JP7686465B2 - Method for producing polysiloxane and use of polysiloxane - Google Patents

Description

The present invention relates to a method for producing a 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.

Curable resin compositions containing organopolysiloxane as a main component 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 preferably used because of their excellent scratch resistance, chemical resistance, etc.

As an example of a resin composition containing an organopolysiloxane having such an epoxy group, Patent Document 1 describes a curable resin composition that contains an alkoxysilane compound having two or more types of epoxy groups as a constituent unit, thereby improving the physical properties of the cured product. Patent Document 2 also describes a technology for using a curable resin composition containing a block-type siloxane compound as an optical semiconductor printed wiring board.

International Publication No. 2020/235524 JP 2014-185263 A

The above technology is excellent, but there is room for improvement in the weather resistance of the resulting cured product.

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.

As a result of intensive research to solve the above problems, the present inventors discovered for the first time that a polysiloxane capable of providing a cured product with excellent weather resistance can be obtained by carrying out a two-stage hydrolysis and dehydration condensation reaction of an alkoxysilane compound having a glycidyloxy group and/or an alkoxysilane compound having an epoxy group, which are the raw materials, in a method for producing polysiloxane, and thus completed the present invention.

Therefore, one aspect of the present invention is a method for producing polysiloxane, which includes: (1) a first polymerization step in which an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group is hydrolyzed and dehydrated in the presence of water and 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 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 hydrolyzed and dehydrated to obtain a solution containing polysiloxane.

According to one aspect of the present invention, it is possible to provide a polysiloxane that can provide a cured product with excellent weather resistance.

One embodiment of the present invention will be described in detail below. Note that unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more, B or less." In addition, all documents described in this specification are incorporated herein by reference.

1. Overview 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 epoxy groups as constituent units has excellent chemical resistance, etc., but there is room for improvement in the weather resistance of the resulting cured product.

The present inventors have conducted research aimed at improving the weather resistance of a cured product (coating film) obtained by curing a polysiloxane having two or more types of silane compounds having epoxy groups as constituent units, and as a result have reached the following findings.
A curable resin composition containing a polysiloxane obtained by a method for producing polysiloxane including: (1) a first polymerization step in which an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group is hydrolyzed and dehydrated and condensed with water and 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, the polysiloxane macromer, and 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) to obtain a solution containing a polysiloxane, can provide a cured product having excellent weather resistance.
The cured product obtained by curing the curable resin composition containing the polysiloxane obtained by the above-mentioned production method has excellent scratch resistance, chemical resistance, and water resistance.

Until now, no polysiloxane has existed that can provide a cured product that is excellent in scratch resistance, chemical resistance, and water resistance as well as weather resistance, and the method for producing polysiloxane according to one embodiment of the present invention is extremely useful.

2. Method for Producing Polysiloxane
A method for producing a polysiloxane according to one embodiment of the present invention (hereinafter referred to as "this production method") is characterized by comprising: (1) a first-stage polymerization step of hydrolyzing and dehydrating condensing an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group 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 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 hydrolyzing and dehydrating condensing the polysiloxane macromer and the alkoxysilane component (II) to obtain a solution containing a polysiloxane.

In this specification, "polysiloxane" refers to an organopolysiloxane formed by one or more types of multiple alkoxysilane compounds forming siloxane bonds between each of the alkoxysilane compounds.

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

In this specification, a block structure refers to a polymer that contains 80 mol% or more of a structural unit derived from a specific alkoxysilane compound out of a total of 100 mol% of all structural units in the block structure, preferably 90 mol% or more, and more preferably 95 mol% or more. In this specification, a structural unit that is contained in 80 mol% or more out of 100 mol% of all structural units that constitute the block structure may be referred to as a main structural unit.

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

As described above, this manufacturing method includes (1) a first-stage polymerization step, (2) a second-stage polymerization step, and, optionally, (3) a dealcoholization step, and (4) an aging step. Each step of this manufacturing method is described in detail below.

<(1) First-stage polymerization step>
The first polymerization step in this production method is a step in which an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group is hydrolyzed and dehydration condensed using water and a neutral salt to obtain a solution containing a polysiloxane macromer.

(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. In each of the above (i) to (iii) aspects, the alkoxysilane component (I) may contain an alkoxysilane compound other than an alkoxysilane compound having a glycidyloxy group and an alkoxysilane compound having an epoxycyclohexyl group (referred to as other alkoxysilane compounds).

(Alkoxysilane Compound Having a Glycidyloxy Group)
The alkoxysilane compound having a glycidyloxy group is one or more types of silane compound having an alkoxy group as a substituent on a silicon atom and an organic group containing a glycidyloxy group.

Specific examples of alkoxysilane compounds having a glycidyloxy group include monoorganotrialkoxysilanes, diorganodialkoxysilanes, and triorganomonoalkoxysilanes, which have an organic group containing a glycidyloxy group as the organic group (organo group). Among them, as an alkoxysilane compound having a glycidyloxy group, a monoorganotrialkoxysilane having an organic group containing a glycidyloxy group as the organic group is preferable. As an alkoxysilane compound having a glycidyloxy group, a monoorganotrialkoxysilane may be used alone, or a combination of a monoorganotrialkoxysilane and a diorganodialkoxysilane may be used, or a combination of a monoorganotrialkoxysilane, a diorganodialkoxysilane, and/or a triorganomonoalkoxysilane may be used. Here, monoorganotrialkoxysilane refers to a silane compound having an organic group with one glycidyloxy group and three alkoxy groups as substituents on the silicon atom, diorganodialkoxysilane refers to a silane compound having an organic group with at least one glycidyloxy group and two alkoxy groups as substituents on the silicon atom, and triorganomonoalkoxysilane refers to a silane compound having an organic group with at least one glycidyloxy group and one alkoxy group as substituents on the silicon atom.

When triorganomonoalkoxysilane and/or tetraalkoxysilane are used as the alkoxysilane component (I), the amount used is not particularly limited as long as it does not impair the effects of the invention. For example, the amount is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less, relative to 100 mol% of the total amount of the alkoxysilane component (I).

Examples of the alkoxy group that the alkoxysilane compound having a glycidyloxy group has as a substituent on the silicon atom include an alkoxy group having 1 to 3 carbon atoms. Specifically, the alkoxy group is a methoxy group, an ethoxy group, or a propoxy group, with the methoxy group and the ethoxy group being preferred, and the methoxy group being more preferred. The alkoxy group may be of only one type, or may be of two or more types mixed together.

Examples of the organic group containing a glycidyloxy group that the alkoxysilane compound having a glycidyloxy group has 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 may be of two or more types mixed together.

An alkoxysilane compound having a glycidyloxy group is sufficient if it contains at least one alkoxy group and at least one organic group containing a glycidyloxy group as a substituent on a silicon atom, and may also contain other organic groups (organic groups not containing a glycidyloxy group).

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 may have a substituent. The number of carbon atoms in the alkyl groups is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 to 2. The number of carbon atoms in the alkenyl groups is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. The other organic groups may be of only one type, or may be of two or more types mixed together.

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, the alkoxysilane compound having an organic group containing a glycidyloxy group includes 1-glycidyloxymethyltrimethoxysilane, 1-glycidyloxymethylmethyldimethoxysilane, 1-glycidyloxymethyltriethoxysilane, 1-glycidyloxymethylmethyldiethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, Examples of the silane 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.

(Alkoxysilane compound having an epoxycyclohexyl group)
The alkoxysilane compound having an epoxycyclohexyl group is one or more types of silane compounds having an alkoxy group as a substituent on a silicon atom and an organic group containing an epoxycyclohexyl group.

Specific examples of alkoxysilane compounds having an organic group containing an epoxycyclohexyl group include monoorganotrialkoxysilanes, diorganodialkoxysilanes, and triorganomonoalkoxysilanes having an organic group containing an epoxycyclohexyl group as the organic group (organo group). Among them, monoorganotrialkoxysilanes are preferred as alkoxysilane compounds having an organic group containing an epoxycyclohexyl group as the organic group (organo group). As an alkoxysilane compound having an epoxycyclohexyl group, monoorganotrialkoxysilanes may be used alone, or may be a combination of monoorganotrialkoxysilanes and diorganodialkoxysilanes, or may be a combination of monoorganotrialkoxysilanes, diorganodialkoxysilanes, and/or triorganomonoalkoxysilanes. Here, monoorganotrialkoxysilane refers to a silane compound having an organic group containing one epoxycyclohexyl group and three alkoxy groups as substituents on a silicon atom, diorganodialkoxysilane refers to a silane compound having an organic group containing at least one epoxycyclohexyl group and two alkoxy groups as substituents on a silicon atom, and triorganomonoalkoxysilane refers to a silane compound having an organic group containing at least one epoxycyclohexyl group and one alkoxy group as substituents on a silicon atom.

When triorganomonoalkoxysilane and/or tetraalkoxysilane are used as the alkoxysilane component (I), the amount used is not particularly limited as long as it does not impair the effects of the invention. For example, the amount 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 the alkoxysilane component (I).

Examples of the alkoxy group that the alkoxysilane compound having an epoxycyclohexyl group has as a substituent on the silicon atom include alkoxy groups having 1 to 3 carbon atoms. Specific examples include methoxy groups, ethoxy groups, and propoxy groups, with methoxy groups and ethoxy groups being preferred, and methoxy groups being more preferred. The alkoxy group may be of only one type, or may be of two or more types mixed together.

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

An alkoxysilane compound having an epoxycyclohexyl group is sufficient if it contains at least one alkoxy group and at least one organic group containing an epoxycyclohexyl group as a substituent on a silicon atom, and may also contain other organic groups (organic groups not containing an epoxycyclohexyl group).

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 may have a substituent. The number of carbon atoms in the alkyl groups is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 to 2. The number of carbon atoms in the alkenyl groups is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. The other organic groups may be of only one type, or may be of two or more types mixed together.

In one embodiment of the present invention, examples of alkoxysilane compounds having an epoxycyclohexyl group include trialkoxysilanes having an epoxycyclohexyl alkyl group, dialkoxysilanes having an epoxycyclohexyl alkyl group and the other organic groups described above, and the like. 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-epoxycyclohexyl)ethyldi ... 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)propyltriethoxysilane, propylmethyldiethoxysilane, 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 of the silane 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.

(Other alkoxysilane compounds)
The other alkoxysilane compound is one or more kinds of silane compounds that have an alkoxy group as a substituent on silicon atom, and do not have an organic group containing a glycidyloxy group and an organic group containing an epoxycyclohexyl group.Specific examples of the other alkoxysilane compound include monoorganotrialkoxysilane, diorganodialkoxysilane, triorganomonoalkoxysilane, and tetraalkoxysilane.The other alkoxysilane compound preferably has at least one kind of monoorganotrialkoxysilane.The other alkoxysilane compound may be only monoorganotrialkoxysilane, or may be a combination of monoorganotrialkoxysilane and diorganodialkoxysilane, or may be a combination of monoorganotrialkoxysilane, diorganodialkoxysilane, triorganomonoalkoxysilane, and/or tetraalkoxysilane compound. Here, monoorganotrialkoxysilane refers to a silane compound having one organic group and three alkoxy groups as substituents on the silicon atom, diorganodialkoxysilane refers to a silane compound having two organic groups and two alkoxy groups as substituents on the silicon atom, and triorganomonoalkoxysilane refers to a silane compound having three organic groups and one alkoxy group as substituents on the silicon atom.

When triorganomonoalkoxysilanes and/or tetraalkoxysilanes are used as the other alkoxysilane compounds, the amount used is not particularly limited as long as it does not impair the effects of the invention. For example, the amount 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 the alkoxysilane component (I).

Other alkoxysilane compounds have alkoxy groups as substituents on silicon atoms, such as alkoxy groups having 1 to 3 carbon atoms. Specific examples include methoxy, ethoxy, and propoxy groups, with methoxy and ethoxy groups being preferred, and methoxy groups being more preferred. The alkoxy groups may be of one type only, or may be of two or more types mixed together.

The organic group that the other alkoxysilane compound has as a substituent on the silicon atom is not particularly limited as long as it is an organic group other than a glycidyloxy group and an epoxycyclohexyl group, and examples thereof include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms. The alkyl group, alkenyl group, and aryl group may be unsubstituted or may have a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 to 2. The number of carbon atoms of the alkenyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. The organic group may be of only one type, or may be of two or more types mixed together.

The other alkoxysilane compounds are not particularly limited as long as they do not have an organic group containing a glycidyloxy group or an organic group containing an epoxycyclohexyl group as a substituent on the silicon atom, and have at least one alkoxy group. In the case where the organic group that the other alkoxysilane compound has as a substituent on the silicon atom is an unsubstituted alkyl group, examples of the alkoxysilane compound include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethylmethyldimethoxysilane, ethyltriethoxysilane, ethylmethyldiethoxysilane, propyltrimethoxysilane, propylmethyldimethoxysilane, propyltriethoxysilane, propylmethyldiethoxysilane, butyltrimethoxysilane, butylmethyldimethoxysilane, butyltriethoxysilane, butylmethyldiethoxysilane, hexyltrimethoxysilane, hexylmethyldimethoxysilane, hexyltriethoxysilane, hexylmethyldiethoxysilane, octyltrimethoxysilane, octylmethyldimethoxysilane, octyltriethoxysilane, octylmethyldiethoxysilane, and the like.

As described above, the organic group that the other alkoxysilane compound has as a substituent on the silicon atom may be an organic group having a substituent. The substituent is not particularly limited, but from the viewpoint of ease of availability, a thiol group, an isocyanate group, a (meth)acryloyl group, a phenyl group, a cyclohexyl group, and a chloro group are preferred.

When the organic group is an alkyl group having a thiol group, other alkoxysilane compounds include, for example, 1-mercaptomethyltrimethoxysilane, 1-mercaptomethylmethyldimethoxysilane, 1-mercaptomethyltriethoxysilane, 1-mercaptomethylmethyldiethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxy ... Examples of such silane include mercaptopropylmethyldiethoxysilane, 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.

When the organic group is an alkyl group having an isocyanate group, other alkoxysilane compounds include, for example, 1-isocyanate methyl trimethoxysilane, 1-isocyanate methyl methyl dimethoxysilane, 1-isocyanate methyl triethoxysilane, 1-isocyanate methyl methyl diethoxysilane, 2-isocyanate ethyl trimethoxysilane, 2-isocyanate ethyl methyl dimethoxysilane, 2-isocyanate ethyl triethoxysilane, 2-isocyanate ethyl methyl diethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl methyl dimethoxysilane, 3-isocyanate propyl triethoxy ... Examples of the isocyanate propyl methyl diethoxy silane include 4-isocyanate butyl trimethoxy silane, 4-isocyanate butyl methyl dimethoxy silane, 4-isocyanate butyl triethoxy silane, 4-isocyanate butyl methyl diethoxy silane, 6-isocyanate hexyl trimethoxy silane, 6-isocyanate hexyl methyl dimethoxy silane, 6-isocyanate hexyl triethoxy silane, 6-isocyanate hexyl methyl diethoxy silane, 8-isocyanate octyl trimethoxy silane, 8-isocyanate octyl methyl dimethoxy silane, 8-isocyanate octyl triethoxy silane, and 8-isocyanate octyl methyl diethoxy silane.

When the organic group is an alkyl group having a (meth)acryloyl group, other alkoxysilane compounds 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)acryloyloxypropyltriethoxy ... Examples of such silane include acryloyloxypropylmethyldiethoxysilane, 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.

When the organic group is an alkyl group having a phenyl group, other alkoxysilane compounds include, for example, benzyltrimethoxysilane, benzyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-phenylpropyltrimethoxysilane, 3-phenylpropyltriethoxysilane, 4-phenylbutyltrimethoxysilane, 4-phenylbutyltriethoxysilane, 5-phenylpentyltrimethoxysilane, 5-phenylpentyltriethoxysilane, 6-phenylhexyltrimethoxysilane, 6-phenylhexyltriethoxysilane, etc.

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

When the organic group is an alkyl group having a chloro group, other alkoxysilane compounds include, for example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 5-chloropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 6-chlorohexyltrimethoxysilane, 6-chlorohexyltriethoxysilane, etc.

When the organic group is an alkenyl group, other alkoxysilane compounds include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allylmethyldimethoxysilane, allyltriethoxysilane, allylmethyldiethoxysilane, etc.

When the organic group is an aryl group, other alkoxysilane compounds include phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenylmethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, etc.

Other alkoxysilane compounds may be used that contain an organic group containing an epoxy group other than a glycidyloxy group and an epoxy group other than an epoxycyclohexyl group as a substituent on a 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.

In one embodiment of the present invention, the alkoxysilane component (I) preferably contains 70 to 100 mol % of monoorganotrialkoxysilane and 0 to 30 mol % of diorganodialkoxysilane, relative to 100 mol % of the total amount of alkoxysilane compounds contained in the alkoxysilane component (I). The proportion of the monoorganotrialkoxysilane 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 be 100 mol %.

In the alkoxysilane component (I), the total amount of the alkoxysilane compound having a glycidyloxy group and the alkoxysilane compound having an epoxycyclohexyl group relative to the total amount of the alkoxysilane compounds contained in the alkoxysilane component (I) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, and may be 100 mol%. In addition, the ratio of the alkoxysilane compound having a glycidyloxy group and the alkoxysilane compound having an epoxycyclohexyl group contained in the alkoxysilane component (I) is not particularly limited, but for example, the alkoxysilane compound having a glycidyloxy group (mol%):alkoxysilane compound 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 and amount (ratio) of the alkoxysilane compound contained in the alkoxysilane compound (I) can be appropriately set taking into consideration the composition and physical properties of the final product, polysiloxane, and the composition of the alkoxysilane component (II) used in the second polymerization step.

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

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 a Group 1 element ion, a Group 2 element ion, a tetraalkylammonium ion, and a guanidinium ion, and an anion selected from the group consisting of a Group 17 element ion excluding fluoride ion, a sulfate ion, a nitrate ion, and a perchlorate ion. 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, and 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, and tetramethylammonium bromide. ammonium, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, guanidinium 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, guanidinium 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, guanidinium 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 , tetrapropylammonium nitrate, tetrabutylammonium nitrate, tetrapentylammonium nitrate, tetrahexylammonium nitrate, guanidinium 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, guanidinium perchlorate, etc. These neutral salts may be used alone or in combination of two or more.

The amount of neutral salt added in the first polymerization step can be appropriately determined depending on the desired degree of 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 even more preferably 50 ppm to 1,000 ppm, relative to the total amount of alkoxysilane component (I).

In the first polymerization step, the polysiloxane macromer obtained by hydrolysis and dehydration condensation of the alkoxysilane component (I) may contain a neutral salt. As a result, the present polysiloxane may also contain a neutral salt. The amount of neutral salt contained in the present 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 the polysiloxane.

(water)
In this production method, the amount of water used in the first polymerization step is preferably 20 to 100 mol%, more preferably 20 to 90 mol%, still 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 contained in the alkoxysilane component (I) (100 mol%). When the amount of water used in the first polymerization step is 20 mol% or more, the hydrolysis and dehydration condensation reaction proceeds sufficiently, and when it is 100 mol% or less, the adhesion and water resistance of the obtained cured product to the substrate can be further improved.

In the first-stage 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 having high solubility in water is preferred since it is used in combination with water. In addition, in order to ensure the solubility of the alkoxysilane component, an organic solvent having 4 or more carbon atoms is preferred. From the above viewpoints, preferred organic solvents include, for example, 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, and 2-propanol, but are not limited thereto. Among these organic solvents, alcohols that are freely miscible with water are particularly preferred, and more specifically, methanol, ethanol, 1-propanol, 2-propanol, and propylene glycol monomethyl ether are preferred.

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

In the first polymerization step, the reaction time for carrying out the hydrolysis and dehydration condensation reaction can be appropriately set by a person skilled in the art, but since a polysiloxane macromer having an appropriate grafting property can be obtained, it is preferably within 6 hours, and more preferably within 4 hours. Furthermore, the lower limit of the reaction time is preferably 30 minutes or more, and more preferably 1 hour or more, since a polysiloxane macromer having a sufficiently high degree of condensation can be obtained.

(Polysiloxane Macromer)
The polysiloxane macromer is a polymer obtained by hydrolysis and dehydration condensation of the alkoxysilane component (I) in the first polymerization step in the present production method. The polysiloxane macromer is a polymer having a block structure in which the alkoxysilane compound having a glycidyloxy group and/or the alkoxysilane compound having an epoxycyclohexyl group, which are used in the first polymerization step, are used as constituent units (main constituent units). In the present production method, the polysiloxane macromer is usually obtained in a state dissolved in an aqueous solution.

In one embodiment of the present invention, the total amount of the structural unit (hereinafter referred to as T1) derived from monoorganotrialkoxysilane and forming one siloxane bond, and the total amount of the structural unit (hereinafter referred to as T2) derived from monoorganotrialkoxysilane and forming two siloxane bonds, relative to the total amount of all alkoxysilane compounds and structural units derived from alkoxysilane compounds contained in the solution containing the polysiloxane macromer (i.e., the solution immediately after the completion of the first-stage polymerization step), is preferably 25 to 60 mol%, more preferably 30 to 55 mol%, and even more preferably 35 to 50 mol%. According to the above configuration, a polysiloxane macromer with sufficiently high grafting properties can be obtained, and therefore a polysiloxane having a block structure can be efficiently obtained in the second-stage polymerization step described below.

In one embodiment of the present invention, the amount of monoorganotrialkoxysilane (hereinafter referred to as T0) that does not form a siloxane bond (i.e., does not undergo dehydration condensation with other alkoxysilane compounds) relative to the total amount of all alkoxysilane compounds and structural units derived from alkoxysilane compounds contained in the solution containing the polysiloxane macromer (100 mol %) is preferably less than 1 mol %, more preferably less than 0.5 mol %, and even more preferably less than 0.1 mol %. According to the above configuration, there is an advantage that the yield of polysiloxane having a block structure is increased in the second polymerization step described below. The lower limit of the amount of T0 is not particularly limited, and may be 0 mol %.

Here, the amount of T0, the amount of T1, and the amount of T2 can be calculated as the ratio ( ^% ) of the peak area originating from T0, T1, and T2 to the total peak area of the peaks originating from Q0, Q1, Q2, Q3, Q4, T0, T1, T2, T3, D0, D1, D2, and M0 and M1 in an aqueous solution containing a polysiloxane macromer, as measured by 29Si-NMR.

Here, Q0 is a tetraalkoxysilane that does not form a siloxane bond and is derived from a tetraalkoxysilane, Q1, Q2, Q3, or Q4 is a structural unit that is derived from a tetraalkoxysilane and forms one, two, three, or four siloxane bonds, T0 is a monoorganotrialkoxysilane that does not form a siloxane bond, T1, T2, or T3 is a monoorganotrialkoxysilane that is derived from a monoorganotrialkoxysilane and forms one, two, three, or four siloxane bonds, is the amount of structural units that form one, two, or three bonds, D0 is a diorganodialkoxysilane that does not form a siloxane bond, D1 or D2 is a structural unit derived from a diorganodialkoxysilane that forms one or two siloxane bonds, M0 is a triorganomonoalkoxysilane that does not form a siloxane bond, and M1 is a structural unit derived from a triorganomonoalkoxysilane that forms one siloxane bond.

Therefore, the amount of T0 can also be expressed as "T0/(Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)." The amount of T1 can also be expressed as "T1/(Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)." The amount of T2 can also be expressed as "T2/(Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)." In addition, the total amount 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)." The amount of T3 can also be expressed as "T3/(Q0+Q1+Q2+Q3+Q4+T0+T1+T2+T3+D0+D1+D2+M0+M1)."

In an aqueous solution containing a polysiloxane macromer, the total amount of T1 and T2 being 25 to 60 mol % means that the polysiloxane macromer contains sufficient reactive functional groups (silanol groups). Therefore, such a polysiloxane macromer can efficiently and sufficiently undergo graft polymerization in the second polymerization step described below.

In this production method, the condensation degree of the obtained polysiloxane macromer is preferably 70 to 90%, more preferably 75 to 85%, because this improves the compatibility between the polysiloxane macromer and the alkoxysilane component (II) in the second polymerization step. Here, the condensation degree of the polysiloxane macromer is a value calculated by the following formula:
Condensation degree (%)={(1×the amount of T1)+(2×the amount of T2)+(3×the amount of T3)}/3
The amounts of T0, T1, and T2 in the aqueous solution containing the polysiloxane macromer and the condensation degree of the polysiloxane macromer can be controlled by adjusting the amount of water used in the hydrolysis/dehydration condensation reaction in the first polymerization step, the type and amount of the neutral salt, the reaction temperature, etc.

The weight average molecular weight (Mw) of the polysiloxane macromer is not particularly limited, but is preferably 500 to 10,000, more preferably 1,000 to 9,000, and even more preferably 1,500 to 8,000, in order to improve the compatibility between the polysiloxane macromer and the alkoxysilane component (II) in the second polymerization step. The weight average molecular weight (Mw) of the polysiloxane macromer is a value calculated in terms of polystyrene using GPC.

<(2) Second-stage polymerization step>
The second polymerization step according to one embodiment of the present invention is a step of 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 an epoxycyclohexyl group in 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 polysiloxane.

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

In addition to the matters explained below, the descriptions in the above (Alkoxysilane Component (I)) section apply appropriately to the alkoxysilane compounds having a glycidyloxy group, the alkoxysilane compounds having an epoxycyclohexyl group, and other alkoxysilane compounds contained in the alkoxysilane component (II).

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

The following describes the case where the alkoxysilane component (I) contains an alkoxysilane compound having a glycidyloxy group, but does not contain an alkoxysilane compound having an epoxycyclohexyl group (hereinafter referred to as Case A).

In case A, the alkoxysilane component (II) may include (A1) an alkoxysilane compound having a glycidyloxy group different from the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (I), (A2) an alkoxysilane compound having an epoxycyclohexyl group, (A3) an alkoxysilane compound having a glycidyloxy group and an alkoxysilane compound having an epoxycyclohexyl group different from the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (I), or (A4) an alkoxysilane compound having a glycidyloxy group and an alkoxysilane compound having an epoxycyclohexyl group, the same as the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (I). In addition, the above embodiments (A1) to (A4) may be combined within a range that does not impair the effects of the present application.

The following describes the case where the alkoxysilane component (I) contains an alkoxysilane compound having an epoxycyclohexyl group, but does not contain an alkoxysilane compound having a glycidyloxy group (hereinafter referred to as case B).

In case B, the alkoxysilane component (II) may include (B1) an alkoxysilane compound having an epoxycyclohexyl group, which is different from the alkoxysilane compound having an epoxycyclohexyl group contained in the alkoxysilane component (I), (B2) an alkoxysilane compound having a glycidyloxy group, (B3) an alkoxysilane compound having an epoxycyclohexyl group and an alkoxysilane compound having a glycidyloxy group, which are different from the alkoxysilane compound having an epoxycyclohexyl group contained in the alkoxysilane component (I), or (B4) an alkoxysilane compound having an epoxycyclohexyl group and an alkoxysilane compound having a glycidyloxy group, which are the same as the alkoxysilane compound having an epoxycyclohexyl group contained in the alkoxysilane component (I). In addition, the above embodiments (B1) to (B4) may be combined within a range that does not impair the effects of the present application.

The following describes the case where the alkoxysilane component (I) contains an alkoxysilane compound having a glycidyloxy group and an alkoxysilane compound having an epoxycyclohexyl group (hereinafter referred to as case C).

In case C, the alkoxysilane component (II) may contain (C1) an alkoxysilane compound having a glycidyloxy group different from the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (I), (C2) an alkoxysilane compound having an epoxycyclohexyl group different from the alkoxysilane compound having an epoxycyclohexyl group contained in the alkoxysilane component (I), (C3) an alkoxysilane compound having a glycidyloxy group different from the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (I), and (C4) An alkoxysilane compound having an epoxycyclohexyl group of a different type from the alkoxysilane compound having an epoxycyclohexyl group contained in the alkoxysilane component (I), and/or an alkoxysilane compound having an epoxycyclohexyl group of the same type as the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (I) may be contained in a composition different from that of the alkoxysilane component (I). In addition, the above embodiments (C1) to (C4) may be combined within a range that does not impair the effects of the present application.

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

For example, in case (A4), the amount of the alkoxysilane compound having a glycidyloxy group contained in the alkoxysilane component (II) relative to the total amount of alkoxysilane compounds having the same type of glycidyloxy group contained in the alkoxysilane component (I) and the 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.

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

For example, in case (C4), the amount of the alkoxysilane compound having the glycidyloxy group contained in the alkoxysilane component (II) relative to the total amount of 100 mol% of the alkoxysilane compounds having the same type of glycidyloxy group contained in the alkoxysilane component (I) and the 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 the alkoxysilane compound having the epoxycyclohexyl group contained in the alkoxysilane component (II) relative to the total amount of 100 mol% of the alkoxysilane compounds having the same type of epoxycyclohexyl group contained in the alkoxysilane component (I) and the 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. In addition, the amount of the alkoxysilane compound having the glycidyloxy group contained in the 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 this case, the amount of the alkoxysilane compound having the epoxycyclohexyl group contained in the alkoxysilane component (II) relative to the total amount 100 mol% of the alkoxysilane compound having the same type of epoxycyclohexyl group contained in the alkoxysilane component (I) and the 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) relative to the total amount of alkoxysilane component (I) and alkoxysilane component (II) (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%.

In this manufacturing method, among the above-mentioned cases A to C, cases (A2) and (B2) are preferred because they are capable of producing polysiloxanes with better weather resistance. In other words, one embodiment of the present invention is more preferably the following embodiment (a) or (b).

(a): A method for producing a polysiloxane, comprising: (1) a first polymerization step of hydrolyzing and dehydrating condensing an alkoxysilane component (I) containing an alkoxysilane compound having a glycidyloxy 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 an epoxycyclohexyl group, and hydrolyzing and dehydrating condensing the mixture to obtain a solution containing a polysiloxane. (b): A method for producing a polysiloxane, comprising: (1) a first polymerization step of hydrolyzing and dehydrating condensing 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, and hydrolyzing and condensing the mixture to obtain a solution containing a polysiloxane.

In one embodiment of the present invention, the types and amounts of the alkoxysilane compounds having a glycidyloxy group, the alkoxysilane compounds having an epoxycyclohexyl group, and the other alkoxysilane compounds per 100 parts by weight of the total weight of the alkoxysilane components (I) and (II) are not particularly limited, but 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 per 100 parts by weight of the total weight of the alkoxysilane components (I) and (II). According to this configuration, the curability of the obtained polysiloxane is sufficiently high, and a cured product (coating film) with excellent scratch resistance can be obtained.

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 water and neutral salt used in the first polymerization step are present in the solution, the hydrolysis and dehydration condensation reaction can be carried out without adding new neutral salt and/or water, but new neutral salt and/or water may be added as necessary.

The reaction temperature during the hydrolysis and dehydration condensation of the polysiloxane macromer and the alkoxysilane component (II) in the second polymerization step can be set as appropriate by those skilled in the art, but for example, it is preferable to heat the solution containing the polysiloxane macromer and the alkoxysilane component (II) to 50°C to 110°C. When the hydrolysis and dehydration condensation reaction is carried out at a temperature of 50°C to 110°C or lower, it becomes easy to produce polysiloxane. In addition, the reaction time during the hydrolysis and dehydration condensation reaction can be set as appropriate by those skilled in the art, but may be, for example, about 10 minutes to 12 hours.

After the second polymerization step (preferably after the dealcoholization step described below, and more preferably after the aging step described below), the reaction system is cooled (for example, to 30°C or less) to obtain polysiloxane in the form of a solution containing polysiloxane.

((3) Dealcoholization step)
The present production method preferably includes a dealcoholization step in which, after the second polymerization step, the alcohol generated by the hydrolysis reaction of the alkoxysilane compound is removed (volatilized) from the solution (solution containing polysiloxane) to obtain a solution containing dealcoholized polysiloxane. When the present production method includes the dealcoholization step, the dehydration condensation reaction proceeds efficiently, and the graft rate of the obtained polysiloxane can be improved.

The dealcoholization step is not particularly limited as long as it can remove the alcohol from the solution, but for example, a method in which the solution is heated and subjected to reduced pressure distillation to remove the alcohol is preferred. The conditions for reduced pressure 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 makes it easier to produce polysiloxanes having a block structure. In the dealcoholization 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.

In addition, in the dealcoholization process, an organic solvent such as propylene glycol methyl ether acetate (PMA), 1-methoxy-2-propanol, butyl acetate, isobutyl acetate, or methyl isobutyl ketone may be added to the solution to adjust the solids concentration (SC) of the solution containing polysiloxane.

((4) Aging process)
The present production method preferably includes an aging step of heating the solution containing the polysiloxane (a solution containing the dealcoholized polysiloxane) after the second polymerization step, preferably after the dealcoholization step. When the present production method includes an aging step, the resulting polysiloxane (polysiloxane after the aging step) can be prevented from changing over time during storage. In the aging step, the temperature at which the solution containing the polysiloxane is heated is not particularly limited, but from the viewpoint of proceeding with the dehydration condensation reaction, it is preferably 40 to 180°C, more preferably 60 to 160°C, and even more preferably 80 to 150°C. In the aging step, the time for heating the solution containing the polysiloxane is not particularly limited, but the dehydration condensation reaction in the aging step is a reaction between polymers and is diffusion-controlled, so there is a risk that the reaction may not be sufficient if the time is short. Therefore, from the viewpoint of proceeding with the dehydration condensation reaction sufficiently, it is preferably 20 minutes to 7 hours, more preferably 40 minutes to 5 hours, and even more preferably 1 to 3 hours. That is, in the aging step, it is particularly preferable to maintain the solution containing the polysiloxane at 80 to 150° C. for 1 to 3 hours.

In addition, in the maturation step, an organic solvent such as propylene glycol methyl ether acetate (PMA), 1-methoxy-2-propanol, butyl acetate, isobutyl acetate, or methyl isobutyl ketone may be added to the solution. These organic solvents have a sufficiently high boiling point, and therefore have the advantage that the temperature of the solution containing the polysiloxane that is subjected to the maturation step can be made sufficiently high.

3. Polysiloxane
In one embodiment of the present invention, there is provided a polysiloxane having two or more block structures each having a different type of alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group as a constituent unit. In addition to the matters described below, the description of the above [2. Method for producing polysiloxane] is appropriately incorporated with respect to this polysiloxane.

The method for providing the polysiloxane is not particularly limited, but for example, it is produced by the method described in [2. Method for producing polysiloxane]. In other words, the polysiloxane is a polymer having a block structure having a constituent unit derived from the alkoxysilane component (I) and a block structure having a constituent unit 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 the polysiloxane is not particularly limited as long as it is two or more, and may be, for example, a triblock structure or a tetrablock structure.

The block structure of the polysiloxane may be (a) composed of only constituent units derived from an alkoxysilane compound having a glycidyloxy group, (b) composed of only constituent units derived from a compound having an epoxycyclohexyl group, or (c) composed of both constituent units derived from an alkoxysilane compound having a glycidyloxy group and constituent units derived from an alkoxysilane compound having an epoxycyclohexyl group. In other words, the polysiloxane may be a polysiloxane having two or more block structures containing an alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group as a constituent unit. In addition, since the alkoxysilane component (I) and the alkoxysilane component (II) have different compositions, the compositions of the constituent units of the block structure contained in the polysiloxane are also different from each other. 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, because this can provide a cured product with better weather resistance.

Among the above (a) to (c), the above (c) is preferred because it can improve the scratch resistance, adhesion, and water resistance of the resulting cured product. In other words, it is preferred that the polysiloxane has 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.

The polysiloxane preferably contains 70 to 100 mol % of monoorganotrialkoxysilane and 0 to 30 mol % of diorganodialkoxysilane relative to the total amount of 100 mol % of the constituent units derived from the alkoxysilane compound having the glycidyloxy group, the constituent units derived from the alkoxysilane compound having the epoxycyclohexyl group, and the constituent units derived from the other alkoxysilane compounds. The proportion of the monoorganotrialkoxysilane 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 be 100 mol %.

In the present polysiloxane, the total amount of the constituent units derived from the alkoxysilane compound having a glycidyloxy group and the constituent units derived from the alkoxysilane compound having an epoxycyclohexyl group relative to the total amount of the constituent units derived from the alkoxysilane compound having a glycidyloxy group, the constituent units derived from the alkoxysilane compound having an epoxycyclohexyl group, and the constituent units derived from the other alkoxysilane compounds is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%, and may be 100 mol%. When the present polysiloxane contains a total of 50 mol% or more of the constituent units derived from the alkoxysilane compound having a glycidyloxy group and the constituent units derived from the alkoxysilane compound having an epoxycyclohexyl group, the density of the epoxy groups that become crosslinking points is increased, the crosslinking density of the obtained cured product is improved, and the scratch resistance can be improved.

In the present polysiloxane, the amount of the constituent units derived from the alkoxysilane compound having a glycidyloxy group relative to the total amount (100 mol%) of the constituent units derived from the alkoxysilane compound having the epoxycyclohexyl group is preferably 10 to 99 mol%, more preferably 20 to 95 mol%, and even more preferably 30 to 90 mol%. The amount of the 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%. According to the above configuration, a polysiloxane having excellent weather resistance and excellent reactivity can be obtained.

In the present polysiloxane, the amount of the constituent unit (hereinafter referred to as T1) derived from monoorganotrialkoxysilane and forming one siloxane bond, the amount of the constituent unit (hereinafter referred to as T2) derived from monoorganotrialkoxysilane and forming two siloxane bonds, and the amount of the constituent unit (hereinafter referred to as T3) derived from monoorganotrialkoxysilane and forming three siloxane bonds are each 3 to 80 mol % out of 100 mol % of all constituent units of the present polysiloxane, and the total amount of the T1, T2, and T3 is preferably 90 to 100 mol %. According to the above configuration, the compatibility and reactivity of the present polysiloxane with other resins (e.g., acrylic polyol) contained in the curable resin composition is good.

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%. 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%. Furthermore, the total amount of T1, T2, and T3 is more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%.

Here, the amount of T1, the amount of T2, and the amount of T3 in the present polysiloxane can be calculated as the ratio (%) of the peak area attributable to T1, T2, and T3 to the ^total peak area of the peak areas attributable to Q1, Q2, Q3, Q4, T1, T2, T3, D1, D2, and M1, respectively, measured by 29Si-NMR.

Here, Q1, Q2, Q3, and Q4 are structural units derived from tetraalkoxysilanes and have one, two, three, or four siloxane bonds, respectively, T1, T2, and T3 are the amount of structural units derived from monoorganotrialkoxysilanes and have one, two, or three siloxane bonds, respectively, D1 and D2 are structural units derived from diorganodialkoxysilanes and have one or two siloxane bonds, and M1 is a structural unit derived from triorganomonoalkoxysilanes and have one siloxane bond.

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)." In addition, the total amount of T1, T2, and T3 can also be expressed as "T1+T2+T3/(Q1+Q2+Q3+Q4+T1+T2+T3+D1+D2+M1)."

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 moieties T3 having a silsesquioxane structure. The silsesquioxane structure is a structure that combines a dense cross-linked structure with flexibility, and contributes to the development of scratch resistance and water resistance in the cured product. Conversely, if the proportion of T3 is 0%, there is no silsesquioxane structure, making it difficult for the polysiloxane to develop the desired physical properties.

The polysiloxane preferably has a silanol group. The fact that the polysiloxane "has a silanol group" can also be evaluated by the degree of condensation of the polysiloxane. The fact that the polysiloxane "has a silanol group" means that the degree of condensation of the polysiloxane is less than 100%. Here, the degree of condensation is a value calculated by the following formula:
Condensation degree (%)={(1×amount of T1)+(2×amount of T2)+(3×amount of T3)}/3
The condensation degree of the present polysiloxane is preferably 90% or less, more preferably 85% or less. If the condensation degree of the present polysiloxane is 90% or less, the compatibility and reactivity of the present polysiloxane with other resins will be good. The lower limit of the condensation degree of the present polysiloxane is not particularly limited, but can be, for example, 70% or more. If the condensation degree of the present polysiloxane is 70% or more, the shrinkage stress when obtaining a cured product (cured coating film) will not be excessively large, and even when a thick cured coating film (for example, a coating film having a thickness of 20 μm or more) is prepared, the occurrence of cracks in the coating film can be suppressed.

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, the amount of alcohol generated in the hydrolysis reaction, and the like.

The weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 2,000 to 20,000, more preferably 3,000 to 15,000, and even more preferably 4,000 to 10,000, 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.

The epoxy equivalent of the polysiloxane is preferably 150 to 400, more preferably 160 to 300, and even more preferably 170 to 250. If the epoxy equivalent of the polysiloxane is 400 or less, the crosslinked structure of the polysiloxane can be sufficiently obtained, and a cured product having high scratch resistance and chemical resistance can be obtained. If the epoxy equivalent is 150 or more, the amount of epoxy groups remaining unreacted in the cured product will be reduced.

In this specification, the epoxy equivalent of a 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 molecule of polysiloxane (average number) When the epoxy equivalent of the polysiloxane cannot be calculated based on the above formula because the composition of the polysiloxane is unknown, etc., the epoxy equivalent of the polysiloxane can be measured in accordance with JIS K7236.

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

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

(Metal Catalyst)
The curable resin composition preferably contains a metal catalyst.As the metal catalyst, for example, an organometallic acid catalyst such as an organoaluminum compound, an organotin compound, an organozinc compound, an organotitanium compound, an organoferric compound, etc. can be suitably used, among which, an organoaluminum compound (hereinafter referred to as an aluminum compound) is preferred.Only one of these metal catalysts may be used alone, or two or more may be used in combination.

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 carboxy groups. These organic groups may be of one type only, or may be of two or more types mixed together.

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

(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 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 having excellent 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, but examples thereof include ethyl acetoacetate, acetyl acetonate, methyl acetoacetate, dimethyl malonate, and the like. Among them, ethyl acetoacetate is preferable because it has good solubility in the present polysiloxane, (meth)acrylic polyol, and solvent.

In the formula (I), among R ¹ , R ² and R ³ , the organic group other than the β-dicarbonyl compound may be, 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, or the like.

The aluminum compound is not particularly limited as long as it has at least one organic group directly bonded to the aluminum atom, but examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), diisopropoxyaluminum ethylacetoacetate, aluminum tris(sec-butoxide), etc. Among these, aluminum tris(ethylacetoacetate) and diisopropoxyaluminum ethylacetoacetate are preferred because they have high solubility in the polysiloxane and (meth)acrylic polyol and high epoxy curing properties (high Lewis acidity). As the aluminum compound, only one of these may be used alone, or multiple types may be used in combination.

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

(Resin Component)
The curable resin composition may contain a resin component (other resin component) in addition to the polysiloxane. Such resin components are not particularly limited, and include, for example, (meth)acrylic polyol, aliphatic alcohol, aromatic alcohol, polyether polyol, polyester polyol, polyolefin polyol, acrylic resin, etc. Only one type of these resin components may be used alone, or two or more types may be used in combination. Among these other resin components, (meth)acrylic polyol is preferred because it can provide a cured product with excellent scratch resistance and chemical resistance.

In this specification, (meth)acrylic polyol refers to a copolymer having two or more hydroxyl groups in the molecule, which is obtained by copolymerizing (e.g., radically polymerizing) a (meth)acrylic monomer and a monomer having a hydroxyl group. The (meth)acrylic polyol is preferably one 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. As the (meth)acrylic polyol, one type of (meth)acrylic polyol may be used alone, or two or more types may be used in combination.

In this specification, the (meth)acrylic monomer contained in the (meth)acrylic polyol is not particularly limited as long as it has a component (meth)acrylic group, but examples thereof include alkyl (meth)acrylates having 1 to 20 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; cycloalkyl (meth)acrylates having 4 to 20 carbon atoms such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; allyl (meth)acrylate; dicyclopentenyl (meth)acrylate; and aralkyl (meth)acrylates having 3 to 20 carbon atoms such as benzyl (meth)acrylate. The (meth)acrylic polyol may contain only one type of these (meth)acrylic monomers, or may contain two or more types. A (meth)acrylic monomer can also be said to be a monomer that has a (meth)acrylic group.

The monomer having a hydroxyl group contained in the (meth)acrylic polyol is not particularly limited, but examples thereof include hydroxyl group-containing vinyl monomers such as 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, and 4-hydroxystyrene vinyl toluene; Examples of the polyoxyalkylene include modified lactones or polyesters having a polymerizable carbon-carbon double bond at the end, such as 1FA-1, PlaccelFA-4, PlaccelFM-1, and PlaccelFM-4 (all manufactured by Daicel Chemical Industries, Ltd.); Blenmer PP series, Blenmer PE series, and Blenmer PEP series (all manufactured by NOF Corp.), 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 Nyukazai Co., Ltd.). The (meth)acrylic polyol may contain only one type of monomer having a hydroxyl group, or may contain two or more types.

By including a (meth)acrylic polyol in this curable resin composition, the polysiloxane and the (meth)acrylic polyol form a structure represented by C-O-Si and crosslink. By forming such a structure, a cured product with excellent adhesion, durability, etc. can be obtained.

The (meth)acrylic polyol may also contain monomers (other monomers) other than the above-mentioned (meth)acrylic monomers and monomers having a hydroxyl group. Examples of other monomers include, but are not limited to, 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. Only one of these other monomers may be used alone, or two or more may be used in combination.

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 contained in the (meth)acrylic polyol, a monomer having a hydroxyl group, and a monomer having a reactive silicon group.

The monomer having a reactive silicon group is not particularly limited, and examples thereof 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, and vinyltrichlorosilane.

The number of hydroxyl groups contained in the (meth)acrylic polyol molecule is not particularly limited as long as it is 2 or more, but is, for example, 3 or more, preferably 5 or more, and more preferably 7 or more. If the number of hydroxyl groups contained in the (meth)acrylic polyol molecule is 3 or more, a dense crosslinked structure can be obtained, and a cured product with excellent scratch resistance can be obtained. In addition, the upper limit of the number of hydroxyl groups contained in the (meth)acrylic polyol molecule is not particularly limited, but is, for example, 50 or less, preferably 40 or less. If the number of hydroxyl groups contained in the (meth)acrylic polyol molecule is 50 or less, the number of hydroxyl groups remaining in the cured product (coating film) after the curing reaction is reduced, and a cured product (coating film) with excellent water resistance can be obtained.

The hydroxyl value of the (meth)acrylic polyol is preferably 20 to 300 mgKOH/g, more preferably 50 to 250 mgKOH/g, even more preferably 80 to 230 mgKOH/g, and particularly preferably 100 to 200 mgKOH/g. If the hydroxyl value of the (meth)acrylic polyol is 20 to 300 mgKOH/g, a curable resin composition having a high crosslink density and excellent scratch resistance and chemical resistance can be obtained. In this specification, the hydroxyl value is a value measured based on the standard of JIS K 1557-1.

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. If the number average molecular weight (Mn) of the (meth)acrylic polyol is 1,000 to 6,000, a cured product having a high crosslink density and excellent scratch resistance and chemical resistance can be obtained.

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 using GPC in terms of polystyrene.

The present curable resin composition preferably contains 5 to 100 parts by weight of the resin component relative to 100 parts by weight of the present polysiloxane, 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. When the content of the resin component in the present curable resin composition is 5 parts by weight or more relative to 100 parts by weight of the present polysiloxane, it can react sufficiently with the present polysiloxane to form a dense crosslinked structure. When the content is 100 parts by weight or less, it has the advantage of not inhibiting the curing reaction of the present polysiloxane alone. When the present curable resin composition contains two or more types of resin components, the total amount of each resin component is the content of the resin component in the present curable resin composition.

(Method for producing (meth)acrylic polyol)
A (meth)acrylic polyol can be produced by polymerizing the above-mentioned (meth)acrylic monomer, a monomer having a hydroxyl group, and optionally other monomers by a known method (for example, by heating in the presence of a polymerization initiator).

The polymerization initiator is not particularly limited, but 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 alone or in combination of two or more.

The amount of the polymerization initiator used when producing the (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 described above. When the amount of the polymerization initiator used is 0.1 part by weight or more, the polymerization reaction proceeds appropriately. Furthermore, when the amount of the polymerization initiator used is 5.0 parts by weight or less, a copolymer with an appropriate molecular weight can be obtained.

(Meth)acrylic polyol 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-based 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, dipentynyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol methyl ether acetate; silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; and the like.

In one embodiment of the present invention, when producing a (meth)acrylic polyol, in addition to the above polymerization initiator,
A chain transfer agent may be used. By using the 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, and examples thereof include n-dodecyl mercaptan, t-dodecyl mercaptan, 2-ethylhexyl thioglycolate, n-octyl mercaptan, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl dimethoxysilane, mercaptoethanol, and α-methylstyrene dimer. These chain transfer agents may be used alone or in combination of two or more.

The amount of the chain transfer agent used when producing the (meth)acrylic polyol is not particularly limited, but 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 the monomer having an acrylic group, the monomer having a hydroxyl group, and the other monomers. When the amount of the 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 terminals of the (meth)acrylic polyol, and the inhibition of curing of the polysiloxane caused by these functional groups can be suppressed. In addition, when the amount of the chain transfer agent used is 10 weight percent or less, the agent is efficiently introduced to the polymer terminals, so there is no risk of it remaining in the curable resin composition as an unreacted substance (plasticizer).

(Polyisocyanate Compound)
The present curable resin composition preferably contains a polyisocyanate compound. When the present curable resin composition contains a polyisocyanate compound, a cured product having excellent scratch resistance can be obtained.

In this specification, a polyisocyanate compound refers to a compound having two or more isocyanate groups in one molecule. In other words, a polyisocyanate compound has two or more isocyanate groups in one molecule.

The number of isocyanate groups in a polyisocyanate compound is not particularly limited as long as it is 2 or more per molecule, but is preferably 2.1 or more per molecule, 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 is preferably, for example, 20 or less, and more preferably 10 or less.

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, in order to achieve good compatibility and reactivity. The number average molecular weight (Mn) of the polysiloxane is a value calculated using GPC in terms of polystyrene.

As the polyisocyanate compound, conventionally known polyisocyanate compounds can be used. Examples of such polyisocyanate compounds include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic aliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds.

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. 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; and the like.

Examples of alicyclic polyisocyanate compounds include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3 diisocyanate compounds such as 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)cyclohexane, and isophorone diisocyanate; cyclo[2,2,1]heptane, 2-(3-isocyanatepropyl)-2,6-di(isocyanatemethyl)-bicyclo[2,2,1]heptane, 3-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-bicyclo[2,2,1]heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-3-(3-isocyanatepropyl)-bicyclo[2,2,1]heptane, 6-(2-isocyanateethyl)-2-isocyanateethyl Compounds having three or more isocyanate groups such as isocyanate methyl-3-(3-isocyanate propyl)-bicyclo[2,2,1]heptane, 5-(2-isocyanate ethyl)-2-isocyanate methyl-2-(3-isocyanate propyl)-bicyclo[2,2,1]heptane, 6-(2-isocyanate ethyl)-2-isocyanate methyl-2-(3-isocyanate propyl)-bicyclo[2,2,1]heptane, etc.

Examples of aromatic aliphatic polyisocyanate compounds include diisocyanate compounds such as 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof; compounds having three or more isocyanate groups such as 1,3,5-triisocyanatomethylbenzene; and the like.

Examples of aromatic polyisocyanate compounds include diisocyanate compounds such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenylether diisocyanate; compounds having three or more isocyanate groups such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI); and the like.

In one embodiment of the present invention, modified products of the various polyisocyanate compounds described above may be used as the polyisocyanate compound. Examples of such modified products include allophanate modified products, biuret modified products, and isocyanurate modified products.

The polyisocyanate compound is preferably a polyisocyanate having a cyclic structure, a linear structure, or a branched structure, and more preferably one or more selected from the group consisting of aromatic polyisocyanates, alicyclic polyisocyanates, and araliphatic polyisocyanates. Polyisocyanates having a cyclic structure in the molecule, such as alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds, are more preferred because they have a significant effect of improving 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.

When an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound is used, the weather resistance of the resulting cured product is excellent, so this is preferred. In particular, hexamethylene diisocyanate, isophorone diisocyanate, and their isocyanurate modifications are preferred.

When using these polyisocyanate compounds, if yellowing becomes a problem, it is preferable to use aliphatic, alicyclic, or araliphatic polyisocyanates, and aliphatic polyisocyanates or alicyclic polyisocyanates are more preferable.

In one embodiment of the present invention, the polyisocyanate compound may be a blocked isocyanate in which the isocyanate group is masked with a blocking agent and inactivated at room temperature. Examples of blocking agents include alcohols, phenols, oximes, triazoles, caprolactams, and β-dicarbonyl compounds such as acetylacetone and ethyl acetoacetate.

The present curable resin composition preferably contains 5 to 150 parts by weight of a polyisocyanate compound per 100 parts by weight of the present 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 content of the polyisocyanate compound per 100 parts by weight of the present polysiloxane in the present curable resin composition 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.

(solvent)
The present curable resin composition preferably further contains a solvent.

As the solvent, various compounds can be used without any particular limitation. More specifically, examples of the solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and petroleum-based solvents, halogen-based solvents such as trichloroethylene, ester-based solvents such as ethyl acetate, butyl acetate, isobutyl acetate (IBAC), and methoxypropyl acetate, ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether-based solvents such as propylene glycol methyl ether acetate (PMA), dibutyl ether, dipentynyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether, and silicone-based solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Among these, ester-based solvents and ether-based solvents are preferred because they have high solubility in the present polysiloxane and (meth)acrylic polyol, and are highly volatile during spray coating, and isobutyl acetate, methoxypropyl acetate, and propylene glycol methyl ether acetate are particularly preferred. These solvents may be used alone or in combination of two or more.

The content of the solvent in the 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 content of the solvent in the curable resin composition is 40% by weight or more, a curable composition having low viscosity, high thixotropy, and excellent workability can be obtained. When the content of the solvent in the curable resin composition is 80% by weight or less, a cured product with a sufficient film thickness can be obtained by a single coating.

(Dehydrating Agent)
The present curable resin composition preferably further contains a dehydrating agent. When the present curable resin composition contains a dehydrating agent, the present curable resin composition has the advantage of having excellent storage stability.

Dehydrating agents are 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.

The content of the dehydrating agent in the 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 the curable resin composition is 0.1% by weight or more, the curable resin composition can exhibit effective dehydration. When the content of the dehydrating agent in the curable resin composition is 10% by weight or less, the dehydrating agent volatilizes without remaining in the cured product (coating film) after drying and curing, and therefore has the advantage of being easily removed from the coating film.

(Stabilizer)
The present curable resin composition preferably further contains a stabilizer. When the present curable resin composition contains a stabilizer, a curable resin composition having excellent storage stability can be provided, and a cured product having excellent adhesion, scratch resistance, and chemical resistance can be provided.

The stabilizer is not particularly limited, but examples thereof include acetylacetone, ethyl acetoacetate, methyl acetoacetate, dimethyl malonate, etc. These stabilizers may be used alone or in combination of two or more.

The content of the stabilizer in the 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 content of the stabilizer in the curable resin composition is 0.5% by weight or more, a curable resin composition with excellent storage stability can be provided. In addition, when the content of the stabilizer in the curable resin composition is 10% by weight or less, the stabilizer is quickly volatilized from the coating liquid/coating film when the curable resin composition (coating liquid/coating film) is dried/cured, which has the advantage of not causing curing inhibition.

(Other ingredients)
The curable resin composition may contain additives that are commonly used in the technical field within the scope of 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, release agents, antistatic agents, lubricants, low shrinkage agents, silicone surfactants, and moisture. The additives may contain only one type, or may contain two or more types. The amount of these additives can be appropriately set by a person skilled in the art depending on the purpose of use.

<Filling material>
The curable resin composition may contain a filler. The filler is not particularly limited, but examples thereof include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, 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, baryte, anhydrous gypsum, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, mica, zinc white, white lead, lithopone, zinc sulfide, shirasu balloons, glass microballoons, organic microballoons of phenolic resins and vinylidene chloride resins, PVC powder, and PMMA powder; and fibrous fillers such as asbestos, glass fibers, and filaments. In addition to the above, color pigments such as titanium oxide, lead chromate, chromium oxide, ultramarine, cobalt blue, cyanine blue, cyanine green, lake red, and quinacridone red can also be used.

The content of the filler in the 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.

<Flame retardants>
The curable resin composition may contain a flame retardant. The flame retardant is not particularly limited, but may be, for example, a phosphorus-based plasticizer such as ammonium polyphosphate or tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, or thermally expandable graphite. These flame retardants may be used alone or in combination of two or more.

As the ammonium polyphosphate, a wide variety of conventionally known ammonium polyphosphates can be used. Among these, from the viewpoint of water resistance, ammonium polyphosphate that is coated with a resin and microencapsulated, or ammonium polyphosphate that has been surface-treated, such as surface-modified ammonium polyphosphate, is preferred, and ammonium polyphosphate whose surface is coated with a melamine formaldehyde resin is even more preferred.

The content of the flame retardant in the 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.

<Dispersant>
The curable resin composition may contain a dispersant. As the dispersant, a pigment dispersion paste obtained by mixing and dispersing a pigment and a dispersant according to a known method can be blended and used. As the dispersant, a commercially available one can 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)-110. , DISPERBYK®-111, DISPERBYK®-112, DISPERBYK®-116, DISPERBYK®-130, DISPERBYK®-140, DISPERBYK®-142, DISPERBYK®-145, DISPERBYK®-161, DISPERBYK®-162, DISPERBYK®-163, DISPERBYK®-164, DISPERBYK®-165, DISPERBYK®-166, DISPERBYK®-167, DISPERBYK®-169, DISPERBYK®-170, DISPERBYK®-171, DISPERBYK®-172, DISPERBYK®-173, DISPERBYK®-174, DISPERBYK®-175, DISPERBYK®-176, DISPERBYK®-177, DISPERBYK®-178, DISPERBYK®-179, DISPERBYK®-180, DISPERBYK®-181, DISPERBYK®-182, DISPERBYK®-183, DISPERBYK®-184, DISPERBYK®-185, DISPERBYK®-186, DISPERBYK®-187, DISPERBYK®-189, DISPERBYK®-190, DISPERBYK®-200, DISPERBYK®-201, DISPERBYK®-202, DISPERBYK®-203, DISPERBYK®-204, DISPERBYK®-205, DISPERBYK®-210, DISPERBYK®-211, DISPERBYK®-212, DISPERBYK®-213, DISPERBYK®-214, DISPER DISPERBYK®-166, DISPERBYK®-167, DISPERBYK®-168, DISPERBYK®-170, DISPERBYK®-171, DISPERBYK®-174, DISPERBYK®-180, DISPERBYK®-182, DISPERBYK®-183, DISPERBYK®-184, DISPERBYK®-185, DISPERBYK (registered trademark) DISPERBYK®-2000, DISPERBYK®-2001, DISPERBYK®-2008, DISPERBYK®-2009, DISPERBYK®-2022, DISPERBYK®-2025, DISPERBYK®-2050, DISPERBYK®-2070, DISPERBYK®-2096, DISPERBYK®-2150, DISPERBYK®-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, DI SPERBYK®-193, DISPERBYK®-194, DISPERBYK®-198, DISPERBYK®-2010, DISPERBYK®-2012, DISPERBYK®-2015, DISPERBYK®-2090, DISPERBYK®-2091, DISPERBYK®-2095 (all manufactured by BYK-Chemie), DISPARLON® 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) DA-703- 50, DISPARLON (registered trademark) DA-7301, DISPARLON (registered trademark) DN-900, DISPARLON (registered trademark) DA-325, DISPARLON (registered trademark) DA-375, DISPARLON (registered trademark) DA-234 (all manufactured by Kusumoto Chemical Industries, Ltd.), EFKAPOLYMER 4550 (manufactured by EFKA), Solsperse (registered trademark) 27000, Solsperse (registered trademark) 41000, Solsperse (registered trademark) 53095 (all manufactured by Avecia), and the like.

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

If the number average molecular weight of the dispersant is 1,000 or more, sufficient dispersion stability can be obtained, and if it is 100,000 or less, there is no risk of the viscosity of the composition becoming too high, resulting in a composition with excellent handleability.

The content of the dispersant in the 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.

<Antifoaming agent>
The curable resin composition may contain an antifoaming agent. The antifoaming agent is not particularly limited, but for example, commercially available antifoaming agents can be used. Such commercially available defoamers include, for example, BYK®-051, BYK®-052, BYK®-053, BYK®-054, BYK®-055, BYK®-057, BYK®-1752, BYK®-1790, BYK®-060N, BYK®-063, BYK®-065, BYK®-066N, BYK®-067A, BYK®-077, BYK®-088, BYK®-141, BYK®-354, BYK®-392, BYK®-011, BYK®-012, BYK®-016, BYK®-018, BYK®-019, BYK®-020, BYK®-023, BYK®-024, BYK®-025, BYK®-026, BYK®-027, BYK®-028, BYK®-029, BYK®-030, BYK®-031, BYK®-032, BYK®-033, BYK®-034, BYK®-035, BYK®-036, BYK®-037, BYK®-038, BYK®-039, BYK®-040, BYK®-041, BYK®-042, BYK®-043, BYK®-044, BYK®-045, BYK®-046, BYK®-047, BYK®-048, BYK®-049, BYK®-050, BYK®-051, BYK®-052, BYK®-053 Defoamers such as BYK-017, BYK-018, BYK-019, BYK-020, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-028, BYK-038, BYK-044, BYK-093, BYK-094, BYK-1610, BYK-1615, BYK-1650, BYK-1730, and BYK-1770 (all manufactured by BYK-Chemie), and DISPARLON OX-88 acrylic defoamers such as DISPARLON (registered trademark) OX-881, DISPARLON (registered trademark) OX-883, DISPARLON (registered trademark) OX-883HF, DISPARLON (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, and DISPARLON (registered trademark) LAP-30; Examples of the antifoaming agent include silicone-based acrylic composite antifoaming agents such as PARLON (registered trademark) OX-66 and DISPARLON (registered trademark) OX-715; vinyl-based antifoaming agents such as DISPARLON (registered trademark) 1950, DISPARLON (registered trademark) 1951, DISPARLON (registered trademark) 1952, DISPARLON (registered trademark) P-410EF, DISPARLON (registered trademark) P-420, DISPARLON (registered trademark) P-450, DISPARLON (registered trademark) P-425 and DISPARLON (registered trademark) PD-7; and silicone-based antifoaming agents such as DISPARLON (registered trademark) 1930N and DISPARLON (registered trademark) 1934 (all manufactured by Kusumoto Chemical Industries, Ltd.).

The content of the defoamer in the 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.

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

The content of the tackifier in the 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.

<Leveling Agent>
The curable resin composition may contain a leveling agent. The leveling agent is not particularly limited, but for example, a commercially available one can be used. Examples of such commercially available leveling agents include BYKETOL (registered trademark)-OK, BYKETOL (registered trademark)-SPECIAL, BYKETOL (registered trademark)-AQ, BYKETOL (registered trademark)-WS (all manufactured by BYK-Chemie), DISPARLON (registered trademark) 1970, DISPARLON (registered trademark) 230, DISPARLON (registered trademark) LF-1980, DISPARLON (registered trademark) LF-1982, DISPARLON (registered trademark) LF-1983, DISPARLON (registered trademark) LF-1984, and DISPARLON (registered trademark) LF-1985 (all manufactured by Kusumoto Chemical Industries, Ltd.).

The content of the leveling agent in the 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.

<Thixotropy imparting agent>
The curable resin composition may contain a thixotropy imparting agent (sagging prevention agent). The sagging prevention agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; and metal soaps such as calcium stearate, aluminum stearate, and barium stearate. The fumed silica shown as a filler can also be used as a thixotropy imparting agent. In addition, when a rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or an organic fiber as described in JP-A-2003-155389 is used, a composition having high thixotropy and good workability can be obtained. These thixotropy imparting agents (sagging prevention agents) may be used alone or in combination of two or more.

The content of the thixotropy-imparting agent in the 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.

<Epoxy resin>
The curable resin composition may contain an epoxy resin. The epoxy resin is not particularly limited, but examples thereof include known epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, glycidyl ester type epoxy resins, hydrogenated bisphenol A (or F) type epoxy resins, glycidyl ether type epoxy resins, amino-containing glycidyl ether resins, and epoxy compounds obtained by addition reaction of these epoxy resins with bisphenol A (or F), polybasic acids, etc.

The content of the epoxy resin in the 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.

<Antioxidants>
The curable resin composition may contain an antioxidant (antiaging agent). When the composition contains an antioxidant, the heat resistance of the obtained cured product can be improved. The antioxidant is not particularly limited, but examples thereof include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. Among them, hindered phenol-based antioxidants are preferred. In one embodiment of the present invention, as the antioxidant, a hindered amine-based light stabilizer such as Tinuvin (registered trademark) 622LD, Tinuvin (registered trademark) 144, CHIMASSORB (registered trademark) 944LD, CHIMASSORB (registered trademark) 119FL (all of which are manufactured by Ciba Specialty Chemicals Inc.); MARKLA-57, MARKLA-62, MARKLA-67, MARKLA-63, MARKLA-68 (all of which are manufactured by Asahi Denka Kogyo Co., Ltd.); Sanol (registered trademark) LS-770, Sanol (registered trademark) LS-765, Sanol (registered trademark) LS-292, Sanol (registered trademark) LS-2626, Sanol (registered trademark) LS-1114, Sanol (registered trademark) LS-744 (all of which are manufactured by Sankyo Co., Ltd.) can also be used.

The content of the antioxidant 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.

<Light stabilizer>
The curable resin composition may contain a light stabilizer. When the composition contains a light stabilizer, photo-oxidation deterioration of the obtained cured product can be prevented. The light stabilizer is not particularly limited, but examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Among them, hindered amine-based compounds are preferred. In particular, a tertiary amine-containing hindered amine-based light stabilizer is preferred because it can improve the storage stability of the composition. More specifically, examples of the tertiary amine-containing hindered amine light stabilizer include light stabilizers such as TINUVIN (registered trademark) 622LD, TINUVIN (registered trademark) 144, and CHIMASSORB (registered trademark) 119FL (all manufactured by BASF); MARKLA-57, LA-62, LA-67, and LA-63 (all manufactured by ADEKA CORPORATION); and SANOL (registered trademark) LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all manufactured by Sankyo Co., Ltd.).

The content of the light stabilizer 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.

<Ultraviolet absorbing agent>
The curable resin composition may contain an ultraviolet absorber. When the composition contains an ultraviolet absorber, the surface weather resistance of the cured product obtained can be improved. The ultraviolet absorber is not particularly limited, but may be, for example, a benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, or metal chelate-based compound, and is particularly preferably a benzotriazole-based compound.

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

The content of the 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.

<Silane coupling agent>
The curable resin composition may contain a silane coupling agent. When the composition contains a silane coupling agent, the adhesiveness can be improved. The silane coupling agent is not particularly limited, but examples thereof include isocyanate group-containing silanes such as γ-isocyanate propyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-isocyanate propyl methyl diethoxysilane, γ-isocyanate propyl methyl dimethoxysilane, (isocyanate methyl) trimethoxysilane, (isocyanate methyl) dimethoxymethylsilane, (isocyanate methyl) triethoxysilane, and (isocyanate methyl) diethoxymethylsilane; γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl triisopropoxysilane, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyl diethoxysilane, γ-(2-aminoethyl) aminopropyl trimethoxysilane, and γ-(2-aminoethyl) aminopropyl methyl 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 -bis[3-(trimethoxysilyl)propyl]ethylenediamine and other amino group-containing silanes; N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine and other ketimine type silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane and other mercapto group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4- Examples of the silane coupling agent include epoxy group-containing silanes such as epoxycyclohexyl)ethyltriethoxysilane; carboxy silanes 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. In addition, derivatives obtained by modifying these, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

The content of the silane coupling agent 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.

The present curable resin composition may contain moisture derived from each of the above components and other components. When the curable resin composition contains moisture, the storage stability of the curable resin composition may be impaired. Therefore, the moisture content in the present curable resin composition is, for example, 0.3% by weight or less, preferably 0.2% by weight or less, and more preferably 0.1% by weight or less, relative to 100% by weight of the total amount of the curable composition. The lower limit is not particularly limited, and may be 0% by weight.

(others)
The curable resin composition may be of one-component type or of multi-liquid type. A one-component curable resin composition is a composition in which all the components are mixed in advance and then sealed and stored. The one-component curable resin composition can provide a cured product by curing with moisture in the air after use. On the other hand, the multi-liquid curable resin composition can provide a cured product by separately producing and storing a first liquid containing a resin component and a second liquid containing a curing catalyst, and mixing the first liquid and the second liquid just before use.

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

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 a first liquid, and more preferably contains the polysiloxane and resin component as a first liquid, and a polyisocyanate compound and a metal catalyst as a 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.

(Method for producing curable resin composition)
The present curable resin composition can be produced by mixing the above-mentioned components (the present polysiloxane and, if necessary, the resin component, the polyisocyanate compound, the metal catalyst, and other components, etc.) by a known method. The mixing method is not particularly limited, but examples thereof include a method using a mixer such as a mixing tank equipped with a propeller-type/paddle-type stirring blade, a planetary mixer, a kneader, a Hobart mixer, a high-speed mixer, a line mixer, a roll mill, a sand mill, an attritor, or a two-shaft mixer.

In addition, when a multi-component curable resin composition is to be prepared, the first and second liquids obtained by the method described below are further mixed to obtain the present curable resin composition. In this case, examples of the method for mixing the first and second liquids include a method of blending each component and mixing them with a hand mixer or a static mixer, a method of kneading at room temperature or under heat using a planetary mixer, a disperser, a roll, a kneader, or the like, and a method of dissolving the components using a small amount of a suitable solvent and mixing them.

In the method for producing the curable resin composition, the above-mentioned components may be mixed simultaneously, or each component may be mixed by repeating the steps of adding, mixing, and homogenizing in sequence. Since a more uniformly mixed composition can be obtained, it is preferable to mix each component by repeating the steps of adding, mixing, and homogenizing in sequence.

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

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

(Second liquid)
The second liquid of the multi-liquid curable resin composition preferably contains a polyisocyanate compound and a metal catalyst. The polyisocyanate compound and the metal catalyst are as described above in the (polyisocyanate compound) and (metal catalyst) sections. The second liquid functions as a curing agent in the multi-liquid curable resin composition.

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 examples thereof include solvents, leveling agents, dehydrating agents, stabilizers, organic resins that do not have hydroxyl groups, etc.

As described above, the multi-component curable resin composition can be prepared by separately producing and storing a first component containing the polysiloxane and a second component containing the curing agent, and then mixing the first and second components just before use to provide a cured product.

The blending ratio of the first liquid to the second liquid in this multi-component curable resin composition can be adjusted as appropriate depending on the application. The blending ratio of the first liquid to 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 blending ratio of the first liquid to the second liquid is 10:1 to 2:1, a multi-component curable resin composition that is easy to mix and unlikely to cause uneven performance can be provided.

The multi-component curable resin composition can further contain a colorant, for example, when the first and second components are mixed. This has the advantage that, for example, a wide range of colors can be provided to match the color of the siding board from a limited number of types of curable resin composition. Therefore, the multi-component curable resin composition can easily meet the market demand for multiple colors, and is suitable for low-rise building applications. The colorant is preferably a paste made by mixing, for example, a pigment, a plasticizer, and, if necessary, a filler, which is easy to work with.

In addition, a retarder can be added to a multi-liquid curable resin composition when mixing the multi-liquid components. This allows the curing speed to be fine-tuned at the work site.

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

The present cured product is formed by curing the present curable resin composition. Preferably, the present cured product is formed by mixing a first liquid (base) containing the present polysiloxane and a resin component with a second liquid (curing agent) containing a polyisocyanate compound and a metal catalyst, and heating and curing the resulting curable resin composition. Note that if the present curable resin composition contains a volatile component such as a solvent, the volatile component volatilizes due to heating during curing. Therefore, the present cured product does not substantially contain the volatile component contained in the present curable resin composition.

The heating temperature when curing the present curable resin composition is not particularly limited, and is usually 50 to 200°C, but 60 to 120°C is preferable, 70 to 110°C is more preferable, and 80 to 100°C is even more preferable. The present cured product can have excellent scratch resistance even when formed at a relatively low temperature of 60 to 120°C.

The heating time for curing the present curable resin composition is not particularly limited, but from the viewpoint of achieving both cost and the progress of the curing reaction, 10 to 120 minutes is preferable, 15 to 100 minutes is more preferable, and 30 to 60 minutes is even more preferable.

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 cure shrinkage are unlikely to occur. It is more preferably 5 to 50 μm, and even more preferably 10 to 40 μm.

(Application)
The present curable resin composition and the present cured product can be used for various 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 members of optical waveguides, adhesives for DVD lamination, pressure sensitive adhesives, dicing tapes, electronic materials, insulating materials (including printed circuit boards, electric wire coatings, etc.), high voltage insulating materials, interlayer insulating films, insulating packings, insulating coating materials, adhesives, highly heat resistant adhesives, highly heat dissipating 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, coats for optical disks, coats for optical fibers, etc.), molding materials (sheets, films, FRP It can be applied to sealing materials, potting materials, sealing materials, sealing materials for light-emitting diodes, reflectors and reflectors for light-emitting diodes, optical semiconductor sealing materials, liquid crystal sealing agents, sealing agents for display devices, sealing materials for electrical materials, sealing materials for solar cells, high heat-resistant sealing materials, resist materials, liquid resist materials, colored resists, dry film resist materials, solder resist materials, materials for color filters, photolithography, materials for electronic paper, materials for holograms, materials for solar cells, materials for fuel cells, display materials, recording materials, vibration-proof materials, waterproof materials, moisture-proof 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 protection materials, linings, soil injection agents, cold and heat storage materials, sealing materials for sterilization treatment equipment, contact lenses, oxygen-enriched membranes, and additives to other resins, etc.

In addition, a laminate containing the present cured product can be obtained by mixing the first and second liquids of the present curable resin composition, applying the resulting mixture to a substrate, and curing the mixture using a heat source to form a cured coating film. The laminate can be suitably used for front panels of personal computers, smartphones, tablets, etc., window glass of automobiles, lamp protection materials for automobiles, films, etc.

The substrate is not particularly limited, and may be, for example, metal (e.g., aluminum, SUS, copper, iron, etc.), ceramics, glass, cement, ceramic substrate, stone, plastic (e.g., polycarbonate (PC), acrylic, ABS, PC-ABS alloy, polyethylene terephthalate (PET), etc.), wood, paper, fiber, etc. The substrate may be a film or sheet. The present curable resin composition can be suitably used for painting automobiles, buildings, home appliances, industrial equipment, etc. Since the present curable resin composition is cured by heating, it is particularly suitable for forming a coating film on the surface of a substrate having a complex shape. In addition, as described above, the present curable resin composition can achieve excellent scratch resistance even when cured at a relatively low temperature 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, so that it has the advantage of being suitable for use with organic substrates.

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

That is, 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 an epoxycyclohexyl group is hydrolyzed and dehydrated and condensed in the presence of water and a neutral salt to obtain a solution containing a polysiloxane macromer;
(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 an epoxycyclohexyl group in 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 polysiloxane;
A method for producing a polysiloxane comprising the steps of:
<2> The method for producing a polysiloxane according to <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 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 (100 mol%), and
The method for producing a polysiloxane according to <1> or <2>, wherein the amount of T0 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 the 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 <1> to <3>, further comprising: (3) a dealcoholization step of heating the solution containing the polysiloxane to obtain a solution containing the dealcoholized polysiloxane.
<5> The method for producing a polysiloxane according to any one of <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 <1> to <5>, wherein the polysiloxane has an epoxy equivalent of 150 to 400.
<7> The method for producing a polysiloxane according to any one of <1> to <6>, wherein the polysiloxane contains a structural unit having a glycidyloxy group and a structural unit having an epoxycyclohexyl group.
<8> The polysiloxane according to claim 8, wherein the block structures include 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 each having an alkoxysilane compound having a glycidyloxy group and/or an epoxycyclohexyl group as a constituent unit,
The composition of the constituent units of the block structure is different from one another in the polysiloxane.
<10> A curable resin composition comprising the polysiloxane according to <8> or <9>.
<11> A multi-component curable resin composition comprising the polysiloxane according to <8> or <9>.
<12> A cured product obtained by curing the curable resin composition according to <10> or the multi-component curable resin composition according to <11>.

The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

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

<Polysiloxane>
(Alkoxysilane Compound)
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (abbreviation "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 Co., Ltd., molecular weight 236.3)
Methyltrimethoxysilane (abbreviation "Me"): ("OFS-6070" manufactured by Dow Toray Co., Ltd.: molecular weight 136.2)
(Neutral salt)
Magnesium chloride hexahydrate (abbreviated as "MgCl ₂ ") (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 203.3)
(water)
Pure water (organic solvent)
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)
Phosphoric acid: (Tokyo Chemical Industry Co., Ltd., molecular weight 97.99)
Potassium hydroxide: (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 56.11)
<Resin Component>
((Meth)acrylic monomer)
Methyl methacrylate (abbreviated as "MMA"): manufactured by Mitsubishi Gas Chemical Co., Ltd. Butyl acrylate (abbreviated as "BA"): manufactured by Nippon Shokubai Co., Ltd. (monomer having a hydroxyl group)
2-Hydroxypropyl methacrylate (abbreviated as "HPMA"): manufactured by Nippon Shokubai Co., Ltd. (other monomers)
Styrene (abbreviation "St"): manufactured by Mitsubishi Chemical Corporation (polymerization catalyst)
2,2'-Azobis(2-methylbutyronitrile): ("V59" manufactured by Wako Pure Chemical Industries, Ltd., 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 product (abbreviated as "N3300"): "Sumidur N3300" manufactured by Covestro Japan Co., Ltd.)
<Metal catalyst>
Aluminum (trisethylacetoacetate) (abbreviated as "ALCH") (manufactured by Kawaken Fine Chemicals Co., Ltd., molecular weight 414.4)
<Other ingredients>
(Stabilizer)
Acetylacetone (abbreviation: "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 carried out by the following methods.

(Scratch resistance)
Using an eraser abrasion tester (manufactured by Mitsumoto Seisakusho Co., Ltd.), a load of 500 g/ ^cm2 was applied to steel wool #0000 on the cured product (coating film) applied to the ABS obtained, and the surface of the cured coating film was reciprocated 10 times with a stroke length of 10 cm, after which the gloss retention of the coating film was measured. Here, the gloss retention of the coating film was a value measured using a Micro Trigloss manufactured by BYK. The scratch resistance of the cured product was evaluated based on the following criteria:
A (pass): Gloss retention rate is 80% or more B (poor): Gloss retention rate is less than 80% (chemical resistance)
0.2 g of a 10% aqueous solution of lactic acid was spotted onto the resulting cured product (coating film) applied to the ABS, and the coating film was left to stand for 1 hour in a hot air dryer adjusted to 80° C. Thereafter, the coating film was visually inspected for changes in color and smoothness, and the chemical resistance of the cured product was evaluated based on the following criteria:
A (Good): No color change, no spot marks. The surface of the coating is smooth and no shrinkage. B (Pass): No color change, only faint spot marks. The surface of the coating is smooth and no shrinkage. C (Fail): The spot marks are slightly whitened, and the surface of the coating is slightly shrinked. D (Poor): The spot marks are clearly whitened, and the surface of the coating is clearly shrinked.

(Moisture resistance)
The obtained cured product (coating film) applied to the ABS was left to stand for a predetermined time in a thermohygrostat adjusted to 80°C, 95% RH, and the appearance change was visually confirmed. The durability of the coating film was evaluated based on the following criteria:
A (Good): No change in appearance after standing for 500 hours. B (Pass): After standing for 500 hours, the cured product turns slightly white (slight), and no bleeding occurs. C (Fail): After standing for 500 hours, the cured product turns white (severe), bleeding occurs on the oil, or cracks occur on the surface of the cured product.
D (Poor): Significant changes in appearance other than whitening, such as cracks, shrinkage, peeling, etc. (Weather resistance)
The obtained cured product (coating film) applied on the ABS was exposed for 200 hours under the condition of a black panel temperature of 63°C using a Sunshine Weather Meter (Sunshine Weather Meter S80, manufactured by Suga Test Instruments Co., Ltd.). The appearance of the coating film after exposure was measured and confirmed by measuring the color difference ΔE (color difference ΔE between the coating film before exposure and the coating film after exposure) using a color difference meter (CR400, manufactured by Kitahama Seisakusho Co., Ltd.) and visually, and the change in appearance of the coating film was evaluated based on the following criteria. ΔE is a value measured according to the L*a*b* color system specified in JIS Z 8729 and is a value calculated by the following formula:
ΔE=(ΔL ² +Δa ² +Δb ² ) ^1/2
In the formula, L* is lightness, and a* and b* are chromaticity.
A (good): ΔE<2, and no significant change in appearance is observed by visual inspection. B (fail): 2≦ΔE, and no significant change in appearance is observed by visual inspection. C (poor): 2≦ΔE, and significant changes such as cracks, shrinkage, peeling, etc. are observed by visual inspection. [Example 1]
(Synthesis Example 1: Preparation of polysiloxane)
In a 2L four-neck flask, 0.14g of Me, 47.02g of EC, 0.038g of _MgCl2 , 26.91g of pure water (62.5 mol% relative to the total alkoxysilyl groups), and 15.89g of methanol were placed as alkoxysilane components (I), and the mixture was heated in an oil bath set at 90°C and reacted for 2 hours to obtain a solution containing a polysiloxane macromer having EC as a main structural unit (first polymerization step). As shown in Table 2, the results of ^29Si -NMR measurements showed that T1 in the solution containing the polysiloxane macromer obtained in the first polymerization step was 10.2 mol%, and T2 was 30.5 mol%. T0 was 0.1%.

Additionally, 0.14 g of Me, 142.92 g of Ge, and 0.28 g of methanol were added as alkoxysilane components (II) to the four-neck flask containing the resulting solution containing polysiloxane macromer, and the reaction was continued for another 4 hours to obtain a solution containing polysiloxane (second polymerization step).

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 generated methanol and remaining water (de-alcoholization process). Furthermore, the oil bath (oil bath after the de-alcoholization process) was heated for 2 hours while maintaining the temperature at 140°C (aging process).

Thereafter, 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 about 200 g of polysiloxane. The SC (solid content) of the polysiloxane in the obtained solution was 70%, the weight average molecular weight (Mw) (polystyrene equivalent) was 7200, and the measurement results of ²⁹ Si-NMR showed that 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%. The SC indicates the weight ratio of the components (solid content) that did not volatilize when the entire amount of the obtained solution containing polysiloxane was heated to 105° C. to the entire amount of the solution containing the polysiloxane. Table 1 shows the types and amounts of the components used in the first polymerization step, the second polymerization step, and the dealcoholization step, as well as the physical properties of the solution containing polysiloxane (or polysiloxane macromer).

(Preparation of Curable Resin Composition)
According to the formulation shown in Table 2, the prepared polysiloxane, ALCH as a metal catalyst, and PMA as a solvent were added in that order to a 225 ml mayonnaise bottle and mixed for 5 minutes using a magnetic stirrer to prepare a curable resin composition having an NV value (nonvolatile content) of 45% by weight. The NV value refers to the ratio (wt%) of the weight of the cured product (coating film) after drying to 100% by weight of the curable resin composition before drying (before curing).

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

[Example 2, Comparative Examples 1 to 5]
Polysiloxanes were prepared in the same manner as in Example 1, except that the amounts and types of each component were changed to those shown in Tables 1 and 2, and the second polymerization step was not carried out in Comparative Examples 1 to 3. Curable resin compositions and cured products were prepared using the polysiloxanes, and the physical properties were measured and evaluated. The results are shown in Table 2.

〔result〕
From Table 2, it was shown that the cured product obtained by curing the curable resin composition containing the polysiloxane of Example 1 has excellent 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 having excellent weather resistance. Furthermore, it was shown that the polysiloxane of Example 1 can provide a curable resin composition that can provide a cured product having excellent physical properties such as scratch resistance, chemical resistance, and moisture resistance.

On the other hand, Table 2 shows that the weather resistance of the cured products obtained from the curable resin compositions containing polysiloxane of Comparative Examples 1 to 5 is poor. In other words, it was shown that if the configuration of the present invention is not satisfied, the cured products obtained by curing the curable resin compositions containing polysiloxane obtained will have poor weather resistance. In particular, Comparative Examples 4 and 5 show that even if a two-stage polymerization process is performed, if a neutral salt is not used, the cured products obtained by curing the curable resin compositions containing polysiloxane obtained will have poor weather resistance.

The curable resin composition containing this polysiloxane can provide a cured product with excellent weather resistance, making it suitable for use as a coating agent, etc.

Claims (6)

(1) a first 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 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 an epoxycyclohexyl group in 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 polysiloxane ,
The neutral salt is one or more selected from the group consisting of magnesium chloride, magnesium bromide, and magnesium iodide.
A method for producing polysiloxane. The method for producing 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). 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 constitutional 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 T0 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 the 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.) The method for producing polysiloxane according to any one of claims 1 to 3 further comprises (3) a dealcoholization step of heating the solution containing the polysiloxane to obtain a solution containing dealcoholized polysiloxane. 5. The method for producing a polysiloxane according to claim 1 , wherein the polysiloxane has an epoxy equivalent of 150 to 400. 6. The method for producing a polysiloxane according to claim 1 , wherein the polysiloxane contains a constituent unit having a glycidyloxy group and a constituent unit having an epoxycyclohexyl group.