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

Abstract

Provided is an organosilicon compound that can form a uniform composition with a condensation-curable silicone compound having dimethylpolysiloxane units and that exhibits good adhesion to a urethane substrate. 【Solution means】An organosilicon compound represented by formula (1). TIFF2026123341000047.tif3072 [R 1 is a divalent hydrocarbon group which may be intervened by a urethane bond or the like and may be substituted with X; R 2 is a monovalent hydrocarbon group; R 3 is R 1 -X or a monovalent hydrocarbon group; X is a group represented by formula (3); n is an integer from 0 to 100 TIFF2026123341000048.tif2074 [R 6 is a divalent hydrocarbon group; R 7 and R 8 are monovalent hydrocarbon groups; m is 0, 1 or 2

Description

[Technical Field]

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

[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] This cured film derived from condensation-curable silicone compounds 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. In other words, Si-OH, which is 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-OM 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. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2012-25876 [Patent Document 2] Japanese Patent Publication No. 2011-162666 [Overview of the Initiative] [Problems that the invention aims to solve]

[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 ineffective for polyurethane.

[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 incorporate a dimethylpolysiloxane skeleton to enhance water repellency, and compositions of compounds having a dimethylpolysiloxane skeleton and condensation-curable silicone compounds, have the problem that, due to the influence of the dimethylpolysiloxane skeleton, the polarity of the compound or composition is low, 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 be used to prepare a uniform composition with a condensation-curable silicone compound having dialkylpolysiloxane units. [Means for solving the problem]

[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] In other words, the present invention is 1. An organosilicon compound represented by the following general formula (1), [ka] [In the formula, R 1 is -OC(O)-NR 4 -or -R 4 NC(O)-O-(R 4 represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. ) represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with at least X, and may have a urethane bond, an oxygen atom, or an NR' group (R' represents a hydrogen atom or a group represented by formula (2) below). [ka] (In the formula, R 5 (where represents a monovalent hydrocarbon group having 1 to 20 carbon atoms and possibly substituted with at least X, Y represents a single bond or oxygen atom, and * represents a bond.) R 2 Each of these independently represents an unsubstituted monovalent hydrocarbon group with 1 to 6 carbon atoms. R 3 R 1 -X(R1 represents the same meaning as described above. ) or a non-substituted 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.

Chemical formula

Chemical formula

Chemical formula

[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 composition exhibits good adhesion to polyurethane substrates due to the effect of the numerous urethane structures contained within the compound. [Brief explanation of the drawing]

[0014] [Figure 1] This is the 1H-NMR chart of the compound obtained in Example 1-1. [Figure 2] This is the 1H-NMR chart of the compounds obtained in Examples 1-2. [Figure 3] This is the 1H-NMR chart of the compounds obtained in Examples 1-3. [Figure 4] This is the 1H-NMR chart of the compounds obtained in Examples 1-4. [Figure 5] This is the 1H-NMR chart of the compounds obtained in Examples 1-5. [Figure 6] This is the 1H-NMR chart of the compounds obtained in Examples 1-6. [Modes for carrying out the invention]

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

[0016] [ka]

[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 formula (2) below).

[0018] [ka]

[0019] R 1The 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 procuring 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] [ka]

[0022] In general formulas (10) and (11), R 4 This 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. R 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. Note, R 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] On the other hand, R 1 However, in a divalent hydrocarbon group that is mediated by an NR' group (R' = general formula (2) above), R 5 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. R 5 The monovalent hydrocarbon group is the above R 4 Similar 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 trialkylsilyl groups, trialkoxysilyl groups, dialkylmonalkoxysilyl groups, monoalkyldialkoxysilyl groups, and substituent X represented by the following general formula (3), where each alkyl group and each alkoxy group has 1 to 3 carbon atoms.

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

[0028] In general formula (3), R 6 This represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 3 to 6 carbon atoms, and more preferably 3 carbon atoms. R 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 standpoint 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. R 7 and R 8 The 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. R 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 it represents an unsubstituted monovalent hydrocarbon group with 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 and 80, more preferably 3 and 60, and even more preferably 6 and 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 3 R 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 formula. 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] [ka] (In the formula, n has the same meaning as above.)

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

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

[0039] [ka] (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] [ka] (In the formula, R 2 , R 6 ~R 8 ,m and n represent the same meanings 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 This 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. R 9The 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 R 9 -NH2(R 9 This represents the same meaning as above. ) Or it represents an unsubstituted monovalent hydrocarbon group with 1 to 6 carbon atoms. R 10 The monovalent hydrocarbon group is the above R 7 and R 8 Examples similar to the base exemplified above can be given. Among these, R 10 R is an alkyl group having 1 to 6 carbon atoms. 9-NH2 is preferred.

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

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

[0048] In general formula (5), R 11 This is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms, which may be substituted with at least one hydroxyl group. R 11 The 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, methyl, propyl, and n-octyl groups are preferred due to the ease of raw material procurement. Note, R 11 Preferably, the monovalent hydrocarbon group has at least one of its hydrogen atoms, particularly the hydrogen atom bonded to the terminal carbon atom, substituted with a hydroxyl group.

[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 isocyanatomethyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatohexyltrimethoxysilane, isocyanatooctyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatopropyltriethoxysilane, isocyanatohexyltriethoxysilane, isocyanatooctyltriethoxysilane, and other isocyanatoalkyltrialkoxysilane compounds; isocyanatomethylmethyldimethoxysilane, isocyanatopropylmethyldimethoxysilane, isocyanatohexylmethyldimethoxysilane, isocyanatooctylmethyldimethoxysilane, 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 reactants 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, and among these, bismuth compounds are preferred. 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, iron stearate, and other iron carboxylates. Specific examples of zirconium compounds include zirconium tetraalkoxides such as zirconium tetrapropoxide and zirconium tetrabutoxide, zirconium dibutoxybis(ethyl acetate), zirconium tetraacetylacetonate, and their partially hydrolyzed 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 it is 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 reactants of compounds (4) and (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 1 mole of theoretical hydroxyl groups contained in the reactants.

[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. Furthermore, the above reaction is preferably carried out 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 can 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 involves reacting a carbonate group-containing organopolysiloxane compound with an amino alcohol, and then reacting it 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] [ka] (In the formula, * represents a bond.)

[0058] In general formula (7), R 12 This represents 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 interposed between them. R 12 The divalent hydrocarbon group can be linear, branched, or cyclic. Specific examples include linear alkylene groups such as methylene, 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, ethylenephenylethylene, and propylenephenylmethylene. Among these, linear alkylene groups and aralkylene groups having 3 to 8 carbon atoms are preferred due to the ease of procuring raw materials.

[0059] R 12 Examples of divalent hydrocarbon groups containing an oxygen atom include alkylene oxyalkylene and alkylene phenylene oxyalkylene groups. Among these, propylene oxymethylene, octylene oxymethylene, and propylene phenylene oxymethylene groups are preferred due to the ease of obtaining raw materials.

[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. As the monovalent hydrocarbon group of R 13 , those similar to the groups exemplified for R 7 and R 8 above can be mentioned. Among these, R 13 is preferably R 12 -Z.

[0061] Note that for compound (7), commercially available ones may be used or it may be manufactured. When manufacturing, it may follow a conventionally known method. For example, a method of subjecting a compound having a cyclic carbonate group and an alkenyl group and a polysiloxane compound having a Si-H structure at both ends or one end of the molecule to a hydrosilylation reaction, a method of reacting a polysiloxane compound having a glycidyl group at both ends or one end of the molecule with carbon dioxide in the presence of a catalyst, etc. can be mentioned.

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

[0063] [Chemical formula] (In the formula, n represents the same meaning as described above.)

[0064] In general formula (9), R 14 represents a substituted or unsubstituted divalent hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 7 carbon atoms. R 14The 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, branched alkylene groups, arylene groups, and aralkylene groups having 2 to 7 carbon atoms are preferred, with linear and branched alkylene groups being more preferred, from the standpoint of ease of raw material procurement. Note, R 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 the base exemplified above can be given. Among these, R 15 is a hydrogen atom, a linear alkyl group, an aryl group, R 14 -OH is preferable.

[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 reactants 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 when reacting the reaction products of compounds (4) and (5) with compound (6) in the above manufacturing method A.

[0068] The mixing ratio of compound (7) and compound (9) is not particularly limited, but preferably it is 0.9 to 1.1 moles, more preferably 0.95 to 1.05 moles, of compound (9) per mole of carbonate group contained in compound (7). The mixing ratio of the reactants of compounds (7) and (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 theoretical mole of hydroxyl groups contained in the reactants.

[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 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. Furthermore, the above reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon in order to prevent hydrolysis of compound (1) and compound (6). The above reaction can proceed without a solvent, but a solvent may also be used. Specific examples of solvents include those similar to those exemplified in manufacturing method A above.

[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 methods, purification by filtration is preferred from the standpoint of manufacturing efficiency.

[0071] Furthermore, the compound (1) obtained in this manner may be diluted with a solvent to facilitate handling. As specific examples of solvents, in addition to the solvents exemplified in the above-mentioned manufacturing methods A or B, silicon-numbered 1 alkoxysilanes can be used. 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 base material The curable composition of the present invention comprises compound (1) and a hydrolyzable group-containing organosilicon compound. The hydrolyzable group-containing organosilicon compounds used in the present invention are not particularly limited as long as they have 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] [ka]

[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, and R 17 x is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and x is an integer from 0 to 2. R 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. R 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] [ka] (In the formula, y is 0, 1, 2, or 3.)

[0080] In general formula (13), R 18 These are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, each independently containing an organosiloxane group represented by the following general formula (13A) at its terminus. R 18 The monovalent hydrocarbon group is the above R 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.

[0081] [ka]

[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 equation (13A), a is 0, 1, 2, or 3, and if a is 0 or 1, multiple OSiR 19 The three groups may undergo desiloxane condensation to form a cyclic siloxane. Furthermore, b represents an integer between 0 and 30, preferably between 0 and 20, and more preferably between 5 and 15. R 19 The combination of a and b is arbitrary and unrestricted. R 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] Such 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 proceeds.

[0086] [ka] (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] [ka] (In the formula, R 18 (This expresses the same meaning as above.)

[0089] In general formula (15), R 20 These are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, each of which may independently contain a sulfur atom or a silicon atom. R 20 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.

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

[0091] Furthermore, R 20 may contain both a sulfur atom and a silicon atom. Specific examples of the monovalent hydrocarbon group when containing both a sulfur atom and a silicon atom include an alkylene thioalkylene dialkylmonoalkoxysilyl group, an alkylene thioalkylene alkyldialkoxysilyl group, an alkylene thioalkylene trialkoxysilyl group, etc.

[0092] In the general formula (15), A each independently represents R 18 , NH-SiA2, or represents an oxygen atom to which A's are bonded. c and d each independently represent 0, 1, or 2, except when c and d are both 0. p represents an integer from 0 to 300, preferably 2 to 100, more preferably 2 to 40. q and r are numbers satisfying 0 < q ≤ 1, 0 ≤ r < 1, and q + r = 1. Further, when the number of NH-SiA2 is e, q is a number satisfying 0 ≤ e / (2p + 4) ≤ 0.5.

[0093] Similar to the polysilazane compound, the compound (15) is obtained by reacting a chlorosiloxane compound represented by the following general formula (16) and / or a both-terminal silanol-modified polysiloxane represented by the following general formula (17) with ammonia in the presence of a solvent, and removing ammonium chloride generated as the reaction proceeds, if necessary together with the compound (14).

[0094]

Chemical formula

[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 this dialkylpolysiloxane unit preferably has a hydrolyzable group or a condensable group in order to integrate it with compound (1) or an organosilicon compound containing a hydrolyzable group. Preferred compounds for this purpose 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] [ka] (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. R 21 The monovalent hydrocarbon group of the above R is 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. R 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 This 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. R 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. R 22 Specific examples of divalent hydrocarbon groups containing an oxygen atom include alkylene oxyalkylene groups, with ethylene oxymethylene and ethylene oxypropylene groups being preferred. R 22 Specific examples of divalent hydrocarbon groups containing a nitrogen atom include alkylene-aminoalkylene groups, with propylene-aminomethylene and propylene-aminopropylene groups being preferred. R 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 It 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. R 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 preferred group is a linear alkyl group, an alkenyl group, or an aryl group. 25 Methyl and ethyl groups are preferred.

[0102] The mixing 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, in the above curable composition, the blending ratio of compound (17), compound (18), and the partial hydrolysate of compound (18), which are components containing dimethylpolysiloxane units, is not particularly limited, but the component 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 solvents, but solvents may be used as long as they do not affect compound (1) or hydrolyzable group-containing organosilicon compounds. Specific examples of solvents include aliphatic hydrocarbon compounds with 5 to 20 carbon atoms such as pentane, hexane, cyclohexane, octane, isooctane, nonane, decane, dodecane, and isododecane; aromatic hydrocarbon compounds with 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 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 elements 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-mentioned 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 partial hydrolysis condensates and titanium acylates. Specific examples of aluminum compounds include aluminum trihydrate, aluminum alkoxide, aluminum acylate, salts of aluminum acylate, aluminosyloxy compounds, and aluminum metal chelate compounds. Specific examples of zinc compounds include zinc octylate 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 afterward, or it may be added by dissolving it in a hydrolyzable group-containing organosilicon compound or a solvent.

[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 prevent moisture from entering, to form 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 progression 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 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 evaporated.

[0110] The curing temperature can range from room temperature to heated temperatures. The temperature at this stage is not particularly limited as long as it does not adversely affect the substrate, but in order 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 15-100%, more preferably 25-80%.

[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. Their form 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, 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 coating 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. Furthermore, in the case of powdered materials such as silica, alumina, talc, and calcium carbonate, a mixing method may be adopted in which the curable composition is directly mixed with the base material using a mixer or mill. [Examples]

[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] [ka]

[0117] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 17.2 g of amino-modified silicone at both ends (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 solution revealed 2200 cm³. -1 The peaks for the isocyanate groups in the vicinity had disappeared, indicating that the reaction was complete. 1 The formation of the target product was also supported by 1H-NMR analysis. 1 The H-NMR chart is shown.

[0118] [Examples 1-2] [ka]

[0119] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 32.0 g of amino-modified silicone at both ends (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 solution revealed 2200 cm³. -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 adjust the concentration to 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] [ka]

[0121] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 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 into it, 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 solution revealed 2200 cm³. -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 The formation of the target product was also supported by 1H-NMR analysis. (See Figure 3) 1 The H-NMR chart is shown.

[0122] [Examples 1-4] [ka]

[0123] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 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 solution revealed 2200 cm³. -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 The formation of the target product was also supported by 1H-NMR analysis. (See Figure 4) 1 The H-NMR chart is shown.

[0124] [Examples 1-5] [ka]

[0125] The inside of a four-necked glass flask equipped with a stirrer, thermometer, and reflux condenser was purged with nitrogen, and 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 solution revealed 2200 cm³. -1 The peaks for the isocyanate groups in the vicinity have disappeared, indicating that the reaction was complete. 1 The formation of the target product was also supported by 1H-NMR analysis. (See Figure 5) 1 The H-NMR chart is shown.

[0126] [Examples 1-6] [ka]

[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 in, 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 17.2 g of isocyanatopropyltrimethoxysilane (0.084 mol) were added, and the mixture was stirred at 60°C for 2 hours. IR analysis of the reaction solution revealed 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 The formation of the target product was also supported by 1H-NMR analysis (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. 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 in. 24.7 g (0.100 mol) of 3-isocyanatopropyltriethoxysilane was then added dropwise at room temperature, and the mixture was aged at the same temperature for 1 hour. IR analysis of the reaction solution revealed 2200 cm³. -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 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 a curable composition. 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 an ethoxy group 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, and the adhesion of the cured films produced from these compositions were evaluated by the following methods. [Appearance] The composition stirred with a vortex mixer was allowed to stand, and the appearance of the composition was visually determined. Those that yielded a uniform and transparent composition were rated as ○, while those that did not become transparent or had insoluble matter were rated as ×. Compositions with an appearance rating of × were not evaluated further. [Adhesion] The obtained composition was applied onto a polyurethane plate (7 cm × 15 cm, manufactured by AS ONE) using a bar coater to a wet thickness of 30 μm, and then cured in an environment at room temperature (approx. 23°C, 55% relative humidity) to produce a cured film. After confirming curing by touch, the test piece was further allowed to stand at room temperature for 2 days to prepare a test specimen. The obtained test specimen was subjected to a cross-cut test (conforming to JIS K 5600), and the surface state was judged from 0 to 5. A smaller number indicates better adhesion. The results are shown in Table 1.

[0132]

Table 1

[0133] As shown in Table 1, it can be seen that the curable compositions prepared in Examples 2-1 to 2-7 exhibit good adhesion to the polyurethane substrate. Also, from the results of Examples 2-2 to 2-7, it can be seen that the organosilicon compounds obtained in Examples 1-1 to 1-6 can also be compatibilized with the hydrolyzable group-containing organosilicon compounds having dimethylpolysiloxane units. On the other hand, from the results of Comparative Example 2-1, it can be seen that even when using an auxiliary agent that enables adhesion to a polycarbonate substrate by adding it to a condensation-curable silicone compound, it cannot adhere to the polyurethane substrate. Also, although the curable silylated urethane resin has a structure that seems to exhibit adhesion to the polyurethane substrate, from the results of Comparative Example 2-2, it can be seen that it cannot be compatibilized with the condensation-curable silicone compound 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). 【Chemistry 1】 [In the formula, R 1 is -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. ) represents a urethane bond, an oxygen atom, or an NR' group (R' represents a hydrogen atom or a group represented by formula (2) below), which may be interposed, and may be a divalent hydrocarbon group having 1 to 20 carbon atoms and possibly substituted with at least X. 【Chemistry 2】 (In the formula, R 5 (where represents a monovalent hydrocarbon group having 1 to 20 carbon atoms and possibly substituted with at least X, Y represents a single bond or oxygen atom, and * represents a bond.) R 2 Each of these independently represents an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. 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 base represented by the following general formula (3), where n is an integer from 0 to 100. 【Transformation 3】 (In the formula, R 6 R represents an unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms. 7 and R 8 Each of these independently represents an unsubstituted monovalent hydrocarbon group with 1 to 6 carbon atoms, where m is 0, 1, or 2, and * represents a bond. However, the organosilicon compound represented by the general formula (1) is R 3 However, R 1 - In the case of X, the molecule has six or more urethane bonds, and the R 3 However, in the case of unsubstituted monovalent hydrocarbon groups with 1 to 6 carbon atoms, they have three or more urethane bonds within the molecule.

2. The following general formula (4) 【Chemistry 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 -NH 2 (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) 【Transformation 5】 (In the formula, R 11 (This represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with at least one hydroxyl group.) After reacting the cyclic carbonate compound represented by , The following general formula (6) 【Transformation 6】 (In the formula, R 6 ~R 8 (And m have the same meaning as above.) A method for producing an organosilicon compound according to claim 1, 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) 【Transformation 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). 【Transformation 8】 (In the formula, * represents a bond.) A cyclic carbonate group-containing organopolysiloxane compound represented by, The following general formula (9) 【Chemistry 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 with the amino alcohol represented by, The following general formula (6) 【Chemistry 10】 (In the formula, R 6 ~R 8 (And m have the same meaning as above.) A method for producing an organosilicon compound according to claim 1, 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.

4. A composition comprising the organosilicon compound according to 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 comprises 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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