JP2021085002A - Curable composition, and cured product - Google Patents

Abstract

To provide a curable composition that does not degrade elongation before and after heat resistance test and a cured product of the curable composition.SOLUTION: A curable composition contains an oxyalkylene polymer having a reactive silicon group represented by more than 1.0 of -SiXaR3-a at one end group by average, and carboxylic acid having a carboxyl group in which an adjacent carbon atom is a quaternary carbon or its salt, in which a content of the carboxylic acid or its salt relative to 100 pts.mass of the oxyalkylene polymer is 0.01 to 20 pts.mass. In the formula 1, R is a monovalent organic group of 1 to 20 carbon atoms, shows an organic group other than a hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, a represents an integer of 1 to 3, when a is 1, R may be the same with or different from each other, and when a is 2 or 3, X may be the same with or different from each other.SELECTED DRAWING: None

Description

The present invention relates to curable compositions and cured products.

The polymer having a reactive silicon group is cured by a hydrolysis reaction to form a flexible rubber-like cured product, and is used for applications such as a sealant and an adhesive. Organic tin catalysts are used as curing catalysts to promote the hydrolysis reaction, but many organic tin catalysts are known to be toxic to living organisms, and there are concerns about their impact on the environment. ..

Patent Document 1 contains, as a curing catalyst, an organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, and one or both of a carboxylic acid and a carboxylic acid metal salt that are non-organic tin catalysts. The curable composition to be used is disclosed. It is described that the curable composition has the same adhesiveness as when an organic tin catalyst is used.

International Publication No. 2006/070637

In adhesive applications for locally heated building materials such as floor heating, the heat may reduce the elongation of the cured product and cause cracks.
When the curable composition described in Patent Document 1 is used as an adhesive for the above-mentioned building members, 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 is the following [1] to [7].
[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 an adjacent carbon atom is a quaternary carbon. A curable composition containing the carboxylic acid or a salt thereof, and having a content of the carboxylic acid or a salt thereof in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the oxyalkylene polymer.
−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. 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.
[2] The curable composition according to [1], 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。
［３］ 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］又は［２］に記載の硬化性組成物。
［４］ 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］〜［３］のいずれか一項に記載の硬化性組成物。
［５］ 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］〜［４］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 atom in the bonding group are a carbon atom, a hydrogen atom, and an oxygen atom. , Nitrogen atom, or sulfur atom. R ² and R ⁴ 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 is a monovalent organic group having 1 to 20 carbon atoms independently, and represents an organic group other than a hydrolyzable group, and Y independently represents a hydroxyl group or a hydrolyzable group. b is an integer of 1-3. If R ⁵ there are a plurality, R ⁵ may be the same or different from each other. When there are a plurality of Y's, the Y's may be the same or different from each other.
[3] The terminal group of the oxyalkylene polymer contains a group that is any of a reactive silicon group, an active hydrogen-containing group, or an unsaturated group represented by the above formula 1, [1] or [2]. The curable composition according to.
[4] The oxyalkylene polymer has two or three terminal groups in one molecule, and each terminal group is 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 [3], which has two groups which are any of the above.
[5] The curable composition according to any one of [1] to [4], wherein the carboxylic acid or a salt thereof is a carboxylic acid or a salt thereof 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。
［６］ 接着剤用である、［１］〜［５］のいずれか一項に記載の硬化性組成物。
［７］ ［１］〜［６］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 represent independently substituted or unsubstituted monovalent hydrocarbon groups or carboxy groups having 1 to 20 carbon atoms, respectively, or R ¹¹ , R ¹² , R ¹³ It is shown that any two or more of the groups and the carbon atom adjacent to the carboxy group in the above formula 3 are integrally formed to form a ring structure having 3 to 16 carbon atoms.
[6] The curable composition according to any one of [1] to [5], which is used for an adhesive.
[7] A cured product of the curable composition according to any one of [1] to [6].

The cured product using the curable composition of the present invention does not lose its elongation before and after the heat resistance test.
The cured product of the present invention does not lose its elongation before and after the heat resistance test.

Definitions of terms herein are as follows.
The numerical range represented by "~" means a numerical range in which the numerical values before and after ~ are the lower limit value and the upper limit value.
The "oxyalkylene polymer" means a polymer having a polyoxyalkylene chain formed from a unit based on a cyclic ether.

The "precursor polymer" is composed of a residue of an initiator, a polyoxyalkylene chain formed by ring-opening addition polymerization of cyclic ether, and a terminal group containing a terminal oxygen atom of the polyoxyalkylene chain, and has a terminal. It is a polymer whose group is a hydroxyl group.
The "derivative of the precursor polymer" is a polymer obtained by converting a hydroxyl group, which is a terminal group of the precursor polymer, into a terminal group containing a functional group capable of reacting with a silylating agent. Examples of the functional group capable of reacting with the silylating agent include an active hydrogen-containing group and an unsaturated group existing at the molecular terminal.
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.
The "active hydrogen" is a hydrogen atom based on the above-mentioned active hydrogen-containing group.
The "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 the precursor polymer or its derivative or an unsaturated group existing at the molecular terminal.

The "silylation rate" of an oxyalkylene polymer having a reactive silicon group is the above-mentioned reactive silicon group with respect to the total number of reactive silicon groups, active hydrogen-containing groups, and unsaturated groups contained in the terminal group of the polymer. Is the ratio of the number of. The value of the silylation rate can be measured 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 a ratio of Mw to Mn (hereinafter, referred to as “Mw / Mn”).

The curable composition of the present embodiment is adjacent to an oxyalkylene polymer (hereinafter referred to as "polymer A") having an average of 1.0 or more reactive silicon groups in one terminal group. Includes a carboxylic acid having a carboxy group in which the 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 triorganosyloxy group.

As R, an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group and a triorganosyloxy group are preferable. 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 preferable. A methyl group or an ethyl group is preferable from the viewpoint of good curability of the polymer having a reactive silicon group and stability of the curable composition. A 1-chloromethyl group is preferable from the viewpoint of a high curing rate of the cured product. A methyl group is particularly preferred because it is readily available.

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, a siloxane bond is rapidly formed, a crosslinked structure is easily formed in the cured product, and the physical property value of the cured product becomes better.

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 from each other.
a is preferably 1 or 2, and a is more preferably 2.

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

<Polymer A>
Polymer A has an initiator residue, a polyoxyalkylene chain formed by ring-opening addition polymerization of cyclic ether, and a terminal group containing a terminal oxygen atom of the polyoxyalkylene chain. The valence of the initiator residue, the number of polyoxyalkylene chains, and the number of end 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. In particular, propylene oxide is preferable.
The polyoxyalkylene chain may be a copolymer chain having two or more kinds of oxyalkylene groups, and in that case, the copolymer chain may be a block copolymer chain or a random copolymer chain.
The polyoxyalkylene chain contained in 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 (oxytetra). Examples thereof include a methylene) chain, a poly (oxyethylene / oxypropylene) chain, and a poly (oxypropylene / oxy-2-ethylethylene) chain. As the polyoxyalkylene chain, a polyoxypropylene chain and a poly (oxyethylene / oxypropylene) chain are preferable, and a polyoxypropylene chain is particularly preferable.

The polymer A has an average of more than 1.0 reactive silicon groups in one terminal group, and more preferably 1.1 to 3.0 from the viewpoint of extensibility. It is more preferably 1.2 to 2.0 pieces.
The total number of divalent or higher valence 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 valence atoms contained in one terminal group is preferably 1 or more, more preferably 4 or more, further 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 atom, nitrogen atom, oxygen atom, sulfur atom and silicon atom, and one or more selected from carbon atom, nitrogen atom, oxygen atom and silicon atom. Is more preferred, and one or more atoms selected from carbon, oxygen and silicon atoms are even more preferred.

The Mn of the polymer A is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 3,000 to 40,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced per mass of the polymer A does not become too large, and it is preferable in that it is easy to achieve both elongation and durability. When it is not more than the upper limit value, the viscosity becomes sufficiently low and the workability is improved.
The molecular weight distribution of the polymer A is preferably 1.60 or less, more preferably 1.40 or less, further 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 not more than the above upper limit value, the extensibility of the cured product is likely to be improved.
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, workability is better.

The polymer A preferably has 2 to 8 terminal groups in one molecule, more preferably 2 to 6 terminals, and further preferably 2 or 3 polymer A.
The polymer A preferably contains a group that is any of a reactive silicon group represented by the above formula 1, an active hydrogen-containing group, or an unsaturated group as a terminal group.

Polymer A has two or three terminal groups in one molecule, and each terminal group is either a reactive silicon group represented by the above formula 1, an active hydrogen-containing group, or an unsaturated group. It is preferable to have two groups.
The polymer A preferably has 4 to 6 groups which are any of a reactive silicon group, an active hydrogen-containing group, or an unsaturated group 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%, still more preferably 65 to 95 mol%.
The silylation rate can be adjusted by the amount of the silylating agent that reacts with the unsaturated group contained in the terminal group of the derivative of the precursor polymer.
When the curable composition contains two or more kinds of polymers A, the average silylation rate in the entire polymer A may be within the above range.

It is preferable that at least one terminal 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 atom in the bonding group are a carbon atom, a hydrogen atom, and an oxygen atom. , Nitrogen atom, or sulfur atom.
_-CH 2 as R ^{1, R 3} is _{-, - 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 thereof include CO-, -CO-O-, -CO-NH-, -CH = N-, and -CH = NN = CH-.
R ¹ is _{-CH 2 -O-CH 2 -,} - CH 2 O -, - CH 2 - are _preferred, -CH ₂ -O-CH 2 - is more preferable.
For R ³ , −CH ₂ − and −C ₂ H ₄ − are preferable, and −CH ₂ − is more preferable.

In the above formula 2, R ² and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, respectively. As the hydrocarbon group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The 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, 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, 5-propylhexyl group can be exemplified.
R ² and R ⁴ are preferably a hydrogen atom, a methyl group and an ethyl group, respectively, and more preferably a hydrogen atom or a methyl group.

In the above equation 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 is independently a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, and Y is independently a hydroxyl group or a hydrolyzable group. Shown. b represents an integer of 1 to 3. If R ⁵ there are a plurality, R ⁵ may be the same or different from each other. When there are a plurality of Y's, the Y's may be the same or different from each other.
^{R 5 of the} above formula 2 is the same as R of the above formula 1.
Y in the above formula 2 is the same as X in the above formula 1.
The b of the above formula 2 is the same as the a of 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 ~R 5, Y, b} , n in the above formula 4 is the same as ^R 1 ^{to R} 5 of formula 2, Y, b, n.

<Method for producing polymer A>
The polymer A is obtained by introducing more than 1.0 of the above reactive silicon groups into one terminal group of the precursor polymer on average.
As a method for producing the polymer A, a method in which an unsaturated group of more than 1.0 is introduced into the terminal group of the precursor polymer on average and then the unsaturated group is reacted with the silylating agent is preferable.
The precursor polymer is an oxyalkylene polymer obtained by ring-opening addition polymerization of cyclic ether 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 terminal groups in the precursor polymer, and the number of terminal groups in the polymer A are the same.

The precursor polymer is preferably a polymer having a hydroxyl group as a terminal group, which is obtained by ring-opening addition polymerization of a cyclic ether to an initiator having a hydroxyl group.
As the initiator, an initiator having 2 to 8 hydroxyl groups is preferable, an initiator having 2 to 6 hydroxyl groups is more preferable, and an initiator having 2 or 3 hydroxyl groups is further preferable. Two or more types of initiators may be used in combination.

Examples of the initiator 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. Polyoxypropylene glycol can be exemplified.
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 kinds of the above initiators may be used in combination.

Conventionally known catalysts can be used as the ring-opening addition polymerization catalyst for ring-opening addition polymerization of cyclic ether as an initiator. For example, an alkali catalyst (KOH or the like), a transition metal compound-porphyrin complex catalyst (organic aluminum) can be used. Examples thereof include a complex obtained by reacting a compound with porphyrin), a composite metal cyanide complex catalyst, and a catalyst composed of a phosphazene compound.

A composite metal cyanide complex catalyst is preferable because the molecular weight distribution of the polymer A can be narrowed and a curable composition having a low viscosity can be easily obtained. As the composite metal cyanide complex catalyst, a conventionally known compound can be used, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. For example, International Publication No. 2003/062301, International Publication No. 2004/067633, JP-A-2004-2697776, JP-A-2005-15786, International Publication No. 2013/065802, JP-A-2015-01162 The compounds and production methods disclosed in the publication can be used.

As a method for introducing more than 1.0 unsaturated groups into one terminal group of the precursor polymer on average, known methods can be used without particular limitation. For example, International Publication No. 2013/180203 can be used. Gazette, International Publication No. 2014/192842, JP-A-2015-105293, JP-A-2015-105322, JP-A-2015-105323, JP-A-2015-105324, International Publication No. 2015/080067, International Publication The methods described in JP-A-2015 / 105122, WO 2015/111577, WO 2016/002907, JP-A-2016-216633, and JP-A-2017-39782 can be used.

As a method of introducing more than 1.0 unsaturated groups into one terminal group of the precursor polymer on average, an epoxy compound having an unsaturated group after allowing an alkali metal salt to act on the precursor polymer. Is then reacted, and then a halogenated hydrocarbon compound having an unsaturated group is reacted.

Examples of the epoxy compound having an unsaturated group include allyl glycidyl ether, metallicyl 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, the 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, ^{R 2} in the formula 5 is the same as ^R 1, ^{R 2} in the formula 4.

By the above reaction, an unsaturated group derived from the epoxy compound having the unsaturated group is introduced into the terminal group of the precursor polymer, and then an unsaturated group derived from the halogenated hydrocarbon compound is introduced into the precursor polymer. Derivatives are obtained. The derivative of the precursor polymer may contain an unreacted active hydrogen-containing group at the terminal group.
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, from the viewpoint of storage stability.

The unsaturated group of the derivative of the precursor polymer is reacted with the silylating agent, and a reactive silicon group is introduced into the terminal group to obtain the polymer A.
As the silylating agent, a compound having both a group capable of reacting with an unsaturated group (for example, a sulfanyl group) and the above-mentioned reactive silicon group, a hydrosilane compound (for example, HSiX _a R _3-a , but X , R and a are the same as those in the above formula 1). Specifically, for example, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxy. Examples thereof include silane, (α-chloromethyl) dimethoxysilane, and (α-chloromethyl) diethoxysilane. From the viewpoint of high activity and good curability, trimethoxysilane, triethoxysilane, methyldimethoxysilane and methyldiethoxysilane are preferable, and methyldimethoxysilane or trimethoxysilane is more preferable.

The above reaction gives polymer A having an average of more than 1.0 reactive silicon groups per 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 an adjacent carbon atom is a quaternary carbon. Two or more kinds of carboxylic acids and salts thereof may be used in combination.

The molecular weight of the compound a is preferably 60 to 500, more preferably 80 to 400, and even more preferably 140 to 300, from the viewpoints that the workability of the obtained composition is improved and the catalytic performance is easily maintained. If 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 viewpoint of improving the workability of the obtained curable composition.

As the compound a, the 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 represent independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, or any of R ¹¹ , R ¹² , and R ¹³ . It is shown that two or more groups and a carbon atom adjacent to the carboxy group in the above formula 3 are integrally formed 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 carbon number and the 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, and an alkyl group and an alkenyl group are preferable, and an alkyl group is more preferable. The alkyl group and the alkenyl group may be linear or branched.

The linear alkyl group includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and n. Examples thereof include a-decyl group, n-undecyl group, lauryl group and stearyl group, and n-butyl group, n-pentyl group, n-hexyl group and n-heptyl group are preferable. The branched alkyl group has a structure in which a hydrogen atom in the linear alkyl group (excluding the hydrogen atom in the terminal carbon) is substituted with an alkyl group. Examples of the alkyl group as the substituent include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl group. The group can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.

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 cyclosidecil group, and a cyclopentyl group and a cyclohexyl group are preferable. It may have a structure in which a hydrogen atom in a cycloalkyl group is substituted with an alkyl group. The alkyl group as the substituent is the same as the alkyl group as the substituent exemplified in the alkyl group of the branch.

Examples of the alkenyl group include those in which the single bond between carbon atoms of any one of the above alkyl groups 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. It may have a structure in which a hydrogen atom in an aryl group is substituted with an alkyl group. The alkyl group as the substituent is the same as the alkyl group as the substituent exemplified in the alkyl group of the branch.

R ¹¹ , R ¹² , and R ¹³ may have a substituent other than the alkyl group, and the substituents include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an amide group, a carboxy group, and 1 carbon number. An alkanoyl group having a monovalent hydrocarbon group of ~ 20 can be exemplified. Hydrocarbon group in the alkanoyl group, the same as the R ¹¹ can be exemplified.

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 Valeric acid, neodecanoic acid, versatic acid, and 2,2-dimethyl-3-hydroxypropionic acid can be exemplified, and 2,2-dimethyloctanoic acid is easy to suppress the decrease in elongation of the cured product before and after the heat resistance test. , 2-Ethyl-2,5-dimethylhexanoic acid, versatic acid, neodecanoic acid are preferred, and versatic acid and neodecanoic acid are more preferred.

Examples of the dicarboxylic acid having two carboxy groups in which the adjacent carbon atom represented by the above formula 3 is a quaternary carbon include 2,2-dimethylpropanediacid (dimethylmalonic acid) and 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 in which the adjacent carbon atom is a quaternary carbon. Examples of the dicarboxylic acid contained are 2,2-dimethyl-1,4-butanedioic acid (2,2-dimethylsuccinic acid) and 2,2-diethyl-1,4-butanedioic acid (2,2-diethylsuccinic acid). ), 2,2-Dimethyl-1,6-pentanedioic acid (2,2-dimethylglutaric acid) can be exemplified.

A ring structure in the case where two groups of R ¹¹ , R ¹² , and R ¹³ and a carbon atom adjacent to the carboxy group in the above formula 3 are integrally formed to form a ring structure having 3 to 16 carbon atoms. Examples thereof include a cycloalkane structure having 3 to 10 carbon atoms, a bicyclo ring structure, and a tricyclo ring structure. The 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 integrated to form a ring structure having 3 to 16 carbon atoms is used. , Adamantane ring structure, aromatic ring structure, bicyclo ring structure, tricyclo ring structure can be exemplified.

The ^{above formula in which any two or more groups of R 11} , R ¹² , and R ¹³ and a carbon atom adjacent to the carboxy group in the above formula 3 are integrally formed to 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] hepter 5-en-2-carboxylic acid. , 1-adamantan carboxylic acid, benzoic acid, 9-anthracene carboxylic acid, anisic acid, isopropyl benzoic acid, salicylic acid, toluic acid, chlorobenzoic acid, 2-methylbicyclo [2.2.1] -5-hepten-2- Carboxylic acid, 2-methyl-7-oxabicyclo [2.2.1] -5-hepten-2-carboxylic acid, 1-adamantancarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2.2.2] Octane-1-carboxylic acid can be exemplified.

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 the adjacent carbon atom in the compound a is a quaternary carbon atom is preferably 1 to 3, more preferably 1 to 2. The number of carboxy groups in which the adjacent carbon atom in the compound a is a secondary or tertiary carbon atom is preferably 3 or less, and more preferably 2 or less. ^{When one group of R 11} , R ¹² , and R ^{13 in} the above formula 3 has one carboxy group in which the adjacent carbon atom is a quaternary carbon atom as a substituent, the compound a is represented by the following formula 6. The compound represented is 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 independently the same as R ¹¹ , R ¹² , and R ¹³ in the above formula 3. R ²¹ and R ²² and ^{carbon atoms adjacent to R 22} may be integrated to form a ring structure. R ²³ , R ^24, and ^{a carbon atom adjacent to R 24} may be integrated to form a ring structure. R ²⁰ represents a single-bonded or substituted or unsubstituted divalent hydrocarbon group having 1 to 19 carbon atoms.

The number of carbon atoms of the divalent hydrocarbon group is preferably 1 to 19, more preferably 1 to 16, and even more preferably 2 to 11.

The total carbon number of R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ is preferably 5 to 50, more preferably 5 to 40, and even more preferably 5 to 30. The carbon number and the 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 alkaneylene group and an arylene group, and an alkylene group and a cycloalkylene group are preferable, and an alkylene group is more preferable. The alkylene group and alkenylene group are linear or branched.

As the alkylene group, cycloalkylene group, alkaneylene group, and arylene group, one hydrogen atom was removed from the alkyl group, cycloalkyl group, alkenyl group, and aryl group exemplified by ^{R 11} , R ¹² , and R ^{13 of the above formula 3.} The group can be exemplified.

R ²⁰ may have a substituent other than the alkyl group, and the 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 thereof include a carboxy group and an alkanoyl group. Hydrocarbon group in the alkanoyl group, the same as the R ¹¹ can be exemplified.

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

Examples of the dicarboxylic acid represented by the above formula 6 include 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 -Pentanedioic acid (2,2,4,4-tetramethyl-1,6-glutaric acid) can be exemplified.

Examples of the salt of the carboxylic acid include a salt of a carboxylic acid and a metal, and a salt of a carboxylic acid and an amine compound.
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, with tin being more preferred.
Examples of the amine compound described below include amine compounds described below, and primary amines such as octylamine and laurylamine and amines having a hydrocarbon group having at least one hetero atom are preferable, and the catalytic activity is higher. Amine having a hydrocarbon group having at least one hetero atom is more preferable.

The curable composition of the present embodiment may further contain an amine compound. The amine compound functions as an auxiliary catalyst 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 cyclo. Aliphatic primary amines such as xylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine , Disetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine and other aliphatic secondary amines; triamiylamine, trihexylamine, trioctylamine and other aliphatic tertiary amines; tri Aliphatic unsaturated amines such as allylamine, oleylamine, etc .; aromatic amines such as aniline, 4-laurylaniline, triphenylamine; morpholin, N-methylmorpholin, N-ethylmorpholin, N-allylmorpholin, 4-( 2-Aminoethyl) morpholin, 3-morpholinopropylamine, 3-amino tetrahydrofuran, monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 2,4 , 6-Tris (dimethylaminomethyl) phenol and other amine compounds with oxygen atoms; and other amines include 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 thereof include 4-methylimidazole, 1,8-diazabicyclo (5,4,0) -7-undecene, and 1,5-diazabicyclo (4,3,0) -5-nonen.
As the primary amine, octylamine and laurylamine are preferable because of their high cocatalytic ability.
As the amine compound having an oxygen atom, 3-morpholinopropylamine is preferable.
Other amines include ethylenediamine, monoethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, 3-methoxypropylamine, 3-lauryloxypropylamine, and N because of their high cocatalytic ability. -Methyl-1,3-propanediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3- (1-piperazinyl) propylamine are preferred.
As the amine compound, 3-diethylaminopropylamine and 3-morpholinopropylamine are more preferable in that they have a higher cocatalyst function, and tend to give a curable composition having good adhesiveness, workability and storage stability. Therefore, 3-diethylaminopropylamine is more preferable.

[Composition of curable composition]
The curable composition is obtained by adding, if necessary, components to the polymer A and the compound a, and mixing them.
The content ratio of the polymer A with respect to the total mass of the curable composition is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, still more preferably 10 to 40% by mass. When the content ratio of the polymer A is within the above range, the strength and elongation of the cured product are more excellent.
The content ratio of the compound a with respect to the total mass of the curable composition is preferably 0.003 to 10% by mass, more preferably 0.1 to 7% by mass, still more preferably 0.2 to 5% by mass. When the content ratio of the compound a is within the above range, the decrease in elongation of the cured product is suppressed before and after the heat resistance test.
The content of compound a with respect to 100 parts by mass of the 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. 10 parts by mass is more preferable. When the content of compound a is not less than the lower limit of the above range, a practical curing rate can be easily obtained, and when it is not more than the upper limit, a practical pot life is likely to be obtained. Excellent.
When the curable composition contains an amine compound, the content ratio of the amine compound 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. ~ 5% by mass is more preferable.
When the curable composition contains an amine compound, the content of the amine compound with respect to 100 parts by mass of the compound a is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and further preferably 15 to 150 parts by mass. preferable.

[Other ingredients]
The curable composition comprises an oxyalkylene polymer having an average of 1.0 or less reactive silicon groups represented by the above formula 1 and a reactive silicon group represented by the above formula 1 in one terminal group. A polymer other than the oxyalkylene polymer having the oxyalkylene polymer and a polymer having no reactive silicon group represented by the above formula 1 may be contained. Examples of the polymer other than the oxyalkylene polymer include vinyl-based polymers such as acrylic acid-based polymers and methacrylic acid-based polymers, saturated hydrocarbon-based polymers, polyester-based polymers, polysulfide-based polymers, and polyamide-based polymers. , Polycarbonate-based polymer, diallyl phthalate-based polymer, and the like.
The curable composition may contain other components. Other components include fillers, plasticizers, thixophilic agents, antioxidants, UV absorbers, light stabilizers, dehydrating agents, adhesives, amine compounds, oxygen curable compounds, photocurable compounds, A curing catalyst (silanol condensation catalyst) can be exemplified.
Other components include International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, JP-A-2015-105293. No., JP-A-2017-039728, JP-A-2017-214541 and the like can be used in combination without limitation.
Two or more kinds 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 Examples described later is 0.10 N. It tends to be / mm ² or more, and further tends to be 0.15 N / mm ² or more. When 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 Examples described later is likely to be ^{0.10 N / mm 2 or more.} Furthermore, it tends to be 0.15 N / mm ^{2 or more.} When 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 of the maximum point elongation after the heat resistance test from the maximum point elongation before the heat resistance test measured by the tensile test shown in Examples described later of the cured product obtained from the curable composition of the present invention is 5% or more. It tends to be 10% or more. If it is 5% or more, cracks are unlikely to occur in the cured product due to heat even in an adhesive application for building members that are locally heated such as floor heating.

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

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

The curable composition is used as a sealing material (for example, an elastic sealing material for construction, a sealing material for double glazing, a sealing material for rust / waterproofing at the end of glass, a sealing material for the back surface of a solar cell, and a sealing material for buildings. Materials, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), electrical insulating materials (insulating coating materials for electric wires / cables), adhesives, and potting materials are suitable.
In particular, it is suitable for adhesive applications used for locally heated parts, and is suitable for adhesive applications used for building members such as floor heating, for example.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Measurement method>
[Molecular weight converted to hydroxyl group]
The hydroxyl group-equivalent molecular weight of the precursor polymer of the oxyalkylene polymer in the following example is calculated by calculating the hydroxyl value of the precursor polymer based on JIS K 1557 (2007), and "56,100 / (hydroxyl value) × (start). It is a value calculated as "the number of active hydrogens of the agent or the number of terminal groups of the precursor polymer)".

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

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

[Tensile test]
According to the test method of the building sealant of JIS A 1439, a test body for a tensile property test was prepared using an aluminum plate as an adherend. The prepared test piece was cured at a temperature of 23 ° C. and a humidity of 50% for 7 days, and further cured at a temperature of 50 ° C. and a humidity of 65% for 7 days to obtain a standard sample. This standard sample was subjected to a tensile test at a tensile speed of 50 mm / min under the condition of 23 ° C. with a Tensilon tester, and the stress (M50, unit: N / mm ² ) and maximum point cohesive force (Tmax) when stretched by 50%. , Unit: N / mm ² ), maximum point elongation (unit:%) tensile properties 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. A tensile test was performed on this heat resistant test sample in the same manner as above, and the stress (M50, unit: N / mm ² ), the maximum point cohesive force (Tmax, unit: N / mm ² ), and the maximum point when stretched by 50% were performed. The tensile properties of elongation (unit:%) were measured.
The rate of change in elongation before and after the heat resistance test was calculated from Equation 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 Equation 7

[Adhesion test]
For the heat-resistant sample after the above tensile test, the surface of the adherend is visually confirmed, CF is the case where the resin component remains on the surface of the adherend, and CF is the case where the resin component does not remain on the adherend. It was evaluated as AF. In the case of CF, the ratio (%) of the area where the resin component remains was calculated with the area of the adherend as 100%.

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

<Synthesis of polymer B>
Propylene oxide was addition-polymerized in the presence of a TBA-DMC catalyst using propylene glycol as an initiator 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 1.15 times equivalent to the hydroxyl group of the precursor polymer b1 was added to alcoholate the hydroxyl group of the precursor polymer b1. Next, methanol was distilled off by heating and reducing pressure, and an excess amount of allyl chloride was added to the hydroxyl group of the precursor polymer b1 to convert the alcoholate group introduced into the terminal group of the polyoxyalkylene chain into an allyl group. The average number of allyl groups introduced into the terminal groups was 1.0. Next, in the presence of chloroplatinic acid hexahydrate, 0.80 times mol of dimethoxymethylsilane was added as a silylating agent to the compound in which the hydroxyl group of the precursor polymer b1 was converted to an allyloxy group, and the temperature was raised to 70 ° C. After reacting for 5 hours, unreacted dimethoxymethylsilane was removed under reduced pressure, and an average of 1.0 or less dimethoxymethylsilyl groups were introduced into one terminal group as reactive silicon groups (a polymer. Polymer B) was obtained.

Neodecanoic acid (manufactured by Strem Chemicals) and dibutyl tin dilaurate (DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.) were used as the curing catalyst.
As the amine compound, 3-diethylaminopropylamine (DEAPA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Manufacturing 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 plasticizer (DINP, diisononyl dilate, Vinicizer 90, manufactured by Kao Co., Ltd.) with respect to 100 parts by mass of the polymer, curing catalyst, amine compound, and polymer of the formulation (unit: parts by mass) shown in Table 2. Part, 1 part by mass of stabilizer (Songnox2450, Songwon product name), 1 part by mass of stabilizer (Ti326, BASF Japan Co., Ltd. product name), Tixogenic agent (Hydrogen hydrous oil-based Tixogenic agent, Disparon 6500) , Kusumoto Kasei Co., Ltd. product name) 3 parts by mass, filler (glue calcium carbonate, white glossy CCR, Shiraishi Kogyo Co., Ltd. product name) 75 parts by mass, filler (heavy calcium carbonate, Whiten SB, Shiraishi Kogyo Co., Ltd.) 75 parts by mass of (product name), 3 parts by mass of dehydrating agent (vinyltrimethoxysilane, KBM-1003, Shin-Etsu Chemical Co., Ltd. product name), adhesiveness-imparting agent (3- (2-aminoethylamino) propyltrimethoxysilane, 1 part by mass of KBM-603 (product name of Shin-Etsu Chemical Co., Ltd.) and 1 part by mass of adhesive-imparting agent (3-glycidyloxypropyltrimethoxysilane, KBM-403, product name of Shin-Etsu Chemical Co., Ltd.) are mixed to form a curable composition. The thing was prepared.
The cured product of the obtained curable composition was evaluated for M50, Tmax, maximum point elongation, and adhesiveness by the above method. 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 in one terminal group is used. Example 5 is a comparative example using an organic tin catalyst. Example 6 is a comparative example in which an oxyalkylene polymer having 1.0 or less reactive silicon groups on average and an organic tin catalyst are used in one terminal group.
In Examples 3 to 6, the elongation decreased before and after the heat resistance test.

Claims (7)

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 in which an adjacent carbon atom is a quaternary carbon. Alternatively, a curable composition containing 0.01 to 20 parts by mass of the carboxylic acid or a salt thereof with respect to 100 parts by mass of the oxyalkylene polymer.
−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. 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. The curable composition according to claim 1, wherein at least one terminal group of the oxyalkylene polymer 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 atom in the bonding group are a carbon atom, a hydrogen atom, and an oxygen atom. , Nitrogen atom, or sulfur atom. R ² and R ⁴ 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 is a monovalent organic group having 1 to 20 carbon atoms independently, and represents an organic group other than a hydrolyzable group, and Y independently represents a hydroxyl group or a hydrolyzable group. b is an integer of 1-3. If R ⁵ there are a plurality, R ⁵ may be the same or different from each other. When there are a plurality of Y's, the Y's may be the same or different from each other. The curability according to claim 1 or 2, wherein the terminal group of the oxyalkylene polymer contains a group that is any one of a reactive silicon group, an active hydrogen-containing group, or an unsaturated group represented by the above formula 1. Composition. The oxyalkylene polymer has two or three terminal groups in one molecule, and each terminal group is either a reactive silicon group represented by the above formula 1, an active hydrogen-containing group, or an unsaturated group. The curable composition according to any one of claims 1 to 3, which has two groups. The curable composition according to any one of claims 1 to 4, wherein the carboxylic acid or a salt thereof is a carboxylic acid represented by the following formula 3 or a salt thereof.

In the above formula 3, R ¹¹ , R ¹² , and R ¹³ represent independently substituted or unsubstituted monovalent hydrocarbon groups or carboxy groups having 1 to 20 carbon atoms, respectively, or R ¹¹ , R ¹² , R ¹³ It is shown that any two or more of the groups and the carbon atom adjacent to the carboxy group in the above formula 3 are integrally formed to form a ring structure having 3 to 16 carbon atoms. The curable composition according to any one of claims 1 to 5, which is for an adhesive. A cured product of the curable composition according to any one of claims 1 to 6.