Method for producing polysiloxane and use of polysiloxane

Abstract

To provide a polysiloxane that can provide a cured product having excellent weather resistance.SOLUTION: A method for producing a polysiloxane includes a first-stage polymerization step for subjecting an alkoxysilane component (I) to hydrolysis and dehydration condensation, and a second-stage polymerization step for subjecting a polysiloxane macromer resulting from the first-stage polymerization step to hydrolysis and dehydration condensation with an alkoxysilane component (II).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing polysiloxane. The present invention also relates to a polysiloxane, a curable resin composition containing the polysiloxane, and a cured product obtained by curing the curable resin composition containing the polysiloxane. [Background technology]

[0002] Curable resin compositions primarily composed of organopolysiloxanes are known as coatings used in a wide range of industries, including construction, home appliances, and automobiles. In particular, resin compositions containing organopolysiloxanes having epoxy groups as functional groups (organo groups) are preferred due to their excellent scratch resistance, chemical resistance, and other properties.

[0003] As an example of a resin composition containing organopolysiloxane having such epoxy groups, Patent Document 1 describes a curable resin composition in which the physical properties of the cured product are improved by including an alkoxysilane compound having two or more types of epoxy groups as a constituent unit. Patent Document 2 also describes a technique for using a curable resin composition containing a block-type siloxane compound as an optical semiconductor printed circuit board. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2020 / 235524 [Patent Document 2] Japanese Patent Publication No. 2014-185263 [Overview of the project] [Problems that the invention aims to solve]

[0005] While the above technology is excellent, there was room for improvement regarding the weather resistance of the resulting cured material.

[0006] Therefore, one aspect of the present invention aims to provide a method for producing polysiloxane that can provide a cured product with excellent weather resistance. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have discovered for the first time that a polysiloxane with excellent weather resistance can be provided by carrying out a two-step hydrolysis and dehydration condensation reaction of an alkoxysilane compound having a glycidyloxy group and / or an alkoxysilane compound having an epoxy group as raw materials, and have completed the present invention.

[0008] Accordingly, one aspect of the present invention is a method for producing polysiloxane, comprising: (1) a first polymerization step of hydrolyzing and dehydrating an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group in the presence of water and a neutral salt to obtain a solution containing a polysiloxane macromer; and (2) a second polymerization step of mixing the solution containing the polysiloxane macromer with an alkoxysilane component (II) containing an alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group in a different composition from that of alkoxysilane component (I), and then hydrolyzing and dehydrating the polysiloxane macromer and the alkoxysilane component (II) to obtain a solution containing polysiloxane. [Effects of the Invention]

[0009] According to one aspect of the present invention, a polysiloxane can be provided that can provide a cured product with excellent weather resistance. [Modes for carrying out the invention]

[0010] One embodiment of the present invention will be described in detail below. Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less". Further, all the documents described in this specification are incorporated herein by reference as reference documents.

[0011] 〔1. Summary of the Invention〕 As described in Patent Document 1, a cured product (coating film) obtained by curing a polysiloxane having two or more types of silane compounds having an epoxy group as a constituent unit is excellent in chemical resistance and the like, but there is room for improvement in the weather resistance of the obtained cured product.

[0012] The inventors of the present invention conducted research to improve the weather resistance of a cured product (coating film) obtained by curing a polysiloxane having two or more types of silane compounds having an epoxy group as a constituent unit, and as a result, obtained the following findings. · (1) A first-stage polymerization step of hydrolyzing and dehydrating and condensing an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group using water and a neutral salt to obtain a solution containing a polysiloxane macromer; and (2) hydrolyzing and dehydrating and condensing the solution containing the polysiloxane macromer, the polysiloxane macromer, and an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group with an alkoxysilane component (II) having a composition different from that of the alkoxysilane component (I) to obtain a solution containing a polysiloxane, a second-stage polymerization step. A curable resin composition containing a polysiloxane obtained by the production method of polysiloxane including these can provide a cured product excellent in weather resistance. · A cured product obtained by curing a curable resin composition containing a polysiloxane obtained by the above production method is also excellent in scratch resistance, chemical resistance, and water resistance.

[0013] A polysiloxane that can provide a cured product excellent in scratch resistance, chemical resistance, water resistance, and also excellent in weather resistance has not existed so far, and the production method of polysiloxane according to one embodiment of the present invention is extremely useful.

[0014] [2. Method for producing polysiloxane] The method for producing a polysiloxane according to an embodiment of the present invention (hereinafter referred to as "this production method") comprises: (1) a first-stage polymerization step of subjecting an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group to hydrolysis and dehydration condensation in the presence of water and a neutral salt to obtain a solution containing a polysiloxane macromer; and (2) a second-stage polymerization step of mixing the solution containing the polysiloxane macromer, the polysiloxane macromer, and an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group with an alkoxysilane component (II) having a composition different from that of the alkoxysilane component (I) and subjecting the polysiloxane macromer and the alkoxysilane component (II) to hydrolysis and dehydration condensation to obtain a solution containing a polysiloxane.

[0015] As used herein, "polysiloxane" is intended to mean an organopolysiloxane formed by one or more alkoxysilane compounds forming siloxane bonds between the alkoxysilane compounds.

[0016] According to this production method, a polysiloxane containing at least two block structures derived from a specific alkoxysilane compound in the molecule is provided. The polysiloxane provided by this production method (hereinafter also referred to as "this polysiloxane") may contain a block structure containing a structural unit derived from an alkoxysilane compound having a glycidyloxy group (i), may contain a block structure containing a structural unit derived from an alkoxysilane compound having an epoxycyclohexyl group (ii), or may contain a block structure containing both a structural unit derived from an alkoxysilane compound having a glycidyloxy group and a structural unit derived from an alkoxysilane compound having an epoxycyclohexyl group (iii).

[0017] In this specification, a block structure refers to a polymer containing at least 80 mol% of a specific alkoxysilane compound as a constituent unit, preferably 90 mol% or more, and more preferably 95 mol% or more, of the total amount of all constituent units in the block structure. In this specification, a constituent unit that accounts for 80 mol% or more of the total amount of all constituent units in the block structure may be referred to as a major constituent unit.

[0018] A polysiloxane having a block structure can also be described as a polymer formed by graft polymerization (second-stage polymerization) of multiple block structures (polymers). In this specification, the block structure (polymer) used in the second-stage polymerization is also referred to as a polysiloxane macromer.

[0019] As described above, this manufacturing method includes (1) a first polymerization step and (2) a second polymerization step, and optionally includes (3) a de-alcoholization step and (4) a maturation step. The following describes each step of this manufacturing method in detail.

[0020] <(1) First polymerization step> In this manufacturing method, the first polymerization step involves hydrolyzing and dehydrating an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group using water and a neutral salt to obtain a solution containing a polysiloxane macromer.

[0021] (alkoxysilane component (I)) The alkoxysilane component (I) according to one embodiment of the present invention contains at least an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group. The alkoxysilane component (I) may (i) contain only an alkoxysilane compound having a glycidyloxy group, (ii) contain only an alkoxysilane compound having an epoxycyclohexyl group, or (iii) contain both an alkoxysilane compound having a glycidyloxy group and an alkoxysilane compound having an epoxycyclohexyl group. Furthermore, in each of the embodiments of (i) to (iii) above, the alkoxysilane component (I) may also contain alkoxysilane compounds other than alkoxysilane compounds having a glycidyloxy group and alkoxysilane compounds having an epoxycyclohexyl group (referred to as other alkoxysilane compounds).

[0022] (Alkoxysilane compounds containing a glycidyloxy group) Alkoxysilane compounds having a glycidyloxy group are one or more silane compounds having an alkoxy group and an organic group containing a glycidyloxy group as substituents on a silicon atom.

[0023] Specific examples of alkoxysilane compounds having a glycidyloxy group include monoorganotrialalkoxysilane, diorganodialkoxysilane, and triorganomonoalkoxysilane, which have an organic group containing a glycidyloxy group as an organic group (organo group). Among these, monoorganotrialalkoxysilane, which has an organic group containing a glycidyloxy group as an organic group, is preferred as the alkoxysilane compound having a glycidyloxy group. As the alkoxysilane compound having a glycidyloxy group, monoorganotrialalkoxysilane may be used alone, or in combination with diorganodialkoxysilane, or in combination with monoorganotrialtrialalkoxysilane, diorganodialkoxysilane, and / or triorganomonoalkoxysilane. Here, a monoorganotrialkoxysilane refers to a silane compound having an organic group with one glycidyloxy group as a substituent on a silicon atom and three alkoxy groups; a diorganodialkoxysilane refers to a silane compound having an organic group with at least one glycidyloxy group as a substituent on a silicon atom and two alkoxy groups; and a triorganomonoalkoxysilane refers to a silane compound having an organic group with at least one glycidyloxy group as a substituent on a silicon atom and one alkoxy group.

[0024] When using triorganomonoalkoxysilane and / or tetraalkoxysilane as alkoxysilane component (I), the amount used is not particularly limited as long as it does not hinder the effects of the invention. For example, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less, based on 100 mol% of the total amount of alkoxysilane component (I).

[0025] Examples of alkoxy groups that a glycidyloxy group-containing alkoxysilane compound may have as substituents on the silicon atom include alkoxy groups having 1 to 3 carbon atoms. Specifically, these include methoxy groups, ethoxy groups, and propoxy groups, with methoxy and ethoxy groups being preferred, and methoxy groups being more preferred. The alkoxy group may be just one type, or two or more types may be mixed together.

[0026] Examples of organic groups containing a glycidyloxy group that an alkoxysilane compound having a glycidyloxy group may have as a substituent on a silicon atom include glycidyloxyalkyl groups such as 1-glycidyloxymethyl group, 2-glycidyloxyethyl group, 3-glycidyloxypropyl group, 4-glycidyloxybutylmethyl group, 6-glycidyloxyhexyl group, and 8-glycidyloxyoctyl group. The glycidyloxy group may be of only one type, or it may be a mixture of two or more types.

[0027] An alkoxysilane compound having a glycidyloxy group only needs to contain at least one alkoxy group and at least one organic group containing a glycidyloxy group as substituents on the silicon atom, and may also contain other organic groups (organic groups that do not contain a glycidyloxy group).

[0028] Examples of such other organic groups include alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms. The alkyl groups, alkenyl groups, and aryl groups may be unsubstituted or substituted. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and still more preferably 1 to 2. The number of carbon atoms in the alkenyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. The other organic groups may be one type or a mixture of two or more types.

[0029] In one embodiment of the present invention, examples of alkoxysilane compounds having a glycidyloxy group include trialkoxysilane compounds having an organic group containing a glycidyloxy group, dialkoxysilane compounds having an organic group containing a glycidyloxy group and other organic groups, trialkoxysilane compounds having a glycidyloxyalkyl group, and dialkoxysilane compounds having a glycidyloxyalkyl group and other organic groups. More specifically, alkoxysilane compounds having an organic group containing a glycidyloxy group include 1-glycidyloxymethyltrimethoxysilane, 1-glycidyloxymethylmethyldimethoxysilane, 1-glycidyloxymethyltriethoxysilane, 1-glycidyloxymethylmethyldiethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxy Examples include propylmethyldiethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 6-glycidyloxyhexyltrimethoxysilane, 6-glycidyloxyhexylmethyldimethoxysilane, 6-glycidyloxyhexyltriethoxysilane, 6-glycidyloxyhexylmethyldiethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 8-glycidyloxyoctylmethyldimethoxysilane, 8-glycidyloxyoctyltriethoxysilane, and 8-glycidyloxyoctylmethyldiethoxysilane. Among these, trialkoxysilane compounds or dialkoxysilane compounds having a 3-glycidyloxypropyl group are preferred, and trialkoxysilane compounds having a 3-glycidyloxypropyl group are particularly preferred.

[0030] (An alkoxysilane compound having an epoxycyclohexyl group) Alkoxysilane compounds having an epoxycyclohexyl group are one or more silane compounds having an alkoxy group and an organic group containing an epoxycyclohexyl group as substituents on a silicon atom.

[0031] Specific examples of alkoxysilane compounds having an organic group containing an epoxycyclohexyl group include monoorganotrialalkoxysilane, diorganodialkoxysilane, and triorganomonoalkoxysilane, which have an organic group containing an epoxycyclohexyl group as the organic group (organo group). Among these, monoorganotrialalkoxysilane is preferred as the alkoxysilane compound having an organic group containing an epoxycyclohexyl group as the organic group (organo group). Monoorganotrialalkoxysilane may be used alone as the alkoxysilane compound having an epoxycyclohexyl group, or in combination with monoorganotrialalkoxysilane and diorganodialkoxysilane, or in combination with monoorganotrialtrialalkoxysilane, diorganodialkoxysilane, and / or triorganomonoalkoxysilane. Here, a monoorganotrialkoxysilane refers to a silane compound having an organic group containing one epoxycyclohexyl group as a substituent on a silicon atom and three alkoxy groups; a diorganodialkoxysilane refers to a silane compound having an organic group containing at least one epoxycyclohexyl group as a substituent on a silicon atom and two alkoxy groups; and a triorganomonoalkoxysilane refers to a silane compound having an organic group containing at least one epoxycyclohexyl group as a substituent on a silicon atom and one alkoxy group.

[0032] When using triorganomonoalkoxysilane and / or tetraalkoxysilane as the alkoxysilane component (I), the amount used is not particularly limited as long as it does not hinder the effects of the invention. For example, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less, based on 100 mol% of the total amount of alkoxysilane component (I).

[0033] Examples of alkoxy groups that can be substituents on the silicon atom of an epoxycyclohexyl group-containing alkoxysilane compound include alkoxy groups having 1 to 3 carbon atoms. Specifically, these include methoxy, ethoxy, and propoxy groups, with methoxy and ethoxy groups being preferred, and methoxy groups being more preferred. The alkoxy group may be just one type, or two or more types may be mixed together.

[0034] Examples of organic groups containing an epoxycyclohexyl group that an alkoxysilane compound having an epoxycyclohexyl group may have as a substituent on a silicon atom include 1-(epoxycyclohexyl)methyl group, 2-(epoxycyclohexyl)ethyl group, 2-(epoxycyclohexyl)propyl group, and 3-(epoxycyclohexyl)propyl group. The epoxycyclohexyl group may be of only one type, or two or more types may be mixed together.

[0035] An alkoxysilane compound having an epoxycyclohexyl group only needs to contain at least one alkoxy group and at least one organic group containing an epoxycyclohexyl group as substituents on the silicon atom, and may also contain other organic groups (organic groups that do not contain an epoxycyclohexyl group).

[0036] Examples of such other organic groups include alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms. The alkyl groups, alkenyl groups, and aryl groups may be unsubstituted or substituted. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and still more preferably 1 to 2. The number of carbon atoms in the alkenyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. The other organic groups may be one type or a mixture of two or more types.

[0037] In one embodiment of the present invention, examples of alkoxysilane compounds having an epoxycyclohexyl group include trialkoxysilane having an epoxycyclohexyl alkyl group, and dialkoxysilane having an epoxycyclohexyl alkyl group and the aforementioned other organic groups. More specifically, 1-(3,4-epoxycyclohexyl)methyltrimethoxysilane, 1-(2,3-epoxycyclohexyl)methyltrimethoxysilane, 1-(3,4-epoxycyclohexyl)methylmethyldimethoxysilane, 1-(3,4-epoxycyclohexyl)methyltriethoxysilane, 1-(3,4-epoxycyclohexyl)methylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 3-(3,4-epoxycyclohexyl) Ropylmethyldiethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butylmethyldimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butylmethyldiethoxysilane, 6-(3,4-epoxycyclohexyl)hexyltrimethoxysilane, 6-(3,4-epoxycyclohexyl)hexylmethyldimethoxysilane Examples include 6-(3,4-epoxycyclohexyl)hexyltriethoxysilane, 6-(3,4-epoxycyclohexyl)hexylmethyldiethoxysilane, 8-(3,4-epoxycyclohexyl)octyltrimethoxysilane, 8-(3,4-epoxycyclohexyl)octylmethyldimethoxysilane, 8-(3,4-epoxycyclohexyl)octyltriethoxysilane, and 8-(3,4-epoxycyclohexyl)octylmethyldiethoxysilane.Among these, trialkoxysilane compounds or dialkoxysilane compounds having a 2-(3,4-epoxycyclohexyl)ethyl group are preferred, and trialkoxysilane compounds having a 2-(3,4-epoxycyclohexyl)ethyl group are particularly preferred.

[0038] (Other alkoxysilane compounds) Other alkoxysilane compounds are one or more silane compounds having an alkoxy group as a substituent on a silicon atom and not having an organic group containing a glycidyloxy group or an organic group containing an epoxycyclohexyl group. Specific examples of other alkoxysilane compounds include monoorganotrial alkoxysilane, diorganodialkoxysilane, triorganomonoalkoxysilane, and tetraalkoxysilane. It is preferable that the other alkoxysilane compound has at least one monoorganotrial alkoxysilane. The other alkoxysilane compound may be monoorganotrial alkoxysilane alone, a combination of monoorganotrial alkoxysilane and diorganodialkoxysilane, or a combination of monoorganotrial alkoxysilane, diorganodialkoxysilane, triorganomonoalkoxysilane, and / or tetraalkoxysilane compounds. Here, a monoorganotrialkoxysilane refers to a silane compound having one organic group and three alkoxy groups as substituents on a silicon atom, a diorganodialkoxysilane refers to a silane compound having two organic groups and two alkoxy groups as substituents on a silicon atom, and a triorganomonoalkoxysilane refers to a silane compound having three organic groups and one alkoxy group as substituents on a silicon atom.

[0039] When using other alkoxysilane compounds, such as triorganomonoalkoxysilanes and / or tetraalkoxysilanes, the amount used is not particularly limited as long as it does not hinder the effects of the invention. For example, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less, based on 100 mol% of the total amount of alkoxysilane component (I).

[0040] Other alkoxysilane compounds may have alkoxy groups as substituents on the silicon atom, such as alkoxy groups having 1 to 3 carbon atoms. Specifically, these include methoxy, ethoxy, and propoxy groups, with methoxy and ethoxy groups being preferred, and methoxy groups being more preferred. The alkoxy group may be just one type, or two or more types may be mixed together.

[0041] Other organic groups that alkoxysilane compounds may have as substituents on the silicon atom are not particularly limited, as long as they are organic groups other than glycidyloxy groups and epoxycyclohexyl groups. Examples include C1-C8 alkyl groups, C2-C8 alkenyl groups, and C6-C12 aryl groups. The alkyl groups, alkenyl groups, and aryl groups may be unsubstituted or substituted. The number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-4, even more preferably 1-3, and still more preferably 1-2. The number of carbon atoms in the alkenyl group is preferably 2-6, more preferably 2-4, and even more preferably 2-3. The organic groups may be one type or a mixture of two or more types.

[0042] Other alkoxysilane compounds are not particularly limited, as long as they do not have organic groups containing a glycidyloxy group or an epoxycyclohexyl group as substituents on the silicon atom, and have at least one alkoxy group. Examples of alkoxysilane compounds in which the organic group having a substituent on the silicon atom is an unsubstituted alkyl group include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, propyltriethoxysilane, propylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, octyltrimethoxysilane, octylmethyldimethoxysilane, octyltriethoxysilane, and octylmethyldiethoxysilane.

[0043] As described above, the organic groups that other alkoxysilane compounds have as substituents on the silicon atom may be substituted organic groups. The substituents are not particularly limited, but due to their availability, thiol groups, isocyanate groups, (meth)acryloyl groups, phenyl groups, cyclohexyl groups, and chloro groups are preferred.

[0044] Other alkoxysilane compounds when the organic group is an alkyl group having a thiol group include, for example, 1-mercaptomethyltrimethoxysilane, 1-mercaptomethylmethyldimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldiethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl Examples include lucaptopropylmethyldiethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 6-mercaptohexyltrimethoxysilane, 6-mercaptohexylmethyldimethoxysilane, 6-mercaptohexyltriethoxysilane, 6-mercaptohexylmethyldiethoxysilane, 8-mercaptooctyltrimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltriethoxysilane, and 8-mercaptooctylmethyldiethoxysilane.

[0045] Other alkoxysilane compounds when the organic group is an alkyl group having an isocyanate group include, for example, 1-isocyanatemethyltrimethoxysilane, 1-isocyanatemethylmethyldimethoxysilane, 1-isocyanatemethyltriethoxysilane, 1-isocyanatemethylmethyldiethoxysilane, 2-isocyanateethyltrimethoxysilane, 2-isocyanateethylmethyldimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethylmethyldiethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3- Examples include socyanate propyl methyldiethoxysilane, 4-isocyanate butyl trimethoxysilane, 4-isocyanate butyl methyl dimethoxysilane, 4-isocyanate butyl triethoxysilane, 4-isocyanate butyl methyldiethoxysilane, 6-isocyanate hexyl trimethoxysilane, 6-isocyanate hexyl methyl dimethoxysilane, 6-isocyanate hexyl triethoxysilane, 6-isocyanate hexyl methyldiethoxysilane, 8-isocyanate octyl trimethoxysilane, 8-isocyanate octyl methyl dimethoxysilane, 8-isocyanate octyl triethoxysilane, and 8-isocyanate octyl methyldiethoxysilane.

[0046] Other alkoxysilane compounds when the organic group is an alkyl group having a (meth)acryloyl group include, for example, 1-(meth)acryloyloxymethyltrimethoxysilane, 1-(meth)acryloyloxymethylmethyldimethoxysilane, 1-(meth)acryloyloxymethyltriethoxysilane, 1-(meth)acryloyloxymethylmethyldiethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, 2-(meth)acryloyloxyethylmethyldimethoxysilane, 2-(meth)acryloyloxyethyltriethoxysilane, 2-(meth)acryloyloxyethylmethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane Examples include liloyloxypropylmethyldiethoxysilane, 4-(meth)acryloyloxybutyltrimethoxysilane, 4-(meth)acryloyloxybutylmethyldimethoxysilane, 4-(meth)acryloyloxybutyltriethoxysilane, 4-(meth)acryloyloxybutylmethyldiethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 6-(meth)acryloyloxyhexylmethyldimethoxysilane, 6-(meth)acryloyloxyhexyltriethoxysilane, 6-(meth)acryloyloxyhexylmethyldiethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, and 8-(meth)acryloyloxyoctylmethyldiethoxysilane.

[0047] Other alkoxysilane compounds when the organic group is an alkyl group having a phenyl group include, for example, benzyltrimethoxysilane, benzyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropyltriethoxysilane, 4-phenylbutyltrimethoxysilane, 4-phenylbutyltriethoxysilane, 5-phenylpentyltrimethoxysilane, 5-phenylpentyltriethoxysilane, 6-phenylhexyltrimethoxysilane, and 6-phenylhexyltriethoxysilane.

[0048] Other alkoxysilane compounds when the organic group is an alkyl group having a cyclohexyl group include, for example, cyclohexylmethyltrimethoxysilane, cyclohexylmethyltriethoxysilane, 2-cyclohexylethyltrimethoxysilane, 2-cyclohexylethyltriethoxysilane, 3-cyclohexylpropyltrimethoxysilane, 3-cyclohexylpropyltriethoxysilane, 4-cyclohexylbutyltrimethoxysilane, 4-cyclohexylbutyltriethoxysilane, 5-cyclohexylpentyltrimethoxysilane, 5-cyclohexylpentyltriethoxysilane, 6-cyclohexylhexyltrimethoxysilane, and 6-cyclohexylhexyltriethoxysilane.

[0049] Other alkoxysilane compounds when the organic group is an alkyl group having a chloro group include, for example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 5-chloropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 6-chlorohexyltrimethoxysilane, and 6-chlorohexyltriethoxysilane.

[0050] Other alkoxysilane compounds in which the organic group is an alkenyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, and allylmethyldiethoxysilane.

[0051] Other alkoxysilane compounds when the organic group is an aryl group include phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and the like.

[0052] Other alkoxysilane compounds may include organic groups containing epoxy groups other than glycidyloxy groups and epoxycyclohexyl groups as substituents on the silicon atom. Examples of such other alkoxysilane compounds include epoxytrimethoxysilane, epoxymethyldimethoxysilane, epoxytriethoxysilane, epoxymethyldiethoxysilane, 1-epoxymethyltrimethoxysilane, 1-epoxymethylmethyldimethoxysilane, 1-epoxymethyltriethoxysilane, 1-epoxymethylmethyldiethoxysilane, 2-epoxyethyltrimethoxysilane, 2-epoxyethylmethyldimethoxysilane, 2-epoxyethyltriethoxysilane, 2-epoxyethylmethyldiethoxysilane, 3-epoxypropyltrimethoxysilane, 3-epoxypropylmethyldi Examples include methoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxypropylmethyldiethoxysilane, 4-epoxybutyltrimethoxysilane, 4-epoxybutylmethyldimethoxysilane, 4-epoxybutyltriethoxysilane, 4-epoxybutylmethyldiethoxysilane, 6-epoxyhexyltrimethoxysilane, 6-epoxyhexylmethyldimethoxysilane, 6-epoxyhexyltriethoxysilane, 6-epoxyhexylmethyldiethoxysilane, 8-epoxyoctyltrimethoxysilane, 8-epoxyoctylmethyldimethoxysilane, and 8-epoxyoctyltriethoxysilane.

[0053] In one embodiment of the present invention, the alkoxysilane component (I) preferably contains 70 to 100 mol% monoorganotrialalkoxysilane and 0 to 30 mol% diorganodialkoxysilane, based on 100 mol% of the total amount of alkoxysilane compounds contained in the alkoxysilane component (I). The proportion of monoorganotrialalkoxysilane is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, particularly preferably 99 mol% or more, and may also be 100 mol%.

[0054] In alkoxysilane component (I), the total amount of alkoxysilane compounds having a glycidyloxy group and alkoxysilane compounds having an epoxycyclohexyl group, relative to 100 mol% of the total amount of alkoxysilane compounds contained in alkoxysilane component (I), is preferably 50 to 100 mol%, more preferably 60 to 100%, even more preferably 70 to 100 mol%, and may be 100 mol%. Furthermore, the ratio of alkoxysilane compounds having a glycidyloxy group and alkoxysilane compounds having an epoxycyclohexyl group contained in alkoxysilane component (I) is not particularly limited, but for example, the ratio of alkoxysilane compounds having a glycidyloxy group (mol%) to alkoxysilane compounds having an epoxycyclohexyl group (mol%) may be 100:0 to 0:100, 95:5 to 5:95, 90:10 to 10:90, or 80:20 to 20:80. The type of alkoxysilane compound contained in alkoxysilane compound (I) and its amount (ratio) can be appropriately determined considering the composition and physical properties of the final product, polysiloxane, as well as the composition of alkoxysilane component (II) used in the second polymerization step.

[0055] (Neutral salt) In this manufacturing method, a neutral salt is added during the hydrolysis and dehydration condensation reaction of the alkoxysilane component (I) in the first polymerization step. By adding a neutral salt, the dehydration condensation reaction can be promoted, the deactivation of the glycidyloxy group and epoxycyclohexyl group can be suppressed, and a cured product with excellent adhesion and scratch resistance can be obtained. The neutral salt can also be called a neutral salt catalyst because it functions as a dehydration condensation catalyst.

[0056] In this specification, a neutral salt refers to a salt formed from a strong acid and a strong base. Specifically, it is a salt consisting of a combination of a cation selected from the group consisting of Group 1 element ions, Group 2 element ions, tetraalkylammonium ions, and guanidinium ions, and an anion selected from the group consisting of Group 17 element ions (excluding fluoride ions), sulfate ions, nitrate ions, and perchlorate ions. Examples of neutral salts include lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, guanidium chloride; lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, radium bromide, tetramethylammonium bromide Iopropylammonium, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, guanidium bromide; lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, radium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrahexylammonium iodide, guanidium iodide;Lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, francium sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate, tetramethylammonium sulfate, tetraethylammonium sulfate, tetrapropylammonium sulfate, tetrabutylammonium sulfate, tetrapentylammonium sulfate, tetrahexylammonium sulfate, guanidium sulfate; lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, francium nitrate, beryllium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, radium nitrate, tetramethylammonium nitrate, tetraethylammonium nitrate Examples include nium, tetrapropylammonium nitrate, tetrabutylammonium nitrate, tetrapentylammonium nitrate, tetrahexylammonium nitrate, guanidium nitrate; lithium perchlorate, sodium perchlorate, potassium perchlorate, rubidium perchlorate, cesium perchlorate, francium perchlorate, beryllium perchlorate, magnesium perchlorate, calcium perchlorate, strontium perchlorate, barium perchlorate, radium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrapropylammonium perchlorate, tetrabutylammonium perchlorate, tetrapentylammonium perchlorate, tetrahexylammonium perchlorate, guanidium perchlorate, etc. These neutral salts may be used individually or in combination of two or more types.

[0057] The amount of neutral salt added in the first polymerization step can be appropriately determined according to the desired progress of the hydrolysis-dehydration condensation reaction, but is preferably 1 ppm to 100,000 ppm, more preferably 10 ppm to 10,000 ppm, even more preferably 20 ppm to 5,000 ppm, and still more preferably 50 ppm to 1,000 ppm relative to the total amount of alkoxysilane component (I).

[0058] In the first polymerization step, the polysiloxane macromer obtained by hydrolysis and dehydration condensation of alkoxysilane component (I) may contain a neutral salt. As a result, the polysiloxane may also contain a neutral salt. The amount of neutral salt contained in the polysiloxane is preferably 0.001 to 1 part by weight or less, more preferably 0.005 to 0.1 parts by weight, and even more preferably 0.01 to 0.05 parts by weight per 100 parts by weight of polysiloxane.

[0059] (water) In this manufacturing method, the amount of water used in the first polymerization step is preferably 20 to 100 mol%, more preferably 20 to 90 mol%, even more preferably 25 to 80 mol%, even more preferably 30 to 80 mol%, and particularly preferably 30 to 60 mol% based on the total amount of alkoxy groups directly bonded to silicon atoms in the alkoxysilane component (I). If the amount of water used in the first polymerization step is 20 mol% or more, the hydrolysis and dehydration condensation reaction proceeds sufficiently, and if it is 100 mol% or less, the adhesion and water resistance of the resulting cured product to the substrate can be further improved.

[0060] In the first polymerization step according to one embodiment of the present invention, an organic solvent other than water may be used in addition to water. As such an organic solvent, an organic solvent with high solubility in water is preferred because it is used in combination with water. Furthermore, in order to ensure the solubility of the alkoxysilane component, an organic solvent with 4 or more carbon atoms is preferred. From the above viewpoint, preferred organic solvents include, but are not limited to, propylene glycol methyl ether acetate, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, methanol, ethanol, 1-propanol, 2-propanol, etc. Among these organic solvents, alcohols that are optionally miscible with water are particularly preferred, and more specifically, methanol, ethanol, 1-propanol, 2-propanol, and propylene glycol monomethyl ether are preferred.

[0061] In the first polymerization step, the reaction temperature for hydrolysis and dehydration condensation of alkoxysilane component (I) can be appropriately set by those skilled in the art. For example, an aqueous solution containing alkoxysilane component (I) and a neutral salt may be heated to 50°C to 110°C, and it is preferable to heat it to 50°C to 90°C. Carrying the hydrolysis and dehydration condensation reaction at a temperature of 50°C to 110°C makes it easier to produce polysiloxane macromers. Furthermore, heating at a temperature of 50°C to 90°C or lower is preferable because (a) a polysiloxane macromer with appropriate graftability can be obtained, and (b) unintended evaporation of alcohol produced by the hydrolysis and dehydration condensation reaction can be prevented.

[0062] Furthermore, in the first polymerization step, the reaction time for the hydrolysis-dehydration condensation reaction can be appropriately set by those skilled in the art, but it is preferably within 6 hours, and more preferably within 4 hours, in order to obtain a polysiloxane macromer with appropriate graftability. Also, the lower limit of the reaction time is preferably 30 minutes or more, and more preferably 1 hour or more, in order to obtain a polysiloxane macromer with a sufficiently high degree of condensation.

[0063] (Polysiloxane macromer) Polysiloxane macromers are polymers obtained by hydrolysis and dehydration condensation of alkoxysilane component (I) in the first polymerization step of this manufacturing method. The above polysiloxane macromers are polymers having a block structure in which alkoxysilane compounds having glycidyloxy groups and / or alkoxysilane compounds having epoxycyclohexyl groups, which are subjected to the first polymerization step, are constituent units (main constituent units). In this manufacturing method, polysiloxane macromers are usually obtained in a dissolved state in aqueous solution.

[0064] In one embodiment of the present invention, in a solution containing a polysiloxane macromer (i.e., the solution immediately after the completion of the first polymerization step), the amount of a component unit derived from monoorganotrialalkoxysilane that forms one siloxane bond (hereinafter referred to as T1) and the total amount of a component unit derived from monoorganotrialalkoxysilane that forms two siloxane bonds (hereinafter referred to as T2) are preferably 25 to 60 mol%, more preferably 30 to 55 mol%, and even more preferably 35 to 50 mol%, relative to 100 mol% of the total amount of component units derived from the total alkoxylane compound and alkoxysilane compound. With the above configuration, a polysiloxane macromer with sufficiently high graftability can be obtained, and a polysiloxane having a block structure can be efficiently obtained in the second polymerization step described later.

[0065] Furthermore, in one embodiment of the present invention, the amount of monoorganotrialalkoxysilane (hereinafter referred to as T0) that does not form siloxane bonds (i.e., has not undergone dehydration condensation with other alkoxysilane compounds) relative to 100 mol% of the total amount of alkoxylane compounds and constituent units derived from alkoxysilane compounds in the solution containing the polysiloxane macromer is preferably less than 1 mol%, more preferably less than 0.5 mol%, and even more preferably less than 0.1 mol%. The above configuration has the advantage of increasing the yield of polysiloxane having a block structure in the second polymerization step described later. The lower limit of the amount of T0 is not particularly limited and may be 0 mol%.

[0066] Here, the amount of T0, the amount of T1, and the amount of T2 are, 29 The peak area can be calculated as the percentage (%) of the peak areas derived from T0, T1, and T2 relative to the total peak area of ​​the peaks derived from Q0, Q1, Q2, Q3, Q4, T0, T1, T2, T3, D0, D1, D2, and M0, M1 in an aqueous solution containing polysiloxane macromers, as measured by Si-NMR.

[0067] Here, Q0 is a tetraalkoxysilane that does not form siloxane bonds, and Q1, Q2, Q3, or Q4 are constituent units derived from the tetraalkoxysilane that form one, two, three, or four siloxane bonds, respectively. T0 is a monoorganotrialalkoxysilane that does not form siloxane bonds, and T1, T2, or T3 are constituent units derived from the monoorganotrialalkoxysilane that form siloxane bonds. D0 is the amount of constituent units forming one, two, or three siloxane bonds, D1 or D2 is a constituent unit derived from a diorganodialkoxysilane that forms one or two siloxane bonds, M0 is a triorganomonalkoxysilane that does not form a siloxane bond, and M1 is a constituent unit derived from a triorganomonalkoxysilane that forms one siloxane bond.

[0068] Therefore, the amount T0 can also be expressed as "T0 / (Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)". The amount T1 can also be expressed as "T1 / (Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)". The amount T2 can also be expressed as "T2 / (Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)". Furthermore, the sum of T1 and T2 can also be expressed as "(T1+T2) / (Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)". Also, the amount of T3 can be expressed as "T3 / (Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)".

[0069] In an aqueous solution containing a polysiloxane macromer, a total amount of T1 and T2 of 25-60 mol% indicates that the polysiloxane macromer contains a sufficient amount of reactive functional groups (silanol groups). Therefore, such a polysiloxane macromer can undergo efficient and sufficient graft polymerization in the second polymerization step described later.

[0070] In this manufacturing method, the degree of condensation of the resulting polysiloxane macromer is preferably 70-90%, and more preferably 75-85%, because it ensures good compatibility between the polysiloxane macromer and the alkoxylane component (II) in the second polymerization step. Here, the degree of condensation of the polysiloxane macromer is calculated using the following formula: Degree of condensation (%) = {(1 × amount of T1) + (2 × amount of T2) + (3 × amount of T3)} / 3 The amounts of T0, T1, and T2 in an aqueous solution containing polysiloxane macromers, as well as the degree of condensation of the polysiloxane macromers, can be controlled by adjusting the amount of water used in the hydrolysis-dehydration condensation reaction in the first polymerization step, as well as the type and amount of neutral salts and the reaction temperature.

[0071] The weight-average molecular weight (Mw) of the polysiloxane macromer is not particularly limited, but is preferably 500 to 10000, more preferably 1000 to 9000, and even more preferably 1500 to 8000, as this ensures good compatibility between the polysiloxane macromer and the alkoxylane component (II) in the second polymerization step. The weight-average molecular weight (Mw) of the polysiloxane macromer is calculated using GPC in terms of polystyrene equivalent.

[0072] <(2) Second polymerization step> A second polymerization step according to one embodiment of the present invention involves mixing a solution containing the polysiloxane macromer obtained in the first polymerization step with an alkoxysilane component (II) containing an alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group in a different composition from the alkoxysilane component (I), and then hydrolyzing and dehydrating the polysiloxane macromer and the alkoxysilane component (II) to obtain a solution containing polysiloxane.

[0073] (alkoxysilane component (II)) Alkoxysilane component (II) according to one embodiment of the present invention comprises an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group in a different composition from that of alkoxysilane component (I). Here, "containing an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group in a different composition from that of alkoxysilane component (I)" means that alkoxysilane component (II) contains an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group in a different amount (ratio) and / or a different type from that of alkoxysilane component (I) subjected to the first polymerization step. In addition, alkoxysilane component (II) may also contain other alkoxysilane compounds in addition to the alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group.

[0074] Furthermore, with respect to alkoxysilane compounds having a glycidyloxy group, alkoxysilane compounds having an epoxycyclohexyl group, and other alkoxysilane compounds included in alkoxysilane component (II), the information in section (alkoxysilane component (I)) above shall be appropriately applied in addition to the matters described below.

[0075] In the second polymerization step according to one embodiment of the present invention, as described above, the composition of alkoxysilane component (II) is appropriately adjusted to match the composition of alkoxysilane component (I). The relationship between alkoxysilane component (I) and alkoxysilane component (II) will be explained in detail below.

[0076] The case in which alkoxysilane component (I) includes an alkoxysilane compound having a glycidyloxy group and does not include an alkoxysilane compound having an epoxycyclohexyl group (hereinafter referred to as case A) will be explained.

[0077] In case A, alkoxysilane component (II) may include (A1) an alkoxysilane compound having a glycidyloxy group of a different type from the alkoxysilane compound having a glycidyloxy group included in alkoxysilane component (I), (A2) an alkoxysilane compound having an epoxycyclohexyl group, (A3) an alkoxysilane compound having a glycidyloxy group of a different type from the alkoxysilane compound having a glycidyloxy group included in alkoxysilane component (I), and an alkoxysilane compound having an epoxycyclohexyl group, or (A4) an alkoxysilane compound having a glycidyloxy group of the same type as the alkoxysilane compound having a glycidyloxy group included in alkoxysilane component (I), and an alkoxysilane compound having an epoxycyclohexyl group. Furthermore, the embodiments described above (A1) to (A4) may be combined to the extent that they do not impede the effects of the present invention.

[0078] The case in which alkoxysilane component (I) includes an alkoxysilane compound having an epoxycyclohexyl group and does not include an alkoxysilane compound having a glycidyloxy group (hereinafter referred to as case B) will be explained.

[0079] In case B, alkoxysilane component (II) may include (B1) an alkoxysilane compound having an epoxycyclohexyl group of a different type from the alkoxysilane compound having an epoxycyclohexyl group included in alkoxysilane component (I), (B2) an alkoxysilane compound having a glycidyloxy group, (B3) an alkoxysilane compound having an epoxycyclohexyl group of a different type from the alkoxysilane compound having an epoxycyclohexyl group included in alkoxysilane component (I), and an alkoxysilane compound having a glycidyloxy group, or (B4) an alkoxysilane compound having an epoxycyclohexyl group of the same type as the alkoxysilane compound having an epoxycyclohexyl group included in alkoxysilane component (I), and an alkoxysilane compound having a glycidyloxy group. Furthermore, the embodiments described above (B1) to (B4) may be combined to the extent that they do not impede the effects of the present invention.

[0080] The case in which the alkoxysilane component (I) includes an alkoxysilane compound having a glycidyloxy group and an alkoxysilane compound having an epoxycyclohexyl group (hereinafter referred to as case C) will be explained.

[0081] In case C, alkoxysilane component (II) may include (C1) an alkoxysilane compound having a glycidyloxy group of a different type from the alkoxysilane compound having a glycidyloxy group included in alkoxysilane component (I), (C2) an alkoxysilane compound having an epoxycyclohexyl group of a different type from the alkoxysilane compound having an epoxycyclohexyl group included in alkoxysilane component (I), and (C3) an alkoxysilane compound having a glycidyloxy group of a different type from the alkoxysilane compound having a glycidyloxy group included in alkoxysilane component (I), and (C4) The alkoxysilane compound having an epoxycyclohexyl group may be of a different type from the alkoxysilane compound having an epoxycyclohexyl group contained in alkoxysilane component (I), and (C4) the alkoxysilane compound having a glycidyloxy group of the same type as the alkoxysilane compound having a glycidyloxy group contained in alkoxysilane component (I), and / or the alkoxysilane compound having an epoxycyclohexyl group of the same type as the alkoxysilane compound having an epoxycyclohexyl group contained in alkoxysilane component (I), may be included in a composition different from that of alkoxysilane component (I). Furthermore, the embodiments of (C1) to (C4) above may be combined to the extent that they do not impede the effects of the present invention.

[0082] In cases A to C above, the composition and amount of the alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group, as well as other alkoxysilane compounds used in the second polymerization step (i.e., the composition and amount of alkoxysilane component (II)) can be appropriately set considering the amount of the alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group, as well as other alkoxysilane compounds used in the first polymerization step (i.e., the composition and amount of alkoxysilane component (I)). In this manufacturing method, the total amount of alkoxysilane compounds used in the first polymerization step and alkoxysilane compounds used in the second polymerization step is proportional to the amount of constituent units constituting the resulting polysiloxane. Therefore, the amount, ratio, and composition of the alkoxysilane compound used in the first polymerization step and alkoxysilane compound used in the second polymerization step can be determined in cases A to C above so that the ratio (mol%) of each constituent unit in the resulting polysiloxane is a desired value.

[0083] For example, in case (A4), the amount of the alkoxysilane compound having the same type of glycidyloxy group, which is contained in alkoxysilane component (II), relative to 100 mol% of the total amount of the alkoxysilane compound having the same type of glycidyloxy group, which is contained in alkoxysilane component (I) and alkoxysilane component (II), is, for example, 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, even more preferably 3 mol% or less, and particularly preferably 1 mol% or less.

[0084] For example, in case (B4), the amount of the alkoxysilane compound having the same type of epoxycyclohexyl group, contained in alkoxysilane component (II), relative to 100 mol% of the total amount of the alkoxysilane compound having the same type of epoxycyclohexyl group, containing alkoxysilane component (I) and alkoxysilane component (II), is, for example, The amount is 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, even more preferably 3 mol% or less, and particularly preferably 1 mol% or less.

[0085] For example, in case (C4), the amount of alkoxysilane compound having the same type of glycidyloxy group contained in alkoxysilane component (II) relative to 100 mol% of the total amount of alkoxysilane compounds having the same type of glycidyloxy group contained in alkoxysilane component (I) and alkoxysilane component (II) is, for example, (a) 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less. In that case, the amount of alkoxysilane compound having the same type of epoxycyclohexyl group contained in alkoxysilane component (II) relative to 100 mol% of the total amount of alkoxysilane compounds having the same type of epoxycyclohexyl group contained in alkoxysilane component (I) and alkoxysilane component (II) is, for example, 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. Furthermore, the amount of the alkoxysilane compound having a glycidyloxy group contained in alkoxysilane component (II) is (b) 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. In that case, the amount of the alkoxysilane compound having an epoxycyclohexyl group contained in alkoxysilane component (II) relative to the total amount of the alkoxysilane compounds having the same type of epoxycyclohexyl group contained in alkoxysilane component (I) and alkoxysilane component (II) is, for example, 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less. In this manufacturing method, the molar ratio of alkoxysilane component (I) to alkoxysilane component (II) with respect to the total amount of alkoxysilane component (I) and alkoxysilane component (II) of 100 mol% is preferably 15-85 mol%:85-15 mol%, more preferably 20-80 mol%:80-20 mol%, and particularly preferably 25-75 mol%:75-25 mol%.

[0086] In this manufacturing method, among cases A to C described above, cases (A2) and (B2) are preferred because they allow for the production of polysiloxane with superior weather resistance. That is, one embodiment of the present invention is more preferably in the form of (a) or (b) below.

[0087] (a) A method for producing polysiloxane, comprising: (1) a first polymerization step in which an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group is hydrolyzed and dehydrated in the presence of a neutral salt to obtain a solution containing a polysiloxane macromer; and (2) a second polymerization step in which the solution containing the polysiloxane macromer and an alkoxysilane component (II) containing an alkoxysilane compound having an epoxycyclohexyl group are mixed and hydrolyzed and dehydrated to obtain a solution containing polysiloxane. (b): A method for producing polysiloxane, comprising: (1) a first polymerization step of hydrolyzing and dehydrating an alkoxysilane component (I) containing an alkoxysilane compound having an epoxycyclohexyl group in the presence of a neutral salt to obtain a solution containing a polysiloxane macromer; and (2) a second polymerization step of mixing the solution containing the polysiloxane macromer with an alkoxysilane component (II) containing an alkoxysilane compound having a glycidyloxy group, hydrolyzing and condensing the mixture to obtain a solution containing polysiloxane.

[0088] In one embodiment of the present invention, the types and amounts of alkoxysilane compounds having a glycidyloxy group, alkoxysilane compounds having an epoxycyclohexyl group, and other alkoxysilane compounds are not particularly limited, but for example, it is particularly preferable that the total amount of 3-glycidyloxypropyltrialkoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, methyltrialkoxysilane, and phenyltrialkoxysilane is 90 parts by weight or more, based on 100 parts by weight of the total weight of alkoxysilane components (I) and (II). With this configuration, the curability of the resulting polysiloxane is sufficiently high, and a cured product (coating film) with excellent scratch resistance can be obtained.

[0089] The second polymerization step according to one embodiment of the present invention is carried out in a solution containing the polysiloxane macromer obtained in the first polymerization step. Since the solution contains water and a neutral salt used in the first polymerization step, the hydrolysis and dehydration condensation reaction can be carried out without adding a new neutral salt and / or water, but a new neutral salt and / or water may be added as needed.

[0090] In the second polymerization step, the reaction temperature for the hydrolysis and dehydration condensation of the polysiloxane macromer and the alkoxysilane component (II) can be appropriately set by those skilled in the art, but it is preferable to heat the solution containing the polysiloxane macromer and the alkoxysilane component (II) to 50°C to 110°C. Carrying the hydrolysis and dehydration condensation reaction at a temperature of 50°C to 110°C or lower makes it easier to produce polysiloxane. The reaction time for carrying out the hydrolysis and dehydration condensation reaction can also be appropriately set by those skilled in the art, but it may be, for example, 10 minutes to 12 hours.

[0091] After the second polymerization step (preferably after the de-alcoholization step described later, and more preferably after the maturation step described later), the reaction system can be cooled (for example, to 30°C or below) to obtain the polysiloxane in the form of a solution containing the polysiloxane.

[0092] (3) De-alcoholization process This manufacturing method preferably includes a de-alcoholization step after the second polymerization step, in which the alcohol generated by the hydrolysis reaction of the alkoxylane compound is removed (volatilized) from the solution (solution containing polysiloxane) to obtain a solution containing de-alcoholized polysiloxane. When this manufacturing method includes a de-alcoholization step, the dehydration condensation reaction proceeds efficiently, and the grafting rate of the resulting polysiloxane can be improved.

[0093] The de-alcoholization step is not particularly limited as long as it can remove the alcohol from the solution, but for example, a method of heating the solution and distilling off the alcohol by vacuum distillation is preferred. The conditions for vacuum distillation can be appropriately set by those skilled in the art, but the temperature at this time is preferably 50°C to 110°C, as this facilitates the production of polysiloxane having a block structure. In the de-alcoholization step, it is preferable to remove 80 mol% or more of the alcohol generated by the hydrolysis reaction, and more preferably 90 mol% or more of the alcohol.

[0094] Furthermore, in the de-alcoholization process, organic solvents such as propylene glycol methyl ether acetate (PMA), 1-methoxy-2-propanol, butyl acetate, isobutyl acetate, and methyl isobutyl ketone may be added to the solution to adjust the solid content (SC) of the polysiloxane-containing solution.

[0095] ((4) Aging process) The present manufacturing method preferably includes a maturation step in which the solution containing the polysiloxane (the solution containing the de-alcoholized polysiloxane) is heated after the second polymerization step, and preferably after the de-alcoholization step. When the present manufacturing method includes a maturation step, it is possible to suppress the changes in the obtained polysiloxane (polysiloxane after the maturation step) over time during storage. In the maturation step, the temperature at which the solution containing the polysiloxane is heated is not particularly limited, but from the viewpoint of promoting the dehydration condensation reaction, 40 to 180°C is preferred, 60 to 160°C is more preferred, and 80 to 150°C is even more preferred. In the maturation step, the time for which the solution containing the polysiloxane is heated is not particularly limited, but since the dehydration condensation reaction in the maturation step is a reaction between polymers and is diffusion-controlled, there is a risk that the reaction may not proceed sufficiently if the time is short. Therefore, from the viewpoint of allowing the dehydration condensation reaction to proceed sufficiently, 20 minutes to 7 hours is preferred, 40 minutes to 5 hours is more preferred, and 1 to 3 hours is even more preferred. In other words, during the maturation process, it is particularly preferable to maintain the solution containing the polysiloxane at 80 to 150°C for 1 to 3 hours.

[0096] Furthermore, during the maturation process, organic solvents such as propylene glycol methyl ether acetate (PMA), 1-methoxy-2-propanol, butyl acetate, isobutyl acetate, and methyl isobutyl ketone may be added to the solution. These organic solvents have the advantage of having sufficiently high boiling points, which allows the temperature of the polysiloxane-containing solution subjected to the maturation process to be sufficiently high.

[0097] [3. Polysiloxane] One embodiment of the present invention provides a polysiloxane having two or more block structures, each composed of an alkoxysilane compound having a different type of glycidyloxy group and / or epoxycyclohexyl group. With respect to this polysiloxane, in addition to the matters described below, the description in [2. Method for Producing Polysiloxane] above may be appropriately incorporated.

[0098] The method for providing this polysiloxane is not particularly limited, but for example, it may be produced by the method described in section [2. Method for producing polysiloxane]. That is, this polysiloxane is a polymer having block structures having structural units derived from the alkoxysilane component (I) and block structures having structural units derived from the alkoxysilane component (II), and can also be said to be a polymer containing at least two block structures. The number of block structures contained in this polysiloxane is not particularly limited as long as there are two or more, and for example, it may be a triblock structure or a tetrablock structure.

[0099] The block structure of this polysiloxane may (a) consist solely of constituent units derived from alkoxysilane compounds having a glycidyloxy group, (b) consist solely of constituent units derived from compounds having an epoxycyclohexyl group, or (c) contain both constituent units derived from alkoxysilane compounds having a glycidyloxy group and constituent units derived from alkoxysilane compounds having an epoxycyclohexyl group. In other words, this polysiloxane can be said to have two or more block structures that include alkoxysilane compounds having a glycidyloxy group and / or an epoxycyclohexyl group as constituent units. Furthermore, since alkoxysilane component (I) and alkoxysilane component (II) have different compositions, the compositions of the constituent units of the block structure of this polysiloxane are similarly different. In particular, it is preferable that the polysiloxane has a block structure containing an alkoxysilane compound having a glycidyloxy group as a constituent unit, and a block structure containing an alkoxysilane compound having an epoxycyclohexyl group as a constituent unit, in order to provide a cured product with even better weather resistance.

[0100] Of the above (a) to (c), embodiment (c) is preferred because it can improve the scratch resistance, adhesion, and water resistance of the resulting cured product. In other words, it is preferable that the polysiloxane has constituent units derived from an alkoxysilane compound having a glycidyloxy group and constituent units derived from an alkoxysilane compound having an epoxycyclohexyl group.

[0101] The polysiloxane preferably contains 70 to 100 mol% monoorganotrialalkoxysilane and 0 to 30 mol% diorganodialkoxysilane, based on 100 mol% of the total amount of constituent units derived from the alkoxysilane compound having a glycidyloxy group, the alkoxysilane compound having an epoxycyclohexyl group, and the other alkoxysilane compounds. The proportion of monoorganotrialalkoxysilane is preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, particularly preferably 99 mol% or more, and may also be 100 mol%.

[0102] In this polysiloxane, the total amount of constituent units derived from the alkoxysilane compound having a glycidyloxy group, the alkoxysilane compound having an epoxycyclohexyl group, and the other alkoxysilane compounds, relative to 100 mol% of the total amount of constituent units derived from the alkoxysilane compound having a glycidyloxy group, the alkoxysilane compound having an epoxycyclohexyl group, and the other alkoxysilane compounds, is preferably 50 to 100 mol%, more preferably 60 to 100%, even more preferably 70 to 100 mol%, and may be 100 mol%. When this polysiloxane contains a total of 50 mol% or more of constituent units derived from the alkoxysilane compound having a glycidyloxy group and the alkoxysilane compound having an epoxycyclohexyl group, the density of epoxy groups that form crosslinking points increases, improving the crosslinking density of the resulting cured product and improving scratch resistance.

[0103] In this polysiloxane, the amount of constituent units derived from the alkoxysilane compound having a glycidyloxy group, relative to 100 mol% of the total amount of constituent units derived from the alkoxysilane compound having an epoxycyclohexyl group, is preferably 10 to 99 mol%, more preferably 20 to 95 mol%, and even more preferably 30 to 90 mol%. Furthermore, the amount of constituent units derived from the alkoxysilane compound having an epoxycyclohexyl group is preferably 1 to 90 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 70 mol%. With the above configuration, a polysiloxane with excellent weather resistance and reactivity can be obtained.

[0104] Preferably, the polysiloxane has a composition in which, out of 100 mol% of the total constituent units of the polysiloxane, the amount of constituent units derived from monoorganotrialkoxysilane and forming one siloxane bond (hereinafter referred to as T1), the amount of constituent units derived from monoorganotrialkoxysilane and forming two siloxane bonds (hereinafter referred to as T2), and the amount of constituent units derived from monoorganotrialkoxysilane and forming three siloxane bonds (hereinafter referred to as T3) are each 3 to 80 mol%, and the total amount of T1, T2, and T3 is 90 to 100 mol%. With the above composition, the polysiloxane has good compatibility and reactivity with other resins (e.g., acrylic polyols) contained in the curable resin composition.

[0105] In one embodiment of the present invention, the amount of T1 in the polysiloxane is more preferably 3 to 80 mol%, even more preferably 5 to 60 mol%, and particularly preferably 10 to 40 mol%. The amount of T2 in the polysiloxane is more preferably 10 to 80 mol%, even more preferably 15 to 70 mol%, and particularly preferably 20 to 60 mol%. Furthermore, the amount of T3 in the polysiloxane is more preferably 10 to 80 mol%, even more preferably 30 to 75 mol%, and particularly preferably 50 to 70 mol%. Moreover, the total amount of T1, T2, and T3 is more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%.

[0106] Here, the amounts of T1, T2, and T3 in this polysiloxane are: 29 This can be calculated as the percentage (%) of the peak areas derived from T1, T2, and T3 relative to the total peak area of ​​the peaks derived from Q1, Q2, Q3, Q4, T1, T2, T3, D1, D2, and M1, as measured by Si-NMR.

[0107] Here, Q1, Q2, Q3, or Q4 are constituent units derived from tetraalkoxysilane, forming one, two, three, or four siloxane bonds, respectively; T1, T2, or T3 are quantities of constituent units derived from monoorganotrialalkoxysilane, forming one, two, or three siloxane bonds, respectively; D1 or D2 are constituent units derived from diorganodialkoxysilane, forming one or two siloxane bonds; and M1 is a constituent unit derived from triorganomonalokkoxysilane, forming one siloxane bond.

[0108] Therefore, the amount of T1 in this polysiloxane can also be expressed as "T1 / (Q1+Q2+Q3+Q4+T1+T2+T3+D1+D2+M1)". The amount of T2 can also be expressed as "T2 / (Q1+Q2+Q3+Q4+T1+T2+T3+D1+D2+M1)". The amount of T3 can also be expressed as "T3 / (Q1+Q2+Q3+Q4+T1+T2+T3+D1+D2+M1)". Furthermore, the total amounts of T1, T2, and T3 can also be expressed as "T1+T2+T3 / (Q1+Q2+Q3+Q4+T1+T2+T3+D1+D2+M1)".

[0109] In this polysiloxane, a high amount of T3 (e.g., 50 mol% or more) means that many alkoxy groups have been converted to siloxane bonds, and that the polysiloxane contains a large amount of T3, which has a silsesquioxane structure. The silsesquioxane structure is a structure that combines a dense crosslinking structure with flexibility, and it is a structure that contributes to the scratch resistance and water resistance of the cured product. Conversely, if the proportion of T3 is 0%, the silsesquioxane structure is absent, and it becomes difficult to exhibit the desired physical properties of this polysiloxane.

[0110] The polysiloxane preferably has silanol groups. The presence of silanol groups in the polysiloxane can also be evaluated by its degree of condensation. The presence of silanol groups in the polysiloxane means that its degree of condensation is less than 100%. Here, the degree of condensation is a value calculated by the following formula: Degree of condensation (%) = {(amount of 1 × T1) + (amount of 2 × T2) + (amount of 3 × T3)} / 3 The degree of condensation of this polysiloxane is preferably 90% or less, and more preferably 85% or less. If the degree of condensation of this polysiloxane is 90% or less, the compatibility and reactivity between this polysiloxane and other resins will be good. Furthermore, there is no particular lower limit to the degree of condensation of this polysiloxane, but it can be, for example, 70% or more. If the degree of condensation of this polysiloxane is 70% or more, the shrinkage stress when obtaining the cured product (cured coating film) will not become excessively large, and even when creating a thick cured coating film (for example, a coating film thickness of 20 μm or more), the occurrence of cracks in the coating film can be suppressed.

[0111] The amounts of T1, T2, and T3 in this polysiloxane can be controlled by adjusting the amount of water used in the first and second polymerization steps, the type and amount of catalyst, the reaction temperature, and the amount of alcohol removed in the hydrolysis reaction.

[0112] The weight-average molecular weight (Mw) of this polysiloxane is not particularly limited, but is preferably 2000 to 20000, more preferably 3000 to 15000, and even more preferably 4000 to 10000, in order to provide a cured product with excellent scratch resistance and compatibility. The weight-average molecular weight (Mw) of the polysiloxane is a value calculated using GPC in terms of polystyrene equivalent.

[0113] The epoxy equivalent of the polysiloxane is preferably 150 to 400, more preferably 160 to 300, and more preferably 170 to 250. If the epoxy equivalent of the polysiloxane is 400 or less, a sufficiently cross-linked structure of the polysiloxane can be obtained, resulting in a cured product with high scratch resistance and chemical resistance. If it is 150 or more, the amount of unreacted epoxy groups remaining in the cured product will be reduced.

[0114] In this specification, the epoxy equivalent of polysiloxane refers to the molecular weight per epoxy group contained in the polysiloxane, and specifically, is a value calculated based on the following formula: Epoxy equivalent = weight-average molecular weight (Mw) of polysiloxane / number of epoxy groups per polysiloxane molecule (average number). If the epoxy equivalent of polysiloxane cannot be calculated based on the above formula due to reasons such as the composition of the polysiloxane being unknown, the epoxy equivalent of polysiloxane can be measured in accordance with JIS K7236.

[0115] [4. Curable resin composition] In one embodiment of the present invention, a curable resin composition containing the polysiloxane is provided.

[0116] A curable resin composition according to one embodiment of the present invention (hereinafter referred to as "this curable resin composition") is not particularly limited as long as it contains this polysiloxane, and may be, for example, a curable resin composition containing this polysiloxane, a metal catalyst, and optionally other additives, or a curable resin composition containing this polysiloxane, a metal catalyst, a resin component, a polyisocyanate compound, and optionally other additives.

[0117] (Metal catalyst) The curable resin composition preferably contains a metal catalyst. Suitable metal catalysts include organometallic acid catalysts such as organoaluminum compounds, organotin compounds, organozinc compounds, organotitanium compounds, and organoiron compounds, but among these, organoaluminum compounds (hereinafter referred to as aluminum compounds) are preferred. One of these metal catalysts may be used alone, or two or more may be used in combination.

[0118] In this specification, an aluminum compound refers to a compound having at least one organic group directly bonded to an aluminum atom. Examples of such organic groups include alkyl groups, alkoxy groups, β-dicarbonyl groups, and carboxyl groups. These organic groups may be present individually or in combination of two or more types.

[0119] The aluminum compound is preferably a compound represented by the following general formula (I):

[0120]

Chem.

[0121] (In the formula, R 1 , R 2 and R 3 are an alkyl group, an alkoxy group, a β-dicarbonyl group, or a carboxy group. R 1 , R 2 and R 3 may be the same or different.) In the formula (I), it is preferable that at least one of R 1 , R 2 and R 3 is a β-dicarbonyl compound, and it is more preferable that all of R 1 , R 2 and R 3 are β-dicarbonyl compounds. If at least one of R 1 , R 2 and R 3 is a β-dicarbonyl compound, a curable resin composition excellent in storage stability can be obtained. Here, the β-dicarbonyl compound is a compound having a structure in which two carbonyl groups are bonded to one carbon atom. The β-dicarbonyl compound is not particularly limited, and examples thereof include ethyl acetoacetate, acetylacetone, methyl acetoacetate, dimethyl malonate, and the like. Among them, ethyl acetoacetate is preferable because of its good solubility in the present polysiloxane, (meth)acrylic polyol, and solvent.)

[0122] In the formula (I), as the organic groups other than the β-dicarbonyl compound among R 1 , R 2 and R 3 , for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, etc. may be used.)

[0123] The aluminum compound is not particularly limited as long as it has at least one organic group directly bonded to an aluminum atom, but examples include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), diisopropoxyaluminum ethyl acetate, and aluminum tris(sec butoxide). Among these, aluminum tris(ethyl acetate) and diisopropoxyaluminum ethyl acetate are preferred because they have high solubility in the polysiloxane and (meth)acrylic polyol and high epoxy curability (high Lewis acidity). One of these aluminum compounds may be used alone, or multiple types may be used in mixture form.

[0124] The curable resin composition preferably contains 1 to 20 parts by weight of metal catalyst per 100 parts by weight of polysiloxane, more preferably 2 to 17 parts by weight, and even more preferably 3 to 15 parts by weight. When the content of metal catalyst per 100 parts by weight of polysiloxane in the curable resin composition is 1 to 20 parts by weight, sufficient curing catalytic activity can be achieved.

[0125] (Resin components) This curable resin composition may contain other resin components in addition to the polysiloxane. Such resin components are not particularly limited and include, for example, (meth)acrylic polyol aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic resins. One of these resin components may be used alone, or two or more may be used in combination. Among these other resin components, (meth)acrylic polyols are preferred because they provide a cured product with excellent scratch resistance and chemical resistance.

[0126] In this specification, (meth)acrylic polyol refers to a copolymer having two or more hydroxyl groups in its molecule, obtained by copolymerizing (e.g., radical polymerization) a (meth)acrylic monomer and a monomer having a hydroxyl group. It is preferable that the (meth)acrylic polyol is obtained by radical polymerization. The (meth)acrylic polyol can also be said to be a copolymer containing a (meth)acrylic monomer and a monomer having a hydroxyl group. One type of (meth)acrylic polyol may be used alone, or two or more types may be used in combination.

[0127] In this specification, the (meth)acrylic monomers contained in (meth)acrylic polyols are not particularly limited as long as they have a (meth)acrylic group as a component, but examples include C1-C20 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; C4-C20 cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; C3-C20 aralkyl (meth)acrylates such as allyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and benzyl (meth)acrylate. The (meth)acrylic polyol may contain only one of these (meth)acrylic monomers, or it may contain two or more. (Meth)acrylic monomers can also be described as monomers that have a (meth)acrylic group.

[0128] The monomers containing hydroxyl groups in (meth)acrylic polyols are not particularly limited, but examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth)acrylamide, 4-hydroxystyrene vinyltoluene, and other hydroxyl group-containing vinyl monomers; Place Examples include modified lactones or polyesters having polymerizable carbon-carbon double bonds at their termini, such as lFA-1, PlacelFA-4, PlacelFM-1, and PlacelFM-4 (all manufactured by Daicel Chemical Corporation); and polyoxyalkylenes having polymerizable carbon-carbon double bonds at their termini, such as the Bremmer PP series, Bremmer PE series, and Bremmer PEP series (all manufactured by NOF Corporation), A-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, and MPG130-MA (all manufactured by Nippon Emulsifier Co., Ltd.). (Meth)acrylic polyols may contain only one of these monomers having hydroxyl groups, or two or more.

[0129] The inclusion of (meth)acrylic polyol in this curable resin composition causes the polysiloxane and the (meth)acrylic polyol to crosslink and form a CO-Si structure. By forming such a structure, a cured product with excellent adhesion, durability, and other properties can be obtained.

[0130] Furthermore, the (meth)acrylic polyol may contain monomers other than the (meth)acrylic monomers and monomers having hydroxyl groups mentioned above (other monomers). Examples of other monomers are not particularly limited, but include olefin monomers such as ethylene and propylene, styrene monomers, acid monomers such as maleic acid and fumaric acid, and acid anhydrides such as maleic anhydride. These other monomers may be used individually or in combination of two or more.

[0131] Furthermore, the (meth)acrylic polyol may also contain a monomer having a reactive silicon group as another monomer. That is, the (meth)acrylic polyol may be a (meth)acrylic polyol having a reactive silicon group. Such a (meth)acrylic polyol having a reactive silicon group can be obtained, for example, by radical polymerization of an acrylic monomer containing the (meth)acrylic polyol, a monomer having a hydroxyl group, and a monomer having a reactive silicon group.

[0132] The monomer having a reactive silicon group is not particularly limited, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(n-propoxy)silane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, trimethoxysilylpropylallylamine, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane, γ- Examples include (meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, etc.

[0133] The number of hydroxyl groups contained in the molecule of (meth)acrylic polyol is not particularly limited as long as it is two or more, but for example, it is three or more, preferably five or more, and more preferably seven or more. If the number of hydroxyl groups contained in the molecule of (meth)acrylic polyol is three or more, a dense crosslinked structure can be obtained, and a cured product with excellent scratch resistance can be obtained. Furthermore, there is no particular upper limit to the number of hydroxyl groups contained in the molecule of (meth)acrylic polyol, but for example, it is 50 or less, preferably 40 or less. If the number of hydroxyl groups contained in the molecule of (meth)acrylic polyol is 50 or less, the number of hydroxyl groups remaining in the cured product (coating film) after the curing reaction will be small, and a cured product (coating film) with excellent water resistance can be obtained.

[0134] The hydroxyl value of (meth)acrylic polyol is preferably 20 to 300 mg KOH / g, more preferably 50 to 250 mg KOH / g, even more preferably 80 to 230 mg KOH / g, and particularly preferably 100 to 200 mg KOH / g. When the hydroxyl value of (meth)acrylic polyol is 20 to 300 mg KOH / g, a curable resin composition with high crosslinking density and excellent scratch resistance and chemical resistance can be obtained. In this specification, the hydroxyl value is the value measured according to the standard of JIS K 1557-1.

[0135] The number-average molecular weight (Mn) of the (meth)acrylic polyol is preferably 1,000 to 6,000, more preferably 1,500 to 5,000, even more preferably 2,000 to 4,500, and particularly preferably 2,500 to 4,200. When the number-average molecular weight (Mn) of the (meth)acrylic polyol is 1,000 to 6,000, a cured product with high crosslinking density and excellent scratch resistance and chemical resistance can be obtained.

[0136] The weight-average molecular weight (Mw) of the (meth)acrylic polyol is not particularly limited, but from the viewpoint of compatibility and reactivity of the (meth)acrylic polyol, it is preferably 2,000 to 12,000, more preferably 3,000 to 10,000, and even more preferably 4,000 to 9,000. The weight-average molecular weight (Mw) of the (meth)acrylic polyol is a value calculated on a polystyrene basis using GPC.

[0137] The curable resin composition preferably contains 5 to 100 parts by weight of resin components, more preferably 10 to 90 parts by weight, even more preferably 15 to 80 parts by weight, and particularly preferably 20 to 70 parts by weight, per 100 parts by weight of polysiloxane. When the resin component content in the curable resin composition is 5 parts by weight or more per 100 parts by weight of polysiloxane, it can react sufficiently with the polysiloxane to form a dense crosslinked structure. Furthermore, when the content is 100 parts by weight or less, it has the advantage of not inhibiting the curing reaction of the polysiloxane alone. When the curable resin composition contains two or more types of resin components, the total amount of each resin component is the total resin component content in the curable resin composition.

[0138] (Meth)acrylic polyol manufacturing method (Meth)acrylic polyols can be produced by polymerizing the above-mentioned (meth)acrylic monomer, a monomer having a hydroxyl group, and optionally other monomers by known methods (for example, by heating in the presence of a polymerization initiator).

[0139] The polymerization initiator is not particularly limited, but it is preferably an initiator that can generate radicals by heating (radical polymerization initiator). Examples of such polymerization initiators include organic peroxides such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, and diisopropyl peroxycarbonate. These polymerization initiators may be used individually or in combination of two or more.

[0140] The amount of polymerization initiator used when producing (meth)acrylic polyol is not particularly limited, but is preferably 0.1 to 5.0 parts by weight, more preferably 0.3 to 4.0 parts by weight, and even more preferably 0.5 to 2.0 parts by weight, per 100 parts by weight of the total amount of the monomer having an acrylic group, the monomer having a hydroxyl group, and the other monomers. If the amount of polymerization initiator used is 0.1 parts by weight or more, the polymerization reaction proceeds appropriately. If the amount of polymerization initiator used is 5.0 parts by weight or less, a copolymer with an appropriate molecular weight can be obtained.

[0141] (Meth)acrylic polyols may be produced by polymerizing a (meth)acrylic monomer, a monomer having a hydroxyl group, and optionally other monomers in the presence of a solvent. Such solvents are not particularly limited, but examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum solvents; halogen solvents such as trichloroethylene; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate (IBAC); ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as dibutyl ether, dipentinyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol methyl ether acetate; and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0142] In one embodiment of the present invention, when producing a (meth)acrylic polyol, in addition to the polymerization initiator, A chain transfer agent may be used. By using a chain transfer agent, the molecular weight (number average molecular weight) of the (meth)acrylic polyol can be controlled to a suitable range. The chain transfer agent is not particularly limited, but examples include n-dodecyl mercaptan, t-dodecyl mercaptan, 2-ethylhexyl thioglycolate, n-octyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmaildimethoxysilane, mercaptoethanol, α-methylstyrene dimer, etc. These chain transfer agents may be used individually or in combination of two or more types.

[0143] The amount of the chain transfer agent used when producing (meth)acrylic polyol is not particularly limited, but for example, it is preferably 0.5 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, and even more preferably 0.5 to 6 parts by weight, per 100 parts by weight of the total amount of monomers having acrylic groups, monomers having hydroxyl groups, and other monomers. If the amount of chain transfer agent used is 0.5 parts by weight or more, functional groups (nitrile groups, carboxyl groups, ester groups, etc.) derived from the polymerization initiator (radical generator) are not introduced to the polymer ends of the (meth)acrylic polyol, and the inhibition of curing of the polysiloxane by these functional groups can be suppressed. Furthermore, if the amount of chain transfer agent used is 10 parts by weight or less, it is efficiently introduced to the polymer ends, so there is no risk of it remaining in the curable resin composition as unreacted material (plasticizer).

[0144] (Polyisocyanate compounds) The curable resin composition preferably contains a polyisocyanate compound. By including a polyisocyanate compound in the curable resin composition, a cured product with excellent scratch resistance can be obtained.

[0145] In this specification, a polyisocyanate compound is defined as a compound having two or more isocyanate groups in one molecule. That is, a polyisocyanate compound has two or more isocyanate groups in one molecule.

[0146] The number of isocyanate groups in a polyisocyanate compound is not particularly limited as long as there are two or more per molecule, but it is preferably 2.1 or more, more preferably 2.3 or more, and even more preferably 2.5 or more. The upper limit of the number of isocyanate groups in a polyisocyanate compound is not particularly limited, but for example, it is preferably 20 or less, and more preferably 10 or less.

[0147] The number-average molecular weight (Mn) of the polyisocyanate compound is not particularly limited, but is preferably 150 to 1000, more preferably 200 to 800, and even more preferably 300 to 700, as this results in good compatibility and reactivity. The number-average molecular weight (Mn) of this polysiloxane was calculated using GPC in terms of polystyrene equivalent.

[0148] Conventional known polyisocyanate compounds can be used as the polyisocyanate compound. Examples of such polyisocyanate compounds include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic aliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, and the like.

[0149] Examples of aliphatic polyisocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate. Examples include diisocyanate compounds such as methyl caproate; compounds having three or more isocyanate groups, such as lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, and 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane.

[0150] Examples of alicyclic polyisocyanate compounds include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and 1,3 -Diisocyanate compounds such as bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate; 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethylisocyanate cyclohexane, 3-isocyanate methyl-3,3,5-trimethylcyclohexyl isocyanate, 2-(3-isocyanate propyl)-2,5-di(isocyanate methyl)-bis(isocyanate methyl) Chlo[2,2,1]heptane, 2-(3-isocyanatetopropyl)-2,6-di(isocyanatemethyl)-bicyclo[2,2,1]heptane, 3-(3-isocyanatetopropyl)-2,5-di(isocyanatemethyl)-bicyclo[2,2,1]heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane, 6-(2-isocyanateethyl)-2-i Examples include compounds having three or more isocyanate groups, such as socyanatemethyl-3-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane, and 6-(2-isocyanateethyl)-2-isocyanatemethyl-2-(3-isocyanatetopropyl)-bicyclo[2,2,1]heptane.

[0151] Examples of aromatic aliphatic polyisocyanate compounds include diisocyanate compounds such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanate-1-methylethyl)benzene or mixtures thereof; and compounds having three or more isocyanate groups, such as 1,3,5-triisocyanatemethylbenzene.

[0152] Examples of aromatic polyisocyanate compounds include diisocyanate compounds such as m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4′-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 4,4′-diphenylmethanediisocyanate, 2,4- or 2,6-tolylenediisocyanate, 4,4′-toluidinediisocyanate, and 4,4′-diphenyletherdiisocyanate; and compounds having three or more isocyanate groups such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, 4,4′-diphenylmethane-2,2′,5,5′-tetraisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0153] In one embodiment of the present invention, modified versions of the various polyisocyanate compounds mentioned above may be used as the polyisocyanate compound. Examples of such modified versions include allophanate modified versions, biuret modified versions, isocyanurate modified versions, and the like.

[0154] The polyisocyanate compound is preferably a polyisocyanate having a cyclic, linear, or branched structure, and more preferably one or more selected from the group consisting of aromatic polyisocyanates, alicyclic polyisocyanates, and aromatic aliphatic polyisocyanates. Polyisocyanates having a cyclic structure in the molecule, such as alicyclic polyisocyanate compounds, aromatic aliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds, are more preferred because they significantly improve the physical properties (adhesion, toughness, impact resistance) of the resulting cured product. Among these, aromatic polyisocyanates are even more preferred, and 4,4′-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI) are particularly preferred because the resulting curable resin composition has excellent adhesion.

[0155] Aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are preferred because the resulting cured products exhibit excellent weather resistance. In particular, hexamethylene diisocyanate, isophorone diisocyanate, and their isocyanurate-modified derivatives are preferred.

[0156] When yellowing is a problem when using these polyisocyanate compounds, it is preferable to use aliphatic, alicyclic, or aromatic aliphatic polyisocyanates, with aliphatic or alicyclic polyisocyanates being more preferable.

[0157] In one embodiment of the present invention, the polyisocyanate compound may be a blocked isocyanate obtained by masking the isocyanate group with a blocking agent and inactivating it at room temperature. Examples of blocking agents include alcohols, phenols, oximes, triazoles, caprolactams, and β-dicarbonyl compounds such as acetylacetone and acetate acetate.

[0158] The curable resin composition preferably contains 5 to 150 parts by weight of a polyisocyanate compound per 100 parts by weight of the polysiloxane, more preferably 10 to 120 parts by weight, even more preferably 12 to 100 parts by weight, and particularly preferably 15 to 70 parts by weight. When the polyisocyanate compound content in the curable resin composition per 100 parts by weight of the polysiloxane is 5 parts by weight or more, a cured product with excellent elastic modulus can be provided, and when it is 150 parts by weight or less, a cured product with sufficient toughness can be provided.

[0159] (solvent) The curable resin composition preferably further contains a solvent.

[0160] Various compounds can be used as solvents, without any particular limitations. More specifically, examples of solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum-based solvents; halogen solvents such as trichloroethylene; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate (IBAC), and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as propylene glycol methyl ether acetate (PMA), dibutyl ether, dipentinyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Among these, ester solvents and ether solvents are preferred because they have high solubility in the polysiloxane and (meth)acrylic polyol, and high volatility during spray coating, with isobutyl acetate, methoxypropyl acetate, and propylene glycol methyl ether acetate being particularly preferred. These solvents may be used individually or in combination of two or more.

[0161] The solvent content in this curable resin composition is preferably 40 to 80% by weight, more preferably 45 to 75% by weight, and even more preferably 50 to 70% by weight, based on 100% by weight of the total amount of the curable resin composition. When the solvent content in this curable resin composition is 40% by weight or more, a curable composition with low viscosity, high thixotropy, and excellent workability can be obtained. Furthermore, when the solvent content in this curable resin composition is 80% by weight or less, a cured product with sufficient film thickness can be obtained in a single coating.

[0162] (Dehydrating agent) The curable resin composition preferably further contains a dehydrating agent. When the curable resin composition contains a dehydrating agent, it has the advantage of excellent storage stability.

[0163] The dehydrating agent is not particularly limited, but examples include tosyl isocyanate, vinyltrimethoxysilane, calcium oxide, zeolite, p-toluenesulfonyl isocyanate, 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine, etc. These dehydrating agents may be used alone or in combination of two or more.

[0164] The content of the dehydrating agent in this curable resin composition is, for example, 0.1 to 10% by weight, preferably 0.5 to 7.0% by weight, and more preferably 1.0 to 5.0% by weight, based on 100% by weight of the total amount of the curable resin composition. When the content of the dehydrating agent in this curable resin composition is 0.1% by weight or more, effective dehydration can be achieved for the curable resin composition. Furthermore, when the content of the dehydrating agent in this curable resin composition is 10% by weight or less, it has the advantage of being easy to remove from the coating film because it volatilizes without remaining on the cured product (coating film) after drying and curing.

[0165] (Stabilizer) Preferably, the curable resin composition further contains a stabilizer. When the curable resin composition contains a stabilizer, it is possible to provide a curable resin composition with excellent storage stability, and a cured product with excellent adhesion, scratch resistance, and chemical resistance.

[0166] The stabilizers are not particularly limited, but examples include acetylacetone, ethyl acetoacetate, methyl acetoacetate, and dimethyl malonate. These stabilizers may be used individually or in combination of two or more.

[0167] The stabilizer content in this curable resin composition is, for example, 0.5 to 10% by weight, preferably 1.0 to 5.0% by weight, and more preferably 1.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition. When the stabilizer content in this curable resin composition is 0.5% by weight or more, a curable resin composition with excellent storage stability can be provided. Furthermore, when the stabilizer content in this curable resin composition is 10% by weight or less, it has the advantage of not causing curing inhibition because it rapidly volatilizes from the coating liquid / coating film during drying and curing of the curable resin composition (coating liquid / coating film).

[0168] (Other ingredients) The curable resin composition may contain additives commonly used in the art, to the extent that it achieves the effects of the present invention. Examples of such additives include fillers, flame retardants, dispersants, defoamers, plasticizers, tackifiers, leveling agents, thixotropic agents, epoxy resins, antioxidants, light stabilizers, UV absorbers, silane coupling agents, hydrolysis stabilizers, titanate coupling agents, aluminate coupling agents, mold release agents, antistatic agents, lubricants, low shrinkage agents, silicone surfactants, and water. The composition may contain only one additive or two or more additives. The amounts of these additives can be appropriately determined by those skilled in the art depending on their intended use.

[0169] <Filling material> This curable resin composition may contain fillers. The fillers are not particularly limited, but examples include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrated silicic acid, and carbon black; powdered fillers such as heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, diatomaceous earth, calcined clay, clay, talc, barite, anhydrous gypsum, titanium dioxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc oxide, mica, zinc oxide, lead white, lithopone, zinc sulfide, shirasu balloons, glass microballoons, organic microballoons of phenolic resin or vinylidene chloride resin, PVC powder, PMMA powder, etc.; and fibrous fillers such as asbestos, glass fibers, and filaments. In addition to the above, other coloring pigments such as titanium dioxide, lead chromate, chromium oxide, ultramarine, cobalt blue, cyanine blue, cyanine green, lake red, and quinacridone red can also be used.

[0170] The filler content in this curable resin composition is, for example, 1.0 to 50% by weight, preferably 5.0 to 40% by weight, and more preferably 10 to 30% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0171] <Flame retardant> This curable resin composition may contain a flame retardant. The flame retardant is not particularly limited, but examples include ammonium polyphosphate, phosphorus-based plasticizers such as tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite. These flame retardants may be used individually or in combination of two or more.

[0172] A wide range of conventionally known ammonium polyphosphates can be used as the aforementioned ammonium polyphosphate. Among these, from the viewpoint of water resistance, surface-treated ammonium polyphosphates such as ammonium polyphosphate coated with resin and microencapsulated, or surface-modified ammonium polyphosphate, are preferred, and those whose surface is coated with melamine formaldehyde resin are even more preferred.

[0173] The flame retardant content in this curable resin composition is, for example, 0.1 to 10% by weight, preferably 0.5 to 5.0% by weight, and more preferably 1.0 to 4.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0174] <Dispersant> This curable resin composition may contain a dispersant. As a dispersant, a pigment dispersion paste obtained by mixing and dispersing a pigment and a dispersant according to a known method can be incorporated and used. Commercially available dispersants can also be used. For example, ANTI-TERRA(registered trademark)-U, ANTI-TERRA(registered trademark)-U100, ANTI-TERRA(registered trademark)-204, ANTI-TERRA(registered trademark)-205, DISPERBYK(registered trademark)-101, DISPERBYK(registered trademark)-102, DISPERBYK(registered trademark)-103, DISPERBYK(registered trademark)-106, DISPERBYK(registered trademark)-108, DISPERBYK(registered trademark)-109, DISPERBYK(registered trademark) Trademark)-110, DISPERBYK(Registered Trademark)-111, DISPERBYK(Registered Trademark)-112, DISPERBYK(Registered Trademark)-116, DISPERBYK(Registered Trademark)-130, DISPERBYK(Registered Trademark)-140, DISPERBYK(Registered Trademark)-142, DISPERBYK(Registered Trademark)-145, DISPERBYK(Registered Trademark)-161, DISPERBYK(Registered Trademark)-162, DISPERBYK(Registered Trademark)-163, DISPERBYK(Registered Trademark) Registered Trademark)-164, DISPERBYK(Registered Trademark)-166, DISPERBYK(Registered Trademark)-167, DISPERBYK(Registered Trademark)-168, DISPERBYK(Registered Trademark)-170, DISPERBYK(Registered Trademark)-171, DISPERBYK(Registered Trademark)-174, DISPERBYK(Registered Trademark)-180, DISPERBYK(Registered Trademark)-182, DISPERBYK(Registered Trademark)-183, DISPERBYK(Registered Trademark)-184, DISPERBYK( Registered Trademark)-185, DISPERBYK(Registered Trademark)-2000, DISPERBYK(Registered Trademark)-2001, DISPERBYK(Registered Trademark)-2008, DISPERBYK(Registered Trademark)-2009, DISPERBYK(Registered Trademark)-2022, DISPERBYK(Registered Trademark)-2025, DISPERBYK(Registered Trademark)-2050, DISPERBYK(Registered Trademark)-2070, DISPERBYK(Registered Trademark)-2096, DISPERBYK(Registered Trademark)-2150,DISPERBYK(registered trademark)-2155, DISPERBYK(registered trademark)-2163, DISPERBYK(registered trademark)-2164, BYK(registered trademark)-P104, BYK(registered trademark)-P104S, BYK(registered trademark)-P105, BYK(registered trademark)-9076, BYK(registered trademark)-9077, BYK(registered trademark)-220S, ANTI-TERRA(registered trademark)-250, DISPERBYK(registered trademark)-187, DISPERBYK(registered trademark)-190, DISPERBYK(registered trademark)-191 DISPERBYK(registered trademark)-192, DISPERBYK(registered trademark)-193, DISPERBYK(registered trademark)-194, DISPERBYK(registered trademark)-198, DISPERBYK(registered trademark)-2010, DISPERBYK(registered trademark)-2012, DISPERBYK(registered trademark)-2015, DISPERBYK(registered trademark)-2090, DISPERBYK(registered trademark)-2091, DISPERBYK(registered trademark)-2095 (all manufactured by Big Chemie), DISPARLON(registered trademark) )2150, DISPARLON(registered trademark)KS-860, DISPARLON(registered trademark)KS-873N, DISPARLON(registered trademark)7004, DISPARLON(registered trademark)1831, DISPARLON(registered trademark)1850, DISPARLON(registered trademark)1860, DISPARLON(registered trademark)DA-1401, DISPARLON(registered trademark)PW-36, DISPARLON(registered trademark)DA-1200, DISPARLON(registered trademark)DA-550, DISPARLON(registered trademark) Examples include DA-703-50, DISPARLON® DA-7301, DISPARLON® DN-900, DISPARLON® DA-325, DISPARLON® DA-375, DISPARLON® DA-234 (all manufactured by Kusumoto Kasei Co., Ltd.), EFKA POLYMER 4550 (manufactured by EFKA), Solspers® 27000, Solspers® 41000, Solspers® 53095 (all manufactured by Abyssia).

[0175] The number-average molecular weight of the dispersant is preferably 1,000 to 100,000, preferably 2,000 to 50,000, and more preferably 4,000 to 50,000.

[0176] If the number-average molecular weight of the dispersant is 1000 or more, sufficient dispersion stability can be obtained, and if it is 100,000 or less, there is no risk of the composition becoming too viscous, resulting in a composition with excellent handling properties.

[0177] The dispersant content in this curable resin composition is, for example, 0.1 to 10% by weight, preferably 0.3 to 5.0% by weight, and more preferably 0.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0178] <Antifoaming agent> This curable resin composition may contain an antifoaming agent. The antifoaming agent is not particularly limited, but commercially available ones can be used. Examples of such commercially available antifoaming agents include BYK(registered trademark)-051, BYK(registered trademark)-052, BYK(registered trademark)-053, BYK(registered trademark)-054, BYK(registered trademark)-055, BYK(registered trademark)-057, BYK(registered trademark)-1752, BYK(registered trademark)-1790, BYK(registered trademark)-060N, BYK(registered trademark)-063, BYK(registered trademark)-065, BYK(registered trademark)-066N, BYK(registered trademark)-067A, BYK(registered trademark)-077, and BYK(registered trademark). -088, BYK(registered trademark)-141, BYK(registered trademark)-354, BYK(registered trademark)-392, BYK(registered trademark)-011, BYK(registered trademark)-012, BYK(registered trademark)-017, BYK(registered trademark)-018, BYK(registered trademark)-019, BYK(registered trademark)-020, BYK(registered trademark)-021, BYK(registered trademark)-022, BYK(registered trademark)-023, BYK(registered trademark)-024, BYK(registered trademark)-025, BYK(registered trademark)-028, BYK(registered trademark)-038, BY Antifoaming agents such as K(registered trademark)-044, BYK(registered trademark)-093, BYK(registered trademark)-094, BYK(registered trademark)-1610, BYK(registered trademark)-1615, BYK(registered trademark)-1650, BYK(registered trademark)-1730, BYK(registered trademark)-1770 (all manufactured by Big Chemie Co., Ltd.), and DISPARLON(registered trademark)OX-880EF, DISPARLON(registered trademark)OX-881, DISPARLON(registered trademark)OX-883, DISPARLON(registered trademark)OX-883HF, DI Acrylic defoamers such as SPARLON(registered trademark) OX-70, DISPARLON(registered trademark) OX-77EF, DISPARLON(registered trademark) OX-60, DISPARLON(registered trademark) OX-710, DISPARLON(registered trademark) OX-720, DISPARLON(registered trademark) OX-720EF, DISPARLON(registered trademark) OX-750HF, DISPARLON(registered trademark) LAP-10, DISPARLON(registered trademark) LAP-20, DISPARLON(registered trademark) LAP-30, etc.Examples include silicone-acrylic composite defoamers such as DISPARLON® OX-66 and DISPARLON® OX-715, vinyl-based defoamers such as DISPARLON® 1950, DISPARLON® 1951, DISPARLON® 1952, DISPARLON® P-410EF, DISPARLON® P-420, DISPARLON® P-450, DISPARLON® P-425, and DISPARLON® PD-7, and silicone-based defoamers such as DISPARLON® 1930N and DISPARLON® 1934 (all manufactured by Kusumoto Kasei Co., Ltd.).

[0179] The amount of the defoaming agent in this curable resin composition is, for example, 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, and more preferably 0.3 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0180] <Tackifier> This curable resin composition may contain a tackifier. The tackifier is not particularly limited, and any tackifier commonly used at room temperature, whether solid or liquid, can be used. Specifically, examples include styrene-based block copolymers such as styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylenebutylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS), as well as their hydrogenated derivatives, phenol resins, modified phenol resins (e.g., cashew oil-modified phenol resin, tall oil-modified phenol resin, etc.), terpene phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone indene resins, rosin-based resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene-based resins, styrene copolymer resins, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene-based resins, DCPD resins, and petroleum resins. The above tackifiers may be used individually or in combination of two or more types.

[0181] The content of the tackifier in this curable resin composition is, for example, 0.1 to 10% by weight, preferably 0.3 to 5.0% by weight, and more preferably 0.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0182] <Leveling agent> This curable resin composition may contain a leveling agent. The leveling agent is not particularly limited, but commercially available ones can be used. Examples of such commercially available leveling agents include BYKETOL®-OK, BYKETOL®-SPECIAL, BYKETOL®-AQ, BYKETOL®-WS (all manufactured by BYKETOL®), DISPARLON® 1970, DISPARLON® 230, DISPARLON® LF-1980, DISPARLON® LF-1982, DISPARLON® LF-1983, DISPARLON® LF-1984, and DISPARLON® LF-1985 (all manufactured by Kusumoto Chemical Co., Ltd.).

[0183] The leveling agent content in this curable resin composition is, for example, 0.05 to 5.0% by weight, preferably 0.1 to 4.0% by weight, and more preferably 0.2 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0184] <Thixotropic agent> This curable resin composition may contain a thixotropic agent (anti-sagging agent). While not particularly limited, examples of anti-sagging agents include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. The fumed silica mentioned above as a filler can also be used as a thixotropic agent. Furthermore, using rubber powder with a particle size of 10 to 500 μm, as described in Japanese Patent Publication No. 11-349916, or organic fibers, as described in Japanese Patent Publication No. 2003-155389, can yield a composition with high thixotropy and good workability. These thixotropic agents (anti-sagging agents) may be used individually or in combination of two or more.

[0185] The content of the thixotropic agent in this curable resin composition is, for example, 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, and more preferably 0.3 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0186] <Epoxy resin> This curable resin composition may contain an epoxy resin. The epoxy resin is not particularly limited, but examples of known epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, hydrogenated bisphenol A (or F) type epoxy resin, glycidyl ether type epoxy resin, aminoglycidyl ether resin, and epoxy compounds obtained by adding bisphenol A (or F) compounds, polybasic acids, etc., to these epoxy resins.

[0187] The epoxy resin content in this curable resin composition is, for example, 5.0 to 50% by weight, preferably 7.0 to 40% by weight, and more preferably 10 to 30% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0188] <Antioxidant> This curable resin composition may contain an antioxidant (anti-aging agent). When the composition contains an antioxidant, the heat resistance of the resulting cured product can be improved. The antioxidant is not particularly limited, but examples include hindered phenols, monophenols, bisphenols, and polyphenols. Among these, hindered phenols are preferred. In one embodiment of the present invention, as an antioxidant, hindered amine-based photostabilizers such as Chinuvin® 622LD, Chinuvin® 144, CHIMASSORB® 944LD, CHIMASSORB® 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARKLA-57, MARKLA-62, MARKLA-67, MARKLA-63, MARKLA-68 (all manufactured by Asahi Denka Kogyo Co., Ltd.); Sanol® LS-770, Sanol® LS-765, Sanol® LS-292, Sanol® LS-2626, Sanol® LS-1114, Sanol® LS-744 (all manufactured by Sankyo Co., Ltd.) may also be used.

[0189] The antioxidant content in this curable resin composition is, for example, 0.1 to 5.0% by weight, preferably 0.3 to 4.0% by weight, and more preferably 0.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0190] <Light stabilizer> This curable resin composition may contain a light stabilizer. When the composition contains a light stabilizer, photo-oxidative degradation of the resulting cured product can be prevented. The light stabilizer is not particularly limited, but examples include benzotriazole, hindered amine, and benzoate compounds. Among these, hindered amine compounds are preferred. In particular, tertiary amine-containing hindered amine light stabilizers are preferred because they can improve the storage stability of the composition. More specifically, examples of tertiary amine-containing hindered amine light stabilizers include CHINUVIN® 622LD, CHINUVIN® 144, CHIMASSORB® 119FL (all manufactured by BASF); MARK LA-57, LA-62, LA-67, LA-63 (all manufactured by ADEKA Corporation); and SANOL® LS-765, LS-292, LS-2626, LS-1114, LS-744 (all manufactured by Sankyo Co., Ltd.).

[0191] The content of the light stabilizer in this curable resin composition is, for example, 0.1 to 5.0% by weight, preferably 0.3 to 4.0% by weight, and more preferably 0.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0192] <UV absorber> This curable resin composition may contain an ultraviolet absorber. When the composition contains an ultraviolet absorber, the surface weather resistance of the resulting cured product can be improved. The ultraviolet absorber is not particularly limited, but examples include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate compounds, with benzotriazole-based compounds being particularly preferred.

[0193] In one embodiment of the present invention, it is particularly preferable to use a mixture of a phenol-based or hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber.

[0194] The amount of ultraviolet absorber in the curable resin composition is, for example, 0.1 to 5.0% by weight, preferably 0.3 to 4.0% by weight, and more preferably 0.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0195] <Silane coupling agent> The curable resin composition may contain a silane coupling agent. When the composition contains a silane coupling agent, adhesion can be improved. The silane coupling agent is not particularly limited, but examples include isocyanate group-containing silanes such as γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropylmethyldiethoxysilane, γ-isocyanatetopropylmethyldimethoxysilane, (isocyanatemethyl)trimethoxysilane, (isocyanatemethyl)dimethoxymethylsilane, (isocyanatemethyl)triethoxysilane, and (isocyanatemethyl)diethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-(2-aminoethyl)aminopropylmethyl Dimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N T-Silanes containing amino groups such as bis[3-(trimexysilyl)propyl]ethylenediamine; Ketimine-type silanes such as N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine; Silanes containing mercapto groups such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4- Examples include epoxy group-containing silanes such as epoxycyclohexyl(ethyltriethoxysilane); carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis(2-methoxyethoxy)silane, and N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, and methacryloyloxymethyltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such as tris(3-trimethoxysilylpropyl)isocyanurate. Furthermore, derivatives obtained by modifying these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkyl silanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0196] The silane coupling agent content in this curable resin composition is, for example, 0.1 to 5.0% by weight, preferably 0.3 to 4.0% by weight, and more preferably 0.5 to 3.0% by weight, based on 100% by weight of the total amount of the curable resin composition.

[0197] This curable resin composition may contain moisture derived from the above-mentioned components and other components. If the curable resin composition contains moisture, the storage stability of the curable resin composition may be impaired. Therefore, the moisture content in this curable resin composition is preferably 0.3% by weight or less, more preferably 0.2% by weight or less, and more preferably 0.1% by weight or less, based on 100% by weight of the total amount of the curable resin composition. The lower limit is not particularly limited and may be 0% by weight.

[0198] (others) The curable resin composition may be a one-component type or a multi-component type. A one-component curable resin composition is prepared by pre-mixing all the components and then sealing and storing it. A one-component curable resin composition can provide a cured product by curing with moisture in the air after use. On the other hand, a multi-component curable resin composition can provide a cured product by separately manufacturing and storing a first liquid containing resin components and a second liquid containing a curing catalyst, and mixing the first liquid and the second liquid immediately before use.

[0199] In one embodiment of the present invention, the curable resin composition is preferably a multi-component curable resin composition.

[0200] In this embodiment, the multi-component curable resin composition preferably contains the polysiloxane and resin component (e.g., (meth)acrylic polyol) in the curable resin composition as the first liquid, and more preferably contains the polysiloxane and resin component as the first liquid, and a polyisocyanate compound and a metal catalyst as the second liquid. The first liquid can be said to be the main component of the multi-component curable resin composition, and the second liquid can be said to be the curing agent of the multi-component curable resin composition.

[0201] (Method for producing curable resin compositions) The curable resin composition can be produced by mixing the above-mentioned components (the polysiloxane and, if necessary, resin components, polyisocyanate compounds, metal catalysts, and other components) by known methods. The mixing method is not particularly limited, but examples include using a mixing machine such as a mixing tank with stirring blades such as propeller-type / oar-type, a planetary mixer, a kneader, a hobbalt mixer, a high-speed mixer, a line mixer, a roll mill, a sand mill, an attritor, or a twin-shaft mixer.

[0202] Furthermore, when a multi-component curable resin composition is obtained, the curable resin composition is obtained by further mixing the first and second liquids obtained by the method described below. In this case, methods for mixing the first and second liquids include, for example, mixing each component with a hand mixer or static mixer, kneading at room temperature or under heating using a planetary mixer, disperser, roll, kneader, etc., or dissolving the components using a small amount of a suitable solvent and then mixing.

[0203] In the method for producing this curable resin composition, the above-mentioned components may be mixed simultaneously, or each component may be added, mixed, and homogenized sequentially. It is preferable to add each component, mix, and homogenize sequentially, as this yields a more uniformly mixed composition.

[0204] (Multi-component curable resin composition) In one embodiment of the present invention, a multi-component curable resin composition containing the polysiloxane as the first liquid is provided (hereinafter referred to as the multi-component curable resin composition). By using the multi-component curable resin composition containing the polysiloxane as the first liquid, a cured product with excellent weather resistance can be obtained.

[0205] (1st liquid) The first liquid of this multi-component curable resin composition comprises the polysiloxane and, preferably, a resin component. The polysiloxane and resin component are as described in sections [3. Polysiloxane] and (Resin Component) above, respectively.

[0206] (2nd liquid) The second liquid of this multi-component curable resin composition preferably contains a polyisocyanate compound and a metal catalyst. The polyisocyanate compound and metal catalyst are those described in the above sections (Polyisocyanate Compound) and (Metal Catalyst), respectively. The second liquid functions as a curing agent in the multi-component curable resin composition.

[0207] In one embodiment of the present invention, the second liquid may contain other components in addition to the polyisocyanate compound and the metal catalyst. Such components are not particularly limited and include, for example, solvents, leveling agents, dehydrating agents, stabilizers, and organic resins that do not have hydroxyl groups.

[0208] As described above, this multi-component curable resin composition can be prepared by separately manufacturing and storing a first liquid containing the polysiloxane and a second liquid containing a curing agent, and then mixing the first liquid and the second liquid immediately before use to provide a cured product.

[0209] The mixing ratio of the first liquid and the second liquid in this multi-component curable resin composition can be appropriately adjusted depending on the application. The mixing ratio of the first liquid and the second liquid in this multi-component curable resin composition is, for example, 20:1 to 1:1, preferably 15:1 to 2:1, and more preferably 10:1 to 3:1. If the mixing ratio of the first liquid and the second liquid is 10:1 to 2:1, a multi-component curable resin composition that is easy to mix and less prone to performance inconsistencies can be provided.

[0210] This multi-component curable resin composition allows for the addition of colorants and other substances during the mixing of the first and second components. This offers advantages such as providing a wide range of sealants in various colors to match the siding boards, even from a limited selection of curable resin compositions. Therefore, multi-component curable resin compositions can easily meet market demands for multi-color options and are suitable for applications such as low-rise buildings. For colorants, a paste made by mixing pigments, plasticizers, and fillers as needed is preferable due to its high workability.

[0211] Furthermore, in multi-component curable resin compositions, a retarder can be added during the mixing of the multi-component components. This allows for fine-tuning of the curing speed at the work site.

[0212] [5. Cured product] In one embodiment of the present invention, a cured product (hereinafter referred to as "the cured product") obtained by curing the curable resin composition or the multi-component curable resin composition is provided. Hereinafter, "the curable resin composition" and "the multi-component curable resin composition" may be collectively referred to as "the curable resin composition, etc."

[0213] This cured product is formed by curing this curable resin composition, etc. Preferably, this cured product is formed by mixing a first liquid (main component) containing this polysiloxane and resin components with a second liquid (curing agent) containing a polyisocyanate compound and a metal catalyst, and then heating and curing the resulting curable resin composition. If this curable resin composition contains volatile components such as solvents, these volatile components will volatilize due to heating during curing. Therefore, this cured product is substantially free of the volatile components contained in this curable resin composition.

[0214] The heating temperature for curing this curable resin composition is not particularly limited, but is usually 50 to 200°C, however, 60 to 120°C is preferred, 70 to 110°C is more preferred, and 80 to 100°C is even more preferred. The cured product can have excellent scratch resistance even when formed at relatively low temperatures such as 60 to 120°C.

[0215] The heating time for curing this curable resin composition is not particularly limited, but from the viewpoint of balancing cost and the progress of the curing reaction, 10 to 120 minutes is preferred, 15 to 100 minutes is more preferred, and 30 to 60 minutes is even more preferred.

[0216] The thickness of the cured product is not particularly limited, but is preferably 1 to 100 μm. If the thickness of the cured product is 1 μm or more, the scratch resistance and water resistance of the cured coating film (cured product) will be good. If the thickness of the cured product is 100 μm or less, cracks due to curing shrinkage are less likely to occur. More preferably, it is 5 to 50 μm, and even more preferably 10 to 40 μm.

[0217] (Application) This curable resin composition and its cured products can be used in a variety of applications. For example, transparent materials, optical materials, optical lenses, optical films, optical sheets, adhesives for optical components, optical adhesives for optical waveguide coupling, adhesives for fixing peripheral components of optical waveguides, adhesives for bonding DVDs, adhesives, dicing tapes, electronic materials, insulating materials (including printed circuit boards, wire insulation, etc.), high-voltage insulating materials, interlayer insulating films, insulating packings, insulating coatings, adhesives, high-heat-resistant adhesives, high-heat-dissipation adhesives, optical adhesives, adhesives for LED elements, adhesives for various substrates, adhesives for heat sinks, paints, inks, colored inks, coating materials (including hard coats, sheets, films, coatings for optical discs, coatings for optical fibers, etc.), molding materials (sheets, films, FRP) It can be applied to sealing materials, potting materials, encapsulating materials, encapsulating materials for light-emitting diodes, reflectors and reflectors for light-emitting diodes, optoelectronic semiconductor encapsulating materials, liquid crystal sealants, sealants for display devices, encapsulating materials for electrical materials, encapsulating materials for solar cells, high heat-resistant sealants, resist materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, materials for color filters, materials for photopolymerization, materials for electronic paper, materials for holograms, materials for solar cells, materials for fuel cells, display materials, recording materials, vibration-damping materials, waterproofing materials, moisture-proofing materials, heat-shrinkable rubber tubes, O-rings, photosensitive drums for copiers, solid electrolytes for batteries, and gas separation membranes. In addition, it can be applied to concrete protective materials, linings, soil injection agents, thermal storage materials, sealants for sterilization equipment, contact lenses, oxygen enrichment membranes, and as an additive to other resins, etc.

[0218] Furthermore, by mixing the first and second liquids of this curable resin composition, applying the resulting mixture to a substrate, and curing the mixture using a heat source to form a cured coating, a laminate containing this cured material can be obtained. This laminate can be suitably used for front panels of personal computers, smartphones, tablets, etc., windows of automobiles, protective materials for lamps of automobiles, films, and the like.

[0219] The substrate is not particularly limited and may be, for example, metal (e.g., aluminum, stainless steel, copper, iron, etc.), ceramics, glass, cement, ceramic substrates, stone, plastics (e.g., polycarbonate (PC), acrylic, ABS, PC-ABS alloy, polyethylene terephthalate (PET), etc.), wood, paper, fibers, etc. The substrate may also be a film or a sheet. This curable resin composition can be suitably used for coating automobiles, buildings, home appliances, industrial equipment, etc. Since this curable resin composition hardens upon heating, it is particularly suitable for forming a coating film on the surface of substrates with complex shapes. Furthermore, as described above, this curable resin composition can achieve excellent scratch resistance even when cured at relatively low temperatures of 60 to 120°C. Therefore, even if the substrate is an organic substrate, damage to the substrate due to heating during curing can be suppressed, giving it the advantage of being suitably usable on organic substrates as well.

[0220] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0221] In other words, one aspect of the present invention includes the following: <1> (1) A first polymerization step in which an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group is hydrolyzed and dehydrated in the presence of water and a neutral salt to obtain a solution containing a polysiloxane macromer, (2) A second polymerization step in which the solution containing the polysiloxane macromer and an alkoxysilane component (II) containing an alkoxysilane compound having a glycidyloxy group and / or epoxycyclohexyl group in a different composition from the alkoxysilane component (I) are mixed, and the polysiloxane macromer and the alkoxysilane component (II) are hydrolyzed and dehydrated to obtain a solution containing polysiloxane, A method for producing polysiloxanes containing [the specified ingredient]. <2> The total amount of 3-glycidyloxypropyltrialkoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, methyltrialkoxysilane, and phenyltrialkoxysilane is 90 parts by weight or more per 100 parts by weight of the total weight of alkoxysilane component (I) and alkoxysilane component (II). <1> A method for producing polysiloxane as described above. <3> The total amount of T1 and T2 in the solution containing the polysiloxane macromer is 25 to 60 mol%, relative to 100 mol% of the total amount of the alkoxylane compound derived from the alkoxysilane component (I) and the constituent units derived from the alkoxysilane component (I), and The amount of T0 is less than 1 mol%, <1> or <2> A method for producing polysiloxane as described above.

[0222] (Here, T1 or T2 is a constituent unit of the polysiloxane macromer that is derived from a monoorganotrialkoxysilane and forms one or two siloxane bonds, respectively, and T0 is a monoorganotrialkoxysilane that does not form siloxane bonds and is contained in the solution containing the polysiloxane macromer.) <4> Furthermore, (3) a de-alcoholization step is included, in which the solution containing the polysiloxane is heated to obtain a solution containing de-alcoholized polysiloxane. <1> ~ <3> A method for producing polysiloxane as described in any one of the following. <5> Furthermore, (4) a maturation step in which the solution containing the polysiloxane is heated, <1> ~ <4> A method for producing polysiloxane as described in any one of the following. <6> The epoxy equivalent of the polysiloxane is 150 to 400. <1> ~ <5> A method for producing polysiloxane as described in any one of the following. <7> The polysiloxane comprises a structural unit having a glycidyloxy group and a structural unit having an epoxycyclohexyl group. <1> ~ <6> A method for producing polysiloxane as described in any one of the following. <8> The polysiloxane according to claim 8, comprising, as the block structure, a block structure containing an alkoxysilane compound having a glycidyloxy group as a constituent unit, and a block structure containing an alkoxysilane compound having an epoxycyclohexyl group as a constituent unit. <9> A polysiloxane having two or more block structures in which alkoxysilane compounds having a glycidyloxy group and / or epoxycyclohexyl group are constituent units, The composition of each constituent unit of the block structure is different for each polysiloxane. <10> <8> or <9> A curable resin composition containing the polysiloxane described above. <11> <8> or <9> A multi-component curable resin composition containing the polysiloxane described above. <12> <10> The curable resin composition described above, or <11> A cured product obtained by curing the multi-component curable resin composition described in [the relevant document]. [Examples]

[0223] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. It is not something that should be done.

[0224] 〔material〕 The following materials were used in the examples and comparative examples.

[0225] <Polysiloxane> (Alkoxysilane compounds) 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane (abbreviated as "EC"): (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 246.3) 3-Glycidyloxypropyltrimethoxysilane (abbreviated as "Ge"): (OFS-6040 manufactured by Dow Toray Industries, Ltd., molecular weight 236.3) Methyltrimethoxysilane (abbreviated as "Me"): (OFS-6070 manufactured by Dow Toray Industries, Ltd.; molecular weight 136.2) (Neutral salt) Magnesium chloride hexahydrate (abbreviated as "MgCl2") (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 203.3) (water) pure water (Organic solvents) Propylene glycol methyl ether acetate (abbreviated as "PMA"): (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 132.2) Ethanol: (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 46.07) (Other polymerization catalysts) Phosphate: (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 97.99) Potassium hydroxide: (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 56.11) <Resin components> ((meth)acrylic monomers) Methyl methacrylate (abbreviated as "MMA"): Manufactured by Mitsubishi Gas Chemical Company, Inc. Butyl acrylate (abbreviated as "BA"): Manufactured by Nippon Shokubai Co., Ltd. (Monomers containing hydroxyl groups) 2-Hydroxypropyl methacrylate (abbreviated as "HPMA"): Manufactured by Nippon Shokubai Co., Ltd. (Other monomers) Styrene (abbreviated as "St"): Manufactured by Mitsubishi Chemical Corporation (Polymerization catalyst) 2,2′-Azobis(2-methylbutyronitrile): (Wako Pure Chemical Industries, Ltd. "V59", molecular weight 192.3) (Chain transfer agent) n-Dodecyl mercaptan (abbreviation "nDM", molecular weight 202): Manufactured by Wako Pure Chemical Industries, Ltd. t-Dodecyl mercaptan (abbreviation "tDM", molecular weight 202): Manufactured by Wako Pure Chemical Industries, Ltd. 2-ethylhexyl thioglycolate (abbreviation "M-8", molecular weight 204): Manufactured by Wako Pure Chemical Industries, Ltd. n-Octyl mercaptan (abbreviation "M-14", molecular weight 146): Manufactured by Wako Pure Chemical Industries, Ltd. <Polyisocyanate compounds> Average trimer of hexamethylene diisocyanate (isocyanurate modified form (abbreviated as "N3300"): "Sumijoule N3300" manufactured by Covestro Japan Co., Ltd.) <Metal catalyst> Aluminum (trisethylacetate) (abbreviation "ALCH") (manufactured by Kawaken Fine Chemical Co., Ltd., molecular weight 414.4) <Other ingredients> (Stabilizer) Acetylacetone (abbreviated as "AcAc"): (Manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 100.1) [Measurement and evaluation methods] Measurements and evaluations in the examples and comparative examples were performed using the following methods.

[0226] (Scratch resistance) Using an eraser abrasion tester (manufactured by Mitsumoto Seisakusho Co., Ltd.), the cured product (coating) applied to the ABS was subjected to a 500 g / cm³ test with steel wool #0000. 2 The gloss retention rate of the cured coating was measured after applying a load and moving the surface of the coating back and forth 10 times with a stroke length of 10 cm. Here, the gloss retention rate of the coating was measured using a BYK Microtrigloss. The scratch resistance of the cured material was evaluated based on the following criteria: A (Pass): Gloss retention rate of 80% or higher B (Defective): Gloss retention rate is less than 80% (Chemical resistance) To the cured product (coating) applied to the obtained ABS, 0.2 g of a 10% lactic acid aqueous solution was spotted onto the coating and left to stand for 1 hour in a hot air dryer adjusted to 80°C. Afterward, the color and smoothness changes of the coating were visually inspected, and the chemical resistance of the cured product was evaluated based on the following criteria: A (Good): There is no change in color, and no spot marks remain. Also, the surface of the paint film is smooth and there is no curling. B (Pass): No color change, only faint spot marks remain. The surface of the paint film is smooth and there is no wrinkling. C (Fail): Spot marks show slight whitening, and slight wrinkling occurs on the surface of the paint film. D (Defective): Spot marks are clearly whitened, and the surface of the paint film is clearly wrinkled.

[0227] (Moisture resistance) The cured product (coating) applied to the obtained ABS was left to stand for a specified time in a constant temperature and humidity chamber adjusted to 80°C, 95%, and RH, and the change in appearance was visually confirmed. The durability of the coating was evaluated based on the following criteria: A (Good): No change in appearance after 500 hours of standing. B (Pass): After 500 hours of standing, the hardened material shows slight whitening (mild), and no bleeding occurs. C (Failure): After 500 hours of standing, the hardened material shows severe whitening, oily bleed occurs, or cracks appear on the surface of the hardened material. D (Defective): Shows significant changes in appearance other than whitening, such as cracks, curling, or peeling. (weather resistance) The cured product (coating) applied to the obtained ABS was exposed for 200 hours under conditions of a black panel temperature of 63°C using a sunshine weather meter (S80, manufactured by Suga Test Instruments Co., Ltd.). The appearance of the coating after exposure was measured and confirmed by color difference ΔE (color difference ΔE between the coating before exposure and the coating after exposure) using a color difference meter (CR400, manufactured by Kitahama Seisakusho Co., Ltd.) and by visual inspection, and the change in the appearance of the coating was evaluated based on the following criteria. Note that ΔE is a value measured according to the L*a*b* color system specified in JIS Z 8729 and is calculated by the following formula: ΔE=(ΔL 2 +Δa 2 +Δb 2 ) 1 / 2 In the formula, L* represents lightness, and a* and b* represent chromaticity. A (Good): ΔE < 2, and no significant visible changes in appearance. B (Failure): 2 ≤ ΔE, and no significant visual change. C (Defective): 2 ≤ ΔE, and significant changes such as cracks, shrinkage, or peeling are visible to the naked eye. [Example 1] (Synthesis Example 1: Preparation of Polysiloxane) In a 2L four-necked flask, 0.14g of Me and 47.02g of EC were added as alkoxysilane component (I), along with 0.038g of MgCl2, 26.91g of pure water (62.5 mol% relative to the total alkoxysilyl groups), and 15.89g of methanol. The mixture was heated in an oil bath set to 90°C and reacted for 2 hours to obtain a solution containing a polysiloxane macromer with EC as the main constituent unit (first polymerization step). As shown in Table 2, 29 Si-NMR measurements revealed that the T1 in the solution containing the polysiloxane macromer obtained in the first polymerization step was 10.2 mol%, the T2 was 30.5 mol%, and the T0 was 0.1%.

[0228] To the four-necked flask containing the solution obtained from the polysiloxane macromer, 0.14 g of Me, 2.92 g of Ge, and 0.28 g of methanol were added as alkoxysilane component (II), and the mixture was reacted for a further 4 hours to obtain a solution containing polysiloxane (second polymerization step).

[0229] 54.44 g of PMA was added to the reaction system, and atmospheric distillation was carried out for 2 hours using an oil bath with the temperature set to 140°C, removing a total of 93.33 g of methanol and residual water (de-alcoholization step). Furthermore, the oil bath (oil bath after the de-alcoholization step) was heated for 2 hours while maintaining the temperature at 140°C (maturation step).

[0230] Subsequently, 4.2 g of AcAc was added to the reaction system as a stabilizer, and 1.36 g of PMA was added to adjust the SC, thereby obtaining a solution containing approximately 200 g of polysiloxane. The SC (solids content) of the polysiloxane in the obtained solution was 70%, and the weight-average molecular weight (Mw) (polystyrene equivalent) was 7200. 29From the Si-NMR measurement results, the ratio of T1 / T2 / T3 was 7 / 32 / 61, the amount of T3 (T3 / (Q1+Q2+Q3+Q4+T1+T2+T3+D1+D2+M1)×100) was 59 mol%, and the degree of condensation was 84.5%. SC represents the weight percentage of the components (solids) that did not volatilize when the entire amount of the obtained polysiloxane-containing solution was heated to 105°C, relative to the total amount of the polysiloxane-containing solution. Table 1 shows the types and amounts of each component used in the first polymerization step, the second polymerization step, and the de-alcoholization step described above, as well as the physical properties of the solution containing polysiloxane (or polysiloxane macromer).

[0231] [Table 1]

[0232] (Preparation of curable resin composition) According to the formulations listed in Table 2, the prepared polysiloxane, the metal catalyst ALCH, and the solvent PMA were added sequentially to a 225 ml mayonnaise bottle and mixed for 5 minutes using a magnetic stirrer to prepare a curable resin composition with an NV value (Nonvolatile content) of 45% by weight. The NV value refers to the ratio (by weight) of the weight of the cured product (coating film) after drying to 100% by weight of the curable resin composition before drying (before curing).

[0233] (Preparation of cured material (coating film)) The prepared curable resin composition was applied to a 50 × 150 × 2 mm ABS substrate using a No. 40 bar coater. The substrate was then placed in a hot air dryer set to 80°C for 30 minutes to remove the solvent and cure the applied curable resin composition, resulting in a dry cured product (coating) with a thickness of approximately 0.030 mm. Furthermore, the scratch resistance, chemical resistance, moisture resistance, and weather resistance of the obtained cured product were evaluated. The results are shown in Table 2.

[0234] [Example 2, Comparative Examples 1-5] The addition amounts and types of the respective components were changed to the amounts described in Tables 1 and 2, and polysiloxanes were prepared (Synthesis Examples 2 to 7) in the same manner as in Example 1 except that the second polymerization step was not carried out in Comparative Examples 1 to 3. Using the obtained polysiloxanes, curable resin compositions and cured products were produced, and each physical property was measured and evaluated. The results are shown in Table 2.

[0235]

Table 2

[0236] 〔Results〕 From Table 2, it was shown that the cured product obtained by curing the curable resin composition containing the polysiloxane of Example 1 was excellent in weather resistance. That is, it was shown that the curable resin composition containing the polysiloxane produced according to one embodiment of the present invention can provide a cured product excellent in weather resistance. Furthermore, it was shown that the polysiloxane of Example 1 can provide a curable resin composition that can provide a cured product excellent in physical properties such as scratch resistance, chemical resistance, and moisture resistance.

[0237] On the other hand, from Table 2, the curable resin compositions containing the polysiloxanes of Comparative Examples 1 to 5 had poor weather resistance of the obtained cured products. That is, it was shown that when the configuration of the present invention was not satisfied, the cured product obtained by curing the curable resin composition containing the obtained polysiloxane had poor weather resistance. In particular, from Comparative Examples 4 to 5, even when the two-step polymerization process was carried out, when a neutral salt was not used, it was shown that the cured product obtained by curing the curable resin composition containing the obtained polysiloxane had poor weather resistance.

Industrial Applicability

[0238] Since the curable resin composition containing the present polysiloxane can provide a cured product excellent in weather resistance, it can be suitably used for coating agents and the like.

Claims

1. (1) a first-stage polymerization step in which an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group is subjected to hydrolysis and dehydration condensation in the presence of water and a neutral salt to obtain a solution containing a polysiloxane macromer; (2) a second-stage polymerization step in which the solution containing the polysiloxane macromer is mixed with an alkoxysilane component (II) containing an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group in a composition different from that of the alkoxysilane component (I), and the polysiloxane macromer and the alkoxysilane component (II) are subjected to hydrolysis and dehydration condensation to obtain a solution containing polysiloxane; and A method for producing polysiloxane, comprising:

2. 2. The method for producing a polysiloxane according to claim 1, wherein the total amount of 3-glycidyloxypropyltrialkoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, methyltrialkoxysilane, and phenyltrialkoxysilane is 90 parts by weight or more relative to 100 parts by weight of the total weight of the alkoxysilane component (I) and the alkoxysilane component (II).

3. the total amount of T1 and T2 is 25 to 60 mol % relative to 100 mol % of the total amount of the alkoxysilane compound derived from the alkoxysilane component (I) and the structural unit derived from the alkoxysilane component (I) contained in the solution containing the polysiloxane macromer; and 3. The method for producing a polysiloxane according to claim 1 or 2, wherein the amount of TO is less than 1 mol%. (Here, T1 and T2 are each a constituent unit derived from a monoorganotrialkoxysilane and forming one or two siloxane bonds among all constituent units of the polysiloxane macromer, and T0 is a monoorganotrialkoxysilane that does not form a siloxane bond and is contained in the solution containing the polysiloxane macromer.)

4. The method for producing a polysiloxane according to any one of claims 1 to 3, further comprising: (3) a dealcoholization step of heating the solution containing the polysiloxane to obtain a solution containing a dealcoholized polysiloxane.

5. The method for producing a polysiloxane according to any one of claims 1 to 4, further comprising: (4) an aging step of heating the solution containing the polysiloxane.

6. The method for producing a polysiloxane according to any one of claims 1 to 5, wherein the polysiloxane has an epoxy equivalent of 150 to 400.

7. 7. The method for producing a polysiloxane according to claim 1, wherein the polysiloxane comprises a structural unit having a glycidyloxy group and a structural unit having an epoxycyclohexyl group.

8. A polysiloxane having two or more block structures each having an alkoxysilane compound having a glycidyloxy group and / or an epoxycyclohexyl group as a constituent unit, The polysiloxanes have different compositions of the constituent units of the block structure.

9. 9. The polysiloxane according to claim 8, wherein the block structures include a block structure containing an alkoxysilane compound having a glycidyloxy group as a structural unit, and a block structure containing an alkoxysilane compound having an epoxycyclohexyl group as a structural unit.

10. A curable resin composition comprising the polysiloxane according to claim 8 or 9.

11. A multi-component curable resin composition comprising the polysiloxane according to claim 8 or 9.

12. A cured product obtained by curing the curable resin composition according to claim 10 or the multi-component curable resin composition according to claim 11.