example 1-1, except that the amount of silanol-modified polydimethylsiloxane used was changed to 15 g (0.010 mol as silanol) and 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was changed to 4.8 g (0.011 mol) of 2-ethoxy-2-methyl-N-triethoxysilyloctyl-1-aza-2-silacyclopentane. When the product was subjected to IR analysis, the peaks derived from silanol had disappeared, and 19 g of a polysiloxane compound 4 modified at both ends with alkoxysilylalkylaminopropyl was obtained as a colorless, transparent liquid.

[0083] [Synthesis Example 1-5] Synthesis of both-end alkoxysilylalkylaminopropyl-modified polysiloxane compound 5 [ka]

[0084] The reaction was carried out in the same manner as in Synthesis Example 1-1, except that the amount of silanol-modified polydimethylsiloxane used was changed to 15 g (0.010 mol as silanol) and 51.0 g of 2,2-dimethoxy-N-trimethoxysilylpropyl-1-aza-2-silacyclopentane was changed to 3.9 g (0.011 mol) of 2-methoxy-2-methyl-N-trimethoxysilylpropylthioethyl-1-aza-2-silacyclopentane. When the product was subjected to IR analysis, the peaks derived from silanol had disappeared, and 18 g of polysiloxane compound 5 modified at both ends with alkoxysilylpropylaminopropyl was obtained as a colorless, transparent liquid.

[0085] [Synthesis Example 1-6] Synthesis of Polysilazane 2 A four-neck glass flask equipped with a stirrer, gas feed tube, thermometer, and reflux condenser was purged with nitrogen. While nitrogen gas was vented through the open end of the reflux condenser to prevent the inclusion of external air, 148.3 g (0.675 mol) of hexyltrichlorosilane, 29.2 g (0.225 mol) of dimethyldichlorosilane, and 700 g of cyclopentyl methyl ether (as solvent) were charged to obtain a homogeneous solution. The solution was cooled to below 10°C, and ammonia gas was fed into the solution through the feed tube. The ammonia feed was continued for 7 hours while cooling the reaction solution so that the temperature did not exceed 30°C. The ammonia feed was then stopped, and nitrogen gas was blown through the feed tube for 2 hours to purge excess ammonia gas. The reaction solution was filtered to remove ammonium chloride, yielding polysilazane 2. To this reaction solution, 105 g of isoparaffin solvent (IP Clean LX, manufactured by Idemitsu Kosan Co., Ltd., the same applies hereinafter) was added to obtain 210.0 g of composition 7 (concentration 50%) as a colorless, transparent solution. When the obtained composition 7 was subjected to IR analysis, a peak at 922 cm due to the Si-N-Si structure was observed. -1 , the peak at 3,370 cm originating from NH -1GPC analysis revealed a weight-average molecular weight of 2,700, confirming the formation of the desired polysilazane 2.

[0086] [Synthesis Example 1-7] Synthesis of polysiloxazane A four-neck glass flask equipped with a stirrer, gas feed tube, thermometer, and reflux condenser was purged with nitrogen. Nitrogen gas was passed through the open end of the reflux condenser to prevent the inclusion of external air. 65.9 g (0.300 mol) of hexyltrichlorosilane, 45.0 g of a silanol-terminated polydimethylsiloxane with a weight-average molecular weight of 3,000, and 295.6 g of cyclopentyl methyl ether (as solvent) were charged and stirred at room temperature for 1 hour. 42.3 g (0.300 mol) of methylvinyldichlorosilane and 76.8 g of cyclopentyl methyl ether were added and stirred to obtain a homogeneous reaction solution. The reaction solution was cooled to below 10°C, and ammonia gas was fed into the reaction solution through the feed tube. The ammonia feed was continued for 6 hours while the reaction solution was cooled so that the temperature did not exceed 30°C. The ammonia feed was then stopped, and nitrogen gas was blown through the feed tube for 2 hours to purge the excess ammonia gas. To this reaction solution, 131.5 g of 48% by mass aqueous sodium hydroxide solution was slowly added, followed by 270.6 g of water, and the mixture was stirred at room temperature for 1 hour. The mixture was then allowed to stand, and the lower layer was removed. The upper layer was concentrated at 100°C / 18 kPa, and then further concentrated at 120°C / 4 kPa. Next, 110.9 g of toluene was added to the resulting concentrate, and the mixture was filtered through a 1 μm membrane filter, yielding 219.6 g of a colorless, transparent solution.

[0087] Next, the inside of a four-necked glass flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was purged with nitrogen, and 16.9 g (0.086 mol) of mercaptopropyltrimethoxysilane and 16.9 g of toluene were charged and heated to 90° C. To this was added a mixture of 80.0 g of the colorless, transparent solution obtained above and 0.168 g (0.000874 mol) of 2,2′-azobis(2-methylbutyronitrile) via the dropping funnel over 2.5 hours, and the mixture was stirred for 1 hour while maintaining the same temperature, yielding a polysiloxazane. To the resulting polysiloxazane 1, 60.0 g of isoparaffin solvent was added, and the mixture was concentrated at 100°C / 15 kPa and then further concentrated at 100°C / 4 kPa. The nonvolatile content of the resulting reaction solution was measured using an infrared moisture meter (FD-720, Kett Electric Laboratory) at 105°C / 3 hours, and the nonvolatile content was found to be 53.8%. 7.5 g of isoparaffin solvent was added to the reaction solution to adjust the nonvolatile content to 50%, yielding composition 1. The obtained composition 1 was subjected to IR analysis, and the 932 cm -1 , 1,190cm -1 , a peak at 1,092 cm due to Si-O-Si -1 , the peak at 3,391 cm originating from NH -1 GPC analysis revealed a weight-average molecular weight of 5,300, confirming the formation of the desired polysiloxazane.

[0088] The compounds used in the following examples and comparative examples are shown below. (1) Alkoxysilylalkylaminoalkyl-modified polysiloxane compound Amino-modified polysiloxane compounds having alkoxysilyl alkyl groups: Alkoxysilylpropylaminopropyl-modified polysiloxane compounds 1 to 5 (referred to as compounds 1 to 5) Amino-modified polysiloxane compound without alkoxysilyl alkyl groups: X-22-161B (Shin-Etsu Chemical Co., Ltd.) (2) Hydrolyzable group-containing organosilicon compounds KR-500: Hydrolyzable silicone compound containing methyl and methoxy groups (Shin-Etsu Chemical Co., Ltd.) X-40-9227: Hydrolyzable silicone compound containing methyl, phenyl, and methoxy groups (Shin-Etsu Chemical Co., Ltd.) KR-400: A mixture of a hydrolyzable silicone compound containing methyl and methoxy groups and a curing catalyst (Shin-Etsu Chemical Co., Ltd.) Ethyl silicate 40: Partial hydrolysis condensate of tetraethoxysilane (manufactured by Colcoat Co., Ltd.) Polysilazane 1: Reaction product of a polysilazane compound having a methyl group and a hydrogen atom with aminopropyltriethoxysilane (HTA-1500RC, manufactured by Sanwa Chemical Co., Ltd.) Polysilazane 2: Polysilazane obtained in Synthesis Example 1-6 Polysiloxazane: Polysiloxazane obtained in Synthesis Example 1-7 (3) Solvent IP Clean LX: Isoparaffin solvent (Idemitsu Kosan Co., Ltd.) (4) Curing catalyst DX-9740: Aluminum compound (Shin-Etsu Chemical Co., Ltd.) D-25: Titanium compound (Shin-Etsu Chemical Co., Ltd.)

[0089] [Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-5] The alkoxysilylalkylamino-terminated polysiloxane compound obtained in Synthesis Example 1-1, the hydrolyzable group-containing organosilicon compound, the solvent, and the curing catalyst were mixed in the ratios shown in Table 1 below, taking care to prevent moisture from entering, to prepare a curable composition, and the curing time and contact angle were measured by the following methods. The results are shown in Table 1.

[0090] [Curing time] Each curable composition was applied to a polished steel plate (10 cm × 15 cm) using a bar coater to a wet thickness of 30 μm, and then left to stand in an environment of 25°C / 50% relative humidity. After that, a finger was pressed against the coated surface of the test piece every 30 minutes, and the time until the finger no longer left an imprint (tack-free time) was measured and recorded as the curing time.

[0091] [Contact angle] Each curable composition was applied to a polished steel plate (10 cm × 15 cm) using a bar coater to a wet thickness of 30 μm, and then allowed to stand for 2 hours in an environment of 25°C / 50% relative humidity. After curing, the plate was allowed to stand for a further 24 hours at room temperature, and the water contact angle of 2 μL of the resulting cured coating was measured at room temperature using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).

[0092] [Table 1]

[0093] As shown in Table 1, the curable composition containing Compound 1 of the present invention having an alkoxysilylalkyl group on the nitrogen atom was capable of forming a cured coating regardless of the presence or absence of a curing catalyst, and also exhibited high water repellency as evidenced by its high contact angle. On the other hand, the curable composition containing an aminopropyl-modified polysiloxane compound that does not have an alkoxylalkyl group on the nitrogen atom was unable to form a cured coating.

[0094] [Examples 2-1 to 2-6] The alkoxysilylalkylamino-terminated polysiloxane compound obtained in each synthesis example, the hydrolyzable group-containing organosilicon compound, the solvent, and the curing catalyst were mixed in the ratios shown in Table 2 below, taking care to prevent moisture from entering, to prepare a curable composition, and the curing time and contact angle were measured in the same manner as above. The results are shown in Table 2.

[0095] [Table 2]

[0096] As shown in Table 2, the curable composition containing the aminopropyl-modified polysiloxane of the present invention having an alkoxysilyl alkyl group on the nitrogen atom was capable of forming a cured coating and had a high contact angle, demonstrating high water repellency.

Claims

1. A curable composition comprising an alkoxysilylalkylaminopropyl-modified polysiloxane compound represented by the following general formula (1) and a hydrolyzable group-containing organosilicon compound: 【Chemistry 1】 [In the formula, R 1 each independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; R 2 and R 3 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms; R 4 represents a divalent hydrocarbon group having 1 to 20 carbon atoms (excluding methylene groups) which may contain a sulfur atom, a silicon atom, or a urea bond; p is an integer of 1 to 1000; q is 0 or 1; r is 0, 1, or 2; X is a group represented by the following general formula (2) or R 1 3 represents Si. 【Chemistry 2】 (In the formula, R 2 ~R 4 , q and r have the same meanings as above.)

2. 2. The curable composition according to claim 1, wherein the hydrolyzable group-containing organosilicon compound is at least one member selected from the group consisting of alkoxysilanes, partial hydrolysis condensates of alkoxysilanes, polysilazanes, and polysiloxazanes.

3. The curable composition according to claim 1 or 2, which contains a solvent.

4. A curable composition according to any one of claims 1 to 3, which contains as a curing catalyst at least one metal compound selected from the group consisting of titanium compounds, aluminum compounds, zinc compounds and tin compounds.

Images