Organosilicon compound, method for producing same, curable composition, and coated base material

Abstract

The organosilicon compound represented by formula (1) exhibits favorable adhesion to a urethane base material, and permits preparation of a uniform composition with a condensation curable silicone compound having a dimethylpolysiloxane unit. In the formula, R1 represents a divalent hydrocarbon group which may be substituted with X and may have a urethane bond or the like interposed therein, R2 represents a monovalent hydrocarbon group, and R3 represents R1-X or a monovalent hydrocarbon group, X being a group represented by formula (3) and n being an integer of 0-100. (R6 represents a divalent hydrocarbon group, and R7 and R8 each represent a monovalent hydrocarbon group, m being 0, 1 or 2.)　When R3 is R1-X, the organosilicon compound has six or more urethane bonds in the molecule. When R3 is a monovalent hydrocarbon group, the organosilicon compound has three or more urethane bonds in the molecule.

Description

Organosilicon compounds, methods for producing the same, curable compositions, and coating substrates

[0001] This invention relates to organosilicon compounds, methods for producing the same, curable compositions, and coating substrates.

[0002] Alkoxysilanes, silicone oligomers, silicone resins, polysilazanes, and polysiloxazanes (hereinafter also referred to as "condensation-curable silicone compounds") are condensation-curable compounds that have Si-OR (where R is a monovalent hydrocarbon group), Si-OH, or Si-N in their molecules and can form cured films by repeatedly undergoing de-alcoholization condensation, dehydration condensation, or de-amineization condensation.

[0003] By introducing a dimethylpolysiloxane skeleton into the constituent units of the above-mentioned condensation-curable silicone compounds, or by forming compositions with compounds having a dimethylpolysiloxane skeleton, the water repellency of the cured film can be enhanced.

[0004] The cured film derived from this condensation-curable silicone compound is known to exhibit heat resistance, water resistance, weather resistance, and flame retardancy, as well as adhesion to inorganic materials such as glass and metal. Specifically, the Si-OH produced by the hydrolysis condensation of Si-OH, Si-OR, or Si-N present in the condensation-curable silicone compound can condense with M-OH (where M is an inorganic substance) on the surface of the inorganic material to form a Si-O-M bond. As a result, the cured film of the condensation-curable silicone compound is thought to exhibit good adhesion to inorganic materials.

[0005] For the performance of the cured coating to last for a long period, it is important that the cured coating adheres strongly to the object being treated. If the adhesion is poor, or if the cured coating is merely resting on the surface of the object being treated, the coating will easily peel off and fall off due to physical contact, resulting in the loss of the desired effect.

[0006] Japanese Patent Publication No. 2012-25876 Japanese Patent Publication No. 2011-162666

[0007] Condensation-curable silicone compounds are thought to exhibit adhesion to inorganic materials through the mechanism described above. However, some organic materials, such as plastic resins, do not have reactive hydroxyl groups on their surface. Therefore, condensation-curable silicone compounds cannot form covalent bonds through the above mechanism and do not exhibit adhesion.

[0008] Therefore, in order to exhibit adhesion to organic materials such as plastic resins, adhesion can be achieved by adding a compound that has a structure and solubility parameters similar to those of the resin, and also has a structure that can react with condensation-curable silicone compounds. For example, Patent Document 1 discloses ureidosilane as an additive for imparting adhesion to PBT and ABS resins. However, while this additive is effective for PBT and ABS resins, it is not effective for polyurethanes.

[0009] In this regard, Patent Document 2 discloses a silane-modified polyurethane compound as a compound having an alkoxysilyl group that can react with a polyurethane structure and a condensation-curable silicone compound. However, condensation-curable silicone compounds that have a dimethylpolysiloxane skeleton introduced to enhance water repellency, or compositions of compounds having a dimethylpolysiloxane skeleton and condensation-curable silicone compounds, have the problem that the polarity of the compound or composition is low due to the influence of the dimethylpolysiloxane skeleton, and even when a silane-modified polyurethane compound is added, a uniform solution cannot be obtained, and as a result a uniform cured film cannot be obtained.

[0010] The present invention has been made in view of the above circumstances, and aims to provide an organosilicon compound that exhibits good adhesion to a urethane substrate and can prepare a uniform composition with a condensation-curable silicone compound having dialkylpolysiloxane units.

[0011] As a result of diligent research to solve the above problems, the inventors of the present invention have found that by using an organosilicon compound having multiple urethane structures and dialkylpolysiloxane units as an additive, it is possible to not only exhibit good adhesion to urethane substrates but also to produce a uniform composition with condensation-curable silicone compounds having dimethylpolysiloxane units, thus completing the present invention.

[0012] That is, the present invention provides: 1. An organosilicon compound represented by the following general formula (1): [In the formula, R 1 represents a urethane bond, an oxygen atom or an NR' group (R' represents a hydrogen atom or a group represented by the following formula (2)) represented by -O-C(O)-NR 4 - or -R 4 N-C(O)-O-(R 4 represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)) may be interposed, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with at least X, (In the formula, R 5 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted with at least X, Y represents a single bond or an oxygen atom, and * represents a bond.) R 2 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 3 is R 1 -X (R 1 represents the same meaning as described above.) or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is a group represented by the following general formula (3), and n is an integer of 0 to 100. (In the formula, R 6 represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, R 7 and R 8 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, m is 0, 1 or 2, and * represents a bond.) However, in the organosilicon compound represented by the general formula (1), when R 3 is R 1 -X, it has 6 or more urethane bonds in the molecule, and when R 3 is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, it has 3 or more urethane bonds in the molecule. 2. The following general formula (4) (In the formula, R 9 represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms in which at least one NH group may be interposed, and R 10 is R 9 -NH2 (R 9This has the same meaning as above.) or represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R 2 And n have the same meaning as above.) An amino group-containing organopolysiloxane compound represented by the following general formula (5) (In the formula, R 11 ) represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with at least one hydroxyl group.) After reacting a cyclic carbonate compound represented by the following general formula (6) (In the formula, R 6 ~R 8 1 A method for producing an organosilicon compound, comprising the step of reacting an isocyanatoalkylalkoxysilane compound represented by ) in the presence of at least one metal compound selected from the group consisting of titanium compounds, iron compounds, zirconium compounds, tin compounds and bismuth compounds, 3. The following general formula (7) [In the formula, R 12 R represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may have at least one oxygen atom interposed between them. 13 R 12 -Z(R 12 This has the same meaning as above.) or represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R 2 And n have the same meaning as described above, and Z represents a cyclic carbonate group represented by the following general formula (8). (In the formula, * represents a bond.) A cyclic carbonate group-containing organopolysiloxane compound represented by the following general formula (9) [In the formula, R 14 R represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms. 15 is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or R 14 -OH(R) 14 This represents the same meaning as above. ) After reacting the amino alcohol represented by ], the following general formula (6) (In the formula, R 6 ~R 84. A method for producing an organosilicon compound, comprising the step of reacting an isocyanatoalkylalkoxysilane compound represented by ) in the presence of at least one metal compound selected from the group consisting of titanium compounds, iron compounds, zirconium compounds, tin compounds and bismuth compounds; 5. A composition comprising the organosilicon compound of 1 and a hydrolyzable group-containing organosilicon compound comprising at least one selected from the group consisting of alkoxysilane, a partially hydrolyzed condensate of alkoxysilane, silazane, polysilazane and polysiloxazane; 6. The hydrolyzable group-containing organosilicon compound comprising a polydialkylpolysiloxane unit as a constituent unit, the composition of 4; 7. A composition of 4 or 5 comprising at least one metal compound selected from the group consisting of titanium compounds, aluminum compounds, zinc compounds and tin compounds; 8. A cured product of any of the compositions of 4 to 6; 9. A coated substrate having a substrate and a coating formed thereon, wherein the coating is formed from any of the curable compositions of 4 to 6. The present invention provides 8 coated substrates having a coating film containing polyurethane or a polyurethane component on its outermost surface.

[0013] The compounds obtained in this invention have dialkylpolysiloxane units, and therefore exhibit excellent compatibility with condensation-curable silicone compounds containing dialkylpolysiloxane units and compositions containing them. Furthermore, the resulting compositions exhibit good adhesion to polyurethane substrates due to the effect of the numerous urethane structures contained in the compounds.

[0014] Compound obtained in Example 1-1 1 This is an H-NMR chart of the compounds obtained in Examples 1-2. 1 This is an H-NMR chart of the compounds obtained in Examples 1-3. 1 This is an H-NMR chart of the compounds obtained in Examples 1-4. 1 This is an H-NMR chart of the compounds obtained in Examples 1-5. 1 This is an H-NMR chart of the compounds obtained in Examples 1-6. 1 This is an H-NMR chart.

[0015] The present invention will be described in detail below. [1] Organosilicon compound The organosilicon compound of the present invention (hereinafter referred to as "compound (1)") is represented by the following general formula (1).

[0016]

[0017] In general formula (1), R 1 This represents a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, which may contain a urethane bond, an oxygen atom, or an NR' group (where R' represents a hydrogen atom or a group represented by the following formula (2)).

[0018]

[0019] R 1 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as methyltrimethylene and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene, methylenephenylmethylene, ethylenephenylethylene, and propylenephenylmethylene. Among these, linear alkylene groups and aralkylene groups having 3 to 12 carbon atoms are preferred due to the ease of obtaining raw materials.

[0020] R 1 The urethane bond interposed in the divalent hydrocarbon group is represented by either the following general formula (10) or (11).

[0021]

[0022] In general formulas (10) and (11), R 4 R represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms. 4The monovalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, 1-propenyl, butenyl, and pentenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. Among these, R 4 A hydrogen atom is preferred. 4 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with other substituents. Specific examples of these substituents include trialkylsilyl groups, trialkoxysilyl groups, dialkylmonoalkoxysilyl groups, and monoalkyldialkoxysilyl groups, where each alkyl group and each alkoxy group has 1 to 3 carbon atoms.

[0023] R 1 Examples of divalent hydrocarbon groups involving an oxygen atom include alkylene oxyalkylene and phenylene oxyalkylene groups, specifically propylene oxypropylene, octylene oxypropylene, and propylene phenyl oxypropylene groups.

[0024] R 1 However, examples of divalent hydrocarbon groups that can be mediated by an NR' group (R' = hydrogen atom) include alkyleneaminoalkylene groups, specifically propyleneaminoethyl and propyleneaminopropylene groups.

[0025] Meanwhile, R 1 However, in a divalent hydrocarbon group that is mediated by an NR' group (R' = the general formula (2) above), R 5 R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms, and Y represents a single bond or an oxygen atom. 5 The monovalent hydrocarbon group is the above R 4Similar groups to those exemplified above can be cited, and among them, methyl, propyl, octyl, and phenyl groups are preferred due to the ease of raw material procurement.

[0026] Note R 5 The monovalent hydrocarbon group may have some or all of its hydrogen atoms substituted with other substituents. Specific examples of these substituents include each alkyl group, each alkoxy group having 1 to 3 carbon atoms, a trialkylsilyl group, a trialkoxysilyl group, a dialkylmonoalkoxysilyl group, a monoalkyldialkoxysilyl group, and substituent X represented by the following general formula (3).

[0027] (In the formula, m is 0, 1, or 2, and * represents a bond.)

[0028] In general formula (3), R 6 R represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 3 to 6 carbon atoms, and more preferably 3 carbon atoms. 6 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as methyltrimethylene and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene and methylenephenylmethylenemethylene. Among these, linear alkylene groups having 1 to 8 carbon atoms are preferred, and trimethylene groups are more preferred, from the viewpoint of ease of raw material procurement.

[0029] In general formula (3), R 7 and R 8 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. 7 and R 8The monovalent hydrocarbon group can be linear, branched, or cyclic. Specific examples 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, 1-propenyl, butenyl, and pentenyl; and aryl groups such as phenyl. Among these, methyl and ethyl groups are preferred due to the ease of raw material procurement.

[0030] Note R 1 The divalent hydrocarbon group has some or all of its hydrogen atoms, as described above R 5 Similarly, it may be substituted with various substituents including substituent X.

[0031] In general formula (1), R 2 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. 2 The monovalent hydrocarbon group is the above R 7 and R 8 Similar groups to those exemplified above can be cited, and among them, methyl, ethyl, n-propyl, n-butyl, and phenyl groups are preferred due to the ease of raw material procurement.

[0032] In general formula (1), R 3 R 1 -X(R 1 And X has the same meaning as above.) or represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. R 3 The monovalent hydrocarbon group is the above R 2 Examples similar to the base exemplified above can be given.

[0033] In general formula (1), n ​​is an integer between 0 and 100, preferably 1 to 80, more preferably 3 to 60, and even more preferably 6 to 40. If n is too large, the solubility may deteriorate when preparing the curable composition, and if n is too small, the storage stability of compound (1) and the curable composition may be poor.

[0034] Compound (1) of the present invention is R 3R 1 - If it is X, it has 6 or more urethane bonds in the molecule, R 3 R 2 In this case, the molecule has three or more urethane bonds. By containing a large number of urethane bonds, the cured film obtained from the curable composition containing compound (1) exhibits adhesion to the urethane substrate.

[0035] Specific examples of compound (1) include, but are not limited to, those shown in the following formulas. In each of the following formulas, Me represents a methyl group, Et represents an ethyl group, and n-Bu represents a n-butyl group.

[0036] (In the formula, n has the same meaning as above.)

[0037] (In the formula, n has the same meaning as above.)

[0038] (In the formula, n has the same meaning as above.)

[0039] (In the formula, n has the same meaning as above.)

[0040] [2] Method for Producing Organosilicon Compounds The organosilicon compounds of the present invention can be produced, for example, by reacting an amino group-containing organopolysiloxane compound represented by the following general formula (4) (hereinafter referred to as "compound (4)") with a cyclic carbonate compound represented by the following general formula (5) (hereinafter referred to as "compound (5)"), and then reacting it with an isocyanatoalkylalkoxysilane compound represented by the following general formula (6) (hereinafter referred to as "compound (6)") in the presence of a metal compound (hereinafter referred to as "production method A"), or by reacting a cyclic carbonate group-containing organopolysiloxane compound represented by the following general formula (7) (hereinafter referred to as "compound (7)") with an amino alcohol represented by the following general formula (9) (hereinafter referred to as "compound (9)"), and then reacting compound (6) in the presence of a metal compound (hereinafter referred to as "production method B").

[0041] (In the formula, R 2 , R 6 ~R8 (m and n have the same meaning as above.)

[0042] (1) Manufacturing method A Manufacturing method A involves reacting an amino group-containing organopolysiloxane compound with a cyclic carbonate compound, and then reacting it with an isocyanatoalkylalkoxysilane compound in the presence of a metal compound.

[0043] In general formula (4), R 9 R represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 3 to 8 carbon atoms, which may have at least one NH group interposed therein. 9 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, and decylene; branched alkylene groups such as methylethylene, methyltrimethylene, and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene, methylenephenylmethylene, and ethylenephenylethylene. Among these, linear and branched alkylene groups and aralkylene groups having 3 to 8 carbon atoms are preferred from the standpoint of ease of raw material procurement, and trimethylene, pentamethylene, heptamethylene, methylethylene, and methyltrimethylene groups are more preferred.

[0044] R 9 However, divalent hydrocarbon groups that include at least one NH group include alkyleneaminoalkylene, alkyleneaminoarylene, alkyleneaminophenylene, alkyleneaminoalkyleneaminoalkylene groups, and specifically include propyleneaminoethylene, propyleneaminopropylene, octyleneaminoethylene, propyleneamino(methyl)ethylene, propyleneaminophenylene, propyleneaminophenylmethylene, and propyleneaminoethyleneaminoethylene groups.

[0045] R 10 is R 9 -NH2 (R 9 represents the same meaning as described above.) or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. The monovalent hydrocarbon group of R 10 includes those similar to the groups exemplified for R 7 and R 8 above. Among these, R 10 is preferably an alkyl group having 1 to 6 carbon atoms, and R 9 -NH2 is preferred.

[0046] Specific examples of the compound (4) include, but are not limited to, those represented by the following formula.

[0047] (In the formula, n represents the same meaning as described above.)

[0048] In the general formula (5), R 11 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms, which may be substituted with at least one hydroxy group. The monovalent hydrocarbon group of R 11 may be linear, branched or cyclic. Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, texyl, 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl, cyclohexyl groups; alkenyl groups such as vinyl, allyl, 1-propenyl, butenyl, pentenyl groups; aryl groups such as phenyl, tolyl groups; aralkyl groups such as benzyl, phenethyl groups, etc. Among these, methyl, propyl, and n-octyl groups are preferred from the viewpoint of ease of raw material procurement. In addition, at least one of the hydrogen atoms of the monovalent hydrocarbon group of R 11 is preferably substituted with a hydroxy group, particularly the hydrogen atom bonded to the terminal carbon atom.

[0049] Specific examples of compound (5) include propylene carbonate; glycerol carbonate; hydroxyalkyl-1,3-dioxolan-2-ones such as 4-(2-hydroxyethyl)-1,3-dioxolan-2-one, 4-(3-hydroxypropyl)-1,3-dioxolan-2-one, 4-(4-hydroxybutyl)-1,3-dioxolan-2-one, 4-(5-hydroxypentyl)-1,3-dioxolan-2-one, 4-(6-hydroxyhexyl)-1,3-dioxolan-2-one, 4-(7-hydroxyheptyl)-1,3-dioxolan-2-one, and 4-(8-hydroxyoctyl)-1,3-dioxolan-2-one.

[0050] Specific examples of compound (6) include isocyanatoalkyltrialalkoxysilane compounds such as isocyanatomethyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatohexyltrimethoxysilane, isocyanatooctyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatopropyltriethoxysilane, isocyanatohexyltriethoxysilane, and isocyanatooctyltriethoxysilane; isocyanatomethylmethyldimethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatohexylmethyldimethoxysilane, isocyanatooctylmethyldimethoxysilane, and isocyanatomethylmethyldiethoxysilane. Examples include isocyanatoalkylalkyldialkylalkoxysilane compounds such as isocyanatopropylmethyldiethoxysilane, isocyanatohexylmethyldiethoxysilane, and isocyanatooctylmethyldiethoxysilane; and isocyanatoalkyldialkylalkoxysilane compounds such as isoanatomethylmethyldimethylmethoxysilane, isocyanatopropyldimethylmethoxysilane, isocyanatohexyldimethylmethoxysilane, isocyanatooctyldimethylmethoxysilane, isocyanatomethyldimethylethoxysilane, isocyanatopropyldimethylethoxysilane, isocyanatohexyldimethylethoxysilane, and isocyanatooctyldimethylethoxysilane.

[0051] When reacting the reaction products of compounds (4) and (5) with compound (6), metal compounds such as titanium compounds, iron compounds, zirconium compounds, tin compounds, and bismuth compounds are used as catalysts, with bismuth compounds being preferred among these. Specific examples of titanium compounds include tetraalkyl orthotitanates such as tetrabutyl orthotitanate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, and tetraisopropyl orthotitanate, as well as their partial hydrolysis condensates and titanium acylates. Specific examples of iron compounds include iron acetate, iron 2-ethylhexanoate, and iron carboxylates such as iron stearate. Specific examples of zirconium compounds include zirconium tetraalkoxides such as zirconium tetrapropoxide and zirconium tetrabutoxide, zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, and their partial hydrolysis condensates. Specific examples of tin compounds include dioctyltine dioctate and dioctyltine dilaurate. Specific examples of bismuth compounds include bismuth acetate, bismuth 2-ethylhexanoate, bismuth stearate, and other bismuth carboxylic acids.

[0052] The amount of catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 moles, more preferably 0.0005 to 0.05 moles, and even more preferably 0.003 to 0.01 moles per mole of the compound represented by general formula (6).

[0053] The mixing ratio of compound (4) and compound (5) is not particularly limited, but preferably 0.9 to 1.1 moles, more preferably 0.95 to 1.05 moles of compound (5) per mole of amino groups contained in compound (4). The mixing ratio of the reaction product of compound (4) and compound (5) to compound (6) is not particularly limited, but preferably 0.9 to 1.1 moles, more preferably 0.95 to 1.05 moles of compound (6) per mole of theoretical hydroxyl groups contained in the reaction product.

[0054] The reaction temperature is not particularly limited, but both the reaction of compound (4) and compound (5), and the reaction of the reactants of compound (4) and compound (5) with compound (6), are preferably 0 to 200°C, more preferably 20 to 150°C, and even more preferably 50 to 100°C. The reaction time is not particularly limited, but from the viewpoint of product stability, both the reaction of compound (4) and compound (5), and the reaction of the reactants of compound (4) and compound (5) with compound (6), are preferably 1 to 40 hours, more preferably 1 to 20 hours. It is preferable to carry out the above reactions under an inert gas atmosphere such as nitrogen or argon in order to prevent hydrolysis of compound (1) and compound (6).

[0055] The above reaction can proceed without a solvent, but a solvent may also be used. Specific examples of solvents include aliphatic hydrocarbon solvents with 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, heptane, octane, nonane, decane, isooctane, and isododecane; aromatic hydrocarbon solvents with 6 to 10 carbon atoms such as benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, 4-methyltetrahydropyran, cyclopentyl methyl ether, dioxane, and dipropylene glycol dimethyl ether; ester solvents such as ethyl acetate, isopropyl acetate, and butyl acetate; and silicone solvents such as hexamethyldisiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These solvents may be used individually or in mixtures of two or more.

[0056] (2) Manufacturing method B Manufacturing method B is a method in which a carbonate group-containing organopolysiloxane compound is reacted with an amino alcohol, and then reacted with an isocyanatoalkylalkoxysilane compound in the presence of a metal compound. In general formula (7), Z represents a cyclic carbonate group represented by the following general formula (8).

[0057] (In the formula, * represents a bond.)

[0058] In general formula (7), R 12represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 3 to 10 carbon atoms, which may have at least one oxygen atom intervening. R 12 The divalent hydrocarbon group of 12 may be linear, branched or cyclic. Specific examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decylene groups; branched alkylene groups such as methylethylene, methyltrimethylene, methyltetramethylene groups; cyclic alkylene groups such as cyclohexylene, methylenecyclohexylenemethylene groups; linear alkenylene groups such as butenylene, hexenylene, octenylene groups; branched alkenylene groups such as isobutenylene group; arylene groups such as phenylene group; aralkylen groups such as methylenephenylene, methylenephenylenemethylene, ethylenephenyleneethylene, propylenephenylenemethylene groups and the like. Among these, from the viewpoint of easy availability of raw materials, linear alkylene groups and aralkylen groups having 3 to 8 carbon atoms are preferable.

[0059] R 12 Examples of the divalent hydrocarbon group having an intervening oxygen atom of 12 include alkyleneoxyalkylene, alkylene-phenyleneoxyalkylene groups and the like. Among these, from the viewpoint of easy availability of raw materials, propyleneoxymethylene, octyleneoxymethylene, propylenephenyleneoxymethylene groups are preferable.

[0060] In general formula (7), R 13 represents R 12 - Z (R 12 and Z represent the same meaning as described above.) or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon group of R 13 are the same as the groups exemplified for R 7 and R 8 above. Among these, R 13 is preferably R 12 - Z.

[0061] Compound (7) may be a commercially available product or may be manufactured. If manufactured, conventionally known methods may be followed, for example, a method of hydrosilylation of a compound having a cyclic carbonate group and an alkenyl group with a polysiloxane compound having a Si-H structure at both or one of its molecular ends, or a method of reacting a polysiloxane compound having a glycidyl group at both or one of its molecular ends with carbon dioxide in the presence of a catalyst.

[0062] Specific examples of compound (7) include, but are not limited to, those shown in the following formula.

[0063] (In the formula, n has the same meaning as above.)

[0064] In general formula (9), R 14 R represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 7 carbon atoms. 14 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, and decylene; branched alkylene groups such as methylethylene, methyltrimethylene, and methyltetramethylene; cyclic alkylene groups such as cyclohexylene and methylenecyclohexylenemethylene; linear alkenylene groups such as butenylene, hexenylene, and octenylene; branched alkenylene groups such as isobutenylene; arylene groups such as phenylene; and aralkylene groups such as methylenephenylene, methylenephenylmethylene, ethylenephenylethylene, and propylenephenylmethylene. Among these, linear and branched alkylene groups, arylene groups, and aralkylene groups having 2 to 7 carbon atoms are preferred, and linear and branched alkylene groups are more preferred, from the standpoint of ease of raw material procurement. 14 The divalent hydrocarbon group may have some of its hydrogen atoms substituted with hydroxyl groups.

[0065] In general formula (9), R 15 R is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms,14 -OH(R) 14 This represents the same meaning as above. ) R 15 The monovalent hydrocarbon group is the above R 11 Examples similar to those exemplified above can be given. Among these, R is considered to be the most convenient in terms of ease of raw material procurement and the usefulness of the product. 15 is a hydrogen atom, a linear alkyl group, an aryl group, R 14 -OH is preferred.

[0066] Specific examples of compound (9) include amino alcohol compounds having a primary amino group such as aminoethanol, aminopropanol, amino(methyl)ethanol, aminobutanol, aminooctanol, aminocyclohexanemethanol, aminocyclohexaneethanol, aminophenol, and aminobenzyl alcohol; amino alcohol compounds having a secondary amino group such as methylaminoethanol, ethylaminoethanol, butylaminoethanol, octylaminoethanol, phenylaminoethanol, and benzylaminoethanol; dialkanolamines such as diethanolamine, dipropanolamine, and diisopropanolamine; and trialkanolamines such as trimethylolaminomethane.

[0067] When reacting the reaction products of compounds (7) and (9) with compound (6), metal compounds such as titanium compounds, iron compounds, zirconium compounds, tin compounds, and bismuth compounds can be used as catalysts. Specific examples of metal compounds and their amounts used are the same as those used when reacting the reaction products of compounds (4) and (5) with compound (6) in the above-described manufacturing method A.

[0068] The mixing ratio of compound (7) and compound (9) is not particularly limited, but preferably 0.9 to 1.1 moles, more preferably 0.95 to 1.05 moles of compound (9) per mole of carbonate groups contained in compound (7). The mixing ratio of the reaction product of compound (7) and compound (9) to compound (6) is not particularly limited, but preferably 1.0 to 1.5 moles, more preferably 1.0 to 1.25 moles of compound (6) per mole of theoretical hydroxyl groups contained in the reaction product.

[0069] The reaction temperature is not particularly limited, but both the reaction between compound (7) and compound (9), and the reaction between the reactants of compound (7) and compound (9) and compound (6) are the same as in production method A. The reaction time is also not particularly limited, but from the viewpoint of product stability, both the reaction between compound (7) and compound (9), and the reaction between the reactants of compound (7) and compound (9) and compound (6) are preferably 1 to 40 hours, more preferably 1 to 20 hours. The above reactions are preferably carried out under an inert gas atmosphere such as nitrogen or argon to prevent hydrolysis of compound (1) and compound (6). The above reactions can proceed without a solvent, but a solvent may also be used. Specific examples of solvents include those similar to those exemplified in production method A.

[0070] To isolate the target compound (1) from the reaction solution obtained in the above series of reactions, one of the usual purification methods in organic synthesis, such as filtration, distillation, vacuum stripping, various types of chromatography, and treatment with adsorbents, can be appropriately selected and used. Among these, purification by filtration is preferred from the viewpoint of production efficiency.

[0071] Furthermore, the compound (1) obtained in this manner may be diluted with a solvent to facilitate handling. Specific examples of solvents include those exemplified in production methods A or B above, as well as alkoxysilanes with one silicon element. Examples of such compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, diethyldiethoxysilane, and methyltriethoxysilane. Dimethyldimethoxysilane and diethyldiethoxysilane are preferred because they can stabilize compound (1).

[0072] [3] Curable composition, cured product, coating substrate The curable composition of the present invention comprises compound (1) and a hydrolyzable group-containing organosilicon compound. The hydrolyzable group-containing organosilicon compound used in the present invention is not particularly limited as long as it has a functional group that can be hydrolyzed and condensed, but at least one selected from the group consisting of alkoxysilanes, partially hydrolyzed condensates of alkoxysilanes, polysilazanes and polysiloxazanes is preferred.

[0073] Examples of alkoxysilane compounds include the compound represented by the following general formula (12) (hereinafter referred to as "compound (12)").

[0074]

[0075] In general formula (12), R 16 Each of these may independently contain an oxygen atom, and is an unsubstituted monovalent hydrogen group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, R 17 R is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and x is an integer from 0 to 2. 16 The monovalent hydrocarbon group is the above R 11 Similar groups to those exemplified above can be cited, and among them, methyl, ethyl, n-propyl, vinyl, and phenyl groups are preferred due to the ease of raw material procurement. 16 Specific examples of monovalent hydrocarbon groups that include an oxygen atom include alkyloxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxypropyl.

[0076] Specific examples of compound (12) 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.

[0077] The partially hydrolyzed condensate of compound (12) is obtained by adding water to compound (12) in the presence of a catalyst as needed, and heating and stirring as needed. In this case, the alkoxysilane compound used may be used alone or as a mixture of two or more.

[0078] Polysilazane compounds are polycondensates of chlorosilane compounds and ammonia, and are, for example, compounds having repeating units represented by the following general formula (13) (hereinafter referred to as "compound (13)").

[0079] (In the formula, y is 0, 1, 2, or 3.)

[0080] In general formula (13), R 18 Each of these is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, which may each independently contain an organosiloxane group represented by the following general formula (13A) at its terminus. 18 The monovalent hydrocarbon group is the above R 11 Similar groups to those exemplified above can be cited, and among them, linear alkyl groups and aryl groups are preferred due to the ease of raw material procurement.

[0081]

[0082] In equation (13A), R 19 Each of these is 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 (13A), a is 0, 1, 2, or 3, and when a is 0 or 1, there are multiple OSiR 19 The three groups may undergo desiloxane condensation to form a cyclic siloxane. Furthermore, b represents an integer from 0 to 30, preferably from 0 to 20, and more preferably from 5 to 15. R 19 The combination of a and b is arbitrary and unrestricted. 19 The monovalent hydrocarbon group is the above R 11 Similar groups to those exemplified above can be cited, and among them, linear alkyl groups and aryl groups are preferred due to the ease of raw material procurement.

[0083] This kind of R 19 Specific examples of organosiloxane groups represented by the general formula (13A) defined by a and b include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, and tert-butyldiphenylsilyl; polyalkylpolysiloxanil groups such as pentamethyldisiloxanil, heptamethyltrisiloxanil, nonamethyltetrasiloxanil, α-trimethylsilyl-polydimethylsiloxanil, and α-butyldimethylsilyl-polydimethylsiloxanil; and polyalkylcyclopolysiloxanil groups such as pentamethylcyclotrisiloxanil, heptamethylcyclotetrasiloxanil, and nonamethylcyclopentasiloxanil.

[0084] Polysilazane compounds may consist of only one structural unit, as shown in general formula (13), or they may consist of two or more structural units. However, this excludes the case where y = 3 only, i.e., the case of hexaalkyldisilazane.

[0085] Compound (13) is obtained by reacting the following chlorosilane compound (hereinafter referred to as compound (14)) with ammonia in the presence of a solvent as needed, and removing the ammonium chloride produced as the reaction progresses.

[0086] (In the formula, R 18 (And y have the same meaning as above.)

[0087] Polysiloxazane compounds are compounds that contain both a siloxane structure and a silazane structure within their molecule, and are, for example, compounds represented by the following general formula (15) (hereinafter referred to as "compound (15)").

[0088] (In the formula, R 18 (This expresses the same meaning as above.)

[0089] In general formula (15), R 20 Each of these is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, which may each independently contain a sulfur atom or a silicon atom. 20The monovalent hydrocarbon group is the above R 11 Similar groups to those exemplified above can be cited, and among them, linear alkyl groups and aryl groups are preferred due to the ease of raw material procurement.

[0090] Also, R 20 Specific examples of monovalent hydrocarbon groups that include a sulfur atom include alkylentioalkyl groups. 20 Specific examples of monovalent hydrocarbon groups that include a silicon atom include trialkylsilylalkyl, dialkylmonalkoxysilylalkyl, alkyldialkoxysilylalkyl, trialkoxysilylalkyl, etc., and an organosiloxane group represented by general formula (13A) may be included at the end of the monovalent hydrocarbon group.

[0091] Furthermore, R 20 This group may contain both a sulfur atom and a silicon atom. Specific examples of monovalent hydrocarbon groups containing both sulfur and silicon atoms include alkylentioalkyldialkylmonalkoxysilyl groups, alkylentioalkylenealkyldialkoxysilyl groups, and alkylentioalkylentrialkoxysilyl groups.

[0092] In general formula (15), A is independently R 18 , represents either NH-SiO2 or oxygen atoms bonded together with other A atoms. c and d are independently 0, 1, or 2, except when both c and d are 0. p represents an integer from 0 to 300, preferably 2 to 100, and more preferably 2 to 40. q and r are numbers satisfying 0 < q ≤ 1, 0 ≤ r < 1, and q + r = 1. Furthermore, if e is the number of NH-SiO2 atoms, then q is a number satisfying 0 ≤ e / (2p + 4) ≤ 0.5.

[0093] Compound (15) is obtained, similar to the polysilazane compounds, by reacting a chlorosiloxane compound represented by the following general formula (16) and / or a terminally silanol-modified polysiloxane represented by the following general formula (17), and optionally compound (14), with ammonia in the presence of a solvent, and removing the ammonium chloride produced as the reaction progresses.

[0094] (In the formula, R 18 (And p have the same meaning as above.)

[0095] In general formula (16), E is independent of R 18 Alternatively, it represents a chlorine atom, or an oxygen atom bonded to another E atom. In general formula (16), if the number of chlorine atoms is h, then h is a number that satisfies 0 ≤ h / (2p + 2) ≤ 0.5.

[0096] In the curable composition of the present invention, the hydrolyzable group-containing organosilicon compound may be used alone or in combination of multiple components. Examples of combinations of multiple components include a mixture of compound (12) and its partially hydrolyzed condensate, a mixture of the partially hydrolyzed condensate of compound (12) and compound (13), and a mixture of the partially hydrolyzed condensate of compound (12) and compound (15).

[0097] Furthermore, in the curable composition of the present invention, it is preferable to include a component containing dialkylpolysiloxane units in order to impart water repellency, flexibility, and slipperiness to the cured film obtained from the curable composition. The component containing dialkylpolysiloxane units preferably has a hydrolyzable group or a condensable group in order to integrate with compound (1) or the hydrolyzable group-containing organosilicon compound. Suitable compounds include, for example, the compound represented by the above general formula (17), the compound represented by the following general formula (18) (hereinafter referred to as "compound (18)"), and its partially hydrolyzed condensates.

[0098] (In the formula, p has the same meaning as above, and l is 0, 1, or 2.)

[0099] In general formula (18), R 21 Each of these is independently an unsubstituted monovalent hydrogen group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. 21 The monovalent hydrocarbon group of the above R is 11Similar groups to those exemplified above can be cited, and among them, linear alkyl groups and aryl groups are preferred due to the ease of raw material procurement. 21 Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, and isopropoxy groups, with methoxy and ethoxy groups being preferred.

[0100] R 22 R is an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, which may contain an oxygen atom, a nitrogen atom, or a sulfur atom. 22 The divalent hydrocarbon group is the above R 9 Examples of groups similar to those exemplified above include linear alkylene groups and aralkylene groups, which are preferred from the standpoint of ease of raw material procurement. 22 Specific examples of divalent hydrocarbon groups containing an oxygen atom include alkylene oxyalkylene groups, with ethylene oxymethylene and ethylene oxypropylene groups being preferred. 22 Specific examples of divalent hydrocarbon groups containing a nitrogen atom include alkylene-aminoalkylene groups, with propylene-aminomethylene and propylene-aminopropylene groups being preferred. 22 Specific examples of divalent hydrocarbon groups containing a sulfur atom include alkylentioalkylene groups, with ethylenethiomethylene and ethylenethiopropylene groups being preferred.

[0101] R 23 R 21 or R 22 -SiR 24 l (OR 25 ) 3-l Represents R 24 and R 25 Each of these is independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. 24 and R 25 The monovalent hydrocarbon group is the above R 11 Similar to the bases exemplified above, among them, R is a good choice due to the ease of raw material procurement. 24 The R is preferably a linear alkyl group, an alkenyl group, or an aryl group. 25Methyl and ethyl groups are preferred.

[0102] The blending ratio of compound (1) and the hydrolyzable group-containing organosilicon compound in the above curable composition is not particularly limited, but the amount of compound (1) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass, relative to the mass of the curable composition. If the amount of compound (1) is too high, the hardness of the resulting cured film will decrease, and if it is too low, the adhesion effect to the substrate may not be obtained. Furthermore, the blending ratio of compound (17), compound (18), and the partially hydrolyzed product of compound (18), which are components containing dimethylpolysiloxane units in the above curable composition, is not particularly limited, but the amount of components containing dimethylpolysiloxane units is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the mass of the curable composition.

[0103] The above curable composition can be used without a solvent, but a solvent may be used as long as it does not affect compound (1) or the hydrolyzable group-containing organosilicon compounds. 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, dioxane, propylene glycol monomethyl ether acetate, and dipropylene glycol dimethyl ether; ester compounds such as ethyl acetate, isopropyl acetate, and butyl acetate; and acetonitrile. Examples of solvents include aprotic polar compounds such as C1-C12 aliphatic hydrocarbons 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 with 2 to 10 silicon atoms such as hexamethyldisiloxane, octamethyltrisiloxane, tris(trimethylsiloxy)methylsilane, octamethylcyclotetrasiloxane, decamethyltetrasiloxane, and 3,5-diethyloctamethyltetrasiloxane. These solvents may be used individually or in mixtures of two or more. Among these, aliphatic hydrocarbon compounds with 8 to 12 carbon atoms and siloxane compounds with 2 to 5 silicon atoms are particularly preferred from a safety standpoint.

[0104] The amount of solvent used is not particularly limited, but the concentration of compound (1) and the hydrolyzable group-containing organosilicon compound is preferably 0.1 to 90% by mass, more preferably 1 to 90% by mass, and even more preferably 5 to 80% by mass.

[0105] Furthermore, the above curable composition may contain at least one metal compound selected from titanium compounds, aluminum compounds, zinc compounds, and tin compounds as a curing catalyst. Specific examples of titanium compounds include tetraalkyl orthotitanates such as tetrabutyl orthotitanate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, and tetraisopropyl orthotitanate, as well as their partially hydrolyzed condensates and titanium acylates. Specific examples of aluminum compounds include aluminum trihydrate, aluminum alkoxide, aluminum acylate, salts of aluminum acylate, 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 dioctyltine dioctate and dioctyltine dilaurate.

[0106] The amount of 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% by mass, and more preferably 0.1 to 5% by mass, relative to the mass of the curable composition. The curing catalyst may be added to the curable composition later, or it may be dissolved in a hydrolyzable group-containing organosilicon compound or solvent and then added.

[0107] The above-mentioned curable composition may contain one or more other additives selected from pigments, defoamers, lubricants, preservatives, pH adjusters, film-forming agents, antistatic agents, antibacterial agents, dyes, etc., as long as it does not impair its effect.

[0108] The above curable composition is obtained by mixing compound (1) and a hydrolyzable group-containing organosilicon compound with a solvent, curing catalyst, and other additives as needed, while taking care to avoid moisture, to obtain a homogeneous solution. Specifically, moisture contamination can be avoided by handling each component under an inert gas atmosphere such as nitrogen or argon. There are no restrictions on the order in which each component is added, but from the viewpoint of minimizing the progress of hydrolysis, it is preferable to add the curing catalyst last.

[0109] The cured product of the present invention is obtained by curing the above-mentioned curable composition, and specifically, curing occurs through hydrolysis and condensation of the alkoxysilyl group contained in compound (1) and the hydrolyzable group in the hydrolyzable group-containing organosilicon compound. If the curable composition contains a solvent, the solvent may be evaporated beforehand or not, or curing may be carried out while the solvent is being evaporated.

[0110] The curing temperature can range from room temperature to heated. While there are no particular restrictions on the temperature as long as it does not adversely affect the substrate, to maintain reactivity, it is preferably 0 to 250°C, more preferably 20 to 180°C, and even more preferably 20 to 150°C. Furthermore, since it reacts with moisture in the air, the relative humidity is preferably 15 to 100%, more preferably 25 to 80%.

[0111] A coated substrate can also be obtained by coating the surface of a substrate such as an inorganic or organic material with the above-mentioned curable composition, and then curing it by reacting it with moisture in the air. Specific examples of inorganic materials include metals, glass, silica, alumina, talc, calcium carbonate, and carbon. The shape of these materials is not particularly limited, but they may be in the form of plates, sheets, fibers, or powders. As for the glass, commonly used types of glass such as E-glass, C-glass, and quartz glass can be used, and glass fibers may also be used. Glass fibers may be aggregates thereof, for example, bundles of glass-based (filament) fibers with a fiber diameter of 3 to 30 μm, twisted yarns, woven fabrics, etc.

[0112] 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 and rubber materials such as polybutadiene rubber, polyisopropylene rubber, nitrile rubber, neoprene rubber, polysulfide, and urethane rubber. Among these, polyurethane and urethane rubber are preferred. The shape of the base material is not particularly limited, but it may be in the form of a plate, sheet, fiber, or powder.

[0113] Furthermore, the base material may be one in which the above-mentioned organic material components are coated on the outermost surface. Among these, it is preferable that polyurethane or an organic material containing polyurethane (polyurethane component) is coated and dried.

[0114] Known application methods can be used to apply the curable composition to the substrate, such as brush coating, sponge coating, cloth coating, spray coating, wire bar coating, blade coating, roll coating, dipping, and spin coating. In addition, for powdered materials such as silica, alumina, talc, and calcium carbonate, a mixing method may be used in which the curable composition is directly mixed with the substrate using a mixer or mill.

[0115] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0116] [1] Synthesis of organosilicon compounds [Example 1-1]

[0117] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 17.2 g of amino-modified silicone (0.0400 mol as amine, n ≈ 8) and 4.7 g (0.040 mol) of glycerol carbonate were charged, and the mixture was stirred at 60°C for 2 hours. The resulting reaction mixture was cooled to room temperature, and 0.1 g of bismuth catalyst (manufactured by Kusumoto Chemical Co., Ltd., XK-640, bismuth carboxylate, the same applies hereafter) and 16.4 g (0.080 mol) of isocyanatopropyltrimethoxysilane were added, and the mixture was stirred at 60°C for 2 hours. IR analysis of the reaction mixture revealed a reaction coefficient of 2200 cm⁻¹. -1 The peaks for the isocyanate groups in the vicinity had disappeared, indicating that the reaction was complete. 1 H-NMR analysis also supported the formation of the target product. Figure 1 shows 1 The H-NMR chart is shown.

[0118] [Examples 1-2]

[0119] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 32.0 g of amino-modified silicone (0.0400 mol as amine, n ≈ 18) and 4.7 g (0.040 mol) of glycerol carbonate were charged, and the mixture was stirred at 60°C for 2 hours. The resulting reaction mixture was cooled to room temperature, and 0.1 g of bismuth catalyst (manufactured by Kusumoto Chemical Co., Ltd., XK-640, bismuth carboxylate, the same applies hereafter) and 16.4 g (0.080 mol) of isocyanatopropyltrimethoxysilane were added, and the mixture was stirred at 60°C for 2 hours. IR analysis of the reaction mixture revealed a reaction coefficient of 2200 cm⁻¹. -1 The peaks of the isocyanate groups in the vicinity had disappeared, indicating that the reaction was complete. Further, 16.6 g of dimethyldimethoxysilane was added and the mixture was stirred to prepare a concentration of 80%. This solution... 1 The 1H-NMR chart is shown in Figure 2. Analysis after subtracting the peak originating from dimethyldimethoxysilane supported the formation of the target product.

[0120] [Examples 1-3]

[0121] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 17.2 g of amino-modified silicone (0.0400 mol as amine, n ≈ 8) and 4.7 g (0.040 mol) of glycerol carbonate were charged, and the mixture was stirred at 60°C for 2 hours. The resulting reaction mixture was cooled to room temperature, and 0.1 g of bismuth catalyst and 19.8 g (0.080 mol) of isocyanatopropyltriethoxysilane were added, and the mixture was stirred at 60°C for 2 hours. IR analysis of the reaction mixture revealed a reaction ratio of 2200 cm⁻¹. -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 H-NMR analysis also supported the formation of the target product. (See Figure 3) 1 The H-NMR chart is shown.

[0122] [Examples 1-4]

[0123] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 16.8 g of diamino-modified silicone (0.050 mol as amine, n ≈ 10) and 5.1 g (0.050 mol) of propylene carbonate were charged into both ends, and the mixture was stirred at 60°C for 2 hours. The resulting reaction mixture was cooled to room temperature, and 0.1 g of bismuth catalyst and 10.3 g (0.050 mol) of isocyanatopropyltrimethoxysilane were added, and the mixture was stirred at 60°C for 2 hours. IR analysis of the reaction mixture revealed a reaction ratio of 2200 cm⁻¹. -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 H-NMR analysis also supported the formation of the target product. Figure 4 shows... 1 The H-NMR chart is shown.

[0124] [Examples 1-5]

[0125] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen. 17.9 g of carbonate-modified octasiloxane (0.0400 mol as carbonate) and 2.4 g of aminoethanol (0.040 mol) were charged, and the mixture was stirred at 60°C for 2 hours. The resulting reaction mixture was cooled to room temperature, and 0.1 g of bismuth catalyst and 16.4 g of isocyanatopropyltrimethoxysilane (0.080 mol) were added, and the mixture was stirred at 60°C for 2 hours. IR analysis of the reaction mixture revealed a reaction ratio of 2200 cm⁻¹. -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 H-NMR analysis also supported the formation of the target product. (See Figure 5) 1 The H-NMR chart is shown.

[0126] [Examples 1-6]

[0127] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 28.7 g of one-end amino-modified octasiloxane (0.441 mol as amine) and 4.95 g of glycerol carbonate (0.0419 mol) were charged and stirred at 60°C for 2 hours. The resulting reaction mixture was cooled to room temperature, and 0.1 g of bismuth catalyst and 17.2 g of isocyanatopropyltrimethoxysilane (0.084 mol) were added and stirred at 60°C for 2 hours. IR analysis of the reaction mixture revealed a reaction ratio of 1800 cm³. -1 Nearby carbonate group peaks and 2200 cm -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 H-NMR analysis also supported the formation of the target product. (See Figure 6) 1 The H-NMR chart is shown.

[0128] [Comparative Example 1-1] The compound described in Example 2 of Japanese Patent Publication No. 2012-25876 was synthesized by the method shown below. The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 34.1 g (0.100 mol) of bis(3-trimethoxysilylpropyl)amine was charged. 24.7 g (0.100 mol) of 3-isocyanatopropyltriethoxysilane was added dropwise at room temperature, and the mixture was aged at the same temperature for 1 hour. IR analysis of the reaction solution revealed a reaction of 2200 cm⁻¹. -1 The peaks for the isocyanate groups in the vicinity had disappeared, indicating that the reaction was complete.

[0129] [Comparative Example 1-2] A curable silylated urethane resin was obtained according to the method described in Example 4 of Japanese Patent Application Publication No. 2011-162666.

[0130] [2] Preparation of Curable Compositions [Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-4] The organosilicon compounds obtained in Examples 1-1 to 1-5 and the compounds obtained in Comparative Examples 1-1 to 1-2, along with the hydrolyzable group-containing organosilicon compounds, were mixed in the ratios shown in Table 1 below, taking care to prevent moisture from entering. The mixture was then stirred in a vortex mixer to prepare curable compositions. The hydrolyzable group-containing organosilicon compounds used are as follows: Hydrolyzable group-containing organosilicon compound 1: A mixture of a hydrolyzable silicone compound having methyl and methoxy groups and a curing catalyst Hydrolyzable group-containing organosilicon compound 2: A mixture of a hydrolyzable silicone compound having methyl and methoxy groups, a component containing dimethylpolysiloxane units, and a curing catalyst Hydrolyzable group-containing organosilicon compound 3: A mixture of a hydrolyzable silicone compound having ethoxy groups and a component containing dimethylpolysiloxane units

[0131] The appearance of the compositions obtained in Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-4, as well as the adhesion of the cured films prepared from these compositions, were evaluated using the following methods. [Appearance] The compositions stirred in a vortex mixer were allowed to stand, and their appearance was visually assessed. A composition that was uniformly transparent was marked with ○, and a composition that was not transparent or had insoluble matter generated was marked with ×. Compositions that were marked with × for appearance were not further evaluated. [Adhesion] The obtained compositions were applied to a polyurethane board (7 cm x 15 cm, manufactured by AS ONE) using a bar coater to a wet thickness of 30 μm, and then cured at room temperature (approximately 23°C, 55% relative humidity) to produce a cured film. After confirming curing by touch, the test specimens were prepared by letting them stand at room temperature for two more days. A cross-cut test (in accordance with JIS K 5600) was performed on the obtained test specimens, and the surface condition was judged on a scale from 0 to 5. A smaller number indicates better adhesion. The results are shown in Table 1.

[0132]

[0133] As shown in Table 1, the curable compositions prepared in Examples 2-1 to 2-7 exhibit good adhesion to polyurethane substrates. Furthermore, the results from Examples 2-2 to 2-7 indicate that the organosilicon compounds obtained in Examples 1-1 to 1-6 can be compatible with hydrolyzable group-containing organosilicon compounds having dimethylpolysiloxane units. On the other hand, the results from Comparative Example 2-1 show that even with the use of an additive that enables adhesion to polycarbonate substrates when added to condensation-curable silicone compounds, adhesion to polyurethane substrates is not possible. In addition, although the curable silylated urethane resin has a structure that is expected to exhibit adhesion to polyurethane substrates, the results from Comparative Example 2-2 show that it cannot be compatible with condensation-curable silicone compounds having dimethylpolysiloxane units. Furthermore, the results from Comparative Examples 2-3 and 2-4 show that compositions without the compound of the present invention do not exhibit adhesion to polyurethane substrates.

Claims

1. An organosilicon compound represented by the following general formula (1). [In the formula, R 1 , 3 , 1 , 1 , , 3 , 8 , 3 , 6 , 7 represents -O-C(O)-NR 4 - or -R 4 N-C(O)-O-(R 4 represents a urethane bond, an oxygen atom or an NR' group (R' represents a hydrogen atom or a group represented by the following formula (2)), and may be intervened by a divalent hydrocarbon group having at least X and optionally substituted with 1 to 20 carbon atoms. (In the formula, R 5 represents a monovalent hydrocarbon group having at least X and optionally substituted with 1 to 20 carbon atoms, Y represents a single bond or an oxygen atom, and * represents a bond.) R 2 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 3 represents R 1 -X (R 1 represents the same meaning as described above) or an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, X is a group represented by the following general formula (3), and n is an integer of 0 to 100. (In the formula, R 6 represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, R 7 and R 8 each independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, m is 0, 1 or 2, and * represents a bond.) However, in the organosilicon compound represented by the general formula (1), when R 3 is R 1 -X, it has 6 or more urethane bonds in the molecule, and when R 3 is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, it has 3 or more urethane bonds in the molecule.

2. The following general formula (4) (In the formula, R 9 R represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may have at least one NH group interposed therein. 10 R 9 -NH2(R) 9 This has the same meaning as above.) or represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R 2 And n have the same meaning as above.) An amino group-containing organopolysiloxane compound represented by the following general formula (5) (In the formula, R 11 ) represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with at least one hydroxyl group.) After reacting a cyclic carbonate compound represented by the following general formula (6) (In the formula, R 6 ~R 8 A method for producing an organosilicon compound according to claim 1, comprising the step of reacting an isocyanatoalkylalkoxysilane compound represented by ( and m have the same meaning as described above) in the presence of at least one metal compound selected from the group consisting of titanium compounds, iron compounds, zirconium compounds, tin compounds and bismuth compounds.

3. The following general formula (7) [In the formula, R 12 R represents an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may have at least one oxygen atom interposed between them. 13 R 12 -Z(R 12 This has the same meaning as above.) or represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R 2 And n have the same meaning as described above, and Z represents a cyclic carbonate group represented by the following general formula (8). (In the formula, * represents a bond.) A cyclic carbonate group-containing organopolysiloxane compound represented by the following general formula (9) [In the formula, R 14 R represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms. 15 is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or R 14 -OH(R) 14 This represents the same meaning as above. ) After reacting the amino alcohol represented by ], the following general formula (6) (In the formula, R 6 ~R 8 A method for producing an organosilicon compound according to claim 1, comprising the step of reacting an isocyanatoalkylalkoxysilane compound represented by ( and m have the same meaning as described above) in the presence of at least one metal compound selected from the group consisting of titanium compounds, iron compounds, zirconium compounds, tin compounds and bismuth compounds.

4. A composition comprising the organosilicon compound described in claim 1 and a hydrolyzable group-containing organosilicon compound comprising at least one selected from the group consisting of alkoxysilane, a partially hydrolyzed condensate of alkoxysilane, silazane, polysilazane, and polysiloxazane.

5. The composition according to claim 4, wherein the hydrolyzable group-containing organosilicon compound contains a polydialkylpolysiloxane unit as a constituent unit.

6. The composition according to claim 4, comprising at least one metal compound selected from the group consisting of titanium compounds, aluminum compounds, zinc compounds, and tin compounds.

7. A cured product of the composition according to any one of claims 4 to 6.

8. A coated substrate having a base material and a coating formed thereon, wherein the coating is formed from a curable composition according to any one of claims 4 to 6.

9. The coated substrate according to claim 8, wherein the substrate has a coating film containing polyurethane or a polyurethane component on its outermost surface.

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