JP2020152894A - Curable composition and cured product - Google Patents

Abstract

To provide a curable composition giving a cured product excellent in anti-fouling property and self-cleaning properties and to provide a cured product of the curable composition.SOLUTION: There are provided: a curable composition comprising a first organic polymer and a second organic polymer, where the first organic polymer has no siloxane structure and has a reactive silicon group represented by the following formula 1, the second organic polymer has a siloxane structure and contains a unit based on a first monomer and a unit based on a second monomer, the first monomer has no reactive silicon group represented by the following formula 1 and has a siloxane structure and a polymerizable unsaturated group and the second monomer has no reactive silicon group represented by the following formula 1 and no siloxane structure and has a hydrophilic group and a polymerizable unsaturated group; and a cured product of the curable composition. -SiXaR3-a (Formula 1)SELECTED DRAWING: None

Description

The present invention relates to curable compositions and cured products.

A curable composition containing a polymer having a reactive silicon group is used, for example, as a sealing material for joints of outer walls.
It is desirable that the outer wall of the building has excellent antifouling properties and is not easily soiled. Therefore, it is desirable to have a self-cleaning property in which the attached dirt is washed away by rainfall or the like.

Patent Document 1 describes 100 parts by weight of the crosslinkable silyl group-containing organic polymer (A), 0.1 to 30 parts by weight of the reactive silicone oil (B), and 0.1 to 10 parts by weight of the curing catalyst (C). , And a curable composition containing. It is described that when this curable composition is used as a sealing material, it is possible to eliminate the surface tack (stickiness) after curing and to avoid the problem of sand adhering to the outer wall after curing.

Japanese Unexamined Patent Publication No. 2004-18695

In recent years, with the improvement of the self-cleaning property of the outer wall board, the sealing material is also required to be improved in the self-cleaning property so that the dirt on the joints is less noticeable.
However, when the curable composition described in Patent Document 1 is used as a sealing material, the self-cleaning property is not always sufficient.

An object of the present invention is to provide a curable composition having excellent antifouling property and self-cleaning property of the cured product, and a cured product of the curable composition.

The present invention is as follows.
[1] A curable composition containing a first organic polymer and a second organic polymer.
The first organic polymer is a polymer that does not have a siloxane structure and has a reactive silicon group represented by the following formula 1.
The second organic polymer is a polymer having a siloxane structure and containing a unit based on the first monomer and a unit based on the second monomer.
The first monomer is a monomer that does not have a reactive silicon group represented by the following formula 1 and has a siloxane structure and a polymerizable unsaturated group.
The second monomer is a monomer having neither a reactive silicon group or a siloxane structure represented by the following formula 1 and having a hydrophilic group and a polymerizable unsaturated group.
Curable composition.
−SiX _a R _3-a formula 1
In the formula, R represents a monovalent organic group having 1 to 20 carbon atoms other than the hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, a is an integer of 1 to 3, and a is 1. In some cases, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
[2] The curable composition according to [1], wherein the content of the second organic polymer is 1 to 40 parts by mass with respect to 100 parts by mass of the first organic polymer.
[3] The curable composition according to [1] or [2], wherein the first monomer contains a monomer represented by the following formula 2.
CH ₂ = CR ^1- C (= O) OY-SiR ² R ³ O (Si (CH ₃ ) ₂ O) _c- Si (CH ₃ ) ₃ formula 2
In the formula, R ¹ represents a hydrogen atom or a methyl group, Y is a single bond, a linear alkylene group having 1 to 6 carbon atoms, or a carbon in which one hydrogen atom is substituted with an alkyl group having 1 to 3 carbon atoms. Representing an alkylene group of numbers 1 to 6, R ² and R ³ independently represent a hydrogen atom, a methyl group or a trimethyloxysilyl group, and c is an integer of 0 to 150.
[4] The content ratio of the unit based on the first monomer to all the units constituting the second organic polymer in the second organic polymer is 10 to 80% by mass. 1] The curable composition according to any one of [3].
[5] The content ratio of the unit based on the second monomer to all the units constituting the second organic polymer in the second organic polymer is 10 to 80% by mass. 1] The curable composition according to any one of [4].
[6] A unit based on a third monomer in which the second organic polymer further has a reactive silicon group represented by the above formula 1 and has neither a siloxane structure nor a hydrophilic group. The curable composition according to any one of [1] to [5], which comprises.
[7] In the second organic polymer, the content ratio of the unit based on the third monomer to all the units constituting the second organic polymer is 0.1 to 20% by mass. , [6].
[8] The curable composition according to any one of [1] to [7], wherein the number average molecular weight of the second organic polymer is 1,000 to 20,000.
[9] Any of [1] to [8], wherein the total content ratio of the first organic polymer and the second organic polymer in the curable composition is 5 to 80% by mass. The curable composition according to.
[10] The curable composition according to any one of [1] to [9], which is used as a sealing material.
[11] A cured product of the curable composition according to any one of [1] to [10].

According to the present invention, it is possible to provide a curable composition having excellent antifouling property and self-cleaning property of the cured product, and a cured product of the curable composition.

The meanings and definitions of the terms in this specification are as follows.
The numerical range represented by "~" means a numerical range in which the numerical values before and after ~ are the lower limit value and the upper limit value.
The "unit" constituting the polymer means an atomic group directly formed by polymerization of a monomer.
The "oxyalkylene polymer" means a polymer having a polymer chain formed from a unit based on an alkylene oxide monomer.
"Main chain terminal group" means an atom or an atomic group bonded to an atom at the end constituting the main chain.
The "(meth) acrylic acid alkyl ester polymer" is one of a polymer chain formed from a unit based on an acrylic acid alkyl ester monomer and a polymer chain formed from a unit based on a methacrylic acid alkyl ester monomer. Or it means a polymer having both.
"(Meta) acrylic acid" means one or both of acrylic acid and methacrylic acid.
"Ester moiety" means an atomic group bonded to an oxygen atom of an ester bond.

An "unsaturated group" as a terminal group is a monovalent group containing a carbon-carbon unsaturated bond.
The "active hydrogen" means a hydrogen atom having a reactive group to which an alkylene oxide can be ring-opened and added, and means a hydrogen atom bonded to an oxygen atom, a nitrogen atom, a sulfur atom or the like. Also, water shall have active hydrogen.
The "active hydrogen-containing group" means a group having the above-mentioned active hydrogen. The active hydrogen-containing group is also a reactive group that can react with the isocyanate group.
The "silylation rate" is the number of reactive silicon groups relative to the total number of terminal groups that are any of reactive silicon groups, active hydrogen-containing groups, and unsaturated groups in the main chain terminal groups of the oxyalkylene polymer. Is the ratio of. The value of the silylation rate can be measured by NMR (nuclear magnetic resonance) analysis. Further, when the reactive silicon group is introduced into the terminal group in the main chain terminal group of the oxyalkylene polymer by the silylating agent described later, the number of silyl groups of the silylating agent added relative to the number of terminal groups It may be a ratio (mol%).
The "silylating agent" means a compound having a functional group that reacts with an active hydrogen-containing group or an unsaturated group and a reactive silicon group.
The number average molecular weight (hereinafter referred to as “Mn”) and the weight average molecular weight (hereinafter referred to as “Mw”) are polystyrene-equivalent molecular weights obtained by gel permeation chromatography (GPC) measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is a ratio of Mw to Mn (hereinafter, referred to as “Mw / Mn”).

[Curable composition]
The curable composition of the present invention may be referred to as a first organic polymer (hereinafter, may be referred to as "polymer A") and a second organic polymer (hereinafter, may be referred to as "polymer B"). ) And, including.
The curable composition of the present invention may contain two or more kinds of polymers A.
The curable composition of the present invention may contain two or more types of polymer B.
Hereinafter, the polymer A and the polymer B will be described in detail.

<Polymer A (first organic polymer)>
The polymer A does not have a siloxane structure and has a reactive silicon group represented by the following formula 1.
−SiX _a R _3-a formula 1
The meaning of each symbol in Equation 1 is as follows.
R represents a monovalent organic group having 1 to 20 carbon atoms other than the hydrolyzable group.
X represents a hydroxyl group or a hydrolyzable group.
a is an integer of 1 to 3.

R is preferably at least one selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms and a triorganosyloxy group, and is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group and a triorganosyloxy group. At least one selected from the group consisting of is more preferable, and a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group. And at least one selected from the group consisting of triphenylsiloxy groups is more preferred.
R is preferably a methyl group or an ethyl group from the viewpoint of good curability of the polymer A and stability of the curable composition. Further, R is preferably a 1-chloromethyl group because the curing rate of the curable composition of the present invention is high. Further, R is particularly preferably a methyl group from the viewpoint of being easily available.

X is preferably a hydrolyzable group, and the hydrolyzable group includes a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group and an alkenyl. An oxy group is exemplified.
From the viewpoint of mild hydrolyzing property and easy handling, the hydrolyzable group is preferably an alkoxy group, more preferably at least one selected from the group consisting of a methoxy group, an ethoxy group and an isopropoxy group, and more preferably a methoxy group or an ethoxy group. Groups are even more preferred.
When X is a methoxy group or an ethoxy group, a siloxane bond is rapidly formed to easily form a crosslinked structure in the cured product, and the physical property value of the cured product becomes better.

When a is 1, R may be the same or different from each other.
When a is 2 or 3, X may be the same or different from each other.
As for a, 1 or 2 is preferable, and 2 is more preferable.

As the reactive silicon group represented by the above formula 1, a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a methyldimethoxysilyl group, and a methyl Examples thereof include a diethoxysilyl group, an ethyldimethoxysilyl group, a methyldiisopropoxysilyl group, a (1-chloromethyl) dimethoxysilyl group and a (1-chloromethyl) diethoxysilyl group.
From the viewpoint of high activity and good curability, the reactive silicon group represented by the above formula 1 is more than the group consisting of a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group and a methyldiethoxysilyl group. At least one selected is preferable, and a methyldimethoxysilyl group or a trimethoxysilyl group is more preferable.
The polymer A may have two or more reactive silicon groups represented by the above formula 1.

<< Polymer A ¹ and Polymer A ² >>
The polymer A has the above-mentioned reactive silicic acid group and does not have a siloxane structure (hereinafter, may be referred to as “polymer A ¹ ”) and the above-mentioned reactive silicon group and has a siloxane. At least one selected from the group consisting of (meth) acrylic acid ester polymers having no structure (hereinafter, may be referred to as "polymer A ² ") is preferable.
Hereinafter, the polymer A ¹ and the polymer A ² will be described in detail.

(Polymer A ¹ )
The main chain of the polymer A ¹ is a polymer chain composed of an oxyalkylene polymer formed by ring-opening polymerization of one or more kinds of alkylene oxide monomers. If the main chain of the polymer A ¹ is a copolymer chain formed by ring-opening polymerization of two or more alkylene oxides monomers, the polymerization of the two or more alkylene oxides monomer, random copolymer, Either tandem copolymerization or block copolymerization may be used.

As the polymer chain composed of the above oxyalkylene polymer, a polymer chain composed of an ethylene oxide monomer, a polymer chain composed of a propylene oxide monomer, a polymer chain composed of a butylene oxide monomer, and a polymer chain composed of a tetramethylene oxide monomer. , A copolymer chain of ethylene oxide monomer and propylene oxide monomer and a copolymer chain of propylene oxide monomer and butylene oxide monomer are exemplified. As the polymer chain made of the oxyalkylene polymer, a polymer chain made of a propylene oxide monomer is particularly preferable.

Polymer A ¹ is preferably those having 2 to 6 main chain terminal groups per molecule, more preferably those having 2 to 4, more preferably those having 2 or 3.
End groups in the main chain terminal groups of the polymer A ¹ is at least one selected from the group consisting of reactive silicon groups, active hydrogen-containing group and an unsaturated group represented by the above formula 1, the formula 1 At least one selected from the group consisting of a reactive silicon group, a hydroxyl group and an allyl group represented by is preferable. When the main chain terminal group of the polymer A ¹ contains two or more terminal groups, the two or more terminal groups may be the same as each other or may be different from each other.
Examples of the active hydrogen-containing group include a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing a hydrogen atom from a primary amine, a hydrazide group and a sulfanyl group. As the active hydrogen-containing group, a monovalent functional group obtained by removing a hydrogen atom from a hydroxyl group, an amino group, and a primary amine is preferable, and a hydroxyl group is more preferable.
Polymer A ^1, since the preferable those having 0.5 or greater 2.0 or less on average per one main chain terminal groups of the reactive silicon group tends tensile strength of the cured product is improved, 0 It is more preferable to have .6 to 1.9 pieces.
Polymer A ^1, since the preferable those having 0.5 or greater than six on average per molecule the reactive silicon group, is likely to be good tensile strength of the cured product, 1.2 to 3. It is more preferable to have eight.

Of Mn is preferably 2,000 to 100,000 Polymer ^{A 1,} more preferably from 3,000 to 50,000, more preferably 4,000～30,000. When it is within the above range, the extensibility of the cured product is more excellent, and the viscosity tends to be sufficiently low.
The molecular weight distribution of the polymer ^{A 1} is preferably 1.80 or less. From the viewpoint of reducing viscosity, the molecular weight distribution is preferably small, more preferably 1.50 or less, further preferably 1.40 or less, and particularly preferably 1.20 or less.

Polymer A ¹ is one obtained by introducing the main chain terminal the reactive silicon group into groups as described below for precursor polymer, 0.5 or greater 2.0 or less on average one main chain terminal groups Is preferable, and those obtained by introducing 0.6 to 1.9 pieces are more preferable from the viewpoint of improving the tensile strength.
The precursor polymer is an oxyalkylene polymer obtained by ring-opening polymerization of an alkylene oxide monomer in active hydrogen of an initiator having an active hydrogen-containing group in the presence of a ring-opening polymerization catalyst.
As the precursor polymer, a precursor polymer in which an alkylene oxide monomer is ring-opened polymerized with an initiator having a hydroxyl group and whose main chain terminal group is a hydroxyl group is preferable.

The method for producing the polymer A ^{1 is} a method in which one or two unsaturated groups are introduced into one main chain terminal group of the precursor polymer and then the unsaturated group is reacted with a silylating agent, or A method of reacting the active hydrogen-containing group of the main chain terminal group of the precursor polymer with the isocyanate silane compound is preferable.
The precursor polymer is an oxyalkylene polymer obtained by ring-opening polymerization of an alkylene oxide monomer in active hydrogen of an initiator having an active hydrogen-containing group in the presence of a ring-opening polymerization catalyst. The number of active hydrogen of the initiator, the number of main chain terminal groups of the precursor polymer, the number of main chain terminal groups of the polymer A ¹ are the same.
The precursor polymer is preferably a polymer in which the terminal group of the main chain terminal group is a hydroxyl group, in which an alkylene oxide monomer is ring-opened polymerized with an initiator having a hydroxyl group.
As the initiator, an initiator having 2 to 6 hydroxyl groups is preferable, an initiator having 2 to 4 hydroxyl groups is more preferable, and an initiator having 2 or 3 hydroxyl groups is further preferable. Two or more types of initiators may be used in combination.
As an initiator having two hydroxyl groups, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol and low molecular weight Polyoxypropylene glycol is exemplified.
Examples of the initiator having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, sorbitol, pentaerythritol, and low molecular weight polyoxypropylene triol.

A conventionally known catalyst can be used as the ring-opening polymerization catalyst when the alkylene oxide monomer is ring-opened and polymerized as an initiator. For example, an alkali catalyst such as KOH, an organic aluminum compound and porphyrin are reacted. Examples thereof include a transition metal compound-porphyrin complex catalyst, a composite metal cyanide complex catalyst, and a catalyst composed of a phosphazene compound, such as a complex obtained by the above.
It is possible to narrow the molecular weight distribution of the polymer A ^1, the composite metal cyanide complex catalyst from the viewpoint of easily obtained low curable composition viscosity are preferred. A conventionally known compound can be used as the composite metal cyanide complex catalyst, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. For example, in International Publication No. 2003/062301, International Publication No. 2004/067633, Japanese Patent Application Laid-Open No. 2004-2697776, Japanese Patent Application Laid-Open No. 2005-15786, International Publication No. 2013/06582, Japanese Patent Application Laid-Open No. 2015-010162. The disclosed compounds and production methods can be used.
The precursor polymer of the polymer A ^1, the precursor polymer entire main chain terminal group is a hydroxyl group are preferred.

The method for producing the polymer A ^{1 is} a method in which one or two unsaturated groups are introduced into one main chain terminal group of the precursor polymer and then the unsaturated group is reacted with a silylating agent, or the above. A method of reacting the active hydrogen-containing group of the main chain terminal group of the precursor polymer with the isocyanate silane compound is preferable.

As the silylating agent, a compound having both a group capable of reacting with an unsaturated group (for example, a sulfanil group) and the above-mentioned reactive silicon group, and a hydrosilane compound (for example, HSiX _a R _3-a , however, X, R and a are the same as those in the above formula 1). Specifically, for example, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, methoxyethylsilane, methyldiisopropoxy. Examples thereof include silane, (1-chloromethyl) dimethoxysilane, and (1-chloromethyl) diethoxysilane. From the viewpoint of high activity and good curability, trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable, and methyldimethoxysilane or trimethoxysilane is more preferable.

As the isocyanate silane compound, for example, a conventionally known isocyanate silane compound described in JP-A-2011-178955 can be used.

A method of introducing one unsaturated group into one main chain terminal group of the precursor polymer and then reacting the unsaturated group with a silylating agent, or an active hydrogen of the main chain terminal group of the precursor polymer. As a method for urethanizing the containing group and the isocyanate silane compound, a conventionally known method can be used. For example, JP-A-45-363319, JP-A-50-156599, JP-A61-197631 Examples of the method proposed in Japanese Patent Application Laid-Open No. 3-72527, Japanese Patent Application Laid-Open No. 8-231707, Japanese Patent Application Laid-Open No. 2011-178955, US Pat. No. 3,362,557, or US Pat. No. 4,960,844 are mentioned. Be done.

As a method of introducing two unsaturated groups into one main chain terminal group of the precursor polymer, an alkali metal salt is allowed to act on the precursor polymer, and then an epoxy compound having an unsaturated group is reacted. Then, a method of reacting a halogenated hydrocarbon compound having an unsaturated group is preferable.

As a method for introducing more than one unsaturated group into one main chain terminal group of the precursor polymer, a known method can be used without particular limitation. For example, International Publication No. 2013/180203, International. Publication No. 2014/192842, Japanese Patent Application Laid-Open No. 2015-105293, Japanese Patent Application Laid-Open No. 2015-105322, Japanese Patent Application Laid-Open No. 2015-105323, Japanese Patent Application Laid-Open No. 2015-105324, International Publication No. 2015/080067, International Publication No. The methods described in 2015/105122, International Publication No. 2015/111577, International Publication No. 2016/002907, JP-A-2016-216633, or JP-A-2017-39782 can be used.

By the above reaction, an unsaturated group derived from the epoxy compound having the unsaturated group was introduced into the main chain terminal group of the precursor polymer, and then an unsaturated group derived from the halogenated hydrocarbon compound was introduced into the intermediate. Is obtained. The intermediate may be an active hydrogen-containing group in which a part of the terminal group in the main chain terminal group is unreacted.
The number of active hydrogen-containing groups contained in one molecule of the above intermediate is preferably 0.3 or less, more preferably 0.1 or less, from the viewpoint of storage stability.

Silylation rate of the polymer ^{A 1} is preferably 50 mol percent to 100 mol% or less, more preferably 55 to 98 mol%, more preferably 60 to 97 mol%.
The curable composition of the present invention, may include two or more kinds of polymer A ^1, silylated in the average in the entire polymer A ¹ may be within the range described above.

(Polymer A ² )
The main chain of the polymer A ² is a polymer chain formed by addition polymerization of one or more kinds of monomers containing (meth) acrylic acid ester.
The main chain of the polymer A ² has a unit based on a (meth) acrylic acid alkyl ester and a unit based on a monomer having an unsaturated group copolymerizable with the (meth) acrylic acid alkyl ester. May be good.

Examples of the monomer constituting the polymer A ² are conventionally known monomers described in JP-A-3-14068, JP-A-6-21922, or JP-A-11-130931. Can be used.

As a monomer containing a reactive silicon group and an unsaturated group to be copolymerized with the above monomer, vinyl methyl dimethoxysilane, vinyl methyl diethoxysilane, vinyl methyl dichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl Trichlorosilane, tris (2-methoxyethoxy) vinylsilane, (meth) acrylate-3- (methyldimethoxyryl) propyl, (meth) acrylate-3- (trimethoxysilyl) propyl and (meth) acrylate-3-3 (Triethoxysilyl) propyl is exemplified. These may be one kind, or two or more kinds may be used in combination.

The (meth) acrylic acid ester monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 100% by mass with respect to all the monomers constituting the polymer A ² .

The reactive silicon group in the polymer A ² may be introduced into the main chain terminal group, the side chain, or both the main chain terminal group and the side chain.
When a monomer containing a reactive silicon group and a polymerizable unsaturated group and a monomer containing a (meth) acrylic acid ester are polymerized by a free radical polymerization method, a polymer A ² having a reactive silicon group in the side chain. Is obtained.
With living radical polymerization method, polymer A ² having a reactive silicon group as a main chain terminal groups are obtained.

The polymer A ² can be polymerized by a conventionally known polymerization method described in JP-A-2006-257405, JP-A-2006-37076, JP-A-2008-45059, and the like. Conventionally known auxiliary materials such as an initiator required for polymerization can also be used, and reaction conditions such as reaction temperature and reaction pressure can be appropriately selected.
Examples of the polymerization method include a polymerization method using a free radical polymerization initiator by solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization, and living radical polymerization. As a living radical polymerization method, a method using a cobalt porphyrin complex as shown in Journal of American Chemical Society (J. Am. Chem. Soc), 1994, Vol. 116, p. 7943, special table. A transition metal complex using a nitrooxide radical as shown in Japanese Patent Application Laid-Open No. 2003-570378, an organic halide or a sulfonyl halide compound as shown in JP-A-11-130931, etc. as an initiator. Atom Transfer Radical Polymerization (ATRP Method) catalyzed by the above is exemplified. The polymer obtained by living radical polymerization tends to have a narrow molecular weight distribution and a low viscosity.

The Mn of the polymer A ² is preferably 500 to 100,000, more preferably 1,000 to 80,000, and even more preferably 2,000 to 50,000. When it is at least the lower limit of the above range, the extensibility of the cured product is superior, and when it is at least the upper limit, the viscosity tends to be low and the workability is excellent.
The molecular weight distribution of the polymer A ² is preferably 3.0 or less, more preferably 2.5 or less.

The average number of reactive silicon groups per molecule of the polymer A ² is more than 0.5, preferably 1.0 or more. From the viewpoint of strength after curing, 1.2 or more is preferable, and 1.6 or more is more preferable. From the viewpoint of good elongation of the cured product, 4.0 or less is preferable, and 3.0 or less is more preferable.
The average number of reactive silicon groups per molecule of the polymer A ² is calculated by "concentration of the reactive silicon group in the polymer A ² [mol / g] × of Polymer A ² Mn". The concentration [mol / g] of the reactive silicon group in the polymer A ² can be measured by NMR.

(Content ratio of polymer A ¹ and polymer A ² )
When comprising at least one polymer A is selected from the group consisting of polymer A ¹ and polymer A ^2, for the polymer A, is selected from the group consisting of the polymers A ¹ and polymer A ² The content ratio of at least one kind is preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.
When the content ratio of at least one selected from the group consisting of the polymer A ¹ and the polymer A ² is 80% by mass or more of the polymer A, the physical properties of the cured product obtained by curing the curable composition of the present invention are It tends to be better.
If the polymer A containing both polymer ^{A 1} and polymer ^{A 2,} the content ratio of the polymer ^{A 2} to the sum of the polymer ^{A 1} and polymer ^{A 2} is preferably 1 to 70 wt%, 5 ~ 65% by mass is more preferable, and 10 to 60% by mass is further preferable. If it is within the above range, it is more excellent in curability.

<< Polymers other than polymer A ¹ and polymer A ² >>
The polymer A may contain a polymer other than the above-mentioned polymer A ¹ and polymer A ² (hereinafter, may be referred to as “polymer A ³ ”).
The polymer A ^3, the main chain skeleton of the particular polymer as long as it has a reactive silicon group represented by the above formula 1 is not limited. The main chain skeleton, for example, saturated hydrocarbon polymer, a polyester polymer, a vinyl polymer other than the polymer A ^2, polysulfide polymer, polyamide polymer, a polycarbonate polymer, a diallyl phthalate-based heavy Coalescence is mentioned.

<Polymer B (second organic polymer)>
The polymer B has a siloxane structure, and is a unit based on the ^first monomer (hereinafter, may be referred to as “monomer b ¹ ”) and a second monomer (hereinafter, “single”). Includes units based on "polymer b ² ").

<< Monomer b ¹ (first monomer) >>
The monomer b ¹ is a monomer having no reactive silicon group represented by the above formula 1 and having a siloxane structure and a polymerizable unsaturated group.
As the polymerizable unsaturated group of the monomer _{^{b 1, CH 2 = CH-,}} CH 2 = CH-CH 2 -O-, CH 2 = CR 11 -C (= O) O- and _CH 2 = ^{CR 11} - OC (= O)-is exemplified. Here, R ¹¹ is a hydrogen atom, a chlorine atom, a fluorine atom, or a linear or branched alkyl group having 1 to 3 carbon atoms.
The polymerizable unsaturated groups of monomer b ¹ are CH ₂ = CH-, CH ₂ = CH-CH _2- O-, CH ₂ = CH-C (= O) O-, CH ₂ = C (CH _3). ) -OC (= O) O-, CH ₂ = CH-OC (= O)-and CH ₂ = C (CH ₃ ) -OC (= O)-at least one selected from the group is preferred. More preferably, at least one selected from the group consisting of CH ₂ = CH-C (= O) O- and CH ₂ = C (CH ₃ ) -OC (= O) O-.

Siloxane structure of the monomer b ¹ is a structure consisting of main chain by siloxane bonds. Siloxane structure of the monomer b ¹ is an organopolysiloxane structure having an organic group in the side chain. Examples of the organic group include an alkyl group and a trialkyloxysilyl group.

When the polymer B contains a unit based on the monomer b ¹ , the tack on the surface of the obtained cured product is reduced and the antifouling property is improved.

Polymer B, the units derived from monomer b ^1, may contain two or more.
In the polymer B, the content of units based on the polymer monomer ^{b 1} for all units constituting the B is preferably 10 to 80 wt%, more preferably from 15 to 70 wt%, 20 to 60 wt% Is even more preferable.

The monomer b ¹ preferably contains the monomer represented by the following formula 2 in terms of reducing the tack on the surface of the obtained cured product and further enhancing the antifouling property.
CH ₂ = CR ^1- C (= O) OY-SiR ² R ³ O (Si (CH ₃ ) ₂ O) _c- Si (CH ₃ ) ₃ formula 2
The meaning of each symbol in Equation 2 is as follows.
R ¹ represents a hydrogen atom or a methyl group.
Y represents a single bond, a linear alkylene group having 1 to 6 carbon atoms, or an alkylene group having 1 to 6 carbon atoms in which one hydrogen atom is replaced with an alkyl group having 1 to 3 carbon atoms.
R ² and R ³ each independently represent any one selected from the group consisting of a hydrogen atom, a methyl group and a trimethyloxysilyl group.
c is an integer from 0 to 150.

As the monomer represented by the above formula 2, R ¹ is a hydrogen atom or a methyl group and Y is −CH ₂ −, −C ₂ H ₄ − in terms of reducing the tack on the surface of the obtained cured product. _{, -C 3 H 6 -, -} C 4 H 8 -, - C 5 H 10 - and _-C 6 _{H 12} - is any one selected from the group consisting of, ^{R 2} is -H, -CH Any one selected from the group consisting of ₃ and -OSi (CH ₃ ) ₃ , and R ³ selected from the group consisting of -H, -CH ₃ and -OSi (CH ₃ ) _3. A compound that is a species and c is an integer of 0-150 is preferred, R ¹ is -CH ₃ , Y is -C ₃ H _6- , and R ² is -CH ₃ or -OSi (CH). ₃₎ is _3, ^{R 3} is -CH ₃ or -OSi _{(CH 3) 3,} and, c compound is an integer of 0 is more preferred.

The monomer b ¹ may contain two or more types of the monomers represented by the above formula 2.
The content ratio of the unit based on the monomer represented by the above formula 2 with respect to the total mass of the unit based on the monomer b ¹ is preferably 80% by mass or more, more preferably 90% by mass or more.
The ratio of the unit based on the monomer represented by the above formula 2 to the total mass of the unit based on the monomer b ¹ may be 100% by mass.

Specific examples of the monomer b ¹ below.
CH ₂ = CH-C (O =) O-Si (CH ₃ ) _2- O-Si (CH ₃ ) ₃ ,
CH ₂ = C (CH ₃ ) -C (O =) O-Si (CH ₃ ) _2- O-Si (CH ₃ ) ₃ ,
CH ₂ = CH-C (O =) O-Si- (OSI (CH ₃ ) ₃ ) ₃ ,
CH ₂ = CH-C (O =) O-Si (CH ₃ ) _2- O (Si (CH ₃ ) ₂ O) _10- Si (CH ₃ ) ₃ ,
CH ₂ = CH-C (O =) O-Si (CH ₃ ) _2- O (Si (CH ₃ ) ₂ O) _60- Si (CH ₃ ) ₃ ,
CH ₂ = CH-C (O =) O-Si (CH ₃ ) _2- O (Si (CH ₃ ) ₂ O) _130- Si (CH ₃ ) ₃ ,
CH ₂ = C (CH ₃ ) -C (O =) O-Si- (OSI (CH ₃ ) ₃ ) ₃ ,
CH ₂ = C (CH ₃ ) -C (O =) O-Si (CH ₃ ) _2- O (Si (CH ₃ ) ₂ O) ₁₀ --Si (CH ₃ ) ₃ ,
CH ₂ = C (CH ₃ ) -C (O =) O-Si (CH ₃ ) _2- O (Si (CH ₃ ) ₂ O) _60- Si (CH ₃ ) ₃ ,
CH ₂ = C (CH ₃ ) -C (O =) O-Si (CH ₃ ) _2- O (Si (CH ₃ ) ₂ O) _130- Si (CH ₃ ) ₃ ,
CH ₂ = CH-C (= O) O- (CH ₂ ) _3- Si- (OSI (CH ₃ ) ₃ ) ₃ ,
_{CH 2 = CH-C (=} O) O- (CH 2) 3 -Si (CH 3) 2 -O (Si (CH 3) 2 O) 10 -Si (CH 3) 3,
_{CH 2 = CH-C (=} O) O- (CH 2) 3 -Si (CH 3) 2 -O (Si (CH 3) 2 O) 60 -Si (CH 3) 3,
_{CH 2 = CH-C (=} O) O- (CH 2) 3 -Si (CH 3) 2 -O (Si (CH 3) 2 O) 130 -Si (CH 3) 3,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) _3- Si- (OSI (CH ₃ ) ₃ ) ₃ ,
_{CH 2 = C (CH 3)} -C (= O) O- (CH 2) 3 -Si (CH 3) 2 -O (Si (CH 3) 2 O) 10 -Si (CH 3) 3,
_{CH 2 = C (CH 3)} -C (= O) O- (CH 2) 3 -Si (CH 3) 2 -O (Si (CH 3) 2 O) 60 -Si (CH 3) 3, and CH _{2 = C (CH 3) -C} (= O) O- (CH 2) 3 -Si (CH 3) 2 -O (Si (CH 3) 2 O) 130 -Si (CH 3) 3.

<< Monomer b ² (second monomer) >>
The monomer b ² is a monomer having neither a reactive silicon group or a siloxane structure represented by the above formula 1 and having a hydrophilic group and a polymerizable unsaturated group.
As the hydrophilic group of monomer b ² , an alkylene oxide group (-R'O-;R'is an alkylene group), an amino group, a hydroxy group, an acrylamide group (CH ₂ = CHCONH-), a carboxy group, and a phosphoric acid. Examples include a group (-PO ₃ ^2- ), a sulfone group (-SO ₂ (OH)) and a quaternary ammonium group. Here, the number of carbon atoms of R'is preferably 1 to 5, and more preferably 1 to 3.
The hydrophilic group of the monomer b ² is an alkylene oxide group (-R'O-;R'is an alkylene group having 1 to 5 carbon atoms), an amino group, a hydroxy group, and an acrylamide group (CH ₂ = CHCONH-). , Carboxy group, phosphate group (-PO ₃ ^2- ), sulfone group (-SO ₂ (OH)) and quaternary ammonium group, preferably at least one selected from the group, preferably an alkylene oxide group (-R). 'O-;R' is an alkylene group having 1 to 3 carbon atoms), amino group, hydroxy group, an acrylamide group _(CH 2 = CHCONH-), a carboxy group, a phosphoric acid group _(-PO ^{3 2-)} and sulfone group More preferably, at least one selected from the group consisting of (-SO ₂ (OH)).

The polymerizable unsaturated group of the monomer b ^{2 is the same as} the polymerizable unsaturated group of the monomer b ¹ .

Since the polymer B contains a unit based on the monomer b ² , the surface tension of the surface of the obtained cured product tends to be low.

The polymer B may contain two or more units based on the monomer b ² .
The content ratio of the unit based on the monomer b ² to all the units constituting the polymer B in the polymer B is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and 20 to 60% by mass. Is even more preferable.

In the polymer B, the content of units derived from monomers b ² to the sum of the units based on the unit and the monomer b ² based on the monomer b ¹ constituting the polymer B, 10 to 90 wt% Is preferable, and 20 to 80% by mass is more preferable.

The monomer b ² preferably has an alkylene oxide chain represented by − (R'O) _n − in that the dispersion stability of the polymer B becomes better. n represents an integer of 1 to 30.
When n is 2 or more, n (R'O) may be one kind or two or more kinds. When there are two or more types of (R'O), the polymerization may be random polymerization or block polymerization.

The monomer b ² preferably contains the monomer represented by the following formula 3 in that the hydrophilicity of the obtained cured product becomes better.
Q ¹ −Z ² − (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _n R ²¹ Equation 3
The meaning of each symbol in Equation 3 is as follows.
Q ¹ represents a monovalent group containing a polymerizable unsaturated group.
Z ² represents a single bond or a linear alkylene group having 1 to 10 carbon atoms.
R ²¹ represents a hydrogen atom or a methyl group.
m is an integer of 1 to 30, n is an integer of 0 to 25, and m is larger than n.

Q ¹ is preferably CH ₂ = CH-, CH ₂ = CH-CH _2- O-, CH ₂ = CR ^11- C (= O) -O- or CH ₂ = CR ^11- OC (= O)-. ..
R ¹¹ is the same as ^{R 11} in the polymerizable unsaturated group of the monomer ^{b 1.}
m is preferably an integer of 4 to 26.
n is preferably an integer of 1 to 10.
When n is 1 or more and m + n is 3 or more, (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _n in the above formula 3 is a random copolymerization or a tandem copolymerization. And block copolymerization may be used.

As the monomer represented by the above formula 3, in terms of hydrophilicity, Q ₁ is CH ₂ = CR ^11- C (= O) O-, R ¹¹ is a hydrogen atom or a methyl group, and Z. ^A compound in which ² is a single bond, R ²¹ is a methyl group, m is an integer of 1 to 30, and n is an integer of 0 to 20 is preferable, and Q ¹ is CH ₂ = CR ^11- C. (= O) O−, R ¹¹ is a hydrogen atom, Z ² is a single bond, R ²¹ is a methyl group, m is an integer of 4 to 26, and n is 1 to 10. Compounds that are integers of are more preferred.

The monomer b ² may contain two or more types of the monomers represented by the above formula 3.
The content ratio of the unit based on the monomer represented by the above formula 3 with respect to the total mass of the unit based on the monomer b ² is preferably 80% by mass or more, more preferably 90% by mass or more.
The content ratio of the unit based on the monomer represented by the above formula 3 to the total mass of the unit based on the monomer b ² may be 100% by mass.

Specific examples of the monomer represented by the above formula 3 are listed below.
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _2- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _5- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _10- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _24- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _2- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _5- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _8- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _23- H,
_{CH 2 = CH-C (=} O) -O- (CH 2 CH 2 O) 4 - (CH 2 CH 2 (CH 3) O) 3 -H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _5- (CH ₂ CH ₂ (CH ₃ ) O) _2- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _2- CH ₃ ,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _4- CH ₃ ,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _9- CH ₃ ,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _13- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _2- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _4- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _9- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _13- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _23- CH ₃ ,
_{CH 2 = CH-C (=} O) -O- (CH 2 CH 2 O) 4 - (CH 2 CH 2 (CH 3) O) 3 -CH 3, and _{CH 2 = CH-C (=} O) - O- (CH ₂ CH ₂ O) _5- (CH ₂ CH ₂ (CH ₃ ) O) _2- H.

Specific examples of the monomer b ² other than the monomer represented by the above formula 3 are listed below.
CH ₂ = CH-C (= O) -OH,
CH ₂ = C (CH ₃ ) -C (= O) -OH,
CH ₂ = C (CH ₃ ) -C (= O) -CH _2- CH _2- NH ₃ ,
CH ₂ = CH-C (= O) -CH _2- CH _2- NH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -N (CH ₃ ) ₂ ,
CH ₂ = CH-C (= O) -N (CH ₃ ) ₂ ,
CH ₂ = C (CH ₃ ) -C (= O) -N (CH ₂ CH ₂ OCH ₂ CH ₂ ),
CH ₂ = CH-C (= O) -N (CH ₂ CH ₂ OCH ₂ CH ₂ ), and CH ₂ = CH-C (= O) -NH- (CH ₂ ) _3- N ⁺ (CH ₃ ) ₃・ Cl ⁻ .

The total content ratio of the unit based on the monomer b ¹ and the unit based on the monomer b ² to all the units constituting the polymer B in the polymer B is preferably 20 to 100% by mass, preferably 30 to 90% by mass. It is more preferably by mass, more preferably 40 to 80% by mass.

<< Monomers other than monomer b ¹ and monomer b ² >>
In addition to the above-mentioned monomer b ¹ and monomer b ² , the polymer B further includes a third monomer (hereinafter, may be referred to as “monomer b ³ ”) and a fourth polymer described later. (Hereinafter, sometimes referred to as "polymer b ⁴ "), and monomers other than monomer b ¹ , monomer b ² , monomer b ³ and monomer b ^4. (Hereinafter, it may be referred to as "polymer b ⁵ ".) At least one selected from the group consisting of (hereinafter, may be referred to as "polymer b ⁵ ") may be contained.

(Polymer b ³ (third monomer))
Monomer b ³ has a reactive silicon group represented by the above formula 1, a monomer having neither a siloxane structure and a hydrophilic group.
Examples of the hydrophilic group, the same as the hydrophilic group in the monomer b ^2.
Polymer B that comprises units derived from monomer b ^3, self-cleaning properties of the cured product obtained is improved.

Monomer ^{b 3,} for example, Kokoku 3-14068, JP-A No. 6-211922 and JP-or are described in JP-A 11-130931, JP-can be a conventionally known monomer ..

Monomer b ³ has no siloxane structure and a hydrophilic group (meth) acrylic acid esters are preferred.
Specific examples of the monomer b ^3, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane, vinyl methyl dichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, tris (2-methoxyethoxy) vinylsilane, ( -3- (Methyldimethoxyryl) propyl (meth) acrylate, -3- (trimethoxysilyl) propyl (meth) acrylate, -3- (methyldiethoxysilyl) propyl (meth) acrylate and (meth) acrylate -3- (Triethoxysilyl) propyl can be mentioned.
Monomer b ^3, polymerizability is good, from the point of cured product excellent in self-cleaning properties can be obtained, (meth) acrylic acid 3- (methyl-dimethoxy Lil) propyl, (meth) acrylic acid -3 At least one selected from the group consisting of − (trimethoxysilyl) propyl and −3- (methyldiethoxysilyl) propyl (meth) acrylate is preferred.

Polymer B, the units derived from monomer b ^3, may contain two or more.
When the polymer B contains a unit based on the monomer b ³ , the content ratio of the unit based on the monomer b ³ to all the units constituting the polymer B in the polymer B is 0.1 to 20 mass by mass. % Is preferable, 0.5 to 15% by mass is more preferable, and 0.8 to 12% by mass is further preferable.
When the polymer B contains 0.1 to 20% by mass of a unit based on the monomer b ³ , a cured product having better self-cleaning property can be obtained.

When the polymer B contains a unit based on the monomer b ³ , the unit based on the monomer b ¹ and the unit based on the monomer b ² are simple with respect to all the units constituting the polymer B in the polymer B. the total content of the units based on mer ^{b 3} is preferably 25 to 100 wt%, more preferably from 35 to 100 wt%, more preferably 45 to 100 wt%.

If the polymer B comprises units derived from monomer b ^3, in the polymer B, to the sum of units derived units and monomer b ³ based on the monomer b ¹ constituting the polymer B, a single content of units based on mer ^{b 3} is preferably 5 to 80 wt%, more preferably 10 to 75 wt%.
If the polymer B comprises units derived from monomer b ^3, in the polymer B, to the sum of units derived units and monomer b ³ based on the monomer b ² constituting the polymer B, a single content of units based on mer ^{b 3} is preferably 5 to 80 wt%, more preferably 10 to 75 wt%.

(Polymer b ⁴ (fourth monomer))
Polymer B that comprises units derived from monomer b ^4, the hydrophilic of the cured product surface obtained is improved.

Monomer b ^4, the reactive silicon group represented by the above formula 1, none have a siloxane structure and a hydrophilic group, having an alkyl group of 1 to 8 carbon atoms in the ester moiety (meth) acrylic acid It is an ester.

Polymer B, the units derived from monomer b ^4, may contain two or more.
When the polymer B contains a unit based on the monomer b ⁴ , the content ratio of the unit based on the monomer b ⁴ to all the units constituting the polymer B in the polymer B is preferably 80% by mass or less. , 70% by mass or less is more preferable, and 60% by mass or less is further preferable.

When the polymer B contains a unit based on the monomer b ⁴ , the unit based on the monomer b ¹ and the unit based on the monomer b ² are simple with respect to all the units constituting the polymer B in the polymer B. the total content of units based on mer ^{b 4} is preferably 25 to 100 wt%, more preferably from 35 to 100 wt%, more preferably 45 to 100 wt%.

If the polymer B comprises units derived from monomer b ^4, in the polymer B, to the sum of units derived units and monomer b ⁴ based on the monomer b ¹ constituting the polymer B, a single content of units derived from dimer ^{b 4} is preferably 5 to 80 wt%, more preferably 10 to 75 wt%.
If the polymer B comprises units derived from monomer b ^4, in the polymer B, to the sum of units derived units and monomer b ⁴ based on the monomer b ² constituting the polymer B, a single content of units derived from dimer ^{b 4} is preferably 5 to 80 wt%, more preferably 10 to 75 wt%.

The monomer b ⁴ preferably contains a monomer represented by the following formula 4 in that compatibility with the polymer A can be easily obtained.
CH ₂ = C (R ³¹ ) -C (= O) OR ³² formula 4
The meaning of each symbol in Equation 4 is as follows.
R ³¹ represents a hydrogen atom or a methyl group.
R ³² represents an alkyl group having 1 to 8 carbon atoms.

R ³² is preferably an alkyl group having 2 to 8 carbon atoms, and more preferably an alkyl group having 2 to 6 carbon atoms, in terms of compatibility with the polymer A.
The alkyl group may be linear or branched, and a linear alkyl group is preferable in terms of compatibility with the polymer A.

Specific examples of the monomer b ⁴ represented by the above formula 4, (meth) acrylate, (meth) acrylate, (meth) acrylate, propyl (meth) butyl -n- acrylate, (meth ) Isobutyl acrylate, -t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, -2-ethylhexyl (meth) acrylate.

Examples of the monomer b ⁴ represented by the above formula 4 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, -n-butyl (meth) acrylate, and (meth) acrylic. Examples thereof include isobutyl acid acid, -t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and -2-ethylhexyl (meth) acrylate. A group consisting of ethyl (meth) acrylate, propyl (meth) acrylate, -n-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate and -2-ethylhexyl (meth) acrylate. At least one selected from the group consisting of ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and hexyl (meth) acrylate. More preferable.

The monomer b ⁴ may contain two or more types of monomers represented by the above formula 4.
To the total weight of units derived from monomer b ^4, the content of units based on the monomer represented by the above formula 4 is preferably at least 80 mass%, more preferably at least 90 mass%.
The content ratio of the unit based on the monomer represented by the above formula 4 to the total mass of the unit based on the monomer b ⁴ may be 100% by mass.

(Polymer b ⁵ (monomer other than monomer b ¹ , monomer b ² , monomer b ³ and monomer b ⁴ ))

The monomer b ⁵ is not particularly limited as long as it is a monomer capable of forming a polymer with the monomers b ¹ , b ² _, b ³ and b ⁴ .
As monomer b ^5, for example, include the following compounds.
A (meth) acrylic acid ester having an alkyl group having 9 to 24 carbon atoms such as lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.
Vinyl ethers such as vinyl chloride, vinylidene chloride, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether and 2-chloroethyl vinyl ether.
Vinyl halide such as tetrafluoroethylene.
Vinyl esters such as vinyl acetate, vinyl butyrate and vinyl pivalate.
Allyl esters such as allyl acetate and diallyl adipate.
Allyl ethers such as diallyl ethers and 1,3 diallyloxy-2-propanol.
Long-chain alkyl vinyl such as vinyl laurate and vinyl stearate.
Hydrocarbon olefin compounds such as ethylene, propylene and 1,4-butadiene.

Polymer B, the units derived from monomer b ^5, may contain two or more.
When the polymer B contains a unit based on the monomer b ⁵ , the content ratio of the unit based on the monomer b ⁵ to all the units constituting the polymer B in the polymer B is preferably less than 20% by mass. 5, less than 5% by mass is preferable.

<< Mn and molecular weight distribution of polymer B >>
The Mn of the polymer B is preferably 1,000 to 20,000, more preferably 2,000 to 18,000, and even more preferably 3,000 to 16,000. Within the above range, the viscosity of the mixture of the polymer A and the polymer B is further lowered.
The molecular weight distribution of the polymer B is preferably 2.5 or less, more preferably 2.0 or less.

<< Method for producing polymer B >>
The polymer B is obtained by polymerizing a monomer component containing the monomer b ¹ and the monomer b ² in an organic solvent. When the polymer B contains a unit based on the monomer b ³ and a unit based on the monomer b ⁴ , the monomer b ¹ , the monomer b ² , the monomer b ³ and the monomer b ⁴ are used. It is obtained by polymerizing the containing monomer component in an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, methanol, ethanol, 2-propanol, ethyl acetate, butyl acetate, diisopropyl ether, tetrahydrofuran, hexane, toluene, N, N-dimethylformamide and acetonitrile. The organic solvent is preferably ethyl acetate or 2-propanol in that the solubility of the monomer becomes better and the yield becomes better. The organic solvent may be used alone or in combination of two or more.

The polymerization reaction may be polymerized in the same manner as in the polymer A ^2.
In the above polymerization reaction, examples of the initiator include a peroxide polymerization initiator, an azo polymerization initiator, a redox polymerization initiator, a metal compound catalyst and the like. Examples of the radical polymerization initiator include 2,2'-azobisisobutyro, 2,2'-assobis-2-methylbutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and benzoylper. Examples thereof include oxide, t-butyl peroxide, acetyl peroxide, diisopropylperoxydicarbonate and the like.
The polymerization temperature and polymerization time can be appropriately selected depending on the boiling point of the solvent used, the half-life temperature of the initiator, etc., but the polymerization temperature may be 20 to 200 ° C., preferably 50 to 150 ° C., and the polymerization time is several to several. Dozens of hours are preferred.

If necessary, a chain transfer agent can be used in the above polymerization reaction. Examples of the chain transfer agent include n-dodecyl mercaptan, n-octadecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene, mercapto-3- (methyldimethoxyryl) propyl, mercapto-3- (trimethoxyryl) propyl and Examples include mercapto-3- (methyldiethoxylyl) propyl.
When a chain transfer agent is used, the chain transfer agent may be used alone or in combination of two or more.

<Other ingredients>
The curable composition may contain other components other than the polymer A and the polymer B. Other components include, for example, fillers, plasticizers, antioxidants, UV absorbers, light stabilizers, dehydrators, adhesive imparting agents, oxygen curable compounds, photocurable compounds, curing catalysts (silanol condensation catalysts). ) And amine compounds can be exemplified.
Other components include International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, JP-A-2015-105293. No., JP-A-2017-039728, JP-A-2017-214541, and the like, which are conventionally known, can be used in combination without limitation.
Two or more kinds of each component may be used in combination.

Examples of the plasticizer include phthalates (diisonyl phthalate, etc.), epoxy plasticizers (4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, etc.), and paraffin-based plasticizers having 6 to 18 carbon atoms. Examples thereof include hydrocarbons (n-dodecane and the like), acrylic plasticizers (solvent-free acrylic polymers and the like), and polyether plasticizers (oxyalkylene polymers and the like).
If a polymer plasticizer having Mn of 1,000 or more, Mw of 1,000 or more, or a molecular weight of 500 or more per hydroxyl group is used as a part or all of the plasticizer, the surface contamination of the cured product and the surroundings It is preferable in that effects such as reduction of contamination, improvement of dryness of the paint on the cured product, reduction of stain on the surface of the paint, and improvement of weather resistance can be easily obtained.

[Method for producing curable composition]
The curable composition is obtained by synthesizing the polymer A and the polymer B, respectively, adding necessary components to the polymer A and the polymer B, and mixing them.
The total content of the polymer A and the polymer B in the curable composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 60% by mass. When the total content ratio of the polymer A and the polymer B is within the above range, the obtained cured product is excellent in antifouling property and self-cleaning property.

The content of the polymer B with respect to 100 parts by mass of the polymer A is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, still more preferably 3 to 20 parts by mass.
When the content of the polymer B is 1 part by mass or more with respect to 100 parts by mass of the polymer A, the obtained cured product is excellent in antifouling property and self-cleaning property.
When the content of the polymer B is 40 parts by mass or less with respect to 100 parts by mass of the polymer A, the compatibility between the polymer A and the polymer B is more excellent.

The viscosity of the mixture of the polymer A and the polymer B at 25 ° C. is preferably 1.5 to 50 Pa · s, more preferably 2 to 35 Pa · s, still more preferably 4 to 40 Pa · s.
When the viscosity of the mixture of the polymer A and the polymer B at 25 ° C. is 1.5 Pa · s or more, dripping during the work is unlikely to occur.
When the viscosity of the mixture of the polymer A and the polymer B at 25 ° C. is 50 Pa · s or less, the workability becomes better.
The above viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE80 type) at a measurement temperature of 25 ° C. for the rotor No. It is a value obtained by measuring the viscosity under the condition of 4.

Examples of the method for lowering the viscosity of the mixture of the polymer A and the polymer B include a method for lowering the molecular weight of the polymer B.

The curable composition may be a one-component type in which all the ingredients are mixed in advance, sealed and stored, and then cured by the humidity in the air after construction, and the main composition containing at least a component having a reactive silicon group and at least A two-component type may be used in which the curing agent composition containing the curing catalyst is stored separately and the curing agent composition and the main agent composition are mixed before use. A one-component curable composition is preferred because it is easy to install.

The one-component curable composition preferably does not contain water. It is preferable to dehydrate and dry the compounding component containing water in advance, or to dehydrate by reducing the pressure during compounding and kneading.
In the two-component curable composition, the curing agent composition may contain water. Although the main ingredient composition is difficult to gel even if it contains a small amount of water, it is preferable to dehydrate and dry the ingredients in advance from the viewpoint of storage stability.
In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main composition.

The curable composition of the present invention is used as a sealing material (for example, an elastic sealing material for construction, a sealing material for double glazing, a sealing material for rust prevention / waterproofing at the end of glass, a sealing material on the back surface of a solar cell, and construction. Sealing materials for goods, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), electrical insulating materials (insulating coating materials for electric wires / cables), and adhesives are suitable.
In particular, it is suitable for applications that require self-cleaning property, and examples thereof include a sealing material that is applied outdoors.

[Cured product]
The cured product of the present invention is a cured product of the curable composition of the present invention described above.
When the curable composition of the present invention is a one-component type, it is preferable to use the curable composition for construction and to cure it by moisture in the air after construction.
When the curable composition of the present invention is a two-component type of a main agent composition containing at least a component having a reactive silicon group and at least a curing agent composition containing a curing catalyst, the main agent composition and the curing agent composition It is preferable to use it for construction after mixing with and to cure it after construction.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description.

[Measurement method and evaluation method]
<Molecular weight of precursor polymer>
The molecular weight of the oxyalkylene polymer (precursor polymer) obtained by polymerizing the alkylene oxide with the initiator having a hydroxyl group (hereinafter referred to as "hydroxyl conversion molecular weight") is based on the hydroxyl value calculated based on JIS K 1557: 2017. , "56100 / (hydroxyl value of precursor polymer) x number of active hydrogens of initiator" was calculated based on the formula.

<Mn and molecular weight distribution>
Using HLC-8220GPC (product name of Tosoh Corporation), Mw and Mn were measured, and the molecular weight distribution (Mw / Mn) was calculated.

<The average number of reactive silicon groups per molecule in the polymer A ¹ (silyl groups)>
In a method in which an unsaturated group is introduced at the end of the main chain using allyl chloride and a silylating agent is reacted with the unsaturated group to introduce a reactive silicon group, the unsaturated group introduced at the end of the main chain is subjected to. The charge equivalent (molar ratio) of the reactive silicon group of the silylating agent was defined as the silylation rate.
In the reaction between the unsaturated group introduced using allyl chloride and the silylating agent, about 10% of the unsaturated groups do not react with the silylating agent due to a side reaction. Therefore, when less than 90 mol% of unsaturated groups are reacted with the silylating agent, the above charged equivalent is defined as the silylation rate.
The number of silyl groups was calculated based on the silylation rate.

<Average number of reactive silicon groups in one molecule in polymer A ² (number of silyl groups)>
The number of silyl groups in the polymer A ² was calculated by multiplying the concentration [mol / g] of the reactive silicon groups in the polymer calculated by ¹ H-NMR by the Mn measured by the above GPC.

<Contact angle>
The curable composition of each example was cast as a sealing material on a flexible board provided with a groove of about 3 mm (depth) x 30 mm (width), and left for 7 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. Then, a cured product was obtained. At room temperature (25 ° C.), 1 μL of water was allowed to stand on the surface of the cured product, and the contact angles after 5 seconds and 60 seconds were measured.

<Prevention of contamination of cured products (self-cleaning)>
The curable composition of each example was cast as a sealing material on a flexible board provided with a groove of about 3 mm (depth) x 30 mm (width), and left for 7 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. To obtain a cured product.
Red clay was sprinkled on the surface of the obtained cured product, and the flexible board was dropped on the floor from a height of 20 cm three times with the flexible board standing vertically, and the excess red clay was sprinkled to prepare a test piece.
The value of Eab (after contamination) was measured using a color difference meter in the state where the red soil of the obtained test piece was attached.
If Eab (after contamination) is more than 50, it is judged to be defective and is indicated by "x" in the table.
If the Eab (after contamination) is more than 40 and 50 or less, it is judged to be good, and is indicated by "Δ" in the table.
If the Eab (after contamination) is 40 or less, it is judged to be better, and is indicated by "○" in the table.
Next, with the test piece standing vertically, 100 cc of water was sprayed from a distance of 20 cm on the surface sprinkled with red clay, left to dry, and then the red clay adhered to the surface using a color difference meter. The value (after washing with water) was measured.
Similar to the above Eab (after contamination), Eab (after washing with water) was determined and shown in the table.
In addition, the value of the difference represented by the formula [Eab (after contamination) -Eab (after washing with water)] was calculated, and the contamination property of the cured product was evaluated. When the values of Eab (after contamination) and Eab (after washing with water) are both 50 or less and the difference value is more than 5, it is shown that good self-cleaning property is obtained. ..

<tack>
The surface tack after 24 hours of curing was examined. The presence or absence of surface tack was confirmed by touching the surface with a finger. Those with less stickiness on the surface were judged to be good (◯), and those with more stickiness on the surface were judged to be defective (x).

[Synthesis of Polymer A and Polymer B]
<Synthesis of Polymer ^{A 1>}
(Synthesis Example 1: Polymer ^A 1 -1)
Protew oxide is polymerized using glycerin as an initiator and a zinc hexacyanocobaltate complex (hereinafter referred to as "TBA-DMC catalyst") having a ligand of t-butyl alcohol as a catalyst, and has a hydroxyl value equivalent molecular weight of 21. 000 precursor polymers were obtained. Then, 1.15 molar equivalents of a methanol solution of sodium methoxide was added to the hydroxyl group of the precursor polymer to alcorate the precursor polymer. Next, methanol was distilled off by heating and reducing pressure, and an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer to convert the main chain terminal group into an allyl group. Next, in the presence of chloroplatinic acid hexahydrate, 0.65 molar equivalent of methyldimethoxysilane was added as a silylating agent to the converted allyl group of the precursor polymer, and the reaction was carried out at 70 ° C. for 5 hours. is allowed, dimethoxymethylsilyl group as the reactive silicon group was synthesized oxypropylene polymer which is introduced into the main chain end groups (polymer a ¹ -1).
Table 1 shows the number and hydroxyl equivalent molecular weight of the main chain terminal groups of the precursor polymer, and Mn the synthesized polymer A ¹ -1, the average number of reactive silicon groups per Mw / Mn, and 1 molecule.

(Synthesis Example 2: Polymer A ^1-2 )
Propylene oxide was polymerized using propylene glycol as an initiator and a TBA-DMC catalyst to obtain a precursor polymer having a molecular weight equivalent to hydroxyl groups of 15,000. Then, 1.05 mol equivalent of a methanol solution of sodium methoxide was added to the hydroxyl group of the precursor polymer to alcorate the precursor polymer. Next, in the same manner as in Synthesis Example 1, methanol was distilled off, the main chain terminal group of the precursor polymer was further converted to an allyl group, and the allyl group was reacted with a silylating agent to cause a reactive silicon group. An oxypropylene polymer (polymer A ^1-2 ) in which a dimethoxymethylsilyl group was introduced into the main chain terminal group was synthesized.
Table 1 shows the number of main chain terminal groups and the molecular weight in terms of hydroxyl groups of the precursor polymer, and the average number of Mn, Mw / Mn of the synthesized polymer A ^1-2 and the number of reactive silicon groups per molecule.

<Synthesis of polymer A ² >
(Synthesis Example 3: Polymer ^A 2 -1)
100 g of methyl methacrylate, 750 g of butyl acrylate, 150 g of stearyl methacrylate, 26.7 g of γ-methacryloxypropylmethyldimethoxysilane, 7.5 g of n-dodecyl mercaptan and 2,2'-azobis-2-methylbutyronitrile A mixed solution containing 10 g of (V65, product name of Wako Junyakusha, hereinafter referred to as "V65") was added dropwise to 300 g of ethyl acetate heated to 70 ° C. for 2 hours, and then polymerized for 2 hours. was synthesized (meth) acrylic acid ester polymer (polymer ^a 2 -1).
Table 1 shows the number of main chain terminal groups of the precursor polymer, and Mn the synthesized polymer A ² -1, the average number of reactive silicon groups per Mw / Mn, and 1 molecule.

(Synthesis Example 4: Polymer ^A 2 -2)
In this example, using a living radical polymerization method, a compound having two alkenyl groups at the end of the polymerization reaction process for reacting were synthesized following polymer A ² -2.
8.39 g of cuprous bromide and 112 mL of acetonitrile were added to a 2 L flask, and the mixture was heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this, 17.6 g of diethyl 2,5-dibromoadipate, 130 mL of ethyl acrylate, 720 mL of butyl acrylate, and 251 g of stearyl acrylate were added, and the mixture was further heated and stirred at 70 ° C. for 40 minutes. To this, 0.41 mL of pentamethyldiethylenetriamine (hereinafter referred to as "triamine") was added to initiate the reaction. The heating and stirring was continued at 70 ° C., and 2.05 mL of triamine was further added. After 330 minutes from the start of the reaction, 244 mL of 1,7-octadiene and 4.1 mL of triamine were added, and heating and stirring were continued at 70 ° C., and heating was stopped 570 minutes after the start of the reaction.
The resulting reaction solution was filtered and diluted with toluene and the filtrate was heated under reduced pressure treatment to obtain the terminal acrylate polymer having an alkenyl group (polymer X ^1).
The Mn of the polymer X ¹ was 22,800, the molecular weight distribution was 1.40, and the average number of alkenyl groups per molecule of the polymer X ¹ determined by ¹ H-NMR analysis was 2.8.

Then, under a nitrogen atmosphere, to a 2L flask, the obtained polymer ^{X 1} of the total amount of potassium acetate 17.2 g, N, N-dimethylacetamide methyl (hereinafter, referred to as. "DMAc") was added 700mL of 100 The mixture was heated and stirred at ° C. for 10 hours. The reaction solution was heated under reduced pressure to remove DMAc, toluene was added, and the mixture was filtered. The filtrate was heated under reduced pressure to remove volatile matter, and the rest was added to a 2 L flask, and 100 g of an adsorbent (a mixture of Kyoward 500SN and Kyoward 700SN (both Kyowa Chemical product names) in a mass ratio of 1: 1). Was added, and the mixture was heated and stirred at 130 ° C. under a nitrogen stream for 9 hours. The mixture was diluted with toluene, filtered to remove the adsorbent, and toluene in the filtrate was distilled off under reduced pressure to obtain a precursor polymer (polymer X ² ).

Next, 700 g of polymer X ² , 22.2 mL of methyldimethoxysilane, 7.71 mL of methyl orthostate and platinum catalyst (1,1,3,3-tetramethyl-of zero-valent platinum) were placed in a 1 L pressure resistant reaction vessel. 1,3-Divinyldisiloxane complex) was added. The amount of the platinum catalyst used was a 9 × 10 ^-3 molar equivalents relative to the alkenyl group of the polymer X ^2. The mixture in the reaction vessel was heated and stirred at 100 ° C. for 195 minutes. The volatiles in the mixture was distilled off under reduced pressure, to synthesize a polymer having a dimethoxymethylsilyl group (Polymer A ² -2) in the main chain terminal.
Table 1 shows the number of main chain terminal groups of the precursor polymer, and synthesized Mn of polymer A ² -2, the average number of reactive silicon groups per Mw / Mn, and 1 molecule.

The meanings of the terms in Table 1 are as follows.
Number of main chain terminal groups ... Number of main chain terminal groups of precursor polymer hydroxyl weight conversion molecular weight ... Molecular weight of precursor polymer converted to hydroxyl group Mn ... Number of synthesized polymers Average molecular weight Mw / Mn ... Molecular weight distribution reaction of synthesized polymer Average number of sex silicon groups: Average number of reactive silicon groups per molecule of the synthesized polymer

<Synthesis or preparation of polymer B or comparative polymer B>
(Synthesis Example 5: Polymer B1)
As the monomer, 300 g of Cyraplane TM-0701T (manufactured by JNC Corporation) and 200 g of Blemmer AME400 (manufactured by NOF Corporation) were used. A mixed solution prepared by mixing 6 g of n-dodecyl mercaptan and 10 g of V65 with respect to a total mass of 500 g of the monomer was added dropwise to 50 g of 2-propanol heated to 80 ° C. over 2 hours, and then polymerized for 2 hours. Then, a (meth) acrylic acid ester polymer (polymer B1) was synthesized.
Table 2 shows the types of monomers used, the number of parts charged (parts by mass), and the Mn of the synthesized polymer B1.

(Synthesis Examples 6, 7, 10, 11: Polymers B2, B3, Comparative Polymers B8, B9)
Polymers B2 and B3 and comparative polymers B8 and B9 were synthesized in the same manner as in Synthesis Example 5 at a ratio (unit: parts by mass) shown in Table 2 with the total mass of the monomers being 500 g.
Table 2 shows the types of monomers used, the number of parts charged (parts by mass), and the Mn of each synthesized polymer and each comparative polymer for each synthesis example.

(Synthesis Example 8: Polymer B4)
As a monomer, 200 g of TM-0701T, 150 g of AME400, 50 g of Blemmer 50PEP-300 (NOF product name, hereinafter referred to as "50PEP-300"), butyl acrylate (hereinafter referred to as "BA"). 100 g was used. A mixed solution prepared by mixing 10 g of V65 with respect to a total mass of 500 g of the monomer was added dropwise to 50 g of 2-propanol heated to 80 ° C. over 2 hours, and then polymerized for 2 hours to obtain (meth) acrylic. An acid ester polymer (polymer B4) was obtained.
Table 2 shows the types of monomers used, the number of parts charged (parts by mass), and the Mn of the synthesized polymer B4.

(Synthesis Example 9: Polymer B5)
Polymerization was carried out in the same manner as in Synthesis Example 8 except that 200 g of TM-0701T, 200 g of AME400 and 100 g of BA were used as the monomers to obtain a (meth) acrylic acid ester polymer (polymer B5).
Table 2 shows the types of monomers used, the number of parts charged (parts by mass), and the Mn of the synthesized polymer B5.

(Synthesis Example 12: Polymer B10)
Except for using 195 g of TM-0701T, 195 g of AME400, 97.5 g of BA, and 12.5 g of KBE-502 (product name of Shin-Etsu Chemical Co., Ltd., hereinafter referred to as "KBE-502") as a monomer. , Polymerization was carried out in the same manner as in Synthesis Example 8 to obtain a (meth) acrylic acid ester polymer (polymer B10).
Table 2 shows the types of monomers used, the number of parts charged (parts by mass), and the Mn of the synthesized polymer B10.

Each monomer in Table 2 is as follows.
Monomer ^b 1 -1 ... SILAPLANE TM-0701T (JNC Corporation; ^{R 1} is a methyl group in Formula 2, Y is a propylene group, ^{R 2} is ^{_{OSi (CH 3) 3, R}} 3 is OSi _(CH 3) ₃ , compound with 0 c)
Monomer ^b 2 -1 ... Blemmer AME400 (manufactured by NOF Corporation; the methoxy polyethylene glycol acrylate (Formula 3, ^{Q 1} is _{CH 2 = C (CH 3)} -C (= O) O-, bond ^{Z 2} is a single , R ²¹ is a methyl group, m is about 9, and n is 0))
Monomer ^b 2 -2 ... Blenmer 50PEP-300 (manufactured by NOF Corporation; in Formula 3, ^{Q 1} is _{CH 2 = C (CH 3)} -C (= O) O-, Z 2 is a single ^{bond, R 21} Is a compound in which a unit based on ethylene oxide and a unit based on propylene oxide in which H, m is about 3.5, and n is about 2.5 are randomly bonded)
Monomer ^b 3 -1 ... KBE-502 (Shin-Etsu Chemical Co., Ltd .; methacrylic acid-3- (methyldiethoxysilyl) propyl)
Monomer ^b 4 -1 ... butyl acrylate

(Preparation examples 1 and 2)
Preparation Example 1: Comparative Polymer Polymer B6 ... Reactive Silicone Oil (KF8010, manufactured by Toray Dow; Mn = 400)
Preparation Example 2: Comparative Polymer Polymer B7 ... One-end reactive silicone oil (X22-170DX, manufactured by Shin-Etsu Chemical Co., Ltd .; Mn = 5600)
Neither B6 nor B7 contains a unit based on monomer b ¹ to monomer b ⁴ .

<Other ingredients>
(Preparation Examples 1-9: Additives C1 to C9)
Additives C1 to C9 were prepared by mixing the components shown in Table 3.

Each component in Table 3 is as follows.
・ Filler Filler 1 ... Heavy calcium carbonate (Whiten SB, manufactured by Shiraishi Kogyo Co., Ltd.)
Filler 2 ... Colloidal calcium carbonate (white glossy CCR, manufactured by Shiraishi Kogyo Co., Ltd.)
Filler 3 ... Titanium oxide (R-820, manufactured by Ishihara Sangyo Co., Ltd.)
Filler 4 ... Organic balloon (balloon 80GCA, manufactured by Matsumoto Yushi Co., Ltd.)
-Plasticizer Plasticizer 1 ... Acrylic polymer with Mn = 1,500 (ARUFON UP-1110, manufactured by Toagosei Co., Ltd.)
Plasticizer 2 ... An oxyalkylene polymer having two hydroxyl groups per molecule and having a molecular weight equivalent to 2,000 (Exenol 3020, manufactured by AGC Inc.).
Plasticizer 3 ... Diisononyl phthalate (Vinizer 90, manufactured by Kao Corporation)
Plasticizer 4 ... n-dodecane, purity 98.0% (Cactus normal paraffin N-12D, manufactured by JXTG Energy Co., Ltd.)
Plasticizer 5 ... 4,5-Epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl (Sansosizer EPS, manufactured by New Japan Chemical Co., Ltd.)
-Antioxidant Antioxidant 1 ... Hindered phenolic antioxidant (IRGANOX1135, manufactured by BASF)
-UV absorber UV absorber 1 ... Benzotriazole-based UV absorber (Tinuvin 326, manufactured by BASF)
-Light stabilizer Light stabilizer 1 ... Hindered amine-based light stabilizer (Tinuvin 765, manufactured by BASF)
Light stabilizer 2 ... Hindered amine-based light stabilizer (ADEKA STUB LA-63P, manufactured by ADEKA)
-Dehydrating agent Dehydrating agent 1 ... Vinyl trimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.)
-Adhesive-imparting agent Adhesive-imparting agent 1 ... 3-glycidyloxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
Adhesive imparting agent 2 ... 3- (2-aminoethylamino) propyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Amine compound Amine compound 1 ... Laurylamine (manufactured by Junsei Chemical Co., Ltd.)
Amine compound 2 ... Coconut amine (Farmin CS, manufactured by Kao Corporation)
Amine compound 3 ... Ketimine compound (EH-235R-2, manufactured by ADEKA Corporation)
-Oxygen-curable compound Oxygen-curable compound 1 ... Air oxidation-curable compound (tung oil, manufactured by Kimura)
-Photo-curable compound Photo-curable compound 1 ... Trimethylolpropane triacrylate (Aronix M-309, manufactured by Toagosei Co., Ltd.)
-Curing catalyst Catalyst 1 ... Dibutyltin bis (acetylacetonate) (U-220H, manufactured by Nitto Kasei Co., Ltd.)

[Manufacturing of curable composition]
Examples 1 to 14 and Examples 20 to 132 are Examples, and Examples 15 to 19 are Comparative Examples.

(Examples 1 to 19)
Table 4-6 in the formulations shown: polymer (unit mass parts) (Polymer ^A 1 ^{-1~A 2} -2 and polymers B1 to B5, B10), comparative polymer (Comparative Polymer B6～B9) and The additive (additive C1) was mixed to prepare a curable composition.
The formulations shown in Tables 4 to 6 are values (unit: parts by mass) with respect to a total of 100 parts by mass of the polymer A.
The cured product of the obtained curable composition was evaluated for tack, contact angle with water, and stain resistance of the cured product by the above method. The results are shown in Tables 4-6.

In Examples 1 to 14, the tack was good, the surface was confirmed to be hydrophilic by measuring the contact angle of water, and the self-cleaning property was good.

(Examples 20 to 132)
In Examples 1 to 14, the additive was changed from additive C1 to any of additives C2 to C9 to prepare each curable composition, which was evaluated in the same manner as described above.
Examples 20 to 33 are examples in which the additive C2 is added instead of the additive C1 in Examples 1 to 14.
Examples 34 to 47 are examples in which the additive C3 is added instead of the additive C1 in Examples 1 to 14.
Examples 48 to 62 are examples in which the additive C4 is added instead of the additive C1 in Examples 1 to 14.
Examples 63 to 76 are examples in which the additive C5 is added instead of the additive C1 in Examples 1 to 14.
Examples 77 to 90 are examples in which the additive C6 is added instead of the additive C1 in Examples 1 to 14.
Examples 91 to 104 are examples in which the additive C7 is added instead of the additive C1 in Examples 1 to 14.
Examples 105 to 118 are examples in which the additive C8 is added instead of the additive C1 in Examples 1 to 14.
Examples 119 to 132 are examples in which the additive C9 is added instead of the additive C1 in Examples 1 to 14.

In any of Examples 20 to 132, hydrophilicity of the surface was confirmed from the measurement of the contact angle of water, and the self-cleaning property was good.

Claims (11)

A curable composition containing a first organic polymer and a second organic polymer.
The first organic polymer is a polymer that does not have a siloxane structure and has a reactive silicon group represented by the following formula 1.
The second organic polymer is a polymer having a siloxane structure and containing a unit based on the first monomer and a unit based on the second monomer.
The first monomer is a monomer that does not have a reactive silicon group represented by the following formula 1 and has a siloxane structure and a polymerizable unsaturated group.
The second monomer is a monomer having neither a reactive silicon group or a siloxane structure represented by the following formula 1 and having a hydrophilic group and a polymerizable unsaturated group.
Curable composition.
−SiX _a R _3-a formula 1
In the formula, R represents a monovalent organic group having 1 to 20 carbon atoms other than the hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, a is an integer of 1 to 3, and a is 1. In some cases, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other. The curable composition according to claim 1, wherein the content of the second organic polymer is 1 to 40 parts by mass with respect to 100 parts by mass of the first organic polymer. The curable composition according to claim 1 or 2, wherein the first monomer contains a monomer represented by the following formula 2.
CH ₂ = CR ^1- C (= O) OY-SiR ² R ³ O (Si (CH ₃ ) ₂ O) _c- Si (CH ₃ ) ₃ formula 2
In the formula, R ¹ represents a hydrogen atom or a methyl group, Y is a single bond, a linear alkylene group having 1 to 6 carbon atoms, or a carbon in which one hydrogen atom is substituted with an alkyl group having 1 to 3 carbon atoms. Representing an alkylene group of numbers 1 to 6, R ² and R ³ independently represent a hydrogen atom, a methyl group or a trimethyloxysilyl group, and c is an integer of 0 to 150. Claims 1 to 80%, in which the content ratio of the unit based on the first monomer to all the units constituting the second organic polymer in the second organic polymer is 10 to 80% by mass. The curable composition according to any one of 3. Claims 1 to 80%, in which the content ratio of the unit based on the second monomer to all the units constituting the second organic polymer in the second organic polymer is 10 to 80% by mass. The curable composition according to any one of 4. The second organic polymer further comprises a unit based on a third monomer having a reactive silicon group represented by the formula 1 and having neither a siloxane structure nor a hydrophilic group. The curable composition according to any one of claims 1 to 5. The claim that the content ratio of the unit based on the third monomer to all the units constituting the second organic polymer in the second organic polymer is 0.1 to 20% by mass. 6. The curable composition according to 6. The curable composition according to any one of claims 1 to 7, wherein the number average molecular weight of the second organic polymer is 1,000 to 20,000. The method according to any one of claims 1 to 8, wherein the total content ratio of the first organic polymer and the second organic polymer in the curable composition is 5 to 80% by mass. Curable composition. The curable composition according to any one of claims 1 to 9, which is used as a sealing material. A cured product of the curable composition according to any one of claims 1 to 10.