JP7375508B2 - Curable composition and cured product - Google Patents

Description

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

A polymer having a reactive silicon group is cured by a hydrolysis reaction to form a flexible rubber-like cured product, which is used for applications such as sealants and adhesives. Organotin catalysts are used as curing catalysts to promote the above hydrolysis reaction, but many organotin catalysts are known to be toxic to living organisms, and there are concerns about their impact on the environment. .

Patent Document 1 describes an organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, and a curing catalyst containing either or both of a carboxylic acid and a carboxylic acid metal salt as a non-organic tin catalyst. A curable composition is disclosed. It is described that the above-mentioned curable composition has adhesive properties similar to those using an organotin catalyst.

International Publication No. 2006/070637

When adhesives are used for building components that are locally heated, such as underfloor heating, the elongation of the cured product decreases due to the heat, and cracks may occur.
When the curable composition described in Patent Document 1 is used as an adhesive for the above-mentioned building components, the elongation of the cured product decreases before and after the heat resistance test.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable composition whose elongation does not decrease before and after a heat resistance test, and a cured product of the curable composition.

The present invention includes the following [1] to [ 8 ].
[1] An oxyalkylene polymer having an average of more than 1.0 reactive silicon groups represented by the following formula 1 in one terminal group, and a carboxy group in which the adjacent carbon atom is a quaternary carbon. A curable composition containing a carboxylic acid or a salt thereof having a content of 0.01 to 20 parts by mass based on 100 parts by mass of the oxyalkylene polymer (provided that the following (meth) ) Excluding curable compositions containing an acrylic ester polymer (B) and a high molecular weight plasticizer having an average of 0 to 1 reactive silicon group per molecule).
-SiX _a R _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 represents a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3. and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
(Meth)acrylic acid ester polymer (B): A (meth)acrylic acid ester polymer having a reactive silicon group represented by the following formula B1 and having a reactive silicon group equivalent of 0.30 mmol/g or more. Combined.
-SiX ¹ ₃ formula B1
In formula B1, each X ¹ independently represents a hydroxyl group or a hydrolyzable group.
[2] An oxyalkylene polymer having an average of more than 1.0 reactive silicon groups represented by the following formula 1-1 in one terminal group, and a carboxylic acid polymer in which the adjacent carbon atom is a quaternary carbon. A curable composition containing a carboxylic acid or a salt thereof having a group, the content of the carboxylic acid or a salt thereof being 0.01 to 20 parts by mass based on 100 parts by mass of the oxyalkylene polymer (however, the following (Excluding curable compositions containing (meth)acrylic acid ester polymers (B)).
-SiX _a R _3-a formula 1-1
In formula 1-1, R is a monovalent organic group having 1 to 20 carbon atoms and is an organic group other than a hydrolyzable group, X is a hydroxyl group or a hydrolyzable group, and a is 1 to 3 and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
(Meth)acrylic acid ester polymer (B): (meth)acrylic acid ester having a reactive silicon group represented by the following formula B1-1 and having a reactive silicon group equivalent of 0.30 mmol/g or more system polymer.
-SiX ¹ ₃ formula B1-1
In formula B1-1, each X ¹ independently represents a hydroxyl group or a hydrolyzable group.
[3] The curable composition according to [1] or [2] , wherein at least one terminal group of the oxyalkylene polymer contains an atomic group represented by the following formula 2.

上記式２中、Ｒ^１、Ｒ^３はそれぞれ独立に２価の炭素数１～６の結合基を示し、結合基中の炭素原子に結合している原子は、炭素原子、水素原子、酸素原子、窒素原子、又は硫黄原子である。Ｒ^２、Ｒ^４はそれぞれ独立に水素原子又は炭素数１～１０の炭化水素基を示す。ｎは１から１０の整数を示す。Ｒ^５はそれぞれ独立に、炭素数１～２０の１価の有機基であって、加水分解性基以外の有機基を示し、Ｙはそれぞれ独立に水酸基又は加水分解性基を示す。ｂは１～３の整数である。Ｒ^５が複数存在する場合、Ｒ^５は互いに同一でも異なってもよい。Ｙが複数存在する場合、Ｙは互いに同一でも異なってもよい。
［４］ 上記オキシアルキレン重合体の末端基は、上記式１で表される反応性ケイ素基、活性水素含有基、又は不飽和基のいずれかである基を含む、［１］～［３］のいずれか一項に記載の硬化性組成物。
［５］ 上記オキシアルキレン重合体は、１分子中に末端基を２個又は３個有し、各末端基に上記式１で表される反応性ケイ素基、活性水素含有基、又は不飽和基のいずれかである基を２個有する、［１］～［４］のいずれか一項に記載の硬化性組成物。
［６］ 上記カルボン酸又はその塩が下式３で表されるカルボン酸又はその塩である、［１］～［５］のいずれか一項に記載の硬化性組成物。

In the above formula 2, 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 carbon atoms, hydrogen atoms, and oxygen atoms. , nitrogen atom, or sulfur atom. R ² and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. n represents an integer from 1 to 10. R ⁵ each independently represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and Y each independently represents a hydroxyl group or a hydrolyzable group. b is an integer from 1 to 3. When a plurality of R ⁵ 's exist, R ⁵ 's may be the same or different from each other. When there is a plurality of Y's, the Y's may be the same or different from each other.
[ 4 ] The terminal group of the oxyalkylene polymer includes a reactive silicon group represented by the above formula 1, an active hydrogen-containing group, or an unsaturated group, [1] to [3] The curable composition according to any one of the above .
[ 5 ] The oxyalkylene polymer has two or three terminal groups in one molecule, and each terminal group has a reactive silicon group, an active hydrogen-containing group, or an unsaturated group represented by the above formula 1. The curable composition according to any one of [1] to [ 4 ], which has two groups that are any of the following.
[ 6 ] The curable composition according to any one of [1] to [ 5 ], wherein the carboxylic acid or salt thereof is represented by the following formula 3.

上記式３中、Ｒ^１１、Ｒ^１２、Ｒ^１３はそれぞれ独立に置換又は非置換の炭素数１～２０の１価の炭化水素基又はカルボキシ基を示すか、又はＲ^１１、Ｒ^１２、Ｒ^１３のいずれか２つ以上の基と上記式３中のカルボキシ基に隣接する炭素原子とが一体となって炭素数３～１６である環構造を形成していることを示す。
［７］ 接着剤用である、［１］～［６］のいずれか一項に記載の硬化性組成物。
［８］ ［１］～［７］のいずれか一項に記載の硬化性組成物の硬化物。

In the above formula 3, R ¹¹ , R ¹² , and R ¹³ each independently represent a substituted or unsubstituted monovalent hydrocarbon group or carboxy group having 1 to 20 carbon atoms, or R ¹¹ , R ¹² , and R ¹³ Indicates that any two or more of the groups and the carbon atom adjacent to the carboxy group in the above formula 3 together form a ring structure having 3 to 16 carbon atoms.
[ 7 ] The curable composition according to any one of [1] to [ 6 ], which is used for adhesives.
[ 8 ] A cured product of the curable composition according to any one of [1] to [ 7 ].

The cured product using the curable composition of the present invention does not exhibit a decrease in elongation before and after the heat resistance test.
The cured product of the present invention has no decrease in elongation before and after the heat resistance test.

Definitions of terms used in this specification are as follows.
The numerical range represented by "~" means a numerical range whose lower and upper limits are the numbers before and after ~.
"Oxyalkylene polymer" means a polymer having polyoxyalkylene chains formed from cyclic ether-based units.

A "precursor polymer" is composed of a residue of an initiator, a polyoxyalkylene chain formed by ring-opening addition polymerization of a cyclic ether, and a terminal group containing a terminal oxygen atom of the polyoxyalkylene chain. It is a polymer whose group is a hydroxyl group.
A "derivative of a precursor polymer" is a polymer obtained by converting a hydroxyl group, which is a terminal group of a precursor polymer, into a terminal group containing a functional group capable of reacting with a silylating agent. Examples of the functional group that can react with the silylating agent include an active hydrogen-containing group and an unsaturated group present at the end of the molecule.
The "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, a secondary amino group, a hydrazide group, and a sulfanyl group.
"Active hydrogen" is a hydrogen atom based on the above active hydrogen-containing group.
A "silylating agent" is a compound capable of introducing a reactive silicon group by reacting with an active hydrogen-containing group contained in the terminal group of a precursor polymer or a derivative thereof or an unsaturated group present at the end of the molecule.

The "silylation rate" of an oxyalkylene polymer having reactive silicon groups is the ratio of the reactive silicon groups to the total number of reactive silicon groups, active hydrogen-containing groups, and unsaturated groups contained in the terminal groups of the polymer. is the proportion of the number of The value of the silylation rate can be determined by NMR analysis.

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

The curable composition of the present embodiment includes an oxyalkylene polymer (hereinafter referred to as "polymer A") having an average of more than 1.0 reactive silicon groups in one terminal group, and an adjacent A carboxylic acid having a carboxy group whose carbon atom is a quaternary carbon or a salt thereof (hereinafter referred to as "compound a").

<Reactive silicon group>
The reactive silicon group is represented by the following formula 1.
-SiX _a R _3-a formula 1
In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain a hydrolyzable group.
Examples of R include a hydrocarbon group, a halohydrocarbon group, and a triorganosiloxy group.

R is preferably an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group, or a triorganosiloxy group. At least one member 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. It is more preferable that A methyl group or an ethyl group is preferable from the viewpoint of good curability of a polymer having a reactive silicon group and good stability of a curable composition. A 1-chloromethyl group is preferred from the viewpoint of fast curing speed of the cured product. Methyl group is particularly preferred from the viewpoint of easy availability.

In the above formula 1, X represents a hydroxyl group or a hydrolyzable group.
Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group, and an alkenyloxy group.
As X, an alkoxy group is preferable because it has mild hydrolyzability and is easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, siloxane bonds are quickly formed and a crosslinked structure is easily formed in the cured product, resulting in better physical properties of the cured product.

In the above formula 1, a represents an integer of 1 to 3. When a is 1, R may be the same or different from each other. When a is 2 or more, X may be the same or different.
a is preferably 1 or 2, and more preferably 2.

Examples of the reactive silicon group represented by the above formula 1 include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, Examples include diethoxymethylsilyl group, dimethoxyethylsilyl group, diisopropoxymethylsilyl group, chloromethyldimethoxysilyl group, and chloromethyldiethoxysilyl group. From the viewpoint of high activity and good curability, trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, and diethoxymethylsilyl groups are preferred, and dimethoxymethylsilyl and trimethoxysilyl groups are more preferred.

<Polymer A>
Polymer A has an initiator residue, a polyoxyalkylene chain formed by ring-opening addition polymerization of a cyclic ether, and a terminal group containing a terminal oxygen atom of the polyoxyalkylene chain. The valency of the initiator residue, the number of polyoxyalkylene chains, and the number of terminal groups are equal.
Examples of the cyclic ether 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. Particularly preferred is propylene oxide.
The polyoxyalkylene chain may be a copolymer chain having two or more types of oxyalkylene groups, and in that case, the copolymer chain may be a block copolymer chain or a random copolymer chain.
Polyoxyalkylene chains possessed by polymer A include polyoxypropylene chains, polyoxyethylene chains, poly(oxy-2-ethylethylene) chains, poly(oxy-1,2-dimethylethylene) chains, and poly(oxytetra) chains. (methylene) chain, poly(oxyethylene/oxypropylene) chain, and poly(oxypropylene/oxy-2-ethylethylene) chain. As the polyoxyalkylene chain, a polyoxypropylene chain and a poly(oxyethylene/oxypropylene) chain are preferred, and a polyoxypropylene chain is particularly preferred.

Polymer A has an average of more than 1.0 of the above-mentioned reactive silicon groups in one terminal group, and from the viewpoint of elongation properties, it is more preferable that the number is 1.1 to 3.0. More preferably, the number is 1.2 to 2.0.
The total number of divalent or higher-valent atoms contained in one terminal group is preferably 80 or less, more preferably 50 or less, and even more preferably 40 or less.
The total number of divalent or higher atoms contained in one terminal group is preferably 1 or more, more preferably 4 or more, even more preferably 10 or more, and particularly preferably 20 or more.
The divalent or higher-valent atom is preferably one or more atoms selected from carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and silicon atoms, and one or more atoms selected from carbon atoms, nitrogen atoms, oxygen atoms, and silicon atoms. is more preferable, and one or more atoms selected from carbon atoms, oxygen atoms, and silicon atoms are even more preferable.

The Mn of polymer A is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, even more preferably 3,000 to 40,000. It is preferable that Mn is at least the lower limit of the above range because the amount of reactive silicon groups introduced per mass of the polymer A does not become too large and it is easy to achieve both elongation properties and durability. If it is below the upper limit, the viscosity will be sufficiently low and the workability will be better.
The molecular weight distribution of the polymer A is preferably 1.60 or less, more preferably 1.40 or less, even more preferably 1.20 or less, particularly preferably 1.17 or less, and particularly preferably 1.15 or less. The molecular weight distribution of the polymer A is preferably 1.00 or more. When the molecular weight distribution is below the above upper limit, the elongation properties of the cured product tend to improve.
The viscosity of the polymer A at 25° C. is preferably 0.1 to 70 Pa·s, more preferably 0.5 to 60 Pa·s, and even more preferably 1 to 55 Pa·s. If it is within the above range, the workability will be better.

Polymer A preferably has 2 to 8 terminal groups in one molecule, more preferably 2 to 6 terminal groups, and even more preferably 2 or 3 terminal groups.
It is preferable that the polymer A contains a reactive silicon group represented by the above formula 1, an active hydrogen-containing group, or an unsaturated group in the terminal group.

Polymer A has two or three terminal groups in one molecule, and each terminal group is either a reactive silicon group, an active hydrogen-containing group, or an unsaturated group represented by the above formula 1. It is preferable to have two groups.
Polymer A preferably has 4 to 6 groups that are either reactive silicon groups, active hydrogen-containing groups, or unsaturated groups in one molecule.

The "silylation rate" of the polymer A is preferably more than 50 mol% and 100 mol% or less, more preferably 60 to 97 mol%, and even more preferably 65 to 95 mol%.
The silylation rate can be adjusted by adjusting the amount of the silylating agent reacted with the unsaturated group contained in the terminal group of the precursor polymer derivative.
When the curable composition contains two or more types of polymer A, the average silylation rate of the entire polymer A may be within the above range.

It is preferable that at least one end group of the polymer A contains an atomic group represented by the following formula 2.

In the above formula 2, 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 carbon atoms, hydrogen atoms, and oxygen atoms. , nitrogen atom, or 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 CO-, -CO-O-, -CO-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 -.

In the above formula 2, R ² and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
Examples of straight-chain 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, 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 preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

In the above formula 2, n represents an integer of 1 to 10. n is preferably 1 to 7, more preferably 1 to 5, and even more preferably 1.

In the above formula 2, R ⁵ each independently represents a monovalent organic group having 1 to 20 carbon atoms and other than a hydrolyzable group, and Y each independently represents a hydroxyl group or a hydrolyzable group. show. b represents an integer from 1 to 3. When a plurality of R ⁵ 's exist, R ⁵ 's may be the same or different from each other. When there is a plurality of Y's, the Y's may be the same or different from each other.
R ⁵ in the above formula 2 is the same as R in the above formula 1.
Y in the above formula 2 is the same as X in the above formula 1.
b in the above formula 2 is the same as a in the above formula 1.

It is preferable that at least one terminal group of the polymer A is a terminal group represented by the following formula 4.

上記式４のＲ^１～Ｒ^５、Ｙ、ｂ、ｎは、式２のＲ^１～Ｒ^５、Ｙ、ｂ、ｎと同様である。

R ¹ to R ⁵ , Y, b, and n in the above formula 4 are the same as R ¹ to R ⁵ , Y, b, and n in formula 2.

<Method for producing polymer A>
Polymer A is obtained by introducing on average more than 1.0 of the above reactive silicon groups into one terminal group of the precursor polymer.
The method for producing polymer A is preferably a method in which more than 1.0 unsaturated groups are introduced on average into the terminal groups of a precursor polymer, and then the unsaturated groups are reacted with the silylating agent.
The precursor polymer is an oxyalkylene polymer in which a cyclic ether is subjected to ring-opening addition polymerization to active hydrogen of an initiator having an active hydrogen-containing group in the presence of a ring-opening polymerization catalyst. The number of active hydrogens in the initiator, the number of end groups in the precursor polymer, and the number of end groups in polymer A are the same.

The precursor polymer is preferably a polymer whose end group is a hydroxyl group, which is obtained by ring-opening addition polymerization of a cyclic ether to an initiator having a hydroxyl group.
The above-mentioned initiator is preferably an initiator having 2 to 8 hydroxyl groups, more preferably an initiator having 2 to 6 hydroxyl groups, and even more preferably an initiator having 2 or 3 hydroxyl groups. Two or more types of initiators may be used in combination.

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, and low molecular weight An example is polyoxypropylene glycol.
Examples of the initiator having three or more hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, low molecular weight polyoxypropylene triol, pentaerythritol, sorbitol, and sucrose.
Two or more types of the above initiators may be used in combination.

Conventionally known catalysts can be used as ring-opening addition polymerization catalysts when carrying out ring-opening addition polymerization of cyclic ethers as an initiator, such as alkali catalysts (KOH etc.), transition metal compound-porphyrin complex catalysts (organoaluminium Examples include a complex obtained by reacting a compound with a porphyrin), a multimetal cyanide complex catalyst, and a catalyst consisting of a phosphazene compound.

A multi-metal cyanide complex catalyst is preferred because it can narrow the molecular weight distribution of the polymer A and it is easy to obtain a curable composition with low viscosity. A conventionally known compound can be used as the composite metal cyanide complex catalyst, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. For example, 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 above publication can be used.

As a method for introducing more than 1.0 unsaturated groups on average into one terminal group of the precursor polymer, known methods can be used without particular restriction, such as the method described in International Publication No. 2013/180203. Publication, International Publication No. 2014/192842, Japanese Patent Application Publication No. 2015-105293, Japanese Patent Application Publication No. 2015-105322, Japanese Patent Application Publication No. 2015-105323, Japanese Patent Application Publication No. 2015-105324, International Publication No. 2015/080067, International Publication Methods described in WO 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 on average into one terminal group of a precursor polymer, after reacting an alkali metal salt to the precursor polymer, an epoxy compound having an unsaturated group is introduced. A preferred method is to react with a halogenated hydrocarbon compound having an unsaturated group.

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

As the epoxy compound having an unsaturated group, a compound represented by the following formula 5 is preferable.

上記式５のＲ^１、Ｒ^２は、上記式４のＲ^１、Ｒ^２と同じである。

R ¹ and R ² in the above formula 5 are the same as R ¹ and R ² in the above formula 4.

Through the above reaction, an unsaturated group derived from the epoxy compound having the above unsaturated group is introduced into the terminal group of the precursor polymer, and then an unsaturated group derived from the above halogenated hydrocarbon compound is introduced into the precursor polymer. A derivative is obtained. The derivative of the precursor polymer may contain an unreacted active hydrogen-containing group in the terminal group.
The number of active hydrogen-containing groups contained in one molecule of the precursor polymer derivative is preferably 0.3 or less, more preferably 0.1 or less, from the viewpoint of storage stability.

Polymer A is obtained by reacting the unsaturated groups of the derivative of the precursor polymer with a silylating agent to introduce reactive silicon groups into the terminal groups.
As the silylating agent, compounds having both a group capable of reacting with an unsaturated group to form a bond (for example, a sulfanyl group) and the above-mentioned reactive silicon group, and a hydrosilane compound (for example, HSiX _a R _3-a , where X , R and a are the same as in Formula 1 above.) can be exemplified. Specifically, for example, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxy Examples include silane, (α-chloromethyl)dimethoxysilane, and (α-chloromethyl)diethoxysilane. From the viewpoint of high activity and good curability, trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferred, and methyldimethoxysilane or trimethoxysilane is more preferred.

The above reaction yields a polymer A having on average more than 1.0 of the above reactive silicon groups in one terminal group.

<Compound a>
Compound a is a curing catalyst for polymer A. Compound a is a carboxylic acid or a salt thereof having a carboxy group in which the adjacent carbon atom is a quaternary carbon. Two or more types of carboxylic acids and salts thereof may be used in combination.

The molecular weight of compound a is preferably from 60 to 500, more preferably from 80 to 400, even more preferably from 140 to 300, from the viewpoints that the resulting composition has better workability and catalytic performance is easily maintained. In addition, when the molecular weight of compound a cannot be obtained by GPC measurement, the formula weight of compound a is regarded as the molecular weight of compound a.
The melting point of compound a is preferably -50 to 50°C, more preferably -40 to 40°C, and even more preferably -30 to 35°C, from the standpoint of improving the workability of the resulting curable composition.

As the compound a, a compound represented by the following formula 3 is preferable.

上記式３中、Ｒ^１１、Ｒ^１２、Ｒ^１３はそれぞれ独立に置換又は非置換の炭素数１～２０の１価の炭化水素基を示すか、又はＲ^１１、Ｒ^１２、Ｒ^１３のいずれか２つ以上の基と上記式３中のカルボキシ基に隣接する炭素原子とが一体となって炭素数３～１６である環構造を形成していることを示す。

In the above formula 3, R ¹¹ , R ¹² , and R ¹³ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or any one of R ¹¹ , R ¹² , and R ¹³ Indicates that two or more groups and the carbon atom adjacent to the carboxy group in Formula 3 above come together to form a ring structure having 3 to 16 carbon atoms.

The monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 17 carbon atoms, and even more preferably 2 to 12 carbon atoms.

The total carbon number of R ¹¹ , R ¹² and R ¹³ is preferably 3 to 30, more preferably 3 to 24, and even more preferably 6 to 18. The above carbon number and total carbon number include the carbon number of the substituent when R ¹¹ , R ¹² , and R ¹³ have a substituent.

Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, with an alkyl group and an alkenyl group being preferred, and an alkyl group being more preferred. The alkyl group and alkenyl group may be linear or branched.

Straight chain alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- Examples include -decyl group, n-undecyl group, lauryl group, and stearyl group, with n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl group being preferred. The branched alkyl group has a structure in which the hydrogen atoms in the linear alkyl group (excluding the hydrogen atoms in the terminal carbons) are substituted with an alkyl group. Examples of the alkyl group as the above substituent include methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group. Examples thereof include methyl, ethyl, and n-propyl groups.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclosidecyl group, with a cyclopentyl group and a cyclohexyl group being preferred. The cycloalkyl group may have a structure in which a hydrogen atom is substituted with an alkyl group. The alkyl group as the above-mentioned substituent is the same as the alkyl group as the above-mentioned substituent exemplified in the above-mentioned branched alkyl group.

Examples of the alkenyl group include those in which a single bond between any one of the carbon atoms of the above-mentioned alkyl group is replaced with a double bond.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. The aryl group may have a structure in which a hydrogen atom is substituted with an alkyl group. The alkyl group as the above-mentioned substituent is the same as the alkyl group as the above-mentioned substituent exemplified in the above-mentioned branched alkyl group.

R ¹¹ , R ¹² , and R ¹³ may have a substituent other than an alkyl group, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an amide group, a carboxy group, and a carbon number 1 group. An example is an alkanoyl group having ~20 monovalent hydrocarbon groups. Examples of the hydrocarbon group in the alkanoyl group are the same as R ¹¹ above.

Examples of the monocarboxylic acid represented by the above formula 3 include pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, and 2-ethyl -2-Methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethyl Examples include hexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyl-3-hydroxypropionic acid, and 2,2-dimethyloctanoic acid because it tends to suppress the decline in elongation of the cured product before and after the heat resistance test. , 2-ethyl-2,5-dimethylhexanoic acid, versatic acid, and neodecanoic acid are preferred, and versatic acid and neodecanoic acid are more preferred.

The dicarboxylic acids having two carboxy groups whose adjacent carbon atoms are quaternary carbons represented by the above formula 3 include 2,2-dimethylpropanedioic acid (dimethylmalonic acid), 2-ethyl-2-methylpropane Examples include diacid (ethylmethylmalonic acid), 2,2-diethylpropanedioic acid (diethylmalonic acid), phthalic acid, isophthalic acid, and terephthalic acid, and one carboxy group whose adjacent carbon atom is a quaternary carbon. Examples of the dicarboxylic acids include 2,2-dimethyl-1,4-butanedioic acid (2,2-dimethylsuccinic acid), 2,2-diethyl-1,4-butanedioic acid (2,2-diethylsuccinic acid), ), 2,2-dimethyl-1,6-pentanedioic acid (2,2-dimethylglutaric acid).

A ring structure in which two groups among R ¹¹ , R ¹² , and R ¹³ and the carbon atom adjacent to the carboxy group in the above formula 3 come together to form a ring structure having 3 to 16 carbon atoms. Examples include a cycloalkane structure having 3 to 10 carbon atoms, a bicyclo ring structure, and a tricyclo ring structure. When the three groups R ¹¹ , R ¹² , and R ¹³ and the carbon atom adjacent to the carboxy group in the above formula 3 are combined to form a ring structure having 3 to 16 carbon atoms, the ring structure is as follows: , an adamantane ring structure, an aromatic ring structure, a bicyclo ring structure, and a tricyclo ring structure.

The above formula in which any two or more groups of R ¹¹ , R ¹² , R ¹³ and the carbon atom adjacent to the carboxy group in the above formula 3 together form a ring structure having 3 to 16 carbon atoms. Examples of the monocarboxylic acid represented by 3 include 1-methyl-1-cyclopentanecarboxylic acid, 1-methyl-cyclohexanecarboxylic acid, and 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid. , 1-adamantanecarboxylic acid, benzoic acid, 9-anthracenecarboxylic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid, chlorobenzoic acid, 2-methylbicyclo[2.2.1]-5-heptene-2- Carboxylic acid, 2-methyl-7-oxabicyclo[2.2.1]-5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo[2.2.1]heptane-1-carboxylic acid, bicyclo [2.2.2] Octane-1-carboxylic acid is an example.

The number of carboxy groups in compound a is preferably 1 to 6, more preferably 1 to 5. The number of carboxy groups in which adjacent carbon atoms are quaternary carbon atoms in compound a is preferably 1 to 3, more preferably 1 to 2. The number of carboxy groups in which adjacent carbon atoms are secondary or tertiary carbon atoms in compound a is preferably 3 or less, more preferably 2 or less. When one group among R ¹¹ , R ¹² , and R ¹³ in the above formula 3 has one carboxy group whose adjacent carbon atom is a quaternary carbon atom as a substituent, compound a is represented by the following formula 6. The compounds represented are preferred.

上記式６中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４はそれぞれ独立に上記式３のＲ^１１、Ｒ^１２、Ｒ^１３と同様である。Ｒ^２１と、Ｒ^２２と、Ｒ^２２に隣接する炭素原子と、が一体となって環構造を形成していてもよい。Ｒ^２３と、Ｒ^２４と、Ｒ^２４に隣接する炭素原子と、が一体となって環構造を形成していてもよい。Ｒ^２０は単結合又は、置換又は非置換の炭素数１～１９の２価の炭化水素基を表す。

In the above formula 6, R ²¹ , R ²² , R ²³ and R ²⁴ are each independently the same as R ¹¹ , R ¹² and R ¹³ in the above formula 3. R ²¹ , R ²² , and the carbon atom adjacent to R ²² may be combined to form a ring structure. R ²³ , R ²⁴ , and the carbon atom adjacent to R ²⁴ may be combined to form a ring structure. R ²⁰ represents a single bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 19 carbon atoms.

The divalent hydrocarbon group preferably has 1 to 19 carbon atoms, more preferably 1 to 16 carbon atoms, and even more preferably 2 to 11 carbon atoms.

The total carbon number of R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ is preferably from 5 to 50, more preferably from 5 to 40, even more preferably from 5 to 30. The above carbon number and total carbon number include the carbon number of the substituent when R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ have a substituent.

Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, an alkenylene group, and an arylene group, with an alkylene group and a cycloalkylene group being preferred, and an alkylene group being more preferred. Alkylene and alkenylene groups are linear or branched.

As the alkylene group, cycloalkylene group, alkenylene group, and arylene group, one hydrogen atom is removed from the alkyl group, cycloalkyl group, alkenyl group, and aryl group exemplified by R ¹¹ , R ¹² , and R ¹³ in Formula 3 above. Examples include groups.

^R20 may have a substituent other than an alkyl group, and the above-mentioned substituents include an alkoxy group, a halogen atom, a hydroxyl group, an amino group, an amide group, and an adjacent carbon atom is a secondary or tertiary carbon atom. Examples include a carboxy group and an alkanoyl group. Examples of the hydrocarbon group in the alkanoyl group are the same as R ¹¹ above.

When R ²¹ , R ²² , the carboxy group in the above formula 6, and the carbon atom adjacent to R ²¹ and R ²² come together to form a ring structure, or R ²³ and R ²⁴ and the carbon atoms adjacent to the carboxy group, R ²³ , and R ²⁴ in the above formula 6 are combined to form a ring structure, and the ring structure is a cycloalkane having 3 to 10 carbon atoms. Examples include a bicyclo ring structure and a tricyclo ring structure.

The dicarboxylic acid represented by the above formula 6 includes 2,2,3,3-tetramethyl-1,4-butanedioic acid (2,2,3,3-tetramethyl-1,4-succinic acid), 2,2,3,3-tetraethyl-1,4-butanedioic acid (2,2,3,3-tetraethyl-1,4-succinic acid), 2,2,4,4-tetramethyl-1,6 An example is -pentanedioic acid (2,2,4,4-tetramethyl-1,6-glutaric acid).

Examples of the above-mentioned salts of carboxylic acids include salts of carboxylic acids and metals, and salts of carboxylic acids and amine compounds.
Examples of the above metals include tin, lead, bismuth, potassium, calcium, barium, titanium, zirconium, hafnium, vanadium, manganese, iron, cobalt, nickel, and cerium. Bismuth, titanium, iron, and zirconium are preferred, and tin is more preferred.
Examples of the above-mentioned amine compounds include the amine compounds described below, and preferred are primary amines such as octylamine and laurylamine, and amines having a hydrocarbon group having at least one heteroatom, since they have higher catalytic activity. More preferred are amines having a hydrocarbon group with at least one heteroatom.

The curable composition of this embodiment may further contain an amine compound. The amine compound functions as a promoter that promotes the catalytic function of the compound a.
Amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, and cyclohexylamine. Aliphatic primary amines such as xylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine , aliphatic secondary amines such as dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine; Aliphatic unsaturated amines such as allylamine and oleylamine; Aromatic amines such as aniline, 4-laurylaniline, and triphenylamine; Morpholine, N-methylmorpholine, N-ethylmorpholine, N-allylmorpholine, 4-( 2-Aminoethyl)morpholine, 3-morpholinopropylamine, 3-aminotetrahydrofuran, monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 2,4 , 6-tris(dimethylaminomethyl)phenol; and other amines such as dimethylaminoethylamine, diethylaminoethylamine, N-methyl-1,3-propanediamine, 3-(1- Piperazinyl) propylamine, diethylenetriamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, triethylenetetramine, benzylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2-ethyl- Examples include 4-methylimidazole, 1,8-diazabicyclo(5,4,0)-7-undecene, and 1,5-diazabicyclo(4,3,0)-5-nonene.
As the primary amine, octylamine and laurylamine are preferable because of their high cocatalyst ability.
As the amine compound having an oxygen atom, 3-morpholinopropylamine is preferred.
Other amines that have high cocatalyst ability include ethylenediamine, monoethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, 3-methoxypropylamine, 3-lauryloxypropylamine, N -Methyl-1,3-propanediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, and 3-(1-piperazinyl)propylamine are preferred.
As the amine compound, 3-diethylaminopropylamine and 3-morpholinopropylamine are more preferable because they have a higher cocatalyst function, and tend to provide a curable composition with good adhesiveness, workability, and storage stability. Therefore, 3-diethylaminopropylamine is more preferred.

[Composition of curable composition]
The curable composition is obtained by adding and mixing components as required to Polymer A and Compound a.
The content ratio of polymer A to the total mass of the curable composition is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, and even more preferably 10 to 40% by mass. When the content of polymer A is within the above range, the cured product will have better strength and elongation.
The content ratio of compound a to the total mass of the curable composition is preferably 0.003 to 10% by mass, more preferably 0.1 to 7% by mass, and even more preferably 0.2 to 5% by mass. When the content ratio of compound a is within the above range, a decrease in the elongation of the cured product before and after the heat resistance test is suppressed.
The content of compound a with respect to 100 parts by mass of polymer A is 0.01 to 20 parts by mass, preferably 0.05 to 17 parts by mass, more preferably 0.1 to 15 parts by mass, and 0.5 parts by mass. ˜10 parts by mass is more preferable. When the content of compound a is at least the lower limit of the above range, a practical curing speed is likely to be obtained, and when it is below the upper limit, it is easy to obtain a practical pot life. Excellent.
When the curable composition contains an amine compound, the content of the amine compound relative to the total mass of the curable composition is preferably 0.003 to 10% by mass, more preferably 0.1 to 7% by mass, and 0.2% by mass. More preferably, it is 5% by mass.
When the curable composition contains an amine compound, the content of the amine compound is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and further 15 to 150 parts by mass, based on 100 parts by mass of compound a. preferable.

[Other ingredients]
The curable composition is an oxyalkylene polymer having an average of 1.0 or less reactive silicon groups represented by the above formula 1 in one terminal group, and a reactive silicon group represented by the above formula 1. It may contain a polymer other than the oxyalkylene polymer having a reactive silicon group represented by the above formula 1. Polymers other than oxyalkylene polymers include vinyl polymers such as acrylic acid polymers and methacrylic acid polymers, saturated hydrocarbon polymers, polyester polymers, polysulfide polymers, and polyamide polymers. , polycarbonate polymers, and diallyl phthalate polymers.
The curable composition may also contain other components. Other ingredients include fillers, plasticizers, thixotropic agents, antioxidants, ultraviolet absorbers, light stabilizers, dehydrating agents, adhesion agents, amine compounds, oxygen-curable compounds, photo-curable compounds, An example is a curing catalyst (silanol condensation catalyst).
Other components are International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP 2014-88481, JP 2015-10162, JP 2015-105293. Conventionally known materials described in JP-A No. 2017-039728, JP-A No. 2017-214541, etc. can be used in combination without any restriction.
Two or more types of each component may be used in combination.

The stress (M50) of the cured product obtained from the curable composition of the present invention when stretched by 50% before or after the heat resistance test measured by the tensile test shown in the examples below is 0.10N. /mm ² or more, and furthermore, 0.15 N/mm ² or more. If it is 0.10/mm ² or more, good strength can be obtained and it is suitable as an adhesive.

The maximum point cohesive force of the cured product obtained from the curable composition of the present invention before or after the heat resistance test, measured by the tensile test shown in the Examples below, tends to be 0.10 N/mm ² or more. , and even more likely to be 0.15 N/mm ² or more. If it is 0.10 N/mm ² or more, good strength can be obtained and it is suitable as an adhesive.

The rate of change in the maximum point elongation after the heat resistance test relative to the maximum point elongation before the heat resistance test measured by the tensile test shown in the Examples below of the cured product obtained from the curable composition of the present invention is 5% or more. It is likely to be 10% or more. If it is 5% or more, cracks are less likely to occur in the cured product due to heat, even when used as an adhesive for building components that are locally heated, such as in floor heating.

The curable composition may be a one-component type in which all the ingredients are mixed in advance and stored in a sealed container, and then cured by moisture in the air after application. A two-component type may be used, in which the curing agent composition containing the curing catalyst is stored separately and the curing agent composition and the base composition are mixed before use. A one-component curable composition is preferred because it is easy to apply.

It is preferable that the one-component curable composition does not contain water. It is preferable to dehydrate the components containing water in advance or by applying reduced pressure during compounding and kneading.
In a two-component curable composition, the curing agent composition may contain water, and the base composition is difficult to gel even if it contains a small amount of water, but from the viewpoint of storage stability, the ingredients should be dehydrated and dried in advance. It is preferable.
In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component base composition.

The curable composition is used as a sealant (e.g., elastic sealant for construction, sealant for double-glazed glass, anti-rust/waterproof sealant for glass edges, back sealant for solar cells, sealant for buildings). Preferred are materials such as materials, sealants for ships, sealants for automobiles, sealants for roads), electrical insulating materials (insulating coatings for electric wires and cables), adhesives, and potting materials.
In particular, it is suitable for adhesives used in areas that are locally exposed to heat, and for example, suitable for adhesives used for building components such as floor heating.

The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.

<Measurement method>
[Molecular weight in terms of hydroxyl group]
The hydroxyl group-equivalent molecular weight of the precursor polymer of the oxyalkylene polymer in the following examples is determined by calculating the hydroxyl value of the precursor polymer based on JIS K 1557 (2007) and calculating the hydroxyl value of 56,100/(hydroxyl value) x (starting value). The number of active hydrogens in the agent or the number of terminal groups in the precursor polymer).

[Mn and molecular weight distribution]
Mw, Mn, and Mw/Mn were determined using HLC-8220GPC (product name of Tosoh Corporation).

[Average number of reactive silicon groups per molecule in polymer (number of silyl groups)]
In this method, an unsaturated group is introduced into the terminal group of a polymer using allyl chloride and allyl glycidyl ether, and a silylating agent is reacted with the unsaturated group to introduce a reactive silicon group. The charged equivalent (molar ratio) of the reactive silicon group of the silylating agent to the saturated group was defined as the silylation rate.
In the reaction of unsaturated groups introduced using allyl chloride and allyl glycidyl ether with a silylating agent, approximately 10% of the unsaturated groups do not react with the silylating agent due to side reactions. Therefore, when less than 90 mol% of the unsaturated groups are reacted with the silylating agent, the above-mentioned charging equivalent is taken as the silylation rate.
The number of silyl groups per molecule was calculated based on the silylation rate.
The number of silyl groups per molecule was divided by the number of end groups to calculate the number of silyl groups per end group.

[Tensile test]
In accordance with the JIS A 1439 test method for architectural sealants, a test specimen for tensile property testing was prepared using an aluminum plate as an adherend. The prepared test specimen was cured for 7 days at a temperature of 23 degrees and a humidity of 50%, and further cured for 7 days at a temperature of 50 degrees and a humidity of 65% to obtain a standard sample. This standard sample was subjected to a tensile test using a Tensilon tester at 23°C at a tensile speed of 50 mm/min, and the stress at 50% elongation (M50, unit: N/mm ² ), maximum point cohesive force (Tmax) , unit: N/mm ² ) and maximum point elongation (unit: %) were measured.
The above standard sample was further cured at a temperature of 110° C. for 7 days to obtain a heat resistance test sample. This heat resistance test sample was subjected to a tensile test in the same manner as above, and the stress at 50% elongation (M50, unit: N/mm ² ), maximum point cohesive force (Tmax, unit: N/mm ² ), maximum point The tensile properties of elongation (unit: %) were measured.
The rate of change in elongation before and after the heat resistance test was calculated from Formula 7 below.
Rate of change in elongation before and after heat resistance test [%] = (Maximum point elongation of heat resistance test sample - Maximum point elongation of standard sample) / Maximum point elongation of standard sample x 100 Formula 7

[Adhesiveness test]
Visually check the surface of the adherend for the heat-resistant sample after the above tensile test. CF indicates that a resin component remains on the surface of the adherend, and CF indicates that no resin component remains on the adherend surface. It was evaluated as AF. In the case of CF, the area of the adherend was taken as 100%, and the ratio (%) of the area where the resin component remained was calculated.

<Synthesis of Polymer A>
A zinc hexacyanocobaltate complex (hereinafter referred to as "TBA-DMC catalyst") with an Mn of about 2,000 and one hydroxyl group as an end group is used as an initiator, and the ligand is t-butyl alcohol. ) was used as a catalyst to carry out addition polymerization of propylene oxide to obtain a precursor polymer a1 having a hydroxyl group molecular weight of 12,000. Subsequently, a methanol solution of sodium methoxide in an amount equivalent to 1.15 times the hydroxyl groups of the precursor polymer a1 was added to alcoholate the hydroxyl groups of the precursor polymer a1. Next, methanol was distilled off by heating under reduced pressure, and further allyl glycidyl ether was added in an amount of 1.05 times the equivalent of the hydroxyl group of the precursor polymer a1, and the mixture was reacted at 130° C. for 2 hours. Next, a methanol solution of sodium methoxide in an amount of 0.28 molar equivalent to the hydroxyl group of the precursor polymer a1 was added to remove methanol, and further allyl chloride of 2.10 molar equivalent to the hydroxyl group of the precursor polymer a1 was added. was added and reacted at 130° C. for 2 hours, and unreacted allyl chloride was removed from the system under reduced pressure to obtain an oxypropylene polymer (polymer Q1) in which allyl groups were introduced into the terminal groups. The average number of allyl groups introduced into one end group of polymer Q1 was 2.0. Next, in the presence of the platinum divinyldisiloxane complex, 0.80 molar equivalent of dimethoxymethylsilane was added as a silylating agent to the allyl group of polymer Q1, and after reacting at 70°C for 5 hours, unreacted The dimethoxymethylsilane was removed under reduced pressure to obtain a polymer (polymer A) in which an average of more than 1.0 dimethoxymethylsilyl groups as reactive silicon groups were introduced into one terminal group.
The Mn, Mw/Mn, average number of reactive silicon groups per molecule, and number of silyl groups per terminal group of the obtained polymer are shown in Table 1 (the same is shown below).

<Synthesis of polymer B>
Using propylene glycol as an initiator, propylene oxide was addition-polymerized in the presence of a TBA-DMC catalyst to obtain a precursor polymer b1 having a molecular weight in terms of hydroxyl group of 12,000. Subsequently, a methanol solution of sodium methoxide in an amount equivalent to 1.15 times the hydroxyl groups of the precursor polymer b1 was added to alcoholate the hydroxyl groups in the precursor polymer b1. Next, methanol was distilled off by heating under reduced pressure, and an excess amount of allyl chloride relative to the hydroxyl groups of the precursor polymer b1 was added to convert the alcoholate groups introduced into the terminal groups of the polyoxyalkylene chains into allyl groups. The number of allyl groups introduced into the terminal group was 1.0 on average. Next, in the presence of chloroplatinic acid hexahydrate, 0.80 times the mole of dimethoxymethylsilane was added as a silylating agent to the compound in which the hydroxyl group of precursor b1 was converted to an allyloxy group, and the mixture was heated to 70°C. After reacting for 5 hours, unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a polymer in which an average of 1.0 or less dimethoxymethylsilyl groups were introduced into one end group as reactive silicon groups ( Polymer B) was obtained.

As curing catalysts, neodecanoic acid (manufactured by Strem Chemicals) and dibutyltin dilaurate (DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.) were used.
As the amine compound, 3-diethylaminopropylamine (DEAPA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Manufacture of curable composition>
Examples 1 and 2 are examples, and Examples 3 to 6 are comparative examples.

(Examples 1 to 6)
40 parts by mass of a plasticizer (DINP, diisononyl dilate, Vinicizer 90, manufactured by Kao Corporation) per 100 parts by mass of the polymer, curing catalyst, amine compound, and polymer in the formulation (unit: parts by mass) shown in Table 2. 1 part by mass of stabilizer (Songnox 2450, product name of Songwon Co., Ltd.), 1 part by mass of stabilizer (Ti326, product name of BASF Japan Co., Ltd.), thixotropic agent (hydrogenated castor oil-based thixotropic agent, Disparon 6500) , Kusumoto Kasei Co., Ltd. product name), 75 parts by weight of filler (colloidal calcium carbonate, white luster CCR, Shiroishi Kogyo Co., Ltd. product name), filler (ground calcium carbonate, Whiten SB, Shiroishi Kogyo Co., Ltd.) 75 parts by mass of dehydrating agent (vinyltrimethoxysilane, KBM-1003, Shin-Etsu Chemical product name), 3 parts by mass of adhesive agent (3-(2-aminoethylamino)propyltrimethoxysilane, A curable composition was prepared by mixing 1 part by mass of KBM-603 (product name of Shin-Etsu Chemical Co., Ltd.) and 1 part by mass of an adhesion imparting agent (3-glycidyloxypropyltrimethoxysilane, KBM-403, product name of Shin-Etsu Chemical Co., Ltd.). I prepared something.
The cured product of the obtained curable composition was evaluated for M50, Tmax, maximum elongation, and adhesiveness by the methods described above. The results are shown in Table 2.

In Examples 1 and 2, the elongation improved before and after the heat resistance test. Examples 3 and 4 are comparative examples in which an oxyalkylene polymer having an average of 1.0 or less reactive silicon groups per terminal group was used. Example 5 is a comparative example using an organotin catalyst. Example 6 is a comparative example using an oxyalkylene polymer having an average of 1.0 or less reactive silicon groups per end group and an organotin catalyst.
In Examples 3 to 6, the elongation decreased before and after the heat resistance test.

Claims (8)

An oxyalkylene polymer having an average of more than 1.0 reactive silicon groups represented by the following formula 1 in one terminal group, and a carboxylic acid having a carboxy group whose adjacent carbon atom is a quaternary carbon or a salt thereof, and the content of the carboxylic acid or its salt is 0.01 to 20 parts by mass based on 100 parts by mass of the oxyalkylene polymer (however, the following (meth)acrylic acid (excluding curable compositions containing an ester polymer (B) and a high molecular weight plasticizer having an average of 0 to 1 reactive silicon group per molecule).
-SiX _a R _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 represents a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3. and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
(Meth)acrylic acid ester polymer (B): A (meth)acrylic acid ester polymer having a reactive silicon group represented by the following formula B1 and having a reactive silicon group equivalent of 0.30 mmol/g or more. Combined.
-SiX ¹ ₃ formula B1
In formula B1, each X ¹ independently represents a hydroxyl group or a hydrolyzable group. An oxyalkylene polymer having an average of more than 1.0 reactive silicon groups represented by the following formula 1-1 in one terminal group, and a carboxy group whose adjacent carbon atom is a quaternary carbon A curable composition containing a carboxylic acid or a salt thereof, wherein the content of the carboxylic acid or salt thereof is 0.01 to 20 parts by mass based on 100 parts by mass of the oxyalkylene polymer (however, the following (meth) (excluding curable compositions containing acrylic ester polymers (B)).
-SiX _a R _3-a Formula 1-1
In formula 1-1, R is a monovalent organic group having 1 to 20 carbon atoms and is other than a hydrolyzable group, X is a hydroxyl group or a hydrolyzable group, and a is 1 to 3 and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
(Meth)acrylic acid ester polymer (B): (meth)acrylic acid ester having a reactive silicon group represented by the following formula B1-1 and having a reactive silicon group equivalent of 0.30 mmol/g or more system polymer.
-SiX ¹ ₃ Formula B1-1
In formula B1-1, X ¹ each independently represents a hydroxyl group or a hydrolyzable group. The curable composition according to claim 1 or 2 , wherein at least one terminal group of the oxyalkylene polymer contains an atomic group represented by the following formula 2.

In the formula 2, 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 carbon atoms, hydrogen atoms, and oxygen atoms. , nitrogen atom, or sulfur atom. R ² and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. n represents an integer from 1 to 10. R ⁵ each independently represents a monovalent organic group having 1 to 20 carbon atoms other than a hydrolyzable group, and Y each independently represents a hydroxyl group or a hydrolyzable group. b is an integer from 1 to 3. When a plurality of R ⁵ 's exist, R ⁵ 's may be the same or different from each other. When there is a plurality of Y's, the Y's may be the same or different from each other. Any one of claims 1 to 3 , wherein the terminal group of the oxyalkylene polymer includes a reactive silicon group represented by the formula 1, an active hydrogen-containing group, or an unsaturated group. The curable composition described in . The oxyalkylene polymer has two or three terminal groups in one molecule, and each terminal group has one of a reactive silicon group, an active hydrogen-containing group, or an unsaturated group represented by the formula 1. The curable composition according to any one of claims 1 to 4 , which has two groups. The curable composition according to any one of claims 1 to 5 , wherein the carboxylic acid or salt thereof is represented by the following formula 3.

In the formula 3, R ¹¹ , R ¹² , and R ¹³ each independently represent a substituted or unsubstituted monovalent hydrocarbon group or carboxy group having 1 to 20 carbon atoms, or R ¹¹ , R ¹² , and R ¹³ Indicates that any two or more of the groups and the carbon atom adjacent to the carboxy group in Formula 3 above together form a ring structure having 3 to 16 carbon atoms. The curable composition according to any one of claims 1 to 6 , which is used for adhesives. A cured product of the curable composition according to any one of claims 1 to 7 .