JP2022135913A - Curable composition and cured product thereof - Google Patents

Abstract

To provide a curable composition that has excellent depth curability and is also excellent in the flexible durability and weather resistance of a cured product.SOLUTION: A curable composition contains: a polyoxyalkylene polymer A having reactive silicon groups represented by -SiRaX13-a, the number of the reactive silicon groups being more than 1.0 per end group; a polymer B that is at least one selected from a methacrylate polymer B1 having reactive silicon groups represented by -SiX23 and a polyoxyalkylene polymer B2 having reactive silicon groups represented by -SiX23, the number of the reactive silicon groups being more than 0.5 and 1.0 or less per end group; and a condensation catalyst, with the mass ratio between the polymer A and the polymer B of 80/20-95/5.SELECTED DRAWING: None

Description

The present invention relates to a curable composition and its cured product.

Polymers having reactive silicon groups are known to crosslink through the formation of siloxane bonds accompanied by hydrolysis and condensation reactions of the reactive silicon groups to form rubber-like cured products.
It has been proposed to combine polymers having different main chain structures, reactive silicon group structures, reactive silicon group contents, etc., according to various required properties.

Examples of Patent Document 1 include a polyoxyalkylene polymer (A-1) having 0.8 dimethoxymethylsilyl groups per terminal group and 1.6 dimethoxysilyl groups per molecule, and one dimethoxysilyl group. When the polyoxyalkylene polymer (B-1) having 1.7 per terminal group and 3.4 per molecule is added, the skinning time (curing surface 1000 hour weathering test results (Table 1).

Examples of Patent Document 2 include 60 parts by mass of a polyoxyalkylene polymer (B-4) having 1.6 trimethoxysilyl groups per terminal group and 3.2 per molecule, and trimethoxy A cured product of a mixture (BC-4) with 40 parts by mass of a (meth)acrylic acid ester copolymer (C-1) having 1.5 silyl groups per molecule, instead of (B-4) , Compared to the cured product of the mixture (SC-4) using the polyoxyalkylene polymer (S-4) having 0.8 trimethoxysilyl groups per terminal group and 1.6 per molecule, A significant improvement in strength is shown (Table 2).

Examples of Patent Document 3 include a polyoxyalkylene polymer A3 having 0.73 dimethoxysilyl groups per terminal group and 1.46 dimethoxysilyl groups per molecule, and 1 dimethoxymethylsilyl group per terminal group. A curable composition is described in which a polyoxyalkylene polymer A5 having 6 groups and 3.2 groups per molecule and an acrylic acid ester polymer B2 having 2.0 dimethoxymethylsilyl groups per molecule are combined. (Table 4).

Examples of Patent Document 4 include polyoxyalkylene polymer A1 having 1.6 dimethoxymethylsilyl groups per terminal group and 3.2 dimethoxymethylsilyl groups per molecule, and dimethoxymethylsilyl groups at both ends of the main chain. and a polyoxyalkylene polymer C1 having 0.75 dimethoxymethylsilyl groups per molecule and 1.5 dimethoxymethylsilyl groups per molecule, and a dimethoxymethylsilyl group as one terminal group. A curable composition in combination with a polyoxyalkylene polymer D1 having 0.4 per minute and 0.8 per minute is described (Table 3, Example 6).

Japanese Patent No. 6096320 Japanese Patent No. 6275036 JP 2020-117583 A Japanese Patent No. 6579206

A curable composition using a polymer having a reactive silicon group is prepared by separately storing a main component composition containing a component having a reactive silicon group and a curing agent composition containing a condensation catalyst, and storing the main component before use. There is a two-component type in which the composition and the curing agent composition are mixed, and a one-component type in which all the ingredients are mixed in advance and sealed. From the viewpoint of workability, a one-liquid type is desirable.
A one-liquid type curable composition tends to be hardened insufficiently in the deep part because the hardening progresses from the surface toward the inside due to moisture in the air after application.

According to the knowledge of the present inventors, in the combination of polymers implemented in Patent Documents 1 to 4, good deep curability and good stretch durability and weather resistance of the cured product can be achieved at the same time. is difficult.
The present invention provides a curable composition which has good deep-part curability and also good stretch durability and weather resistance of the cured product.

The present invention has the following aspects.
[1] A curable composition comprising the following polymer A, the following polymer B, and a condensation catalyst, wherein A/B, which represents the mass ratio of the polymer A to the polymer B, is 80/20 to 95/5. thing.
Polymer A: A polyoxyalkylene polymer having more than 1.0 reactive silicon groups represented by the following formula 1 per terminal group.
Polymer B: a (meth)acrylic acid ester polymer B1 having a reactive silicon group represented by the following formula 2, and a reactive silicon group represented by the following formula 2, 0.5 per terminal group At least one selected from the group consisting of polyoxyalkylene polymers B2 having more than 1.0 or less.
—SiR _a X ¹ _3-a Formula 1
In Formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X ¹ represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is When it is 1 or 2 and a is 2, X ¹ may be the same or different, and when a is 1, R may be the same or different.
- SiX ² ₃ Formula 2
^In Formula ² , X2 represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and X2 may be the same or different.
[2] The curable composition of [1], wherein the polymer A has a terminal group containing a group represented by Formula 3 or Formula 4 below.

[In Formula 3, R ¹ and R ³ each independently represent a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms in the bonding group are a carbon atom, a hydrogen atom, and an oxygen atom. , a nitrogen atom, or a sulfur atom, R ² and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Si ¹ represents a reactive silicon group represented by Formula 1 above. , n represents an integer of 1 to 10, and Si ¹ may be the same or different. ]

[In Formula 4, R ⁵ represents a single bond or a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms in the bonding group are carbon, hydrogen, oxygen and nitrogen atoms. , or a sulfur atom, X represents a monovalent group represented by any of formulas 5 to 8, and in formulas 5 to 8, R ⁶ is a hydrogen atom or a monovalent hydrocarbon having 1 to 10 carbon atoms R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms, Si ¹ represents a reactive silicon group represented by Formula 1 above, and a plurality of Si ¹ may be the same or different from each other. ]
[3] The curable composition of [1] or [2], wherein the polymer A is linear.
[4] The curable composition according to any one of [1] to [3], wherein the polymer A has a number average molecular weight of 8,000 to 150,000.
[5] The curable composition according to any one of [1] to [4], wherein the polymer B has a number average molecular weight of 5,000 to 50,000.
[6] The curable composition according to any one of [1] to [5], wherein the content of the polymer B1 with respect to the total mass of the polymer B is 45-100% by mass.
[7] The curable composition according to any one of [1] to [6], further comprising polymer C below.
Polymer C: A polyoxyalkylene polymer having two terminal groups, one terminal group being an inert organic group, and a reactive silicon group represented by the above formula 1 or a reactive silicon group represented by the above formula 2 a polyoxyalkylene polymer having a number average molecular weight of from 2,000 to 15,000, containing more than 0 and no more than 0.5 reactive silicon groups per terminal group.
[8] The condensation catalyst contains one or more selected from the group consisting of tetravalent tin catalysts, titanium catalysts, aluminum catalysts, zirconium catalysts, carboxylic acids, carboxylic acid metal salts, and amine compounds [1]- The curable composition according to any one of [7].
[9] Any one of [1] to [8], wherein the content of the condensation catalyst is 0.03 to 0.7 parts by mass with respect to a total of 100 parts by mass of the polymer A and the polymer B curable composition.
[10] The curable composition according to any one of [1] to [9], which is used as a sealant or adhesive.
[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 obtain a curable composition having good deep-part curability, and the cured product having good stretch durability and weather resistance.

The meanings and definitions of the terms used herein are as follows.
A numerical range represented by "~" means a numerical range having lower and upper limits of values before and after ~.
"Polyoxyalkylene polymer" means a polymer having a polyoxyalkylene chain formed from units based on cyclic ethers.
A polyoxyalkylene polymer has a main chain containing a polyoxyalkylene chain and terminal groups bonded to the main chain. The "terminal group" means an atomic group containing an oxygen atom closest to the molecular terminal of the polyoxyalkylene polymer among the oxygen atoms in the polyoxyalkylene chain.
"Active hydrogen-containing group" is at least one selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine and a sulfanyl group bonded to a carbon atom. It is the seed base.
"Active hydrogen" is a hydrogen atom derived from the active hydrogen-containing group and a hydrogen atom derived from the hydroxyl group of water.
An "initiator" is a compound having an active hydrogen-containing group.
An "unsaturated group" is a group having double or triple bonds between carbon atoms.

The number average molecular weight (hereinafter referred to as "Mn") and mass average molecular weight (hereinafter referred to as "Mw") of the polymer are polystyrene equivalent molecular weights obtained by GPC measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is the ratio of Mw to Mn (hereinafter referred to as "Mw/Mn").

The curable composition of this embodiment comprises polymer A, polymer B, and a condensation catalyst.
<Polymer A>
Polymer A is a polyoxyalkylene polymer having a main chain containing a polyoxyalkylene chain and terminal groups bonded to the main chain.
Polymer A has more than 1.0 reactive silicon groups represented by the following formula 1 (hereinafter also referred to as "first reactive silicon groups") per terminal group.
—SiR _a X ¹ _3-a Formula 1
In Formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain hydrolyzable groups.
Examples of R include hydrocarbon groups, halohydrocarbon groups and triorganosiloxy groups.
R is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group and a triorganosiloxy group. at least one selected from the group consisting of 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 a triphenylsiloxy group; is more preferred. A methyl group or an ethyl group is preferable from the viewpoint of good curability of the polymer A and good stability of the curable composition. A methyl group is more preferable because of its easy availability.

In Formula ¹ , X1 represents a hydroxyl group, a halogen atom, or a hydrolyzable group. A hydrolyzable group is a group that can react with water to form a silanol group.
Examples of hydrolyzable groups include alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups.
X ¹ is preferably an alkoxy group because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group or an isopropoxy group, more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, a siloxane bond is rapidly formed, a crosslinked structure is easily formed in the cured product, and the physical properties of the cured product are improved.

In Formula 1, a is 1 or 2. When a is 1, two X ¹ 's may be the same or different. When a is 2, two R's may be the same or different.

Examples of the first reactive silicon group represented by Formula 1 include a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a diisopropoxymethylsilyl group, a dimethylmethoxysilyl group, a diethylmethoxysilyl group, Examples include a dimethylethoxysilyl group, a dimethylisopropoxysilyl group, a chloromethyldimethoxysilyl group, and a chloromethyldiethoxysilyl group. A dimethoxymethylsilyl group and a dimethylmethoxysilyl group are preferable, and a dimethoxymethylsilyl group is more preferable, from the viewpoint that the elongation of the cured product becomes good and the stretch durability is further improved.

The main chain of the polymer A has an initiator residue having two or more active hydrogens and a polyoxyalkylene chain formed by ring-opening addition polymerization of a cyclic ether.
As the initiator, an initiator having two or more hydroxyl groups is preferable, an initiator having two to six hydroxyl groups is more preferable, and an initiator having two or three hydroxyl groups is even more preferable.
Examples of initiators having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, low molecular weight can be exemplified by polyoxypropylene glycol.
Examples of initiators having 3 or more hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, low molecular weight polyoxyethylenetriol, polyoxypropylenetriol, pentaerythritol, sorbitol and sucrose.

Examples of cyclic ethers include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and cyclic ethers other than alkylene oxides such as tetrahydrofuran. Ethylene oxide and propylene oxide are preferred, and propylene oxide is more preferred.
A polyoxyalkylene chain may be a copolymer chain having two or more oxyalkylene groups. The copolymer chain may be a block copolymer chain or a random copolymer chain.
The polyoxyalkylene chain of the polymer A includes a polyoxypropylene chain, a polyoxyethylene chain, a poly(oxy-2-ethylethylene) chain, a poly(oxy-1,2-dimethylethylene) chain, and a poly(oxytetramethylene) chain. ) chain, poly(oxyethylene/oxypropylene) chain, and poly(oxypropylene/oxy-2-ethylethylene) chain. Polyoxypropylene chains and poly(oxyethylene-oxypropylene) chains are preferred, with polyoxypropylene chains being more preferred.

The number of terminal groups of polymer A is preferably 2 to 6, more preferably 2 or 3. The number of terminal groups of polymer A is the same as the number of active hydrogens present in the initiator.
The polymer A preferably has a straight chain shape because it has better deep-part curability and stretch durability. That the polymer A is linear means that the main chain of the polymer A is linear. The linear main chain has a polyoxyalkylene chain formed by ring-opening addition polymerization of an initiator residue having two active hydrogens and a cyclic ether, and has two terminal groups.

The terminal group of polymer A preferably contains one or more selected from the group consisting of a first reactive silicon group, an active hydrogen-containing group, or an unsaturated group.
The total number of the first reactive silicon groups, active hydrogen-containing groups, and unsaturated groups present in the terminal groups of polymer A is preferably 2 to 6 per terminal group, more preferably 2 to 4. preferable.
The number of the first reactive silicon groups in the polymer A is more than 1.0 per terminal group, preferably 1.1 to 3.0, more preferably 1.2 to 2.0. . If it is at least the lower limit of the range, deep-part curability and stretch durability will be better, and if it is at most the upper limit, the elongation of the cured product will tend to be good, and the stretch durability will be better.

Polymer A preferably has a terminal group containing a group represented by Formula 3 or Formula 4 below. X in Formula 4 below is a monovalent group represented by any one of Formulas 5 to 8 below.
Si ¹ in Formulas 3 and 5 to 8 below represents the first reactive silicon group represented by Formula 1 above. When more than one Si ¹ is present on one terminal group, they may be the same or different from each other.

In Formula 3, R ¹ and R ³ each independently represent a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms present in the bonding group are carbon atoms, hydrogen atoms, It is an oxygen atom, a nitrogen atom, or a sulfur atom.
R ¹ and R ³ are —CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₆ H ₁₂ —, —C( CH ₃ ) ₂ -, -CH ₂ O-, -CH ₂ -O-CH ₂ -, -CH ₂ -O-CH ₂ -O-CH ₂ -, -C=C-, -C≡C-, - Examples include C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CH=N- and -CH=N-N=CH-.
R ¹ is preferably -CH ₂ -O-CH ₂ -, -CH ₂ O- or -CH ₂ -, more preferably -CH ₂ -O-CH ₂ -.
R ³ is preferably -CH ₂ - or -C ₂ H ₄ -, more preferably -CH ₂ -.

R ² and R ⁴ in formula 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
As the hydrocarbon group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
Examples of branched alkyl groups include isopropyl group, s-butyl group, t-butyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-propylbutyl group, 3-methylbutyl group, 3-ethylbutyl group and 3-propylbutyl group. group, 2-methylpentyl group, 2-ethylpentyl group, 2-propylpentyl group, 3-methylpentyl group, 3-ethylpentyl group, 3-propylpentyl group, 4-methylpentyl group, 4-ethylpentyl group, 4-propylpentyl group, 2-methylhexyl group, 2-ethylhexyl group, 2-propylhexyl group, 3-methylhexyl group, 3-ethylhexyl group, 3-propylhexyl group, 4-methylhexyl group, 4-ethylhexyl group , 4-propylhexyl group, 5-methylhexyl group, 5-ethylhexyl group and 5-propylhexyl group.
R ² and R ⁴ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group.

n in Formula 3 represents an integer of 1 to 10, preferably 1 to 7, more preferably 1 to 5, and even more preferably 1.

In Formula 4, R ⁵ represents a single bond or a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms present in the bonding group are a carbon atom, a hydrogen atom, an oxygen atom, It is a nitrogen atom or a sulfur atom.
Examples of the divalent linking group for R ⁵ are the same as the examples of the divalent linking group for R ¹ and R ³ above.
R ⁵ is preferably a single bond or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a single bond or an alkylene group having 1 to 3 carbon atoms, even more preferably a single bond or a methylene group.

In Formula 7, R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
Examples of the monovalent hydrocarbon group for R ⁶ are the same as the above examples of the monovalent hydrocarbon group for R ² and R ⁴ .
^R6 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group.

R ⁷ and R ⁸ in Formula 8 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.
As the hydrocarbon group, a linear or branched alkyl group having 1 to 9 carbon atoms is preferable. Examples of alkyl groups for R ⁷ and R ⁸ are the same as those for R ² and R ⁴ above.
Both R ⁷ and R ⁸ are preferably hydrogen atoms.

The Mn of polymer A is preferably 8,000 to 150,000, more preferably 9,000 to 100,000, even more preferably 10,000 to 70,000. When Mn is at least the lower limit of the above range, good stretch durability tends to be obtained, and when it is at most the upper limit, the viscosity of the curable composition tends to be sufficiently low, and good workability tends to be obtained.

<Method for producing polymer A>
Polymer A is a polyoxyalkylene polymer obtained by ring-opening addition polymerization of a cyclic ether to an active hydrogen of an initiator (hereinafter also referred to as "precursor polymer"), a first reactive silicon group, and one It is obtained by introducing more than 1.0 per terminal group.
A method of introducing more than 1.0 unsaturated groups per terminal group to the terminal groups of the precursor polymer and then reacting the unsaturated groups with a silylating agent to introduce reactive silicon groups. preferable.

The precursor polymer is preferably a hydroxyl group-containing polyoxyalkylene polymer having hydroxyl terminal groups, obtained by ring-opening addition polymerization of a cyclic ether to an initiator having a hydroxyl group. The number of hydroxyl groups in the initiator is the same as the number of hydroxyl groups in the hydroxyl-containing polyoxyalkylene polymer.
Particularly preferred is a hydroxyl group-containing polyoxyalkylene polymer having a linear main chain, obtained by ring-opening addition polymerization of a cyclic ether to an initiator having two hydroxyl groups.

As a ring-opening addition polymerization catalyst for ring-opening addition polymerization of a cyclic ether as an initiator, a conventionally known catalyst can be used. a complex obtained by reacting a compound with porphyrin), a double metal cyanide complex catalyst, and a catalyst composed of a phosphazene compound.
A double metal cyanide complex catalyst is preferable because the Mw/Mn of the polymer A can be narrowed and a curable composition having a low viscosity can be easily obtained. A conventionally known compound can be used as the double metal cyanide complex catalyst, and a known method can be adopted as a method for producing a polymer using the double metal cyanide complex. For example, WO 2003/062301, WO 2004/067633, JP 2004-269776, JP 2005-15786, WO 2013/065802, JP 2015-010162 The compounds and production methods disclosed in the publications can be used.

As a method for introducing more than 1.0 unsaturated groups per terminal group to the terminal groups of the precursor polymer, known methods can be used without particular limitation. No., International Publication No. 2014/192842, JP 2015-105293, JP 2015-105322, JP 2015-105323, JP 2015-105324, WO 2015/080067, International The methods described in JP 2015/105122, WO 2015/111577, WO 2016/002907, JP 2016-216633, and JP 2017-39782 can be used.

As a method for introducing more than 1.0 unsaturated groups per terminal group to the terminal group of the precursor polymer, after reacting the precursor polymer with an alkali metal salt, an epoxy compound having an unsaturated group and then reacting a halogenated hydrocarbon compound having an unsaturated group, or reacting a halogenated hydrocarbon compound having a carbon-carbon triple bond after reacting an alkali metal salt on the precursor polymer. A method is preferred.

Examples of alkali metal salts include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide.
Sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferred, and sodium methoxide and potassium ethoxide are more preferred, from the viewpoints of ease of handling and solubility. Sodium methoxide is particularly preferred because of its availability.
The alkali metal salt may be dissolved in a solvent before use.

Examples of epoxy compounds having unsaturated groups include allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide. Allyl glycidyl ether is preferred.

A compound represented by the following formula 9 is preferable as the epoxy compound having an unsaturated group.

前記式９のＲ^１、Ｒ^２は、前記式３のＲ^１、Ｒ^２と同じである。

R ¹ and R ² in Formula 9 are the same as R ¹ and R ² in Formula 3 above.

As the halogenated hydrocarbon compound having an unsaturated group, one or both of a halogenated hydrocarbon compound containing a carbon-carbon double bond and a halogenated hydrocarbon compound containing a carbon-carbon triple bond can be used.
Examples of halogenated hydrocarbon compounds containing carbon-carbon double bonds include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. can. Allyl chloride and methallyl chloride are preferred.
Halogenated hydrocarbon compounds containing carbon-carbon triple bonds include propargyl chloride, 1-chloro-2-butyne, 4-chloro-1-butyne, 1-chloro-2-octyne, 1-chloro-2-pentyne, 1,4-dichloro-2-butyne, 5-chloro-1-pentyne, 6-chloro-1-hexyne, propargyl bromide, 1-bromo-2-butyne, 4-bromo-1-butyne, 1-bromo- 2-octyne, 1-bromo-2-pentyne, 1,4-dibromo-2-butyne, 5-bromo-1-pentyne, 6-bromo-1-hexyne, propargyl iodide, 1-iodo-2-butyne, 4-iodo-1-butyne, 1-iodo-2-octyne, 1-iodo-2-pentyne, 1,4-diiodo-2-butyne, 5-iodo-1-pentyne, 6-iodo-1-hexyne I can give an example. Propargyl chloride, propargyl bromide and propargyl iodide are preferred.
Two or more halogenated hydrocarbon compounds having an unsaturated group may be used in combination.

Through the above reaction, a derivative in which an unsaturated group is introduced into the terminal group of the precursor polymer is obtained. The derivative of the precursor polymer may contain an unreacted active hydrogen-containing group at the terminal group.
From the viewpoint of storage stability, the number of active hydrogen-containing groups contained in the derivative of the precursor polymer is preferably 0.3 or less per molecule, more preferably 0.1 or less.

The unsaturated group of the derivative of the precursor polymer is reacted with a first silylating agent capable of introducing a reactive silicon group (hereinafter also referred to as a "first silylating agent") to the terminal group. A polymer A is obtained by introducing a reactive silicon group of 1.
As the first silylating agent, a compound HSiR _a X ¹ _3-a (R , X ¹ and a are the same as in Formula 1 above).
Examples of the hydrosilane compound include dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, diisopropoxymethylsilane, dimethylmethoxysilane, diethylmethoxysilane, dimethylethoxysilane, dimethylisopropoxysilane, chloromethyldimethoxysilane, chloromethylsilane. Diethoxysilane can be exemplified.

Preferably, the hydroxyl group-containing polyoxyalkylene polymer (precursor polymer) is reacted with an alkali metal salt, then reacted with an epoxy compound having an unsaturated group, and then reacted with a halogenated hydrocarbon compound having an unsaturated group. to obtain an unsaturated group-containing polyoxyalkylene polymer (a derivative of the precursor polymer), and the unsaturated group of the unsaturated group-containing polyoxyalkylene polymer is reacted with the first silylating agent to obtain a polymer A get
Alternatively, after reacting the precursor polymer with an alkali metal salt, a halogenated hydrocarbon compound having a carbon-carbon triple bond is reacted to obtain an unsaturated group-containing polyoxyalkylene polymer (a derivative of the precursor polymer). Then, the polymer A is obtained by reacting the unsaturated group of the unsaturated group-containing polyoxyalkylene polymer with the first silylating agent.
The number of reactive silicon groups per terminal group can be adjusted by the amount of the first silylating agent used.

<Polymer B>
Polymer B is one or more selected from the group consisting of polymer B1 and polymer B2 below.
Polymer B1: A (meth)acrylic acid ester polymer having a reactive silicon group represented by the following formula 2 (hereinafter also referred to as "second reactive silicon group").
Polymer B2: A polyoxyalkylene polymer having more than 0.5 and 1.0 or less second reactive silicon groups represented by the following formula 2 per terminal group.

- SiX ² ₃ Formula 2
In Formula ² , X2 represents a hydroxyl group, a halogen atom, or a hydrolyzable group. Three ^X2s may be the same or different.
Examples of X2 in Formula ² are the same as those of X1 in Formula ¹ , including preferred embodiments.
Examples of the second reactive silicon group represented by Formula 2 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris(2-propenyloxy)silyl group, and a triacetoxysilyl group. . A trimethoxysilyl group and a triethoxysilyl group are preferred, and a trimethoxysilyl group is more preferred, from the viewpoint of better curability.

The number of reactive silicon groups per molecule of polymer B is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. Within the above range, it is easy to adjust the modulus of the cured product to a favorable range.

Mn of polymer B is preferably from 5,000 to 80,000, more preferably from 6,000 to 70,000, still more preferably from 6,000 to 60,000, more than 8,000, more than 60,000 More than 8,000 and 50,000 or less are particularly preferred. When it is at least the lower limit of the above range, the effect of improving weather resistance is excellent. When it is at most the upper limit, the viscosity of the curable composition tends to be sufficiently low, and good workability tends to be obtained.
<<Polymer B1>>
Polymer B1 is a (meth)acrylate polymer having a second reactive silicon group.

The main chain of polymer B1 is formed by polymerizing a monomer containing (meth)acrylic acid ester.
The main chain of the polymer B1 may have units based on a monomer having an unsaturated group copolymerizable with the alkyl (meth)acrylate, in addition to the units based on the alkyl (meth)acrylate. good.
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 the total monomers constituting the polymer B1.

In polymer B1, the second reactive silicon group may be present at the end of the main chain, may be present in a side chain, or may be present in both.
(Polymer B1-i)
Examples of monomers constituting the polymer B1-i having a second reactive silicon group at the end of the main chain include, for example, JP-B-3-14068, JP-A-6-211922, JP-A-11- Conventionally known monomers described in JP-A-130931 can be used.
As the method for polymerizing the polymer B1-i, conventionally known methods described in the literature can be used. Living radical polymerization is preferred because a polymer with a narrow Mw/Mn and low viscosity can be obtained.
The living radical polymerization method uses a cobalt porphyrin complex as described, for example, in J.Am.Chem.Soc., 1994, 116, 7943, Those using nitroxide radicals as shown in JP-A-2003-500378, organic halides and sulfonyl halides as shown in JP-A-11-130931 as initiators, transition Atom transfer radical polymerization (ATRP method) using a metal complex as a catalyst is exemplified.

For example, a living radical polymerization method is used, and a compound having two alkenyl groups is reacted at the end of the polymerization reaction to obtain an unsaturated group-containing acrylic acid ester polymer having an alkenyl group at the end of the main chain. The alkenyl groups of the obtained unsaturated group-containing acrylic acid ester polymer are reacted with the second silylating agent to obtain a polymer B1-i having a second reactive silicon group at the end of the main chain.
As the second silylating agent, a compound having both a group capable of reacting with an unsaturated group to form a bond (eg, a sulfanyl group) and a second reactive silicon group, HSiX ² ₃ (X ² is the above formula 2) can be exemplified.
Examples of the hydrosilane compound include trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, and triacetoxysilane.

(Polymer B1-ii)
As the polymer B1-ii having a second reactive silicon group in the side chain, a monomer containing a second reactive silicon group and an unsaturated group and a monomer containing a (meth)acrylic acid ester are used. A copolymerized (meth)acrylic acid ester polymer can be exemplified.
As the (meth)acrylic acid ester-containing monomer, the monomer used for the polymer B1-i can be used without limitation.
Examples of monomers containing a second reactive silicon group and an unsaturated group include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. These may be used alone or in combination of two or more.
Polymer B1-ii can be polymerized by conventionally known polymerization methods described in JP-A-2006-257405, JP-A-2006-37076, JP-A-2008-45059, and the like. For example, it can be polymerized by radical polymerization. Examples of radical polymerization methods include solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Conventionally known secondary materials such as initiators necessary for polymerization can be used, and reaction conditions such as reaction temperature and reaction pressure can be appropriately selected.

The number of reactive silicon groups per molecule of polymer B1 is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
The number of reactive silicon groups per molecule of polymer B1 is calculated by "the concentration of reactive silicon groups in polymer B1 [mol/g]×Mn of polymer B1". The concentration [mol/g] of reactive silicon groups in polymer B1 can be measured by NMR.

<<Polymer B2>>
Polymer B2 is a polyoxyalkylene polymer having a main chain containing a polyoxyalkylene chain and terminal groups bonded to the main chain.
Polymer B2 has more than 0.5 and 1.0 or less of the second reactive silicon groups represented by Formula 2 per terminal group.

Examples of the main chain of the polymer B2 are the same as those of the polymer A main chain.
The polyoxyalkylene chain of the polymer B2 is more preferably a polyoxypropylene chain, a polyoxyethylene chain, or a poly(oxyethylene-oxypropylene) chain.
The poly(oxyethylene-oxypropylene) chain may be a block copolymer chain or a random copolymer chain. A block copolymer chain having an oxyethylene group block chain on the terminal group side is more preferable.
When the polyoxyalkylene chain of the polymer B2 is a poly(oxyethylene/oxypropylene) chain, the content of oxyethylene groups (hereinafter also referred to as "EO content") is the total mass of the polymer B2. ) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. If it is at least the lower limit of the above range, the cured product will be excellent in deep curability, and if it is at most the upper limit, the cured product will be excellent in stretch durability and water resistance.

The number of terminal groups of polymer B2 is preferably 2 to 5, more preferably 2 or 3. The number of end groups of polymer B2 is the same as the number of active hydrogens present in the initiator.
The terminal group of polymer B2 preferably contains one or more selected from the group consisting of a second reactive silicon group, an active hydrogen-containing group, or an unsaturated group.
The total number of second reactive silicon groups, active hydrogen-containing groups, and unsaturated groups present in the terminal groups of polymer B2 is preferably more than 0.5 and 4.0 or less per terminal group. , preferably 0.60 to 3.0, more preferably 0.65 to 2.0, even more preferably 0.70 to 1.0.
The number of second reactive silicon groups per terminal group of the polymer B2 is more than 0.5 and not more than 1.0, preferably 0.60 to 1.0, and 0.65 to 1.0 is more preferred.

[Method for producing polymer B2]
Polymer B2 is a polyoxyalkylene polymer (precursor polymer) obtained by ring-opening addition polymerization of a cyclic ether to an active hydrogen of an initiator, and more than 0.5 but not more than 1.0 per terminal group. It is obtained by introducing a reactive silicon group of 2.
The precursor polymer is preferably a hydroxyl group-containing polyoxyalkylene polymer having hydroxyl terminal groups, obtained by ring-opening addition polymerization of a cyclic ether to an initiator having a hydroxyl group.
The hydroxyl group-containing polyoxyalkylene polymer can be produced in the same manner as the hydroxyl group-containing polyoxyalkylene polymer in the polymer A.

The method for producing polymer B2 is preferably the following production method (I) or production method (II).
Production method (I): A method of reacting an active hydrogen-containing group present in the terminal group of the precursor polymer with a compound having an isocyanate group and a second reactive silicon group.
Production method (II): After introducing more than 0.5 and 1.0 or less unsaturated groups per terminal group to the terminal groups of the precursor polymer, reacting with the unsaturated groups to form a second A method of reacting a silylating agent capable of introducing a reactive silicon group (hereinafter also referred to as a “second silylating agent”).

In the production method (I), a compound represented by the following formula 10 is preferable as the compound having an isocyanate group and a second reactive silicon group.
O=C=NQ ¹ -SiX ² ₃ (X ² is the same as the above formula 2) Formula 10
In Formula 10, X ² is the same as in Formula 2, and Q ¹ is a divalent organic group having 1 to 20 carbon atoms. Q ¹ is preferably a divalent hydrocarbon group, more preferably an alkylene group. Q ¹ preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms.
Examples of the compound represented by Formula 10 include isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
The reaction between the compound represented by Formula 10 and the precursor polymer can be carried out by a known method.
The number of reactive silicon groups per terminal group of polymer B2 can be adjusted by the molar ratio of the total number of isocyanate groups of the compound represented by formula 10 to the total number of active hydrogens of the precursor polymer.
In this way a polymer B2 is obtained which has more than 0.5 and less than or equal to 1.0 second reactive silicon groups per terminal group.

For the production method (II), a conventionally known method can be used. Methods proposed in each publication such as Japanese Patent Laid-Open No. 8-231707, US Pat. No. 3,632,557, US Pat.
For example, after the precursor polymer is reacted with an alkali metal salt, a halogenated hydrocarbon compound having an unsaturated group is reacted to give more than 0.5 per terminal group to the terminal groups of the precursor polymer. 1.0 or less unsaturated groups are introduced.
Through the above reaction, a derivative in which an unsaturated group is introduced into the terminal group of the precursor polymer is obtained. The derivative of the precursor polymer may contain an unreacted active hydrogen-containing group at the terminal group.
From the viewpoint of storage stability, the number of active hydrogen-containing groups contained in the derivative of the precursor polymer is preferably 0.3 or less per molecule, more preferably 0.1 or less.
The unsaturated group of the derivative of the precursor polymer is reacted with the second silylating agent to introduce the second reactive silicon group into the terminal group, thereby obtaining the polymer B2.

Examples of the alkali metal salt are the same as those of the alkali metal salt in the method for producing the polymer A described above.
Examples of the halogenated hydrocarbon compound are the same as those of the halogenated hydrocarbon compound in the method for producing the polymer A described above. Halogenated hydrocarbon compounds containing carbon-carbon double bonds are preferred.
As the second silylating agent, a compound having both a group capable of reacting with an unsaturated group to form a bond (eg, a sulfanyl group) and a second reactive silicon group, HSiX ² ₃ (X ² is the above formula 2) can be exemplified.
Examples of the hydrosilane compound include trimethoxysilane, triethoxysilane, and triisopropoxysilane.

The content of the polymer B1 is preferably 45 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the polymer B. When it is at least the lower limit of the above range, the effect of improving the weather resistance of the cured product is excellent.

In the curable composition of the present embodiment, A/B representing the mass ratio of polymer A to polymer B is 80/20 to 95/5, preferably 82/18 to 95/5, and 85/15 to 95/5 is more preferred.
When the mass ratio of the polymer A to the polymer B is at least the lower limit of the above range, the deep-part curability of the cured product becomes better. is better.

<Condensation catalyst>
A compound known as a silanol catalyst can be used as the condensation catalyst. For example, silanol catalysts described in International Publication No. 2013-180203, International Publication No. 2015-080067, etc. can be used.
Specific examples include divalent tin catalysts, tetravalent tin catalysts, titanium catalysts, aluminum catalysts, zirconium catalysts, carboxylic acids, carboxylic acid metal salts, and amine compounds.
One selected from the group consisting of tetravalent tin catalysts, titanium catalysts, aluminum catalysts, zirconium catalysts, carboxylic acids, carboxylic acid metal salts, and amine compounds, in that compatibility with other additives is better. The above is preferable.

Examples of divalent tin catalysts include tin versatate, tin 2-ethylhexanoate, tin neodecanoate, and tin vivalate.
Tetravalent tin catalysts include organic tin carboxylates such as dialkyltin dicarboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin monoacetate, dibutyltin maleate, etc.) and dialkoxytin monocarboxylates; Tin chelate compounds such as bis(acetylacetonate), dibutyltin bis(ethylacetoacetate), dibutyltin monoacetylacetonate monoalkoxide; reactants of dialkyltin oxides and ester compounds; A reaction product obtained by the reaction; a reaction product of a dialkyltin oxide and an alkoxysilane compound; and a dialkyltin dialkylsulfide; can be exemplified.
Examples of the ester compounds include phthalate esters such as bis-2-ethylhexyl phthalate, diisononyl phthalate, and dioctyl phthalate; esters of other aliphatic and aromatic carboxylic acids; tetraethylsilicate and partial hydrolysis condensates thereof; can.

Carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, adipic acid, oxalic acid, citric acid, acrylic acid, and methacrylic acid. , benzoic acid, and other organic carboxylic acids having 1 to 20 carbon atoms.

Titanium catalysts, aluminum catalysts, and zirconium catalysts include compounds described in Japanese Patent No. 5225582; carboxylic acid metal salts are compounds described in Japanese Patent No. 4150220; and amine compounds are described in Japanese Patent No. 5226217. can be exemplified.
Condensation catalysts can be used singly or in combination of two or more.
Among the condensation catalysts, a tetravalent tin catalyst and a carboxylic acid are preferable, and a tetravalent tin catalyst is more preferable, since the curability in the deep part is particularly improved.

The content of the condensation catalyst in the curable composition is preferably 0.03 to 0.7 parts by mass, and 0.04 to 0.6 parts by mass, with respect to 100 parts by mass of the total amount of polymer A and polymer B. is more preferable, and 0.04 to 0.55 parts by mass is even more preferable.
If the content of the condensation catalyst is at least the lower limit of the above range, the curability of the cured product will be better, and if it is at most the upper limit, the stretch durability of the cured product will be better.

<Polymer C>
The curable composition of the present embodiment may further contain polymer C.
Polymer C is a polyoxyalkylene polymer having a linear main chain containing a polyoxyalkylene chain and two terminal groups bonded to the main chain, one terminal group being an inert organic group. with more than 0 and no more than 0.5 reactive silicon groups per terminal group and Mn of 2,000 to 15,000.
The reactive silicon group present in polymer C is either the first reactive silicon group represented by Formula 1 above or the second reactive silicon group represented by Formula 2 above.
The reactive silicon group in polymer C is present on the other end group.

The inert organic group which is one terminal group of the polymer C does not contain any of the first reactive silicon group, the second reactive silicon group, the active hydrogen-containing group and the unsaturated group. For example, a terminal group derived from an initiator having one active hydrogen.
The initiator is preferably an initiator having one hydroxyl group. Specific examples include methanol, ethanol, 2-propanol, n-butyl alcohol, isobutyl alcohol, 2-butyl alcohol, t-butyl alcohol, 2-ethylhexanol, decyl alcohol, lauryl alcohol, tridecanol, cetyl alcohol, stearyl alcohol, oleyl monohydric alcohols such as alcohols; and low molecular weight polyoxyalkylene monools.
When the initiator is a monohydric alcohol, one terminal group of the polymer C is a residue obtained by removing active hydrogen from the initiator (for example, an alkoxy group).
When the initiator is a polyoxyalkylene monool, among the residues after removing the active hydrogen from the initiator, the terminal group containing the oxygen atom closest to the terminal of the polymer C (e.g., alkoxy group) is one of the terminal groups. .

The other terminal group of polymer C preferably contains one or more selected from the group consisting of reactive silicon groups, active hydrogen-containing groups and unsaturated groups.
The total number of reactive silicon groups, active hydrogen-containing groups, and unsaturated groups present in the other terminal group is preferably 0.25 to 2.0 per terminal group, and 0.30 to 1.2. more preferably 0.3 to 1.0.
The number of reactive silicon groups per terminal group of the polymer C is more than 0 and 0.5 or less, preferably 0.25 to 0.50, and 0.30 to 0.50. is more preferred.
When the number of reactive silicon groups is within the above range, the stretch durability of the cured product will be better.

[Method for producing polymer C]
Polymer C is a polyoxyalkylene polymer (precursor polymer) obtained by ring-opening addition polymerization of a cyclic ether to an initiator having one active hydrogen, and a first reactive silicon group or a second reactive silicon group. is obtained by introducing more than 0 and 0.5 or less reactive silicon groups per terminal group.
After introducing more than 0 unsaturated groups per terminal group into the precursor polymer, the above-described A method of introducing a reactive silicon group by reacting an unsaturated group with a silylating agent is preferred.
One terminal group of the precursor polymer is an inert organic group derived from the initiator, and the unsaturated group is introduced only to the other terminal group.
The method for introducing more than 0 but not more than 0.5 unsaturated groups per terminal group into the precursor polymer is the same as in method 2 for producing polymer B2.
The method for introducing more than 0.5 unsaturated groups per terminal group into the precursor polymer is the same as the method for producing the polymer A described above.

The derivative of the precursor polymer into which the unsaturated group has been introduced into the precursor polymer in this manner may contain an unreacted active hydrogen-containing group at the other terminal group.
From the viewpoint of storage stability, the number of active hydrogen-containing groups contained in one molecule of the derivative of the precursor polymer is preferably 0.3 or less, more preferably 0.1 or less per molecule.
reacting the unsaturated group of the derivative of the precursor polymer with a first silylating agent or a second silylating agent to form a first reactive silicon group or a second reactive silicon group on the other terminal group; is introduced to obtain polymer C.
The first silylating agent is the same as the first silylating agent in the method for producing polymer A described above. The second silylating agent is the same as the second silylating agent in the method (II) for producing polymer B2.

Mn of the polymer C is 2,000 to 15,000, more preferably 3,000 to 14,000, even more preferably 4,000 to 12,000. Within the above range, the curable composition tends to have a lower viscosity.

Polymer C is not essential, but when the curable composition contains polymer C, the content of polymer C with respect to the total amount of 100 parts by weight of polymer A and polymer B is preferably 1 to 400 parts by weight, and 2 It is more preferably up to 200 parts by mass, and even more preferably 3 to 150 parts by mass.
When the content of the polymer C is at least the lower limit of the above range, a sufficient addition effect is likely to be obtained, and when it is at most the upper limit, the curable composition tends to have a lower viscosity.

<Other ingredients>
The curable composition may contain one or more of the polymer A, the polymer B, the polymer C, and other components that do not correspond to any of the condensation catalysts.
Other components include additives depending on the application of the curable composition. For example, fillers, anti-sagging agents, thixotropic agents, antioxidants, UV absorbers, light stabilizers, dehydrating agents, adhesion imparting agents, amine compounds, modulus modifiers, plasticizers, air oxidation curing compounds, Photocurable compounds and curing catalysts can be exemplified.
Other components are WO 2013/180203, WO 2014/192842, WO 2016/002907, JP 2014-88481, JP 2015-10162, JP 2015-105293 Conventionally known materials described in JP-A-2017-214541 and the like can be used in combination without limitation.

Air oxidative curing compounds include drying oils such as tung oil and linseed oil, alkyd resins obtained by modifying drying oils, acrylic polymers modified with drying oils, silicone resins, polybutadiene, and dienes having 5 to 8 carbon atoms. and diene-based polymers such as polymers and copolymers of , modified products of these polymers and copolymers (maleic modification, boil oil modification, etc.), air-curing polyester compounds, and the like. The air oxidation-curable compound may be used alone or in combination of two or more.
A drying oil having an acid value of 0.05 to 4.0 (unit: mgKOH/g) is preferable from the viewpoint of storage stability of the curable composition.
Although the air oxidation-curable compound is not essential, when the curable composition contains an air oxidation-curable compound, the content of the air oxidation-curable compound with respect to 100 parts by mass of the total weight of the polymer A and the polymer B is 0. 1 to 20 parts by mass is preferable, and 0.5 to 15 parts by mass is more preferable. When the content is at least the lower limit of the range, a sufficient effect of addition is likely to be obtained, and when the content is at most the upper limit, the weather resistance of the cured product becomes better.

Specific examples of adhesion promoters include organic silane coupling agents such as silanes having a (meth)acryloyloxy group, silanes having an amino group, silanes having an epoxy group, and silanes having a carboxyl group; organometallic coupling agents such as aminoethyl-aminoethyl)propyltrimethoxytitanate and 3-mercaptopropyltrimethoxytitanate; and epoxy resins.
A silane having an amino group is preferred in terms of good reactivity with the reactive silicon group. Specific examples of silanes having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3 -(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-(N-vinylbenzyl-2-aminoethyl)-3 -aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane.
An adhesion imparting agent is not essential, but when the curable composition contains an adhesion imparting agent, the content of the adhesion imparting agent with respect to 100 parts by mass of the total mass of the polymer A and the polymer B is 0.1 to 20 mass. parts is preferred, and 0.5 to 10 parts by mass is more preferred. When the content is at least the lower limit of the range, a sufficient addition effect is likely to be obtained, and when the content is at most the upper limit, the stretch durability of the cured product becomes better.

The modulus modifier is preferably a compound having two or more hydroxyl groups from the viewpoint of lowering the modulus of the cured product obtained by curing the curable composition and improving elongation. A compound having a partial structure having hydroxyl groups at at least two bonding positions selected from positions is more preferable. As a modulus modifier when the curable composition contains tetravalent tin as a silanol condensation catalyst, the modulus of the cured product obtained by curing the curable composition is lower and the elongation is better. A compound having a partial structure having hydroxyl groups at at least two bonding positions selected from α-position, β-position and γ-position is preferred from the viewpoint that changes in the surface of the cured product over time are easily suppressed.

Examples of the compound having a partial structure having hydroxyl groups at at least two bonding positions selected from α-position, β-position and γ-position include divalent or higher polyols, carboxylic acid esters and alkyl ethers.
Examples of the above dihydric or higher polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, pinacol, 2,2- Diols such as dimethyl-1,3-propanediol; glycerin, 1,2,6-hexanetriol, 1,1,1-tris(hydroxymethyl)propane, 2,2-bis(hydroxymethyl)butanol, 2 triols such as -methyl-2-hydroxymethyl-1,3-propanediol; polyols having a valence of 4 or more such as pentaerythritol, D-sorbitol, D-mannitol, diglycerin and polyglycerin;
Examples of the carboxylic acid esters include glycerin such as glycerin monostearate, glycerin monoisostearate, glycerin monooleate, glycerin monolaurate, glycerin monopalmitate, glycerin monocaprylate, glycerin monoacetate, and glycerin monobehenate. Monocarboxylic acid esters; diglycerin monostearate, diglycerin monooleate, diglycerin monolaurate, tetraglycerin monostearate, tetraglycerin monooleate, tetraglycerin monolaurate, tetraglycerin distearate, tetraglycerin Polyglycerin carboxylic acid esters such as dioleate, tetraglycerin dilaurate, decaglycerin monostearate, decaglycerin monooleate, decaglycerin monolaurate, decaglycerin distearate, decaglycerin dioleate, decaglycerin dilaurate; Pentaerythritol monocarboxylic acid esters such as pentaerythritol monostearate, pentaerythritol monooleate and pentaerythritol monolaurate; Pentaerythritol dicarboxylic acid esters such as pentaerythritol distearate, pentaerythritol dioleate and pentaerythritol dilaurate ; sorbitan monocarboxylic acid esters such as sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monobehenate; sorbitan distearate, sorbitan dioleate, sorbitan dilaurate, sorbitan dipalmi sorbitan dicarboxylic acid esters such as tate and sorbitan dibehenate;
Examples of the alkyl ethers include glycerin monostearyl ether, glycerin monooleyl ether, glycerin monolauryl ether, glycerin mono-2-ethylhexyl ether and other glycerin monoalkyl ethers; diglycerin monostearyl ether, diglycerin monooleyl ether, di Glycerin monolauryl ether, tetraglycerin monostearyl ether, tetraglycerin monooleyl ether, tetraglycerin monolauryl ether, tetraglycerin distearyl ether, tetraglycerin dioleyl ether, tetraglycerin dilauryl ether, decaglycerin monostearyl ether, decaglycerin mono Polyglycerin alkyl ethers such as oleyl ether, decaglycerin monolauryl ether, decaglycerin distearyl ether, decaglycerin dioleyl ether, decaglycerin dilauryl ether; pentaerythritol monostearyl ether, pentaerythritol monooleyl ether, pentaerythritol monolauryl ether pentaerythritol monoalkyl ethers such as ethers; pentaerythritol dialkyl ethers such as pentaerythritol distearyl ether, pentaerythritol dioleyl ether, and pentaerythritol dilauryl ether; sorbitan monostearyl ether, sorbitan monooleyl ether, sorbitan monolauryl ether, etc. sorbitan monoalkyl ethers; sorbitan dialkyl ethers such as sorbitan distearyl ether, sorbitan dioleyl ether and sorbitan dilauryl ether.

<Curable composition>
The curable composition of this embodiment is obtained by mixing the polymer A, the polymer B, the condensation catalyst, and optionally the polymer C and other components.
The curable composition of the present embodiment is preferably a one-liquid curable composition in which all components are preliminarily blended, sealed and stored, and cured by moisture in the air after application.
The one-part curable composition preferably does not contain moisture. It is preferable to preliminarily dehydrate and dry the ingredients containing water, or dehydrate them by reducing the pressure during the mixing and kneading.
A dehydrating agent may be added to improve storage stability.

The curable composition of the present embodiment is crosslinked by formation of siloxane bonds accompanied by hydrolysis reaction of reactive silicon groups, etc., to obtain a rubber-like cured product.
As a curable composition application, it is particularly suitable for sealants and adhesives.
Sealing materials include elastic sealing materials for buildings, sealing materials for double glazing, sealing materials for rust prevention and waterproofing of glass edges, back sealing materials for solar cells, sealing materials for buildings, sealing materials for ships, and automobiles. road seals and road seals.

The curable composition of the present embodiment can simultaneously achieve good deep curability and good stretch durability and weather resistance of the cured product.
For example, in the evaluation of deep curability described in the examples below, the consistency of the cured product cured at 10 ° C. for 40 hours is 120 or less, and in the evaluation of stretch durability described later, cracks in the cured product Stretch durability is 3,000 times or more when the number of times of expansion and contraction reaches 2.5 mm or more, and the cured product does not fade (whiten) even after 1500 hours in the weather resistance test described later Weather resistance that does not fade (whitening) can be achieved at the same time.

The second reactive silicon group is more reactive than the first reactive silicon group. Polymer A, which has more than 1.0 first reactive silicon groups per terminal group, is excellent in the effect of improving durability, but tends to be insufficient in deep-part curability, especially for one-liquid curing. The cured product obtained from the hardening composition tends to have insufficient deep-part curability. If the first reactive silicon group of the polymer A is changed to the second reactive silicon group, the curability is improved, but the stretch durability tends to be insufficient.
By blending such a polymer A with a polymer B selected from the polymer B1 and the polymer B2 having a second reactive silicon group in a specific ratio, good deep-section curability and cured product It is believed that good stretch durability and weather resistance can be achieved at the same time.

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

≪Measurement method and evaluation method≫
<Mn, Mw/Mn>
Using HLC-8220GPC (product name of Tosoh Corporation), Mw, Mn and Mw/Mn were determined.
<Number of reactive silicon groups>
The number of reactive silicon groups contained in the polymer was measured by the ¹ H-NMR internal standard method.

<Evaluation of Deep Curability (Method for Measuring Consistency)>
450 g of the curable composition was placed in a container (size: length 10.5 cm x width 7.0 cm x depth 4.0 cm), and nitrogen gas was blown from the surface to remove air bubbles. After that, the container was placed horizontally in an atmosphere of 10° C. and cured for 40 hours to obtain a sample. The consistency of the samples was measured using an automatic consistency/penetration tester (RPM-101 model). Specifically, a conical cone made of stainless steel (tip diameter 0.38 mm) was penetrated into the central part of the surface of the sample with a load of 100 g, and the length penetrated in 5 seconds (penetration depth, Unit: mm) was measured, and the value obtained by multiplying the penetration depth by 10 was taken as the value of the consistency. The smaller the consistency value, the better the deep-part curability. Based on the penetration value, evaluation was made according to the following criteria.
A: 70 or less.
B: More than 70 and 90 or less.
C: more than 90 and 120 or less.
D: greater than 120.

<Evaluation of stretch durability (fatigue resistance test)>
It was tested according to the fatigue resistance category CR90 of the fatigue resistance test described in 5.22 of JIS A 1439 (2016). A surface-anodized aluminum surface treated with a primer (MP-2000, product name of Cemedine Co., Ltd.) was used as an adherend.
Cracks in the cured product near the adhesion interface between the adherend and the cured product were observed every 500 times of expansion and contraction, and the number of expansion and contraction was recorded when the crack reached 2.5 mm or more. The greater the number of expansions and contractions, the better the expansion and contraction durability. Based on the number of times of expansion and contraction, evaluation was made according to the following criteria.
A: 5,000 times or more.
B: 4,000 times or more and less than 5,000 times.
C: 3,000 times or more and less than 4,000 times.
D: Less than 3,000 times.

<Weather resistance evaluation (weather resistance test)>
A curable composition was applied to a thickness of 5.0 mm on the surface of a siding board (trade name: Honban, manufactured by Asahi Glass Co., Ltd.) having a size of 5 cm long and 5 cm wide. This was cured for one week under conditions of a temperature of 23° C. and a humidity of 60% to obtain a weather resistance test sample. The weather resistance of the samples was evaluated using a sunshine weatherometer, which is an accelerated weather resistance tester. The surface condition of each sample after 500, 1000, and 1500 hours of test time was visually observed. The color of the surface of the sample was compared with the state before the start of the test, and evaluated according to the following criteria.
A: No change from the state before the start of the test.
B: Partially faded (whitened).
C: All faded (whitened).

≪Synthesis example of polymer≫
(Synthesis Example 1: Polymer A-1)
Polyoxypropylene glycol is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate complex with t-butyl alcohol as a catalyst (hereinafter also referred to as "TBA-DMC catalyst") as a catalyst. A hydroxyl group-containing polyoxyalkylene polymer having hydroxyl groups was obtained.
Then, using sodium methoxide, allyl glycidyl ether and allyl chloride (3-chloro-1-propene), unsaturated groups are introduced into the terminal groups of the hydroxyl group-containing polyoxyalkylene polymer, and the unsaturated group-containing polyoxyalkylene A polymer was obtained. As sodium methoxide, a methanol solution containing 28% by mass of sodium methoxide was used (hereinafter the same).
Specifically, 1.15 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer, and methanol was distilled off under reduced pressure. 1.05 molar equivalents of allyl glycidyl ether was added and reacted at 130° C. for 2 hours. 0.28 molar equivalents of sodium methoxide were added and methanol was removed. 2.10 molar equivalents of allyl chloride was added, reacted at 130° C. for 2 hours, and unreacted allyl chloride was removed under reduced pressure. After purification to remove metal salts, an unsaturated group-containing polyoxyalkylene polymer having 2.0 allyl groups per terminal group was obtained.
Then, the unsaturated group-containing polyoxyalkylene polymer was reacted with dimethoxymethylsilane as a silylating agent to obtain a polymer A-1.
Specifically, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zerovalent platinum (hereinafter also referred to as “platinum catalyst”) is used as a catalyst, and unsaturated group-containing polyoxy Dimethoxymethylsilane was added in an amount of 0.80 molar equivalent to the allyl group of the alkylene polymer, and the mixture was reacted at 70° C. for 5 hours. got 1.
Mn of the resulting polymer A-1, the number of terminal groups per molecule, the number of reactive silicon groups per molecule, the number of reactive silicon groups per terminal group, and the type of reactive silicon group (Reactive silicon groups represented by Formula 1 or Formula 2) are shown in Table 1 (hereinafter the same).

(Synthesis Example 2: Polymer A-2)
Polymer A-2 was obtained in the same manner as in Synthesis Example 1, except that 2.0 molar equivalents of allyl glycidyl ether and 0.53 molar equivalents of dimethoxymethylsilane were used.
(Synthesis Example 3: Polymer A-3)
Polymer A-3 was obtained in the same manner as in Synthesis Example 1, except that the amount of dimethoxymethylsilane added was changed to 0.55 molar equivalents.

(Synthesis Example 4: Polymer A-4)
Polymer A-4 was obtained in the same manner as in Synthesis Example 1, except that the silylating agent was changed to dimethylmethoxysilane.

(Synthesis Example 5: Polymer A-5)
The hydroxyl-containing polyoxyalkylene polymer obtained in Synthesis Example 1 was reacted with sodium methoxide and propargyl bromide to introduce unsaturated groups into the terminal groups of the hydroxyl-containing polyoxyalkylene polymer.
Specifically, sodium methoxide was added in an amount of 1.05 molar equivalents to the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer, and methanol was distilled off under reduced pressure. Then, the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer were reacted with an excessive amount of propargyl bromide to obtain a polyoxyalkylene polymer having 1.0 propargyl groups per terminal group.
Then, the polyoxyalkylene polymer having a propargyl group was reacted with methyldimethoxysilane as a silylating agent to obtain a polymer A-4.
Specifically, in the presence of a platinum catalyst, 3.2 molar equivalents of methyldimethoxysilane is added to the propargyl groups of the propargyl group-containing polyoxyalkylene polymer, and the mixture is reacted at 100° C. for 5 hours. Polymer A-5 was obtained by removing unreacted methyldimethoxysilane under reduced pressure.

(Synthesis Example 6: Polymer A-6)
A hydroxyl group-containing polyoxyalkylene polymer was obtained in the same manner as in Synthesis Example 1.
Next, in Synthesis Example 1, allyl chloride was changed to methallyl chloride (3-chloro-2-methyl-1-propene) to introduce an unsaturated group into the terminal group of the hydroxyl group-containing polyoxyalkylene polymer.
Specifically, in the same manner as in Synthesis Example 1, sodium methoxide is added to a hydroxyl group-containing polyoxyalkylene polymer, methanol is distilled off, and 1.05 molar equivalent of allyl glycidyl ether is added to react, Sodium methoxide was added and methanol was removed. After that, 2.10 molar equivalents of methallyl chloride was added, reacted at 130° C. for 2 hours, and unreacted methallyl chloride was removed under reduced pressure. After purification to remove metal salts, an unsaturated group-containing polyoxyalkylene polymer having 2.0 methallyl groups per terminal group was obtained.
Then, the silylating agent was reacted in the same manner as in Synthesis Example 1 to obtain polymer A-6. The amount of the silylating agent added was 0.8 molar equivalents with respect to methallyl groups.

(Synthesis Example 7: Polymer A-7)
In Synthesis Example 1, the initiator was changed to glycerin. That is, using glycerin as an initiator, propylene oxide was polymerized in the presence of a TBA-DMC catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer.
Polymer A-7 was obtained in the same manner as in Synthesis Example 1 except for the above.

(Synthesis Examples 8 to 13: Polymer A-8 to Polymer A-13)
Polymers A-8 to A-13 were obtained in the same manner as in Synthesis Example 1, except that the molecular weight of the hydroxyl group-containing polyoxyalkylene polymer was changed by adjusting the amount of propylene oxide to be polymerized. .

(Synthesis Example 14: Polymer a-1)
Polymer a-1 was obtained in the same manner as in Synthesis Example 1, except that the amount of dimethoxymethylsilane added was changed to 0.50 molar equivalents.

(Synthesis Example 15: Polymer a-2)
Polymer a-2 was obtained in the same manner as in Synthesis Example 1, except that the silylating agent in Synthesis Example 1 was changed to trimethoxysilane.

(Synthesis Example 16: Polymer a-3)
In Synthesis Example 1, the molecular weight of the hydroxyl group-containing polyoxyalkylene polymer was changed by adjusting the amount of propylene oxide to be polymerized.
Next, by changing the amounts of sodium methoxide, allyl glycidyl ether and allyl chloride used in Synthesis Example 1, an unsaturated group-containing polyoxyalkylene polymer was obtained.
Specifically, 1.0 molar equivalent of sodium methoxide was added to the hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer, and methanol was distilled off under reduced pressure. 1.0 molar equivalent of allyl glycidyl ether was added and reacted at 130° C. for 2 hours. 0.28 molar equivalents of sodium methoxide were added and methanol was removed. 1.79 molar equivalents of allyl chloride was added, reacted at 130° C. for 2 hours, and unreacted allyl chloride was removed under reduced pressure. After purification to remove metal salts, an unsaturated group-containing polyoxyalkylene polymer having 2.0 allyl groups per terminal group was obtained.
Then, the silylating agent in Synthesis Example 1 was changed to trimethoxysilane to obtain polymer a-3. The amount of trimethoxysilane added was 0.8 molar equivalents relative to the allyl groups of the unsaturated group-containing polyoxyalkylene polymer.

(Synthesis Example 17: Polymer B1-1)
An unsaturated group-containing acrylic acid ester polymer was synthesized by a method of reacting a compound having two alkenyl groups at the end of the polymerization reaction using a living radical polymerization method.
Specifically, 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. 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 thereto, and the mixture was further heated and stirred at 70° C. for 40 minutes. To this, 0.41 mL of pentamethyldiethylenetriamine (hereinafter also referred to as "triamine") was added to initiate the reaction. Subsequently, heating and stirring were continued at 70° C., and 2.05 mL of triamine was added. After 330 minutes from the initiation of the reaction, 244 mL of 1,7-octadiene and 4.1 mL of triamine were added, followed by heating and stirring at 70° C., and 570 minutes after the initiation of the reaction, heating was stopped. The resulting reaction solution was diluted with toluene and filtered, and the filtrate was heat-treated under reduced pressure to obtain an unpurified acrylic acid ester polymer having an alkenyl group at the end. The number of alkenyl groups per molecule of the crude acrylate polymer was 2.8. The number of alkenyl groups per molecule is a value determined by ¹ H-NMR analysis (hereinafter the same).
Further, the unpurified acrylic acid ester polymer was purified to obtain an unsaturated group-containing acrylic acid ester polymer.
Specifically, under a nitrogen atmosphere, in a 2 L flask, the total amount of the unpurified acrylate polymer, 17.2 g of potassium acetate, and 700 mL of N,N-dimethylacetamidomethyl (hereinafter referred to as "DMAc") were added. It was added and stirred with heating at 100° C. for 10 hours. The reaction solution was heated under reduced pressure to remove DMAc, and toluene was added and filtered. The filtrate was heated under reduced pressure to remove volatile matter, and the remainder was added to a 2 L flask, and the adsorbent (Kyoward 500SN and Kyoward 700SN (both product names of Kyowa Chemical Industry Co., Ltd.) in a mass ratio of 1:1 mixture). was added, and the mixture was heated and stirred at 130°C for 9 hours under a nitrogen stream. The mixture was diluted with toluene, filtered to remove the adsorbent, and the toluene in the filtrate was distilled off under reduced pressure to obtain an unsaturated group-containing acrylic acid ester polymer.
Then, the unsaturated group-containing acrylic acid ester polymer was reacted with trimethoxysilane as a silylating agent to obtain polymer B1-1.
Specifically, 700 g of an unsaturated group-containing acrylic acid ester polymer, 22.2 mL of trimethoxysilane, 7.71 mL of methyl orthoformate and a platinum catalyst (1,1 , 3,3-tetramethyl-1,3-divinyldisiloxane complex) was added. The amount of the platinum catalyst added was 9×10 ⁻³ molar equivalents with respect to the alkenyl group of the unsaturated group-containing acrylic acid ester polymer. The mixture in the reaction vessel was heated and stirred at 100° C. for 195 minutes. The volatile matter of the reactant was distilled off under reduced pressure to obtain a polymer B1-1 having a terminal trimethoxysilyl group. Mw/Mn in polymer B1-1 was 1.40.

(Synthesis Example 18: Polymer B1-2)
A polymer B1-2 was produced by a polymerization method using a monomer having a reactive silicon group.
Specifically, 50 g of isobutanol was added to a pressure-resistant reactor equipped with a stirrer, and the temperature was raised to about 80°C. The temperature inside the reaction vessel was maintained at about 80° C., and the following mixed solution was added dropwise over 2 hours while stirring under a nitrogen atmosphere to polymerize to obtain a polymer B1-2 having a trimethoxysilyl group in the side chain. .
Mixed solution: 1.65 g of methyl methacrylate, 373.1 g of n-butyl acrylate, 110.0 g of stearyl acrylate, and 3-methacryloxypropyltrimethoxysilane (KBM-503, product name of Shin-Etsu Silicone Co., Ltd.) 6 .5g and 7.3g of 2,2'-azobis-2,4-dimethylvaleronitrile (V-65, product name of Wako Pure Chemical Industries, Ltd.).

(Synthesis Examples 19 to 22: Polymers B1-3 to B1-6)
In Synthesis Example 17, the Mn and Mw/Mn of the crude acrylate polymer were changed. The number of alkenyl groups per molecule was 2.8 in each case. Polymers B1-3 to B1-6 were obtained in the same manner as in Synthesis Example 17 except for the above. Mw/Mn in Polymer B1-3 to Polymer B1-6 were as follows.
Synthesis Example 19: Polymer B1-3, Mw/Mn 1.20.
Synthesis Example 20: Polymer B1-4, Mw/Mn 1.20.
Synthesis Example 21: Polymer B1-5, Mw/Mn 1.40.
Synthesis Example 22: Polymer B1-6, Mw/Mn 1.41.

(Synthesis Example 23: Polymer B2-1)
Propylene oxide was polymerized using polyoxypropylene glycol as an initiator and a zinc hexacyanocobaltate complex having glyme as a ligand (hereinafter also referred to as "Gly-DMC catalyst") as a catalyst. Next, a 48% by mass KOH aqueous solution was added as a catalyst, and after dehydration and alcoholation, ethylene oxide was fed and reacted. After completion of the reaction, the catalyst was neutralized and removed using an adsorbent (Kyowad 600S, product name of Kyowa Chemical Industry Co., Ltd.) to obtain a hydroxyl group-containing polyoxyalkylene polymer. The EO content in the hydroxyl group-containing polyoxyalkylene polymer was 10% by mass.
Then, the hydroxyl group-containing polyoxyalkylene polymer was reacted with a compound having an isocyanate group and a reactive silicon group to obtain a polymer B2-1.
Specifically, the inside of the reactor containing the hydroxyl group-containing polyoxyalkylene polymer was replaced with nitrogen gas, and the inner temperature was maintained at 50° C. while the molar ratio (NCO/OH) of the isocyanate groups to the hydroxyl groups was 0.00. 3-Isocyanatopropyltrimethoxysilane was added so as to obtain 97, and dioctyltin bisisooctylthioglycol (Neostan U-860, product name of Nitto Kasei Co., Ltd.) was added as a catalyst. The temperature was raised to 80°C, and the mixture was stirred while maintaining the temperature at 80°C. After analyzing with a Fourier transform infrared spectrophotometer and reacting until the completion of the reaction between the hydroxyl group and the isocyanate group can be confirmed, 3-mercaptopropyltrimethoxysilane as a storage stabilizer is added to the hydroxyl group-containing polyoxyalkylene polymer. 0.06 part by mass was added to 100 parts by mass to obtain polymer B2-1.

(Synthesis Example 24: Polymer B2-2)
Using polyoxyethylene triol as an initiator, propylene oxide was polymerized in the presence of a Gly-DMC catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer.
Then, in the same manner as in Synthesis Example 23, the hydroxyl group-containing polyoxyalkylene polymer was reacted with 3-isocyanatopropyltrimethoxysilane to obtain polymer B2-2.

(Synthesis Example 25: Polymer B2-3)
Using polyoxypropylene glycol as an initiator, ethylene oxide was polymerized in the presence of a Gly-DMC catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer.
Then, in the same manner as in Synthesis Example 23, the hydroxyl group-containing polyoxyalkylene polymer was allowed to react with 3-isocyanatopropyltrimethoxysilane to obtain polymer B2-3.

(Synthesis Example 26: Polymer B2-4)
Using polyoxypropylene glycol as an initiator, propylene oxide was polymerized in the presence of a TBA-DMC catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer.
Then, using sodium methoxide and allyl chloride, unsaturated groups were introduced into the terminal groups of the hydroxyl group-containing polyoxyalkylene polymer to obtain an unsaturated group-containing polyoxyalkylene polymer.
Specifically, 1.05 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer, and methanol was distilled off under reduced pressure. An excess amount of allyl chloride was added to the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer for reaction, and unreacted allyl chloride was removed under reduced pressure. After purification to remove metal salts, an unsaturated group-containing polyoxyalkylene polymer having 1.0 allyl groups per terminal group was obtained.
Then, the unsaturated group-containing polyoxyalkylene polymer was reacted with trimethoxysilane as a silylating agent to obtain polymer B2-4.
Specifically, in the presence of a platinum catalyst, 1.0 molar equivalent of trimethoxysilane is added to the allyl group of the unsaturated group-containing polyoxyalkylene polymer, and the mixture is reacted at 70°C for 5 hours. Polymer B2-4 was obtained by removing unreacted trimethoxysilane under reduced pressure.

(Synthesis Example 27: Polymer B2-5)
In Synthesis Example 26, the initiator was changed to glycerin. That is, using glycerin as an initiator, propylene oxide was polymerized in the presence of a TBA-DMC catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer.
Polymer B2-5 was obtained in the same manner as in Synthesis Example 26 except for the above.

(Synthesis Example 28: Polymer b-1)
In Synthesis Example 26, the molecular weight of the hydroxyl group-containing polyoxyalkylene polymer was changed by adjusting the amount of propylene oxide to be polymerized.
An unsaturated group-containing polyoxyalkylene polymer was obtained in the same manner as in Synthesis Example 26.
Polymer b-1 was obtained in the same manner as in Synthesis Example 26, except that the silylating agent in Synthesis Example 26 was changed to 0.73 molar equivalents of dimethoxymethylsilane.

(Synthesis Example 29: Polymer b-2)
Polymer b-2 was obtained in the same manner as in Synthesis Example 28, except that the silylating agent was changed to 0.80 molar equivalent of dimethoxymethylsilane.
(Synthesis Example 30: Polymer b-3)
A polymer b-3 was produced by a polymerization method using a monomer having a reactive silicon group.
Specifically, in Synthesis Example 18, 3-methacryloxypropyltrimethoxysilane was changed to 3-methacryloxypropylmethyldimethoxysilane to change the molecular weight. Polymer b-3 was obtained in the same manner as in Synthesis Example 18 except for the above.

(Synthesis Example 31: Polymer b-4)
A polymer b-4 was produced by a method using a living radical polymerization method.
Specifically, in Synthesis Example 17, trimethoxysilane was changed to dimethoxymethylsilane. Polymer b-4 was obtained in the same manner as in Synthesis Example 17 except for the above.

(Synthesis Example 32: Polymer b-5)
In Synthesis Example 26, the TBA-DMC catalyst was changed to a Gly-DMC catalyst, and the molecular weight of the hydroxyl group-containing polyoxyalkylene polymer was changed by adjusting the amount of propylene oxide to be polymerized.
An unsaturated group-containing polyoxyalkylene polymer was obtained in the same manner as in Synthesis Example 26.
Polymer b-5 was obtained in the same manner as in Synthesis Example 26, except that the silylating agent in Synthesis Example 26 was changed to 0.75 molar equivalent of dimethoxymethylsilane.

(Synthesis Example 33: Polymer C-1)
Using n-butyl alcohol as an initiator, propylene oxide was polymerized in the presence of a TBA-DMC catalyst to obtain a hydroxyl group-containing polyoxyalkylene polymer.
Then, in the same manner as in Synthesis Example 26, sodium methoxide and allyl chloride were used to introduce an unsaturated group into one terminal group of the hydroxyl group-containing polyoxyalkylene polymer, one terminal group being a butyloxy group, An unsaturated group-containing polyoxyalkylene polymer having 1.0 (0.5 per terminal group) allyl groups per molecule at the other terminal group was obtained.
Then, the unsaturated group-containing polyoxyalkylene polymer was reacted with dimethoxymethylsilane as a silylating agent to obtain a polymer C-1.
Specifically, in the presence of a platinum catalyst, 1.0 molar equivalent of dimethoxymethylsilane is added to the allyl group of the unsaturated group-containing polyoxyalkylene polymer, and the mixture is reacted at 70° C. for 5 hours. Unreacted dimethoxymethylsilane was removed under reduced pressure to obtain polymer C-1.

(Synthesis Example 34: Polymer C-2)
A hydroxyl group-containing polyoxyalkylene polymer was obtained in the same manner as in Synthesis Example 33.
Then, using sodium methoxide, allyl glycidyl ether and allyl chloride, an unsaturated group was introduced into one terminal group of the hydroxyl group-containing polyoxyalkylene polymer to obtain an unsaturated group-containing polyoxyalkylene polymer.
Specifically, 1.15 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl group-containing polyoxyalkylene polymer, and methanol was distilled off under reduced pressure. 1.05 molar equivalents of allyl glycidyl ether was added and reacted at 130° C. for 2 hours. 0.28 molar equivalents of sodium methoxide were added and methanol was removed. 1.79 molar equivalents of allyl chloride was added, reacted at 130° C. for 2 hours, and unreacted allyl chloride was removed under reduced pressure. Purified to remove metal salts, unsaturated with butyloxy group on one end group and 2.0 allyl groups per molecule (1.0 per end group) on the other end group A group-containing polyoxyalkylene polymer was obtained.
Then, the silylating agent was allowed to react in the same manner as in Synthesis Example 33, except that the amount of the silylating agent added was 0.5 molar equivalents relative to the allyl group, to obtain Polymer C-2.

(Synthesis Example 35: Polymer C-3)
Polymer C-3 was obtained in the same manner as in Synthesis Example 33, except that the silylating agent in Synthesis Example 33 was changed to trimethoxysilane.

(other ingredients)
Additives listed in Tables 2 to 7 are as follows.
Shiraenka CCR: Colloidal calcium carbonate, Shiraishi CCR, product name of Shiraishi Kogyo Co., Ltd.
Whiten SB: Ground calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
R820: Titanium oxide, product name of Ishihara Sangyo Co., Ltd.
Viscolite EL20: colloidal calcium carbonate, product name of Shiraishi Calcium Co., Ltd.;
Disparlon 6500: Fatty acid amide wax, manufactured by Kusumoto Chemical Co., Ltd.
Glycerin monostearate: reagent, manufactured by Tokyo Chemical Industry Co., Ltd.
DINP: Sansocizer DINP, diisononyl phthalate, product name of Shin Nihon Rika Co., Ltd.
DIDP: diisodecyl phthalate, manufactured by Mitsubishi Chemical Corporation.
KBM-1003: Vinyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
A-171: Vinyltrimethoxysilane, SILQUEST A-171, product name of Momentive.
KBM-403: 3-glycidoxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-603: 3-(2-aminoethylamino)propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
A-1120: N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, SILQUEST A-1120, product name of Momentive.
TINUVIN 765: Tertiary amine-containing hindered amine light stabilizer, BASF product name.
TINUVIN 770: Hindered amine light stabilizer, BASF product name.
Sunol LS770: Hindered amine light stabilizer, product name of Sankyo Life Tech.
IRGANOX1135: Hindered phenol antioxidant, BASF product name.
TINUVIN 326: benzotriazole-based UV absorber, BASF product name.
TINUVIN 327: benzotriazole-based UV absorber, BASF product name.
U-220H: Silanol condensation catalyst, dibutyltin bis(acetylacetonate), product name of Nitto Kasei.
Versatic 10: silanol condensation catalyst, neodecanoic acid, product name of Japan Epoxy Resin.
SCAT-32A: Silanol condensation catalyst, divalent tin catalyst, product name of Nitto Kasei Co., Ltd.
Air oxidation curing compound: tung oil, manufactured by Kimura Co., Ltd., acid value 2.0 (unit: mgKOH/g).

<Preparation of curable composition>
Examples 1 to 41 are working examples, and Examples 42 to 50 are comparative examples.
A curable composition was prepared by mixing the polymer, catalyst, air oxidation curable compound, and common component D1 shown in Table 2 according to the formulations shown in Tables 3 to 7.
The cured product of the obtained curable composition was evaluated for deep-part curability, stretch durability and weather resistance by the methods described above. The results are shown in Tables 3-7.

The curable compositions of Examples 1 to 41 were excellent in deep-part curability and excellent in stretch durability and weather resistance of the cured product.
In Examples 1-41, the common component can be changed to D3 or D4 shown in Table 2. The curable compositions obtained by changing the common component to D3 or D4 in Examples 1 to 41 are excellent in deep-part curability, and the cured products thereof are excellent in stretch durability and weather resistance.

Claims (11)

A curable composition comprising the following polymer A, the following polymer B, and a condensation catalyst, wherein A/B, which represents the mass ratio of the polymer A to the polymer B, is 80/20 to 95/5.
Polymer A: A polyoxyalkylene polymer having more than 1.0 reactive silicon groups represented by the following formula 1 per terminal group.
Polymer B: a (meth)acrylic acid ester polymer B1 having a reactive silicon group represented by the following formula 2, and a reactive silicon group represented by the following formula 2, 0.5 per terminal group One or more selected from the group consisting of polyoxyalkylene polymers B2 having more than 1.0 or less.
—SiR _a X ¹ _3-a Formula 1
In Formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X ¹ represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is When it is 1 or 2 and a is 2, X ¹ may be the same or different, and when a is 1, R may be the same or different.
- SiX ² ₃ Formula 2
^In Formula ² , X2 represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and X2 may be the same or different. 2. The curable composition according to claim 1, wherein the polymer A has a terminal group containing a group represented by Formula 3 or Formula 4 below.

[In Formula 3, R ¹ and R ³ each independently represent a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms in the bonding group are a carbon atom, a hydrogen atom, and an oxygen atom. , a nitrogen atom, or a sulfur atom, R ² and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Si ¹ represents a reactive silicon group represented by Formula 1 above. , n represents an integer of 1 to 10, and Si ¹ may be the same or different. ]

[In Formula 4, R ⁵ represents a single bond or a divalent bonding group having 1 to 6 carbon atoms, and the atoms bonded to the carbon atoms in the bonding group are carbon, hydrogen, oxygen and nitrogen atoms. , or a sulfur atom, X represents a monovalent group represented by any of formulas 5 to 8, and in formulas 5 to 8, R ⁶ is a hydrogen atom or a monovalent hydrocarbon having 1 to 10 carbon atoms R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms, Si ¹ represents a reactive silicon group represented by Formula 1 above, and a plurality of Si ¹ may be the same or different from each other. ] 3. The curable composition according to claim 1 or 2, wherein the polymer A is linear. The curable composition according to any one of claims 1 to 3, wherein the polymer A has a number average molecular weight of 8,000 to 150,000. The curable composition according to any one of claims 1 to 4, wherein the polymer B has a number average molecular weight of 5,000 to 50,000. The curable composition according to any one of claims 1 to 5, wherein the content of said polymer B1 relative to the total mass of said polymer B is 45 to 100% by mass. The curable composition according to any one of claims 1 to 6, further comprising polymer C below.
Polymer C: A polyoxyalkylene polymer having two terminal groups, one of which is an inert organic group, and a reactive silicon group represented by the above formula 1 or a reactive silicon group represented by the above formula 2 a polyoxyalkylene polymer having a number average molecular weight of from 2,000 to 15,000, containing more than 0 and no more than 0.5 reactive silicon groups per terminal group. Any one of claims 1 to 7, wherein the condensation catalyst contains one or more selected from the group consisting of tetravalent tin catalysts, titanium catalysts, aluminum catalysts, zirconium catalysts, carboxylic acids, carboxylic acid metal salts, and amine compounds. The curable composition according to claim 1. The content of the condensation catalyst is 0.03 to 0.7 parts by mass with respect to a total of 100 parts by mass of the polymer A and the polymer B, according to any one of claims 1 to 8. Curable composition. The curable composition according to any one of claims 1 to 9, which is used as a sealant or adhesive. A cured product of the curable composition according to any one of claims 1 to 10.