JP2013234225A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that does not contain expensive organometallic compounds, such as a lead compound, that is under strict control recently because of its accumulation properties into human body and hazardousness, and that has a sufficient cure rate and excellent adhesion.SOLUTION: A curable composition includes: an oxyalkylene polymer (A) having a reactive silicon group in which a hydroxyl group or a hydrolyzable group bonds to a silicon atom; and a quaternary ammonium salt (B) comprising a quaternary ammonium cation having a -(RO)Rgroup and an anion derived from a weak acid.

Description

  The present invention relates to a curable composition.

  Conventionally, a polymer having at least one silicon atom-containing group containing a silicon atom having a hydroxyl group or a hydrolyzable group bonded thereto and capable of crosslinking by forming a siloxane bond has been known.

  Various curing catalysts for curing this polymer are known. For example, Patent Document 1 describes the use of an organometallic compound such as dibutyltin dilaurate, tin octylate, lead octylate and the like. Has been. However, organometallic compounds containing tin or lead are expensive. In recent years, since lead compounds and the like are required to be strictly controlled in terms of discharge and disposal from the viewpoint of accumulation and harmfulness to the human body, it is desired that organometallic compounds such as lead compounds be not used as much as possible.

  As a catalyst that does not use such an organometallic compound, a silanol condensation catalyst that cures an organic polymer having a reactive silicon group is known. Patent Document 2 discloses a quaternary ammonium salt as a curing catalyst. . However, when such a quaternary ammonium salt is used as a curing catalyst, it may peel off from the interface between the adherend and the curable composition when the adhesion is evaluated, and the adhesion is not always sufficient.

Japanese Unexamined Patent Publication No. Sho 63-112642 International Publication 2008-023713

  The present invention has been made in view of the above circumstances, and contains a polymer having a reactive silicon group as a curing component, does not contain an organometallic compound, has a sufficient curing rate, and has good adhesiveness. An object is to provide a sex composition.

[1] An oxyalkylene polymer (A) having a reactive silicon group in which a hydroxyl group or a hydrolyzable group is bonded to a silicon atom, and-(RO) _m R ¹⁰ group (R is an alkylene group having 2 to 4 carbon atoms) , M represents an integer of 1 or more, R ¹⁰ represents a hydrogen atom or an alkyl group of 6 or less, provided that when m is 2 or more, Rs may be the same or different from each other) And a quaternary ammonium salt (B) comprising an anion derived from a weak acid.

  According to the present invention, a curable composition containing a reactive silicon group-containing oxyalkylene polymer as a curing component, containing no or almost no organometallic compound, having a sufficient curing rate, and good adhesion. Is obtained.

<Oxyalkylene polymer (A)>
The oxyalkylene polymer (A) of the present invention (hereinafter sometimes referred to as component (A)) is a polymer having a polyoxyalkylene chain. Preferable specific examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, a polyoxyhexylene chain, a polyoxytetramethylene chain, and a “copolymer of two or more cyclic ethers”. And a molecular chain made of a polymer. The main chain of the oxyalkylene polymer (A) may be a molecular chain composed of one kind among these, or may be a molecular chain obtained by combining a plurality of kinds via an ether bond. When the molecular chain is a combination of a plurality of species, they may be bonded via a divalent linking group other than an ether bond. Examples of the divalent linking group include a urethane bond, an ester bond, a carbonate bond, an amide bond, and a urea bond. An ether bond is preferable in that the viscosity of the oxyalkylene polymer can be lowered.

As the oxyalkylene polymer (A), a polymer having only a polyoxypropylene chain as a main chain is particularly preferable. Here, “substantially only polyoxypropylene chain” refers to a molecular chain in which 90 mol% or more of the polyoxyalkylene chain is composed of PO.
The oxyalkylene polymer (A) has a reactive silicon group in which a hydroxyl group or a hydrolyzable group (hereinafter sometimes referred to as a hydroxyl group) is bonded to a silicon atom. It is more preferable to have the reactive silicon group as a substituent at the terminal. The reactive silicon group may be directly bonded to the carbon atom of the polyoxyalkylene chain, or may be directly bonded to the carbon atom of the organic group via another organic group.

As the reactive silicon group, a group represented by the following formula (1) is preferable.
-SiX ¹ _a (R ¹¹ ) _3-a (1)
[R ^{11 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, X ¹ is a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3. However, R ¹¹ when (3-a) is 2 may be the same or different, and X ¹ when a is 2 or 3 may be the same or different. The silicon atom of the formula (1) is preferably bonded to the carbon atom of the oxyalkylene polymer (A).

R ¹¹ does not include a hydrolyzable group described later.

R ¹¹ is preferably an alkyl group having 8 or less carbon atoms, and more preferably a methyl group. When a plurality of R ¹¹ are present in the same molecule, the plurality of R ¹¹ may be the same as or different from each other.

The hydrolyzable group in X ¹ refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group is a group having a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable. More specifically, a methoxy group or an ethoxy group is particularly preferable. When a plurality of hydroxyl groups or hydrolyzable groups are present in the same molecule, the plurality of hydroxyl groups and the like may be the same as or different from each other.

  In formula (1), a is preferably 3 in that the curing rate of the resulting curable composition can be increased.

The reactive silicon group is preferably bonded to the polyoxyalkylene chain via a divalent organic group having a divalent linking group.
Examples of the divalent linking group include the linking groups described in the polyoxyalkylene chain.
However, the silicon atom of the reactive silicon group is bonded to the carbon atom of the oxyalkylene polymer (A).

  As a bivalent organic group, the C1-C10 alkylene group which may have the said bivalent coupling group is preferable.

  As the oxyalkylene polymer (A), a reactive silicon group in which 1, 2, or 3 hydroxyl groups are bonded to a silicon atom can be used.

  When two or more hydroxyl groups are bonded to the silicon atom, the hydroxyl groups may be the same or different. Moreover, when the oxyalkylene polymer (A) has a plurality of reactive silicon groups, all of them may be the same or two or more different groups.

  The silicon atom in the reactive silicon group may have a group other than a hydroxyl group or a hydrolyzable group, and preferably has a monovalent organic group having 1 to 20 carbon atoms. The monovalent organic group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably a methyl group in terms of a high curing rate. .

  The oxyalkylene polymer (A) preferably has an average of 1 to 8 reactive silicon groups, more preferably 1.1 to 5 reactive silicon groups, and 1.1 to 3 reactive silicon groups. Is most preferred. When the number of reactive silicon groups is 8 or less, the elongation of the cured product obtained by curing the curable composition becomes good. Moreover, when the oxyalkylene polymer (A) has one or more reactive silicon groups, a curable composition having sufficient hardness and curability can be obtained.

  The oxyalkylene polymer (A) is, for example, a polyoxyalkylene chain-containing polymer having a polyoxyalkylene chain as a main chain and a hydroxyl group, an unsaturated group, etc. as a functional group for introducing a reactive silicon group. It can manufacture by introduce | transducing a reactive silicon group with respect to (P).

  In the polyoxyalkylene chain-containing polymer (P), the number of functional groups for introducing reactive silicon groups is preferably 1 to 8 on average per molecule of the polymer (P). It is more preferable to have ~ 5, and it is most preferable to have 1.1-3. When the number of reactive silicon groups is 8 or less, the elongation of the cured product obtained by curing the curable composition becomes good. Moreover, when the oxyalkylene polymer (A) has one or more reactive silicon groups, a curable composition having sufficient hardness and curability can be obtained. Of the polyoxyalkylene chain-containing polymer (P), a polyoxyalkylene chain-containing polymer having a hydroxyl group (hereinafter also referred to as a polyoxyalkylene chain-containing polymer (pP) having a hydroxyl group) includes, for example, a catalyst and It can be obtained by ring-opening polymerization of a cyclic ether compound in the presence of an initiator. As the initiator in this case, a hydroxy compound having one or more hydroxyl groups can be used.

  Preferred examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and tetrahydrofuran. Examples of the catalyst include alkali metal catalysts such as potassium compounds and cesium compounds, compound metal cyanide complex catalysts, compound catalysts having a P = N bond such as metal porphyrin catalysts and phosphazene compounds. As the double metal cyanide complex, a complex mainly composed of zinc hexacyanocobaltate is preferable, and an ether and / or alcohol complex is particularly preferable. In this case, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) or the like is preferable as the ether, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As the alcohol, tert-butanol is preferred.

  The polyoxyalkylene chain-containing polymer (pP) having a hydroxyl group preferably has a relatively high molecular weight. Specifically, the number average molecular weight (Mn) of the polyoxyalkylene chain-containing polymer (pP) is preferably from 2,000 to 50,000, particularly preferably from 4,000 to 30,000.

  As a method for introducing a reactive silicon group into the polyoxyalkylene chain-containing polymer (P) as a raw material, a known method can be used. For example, there is the method (a), (b), (c), (d), (e) or (f) described in paragraphs 0022 to 0037 of the republished 2009/104700 publication.

  The method (b), (c), (d) or (e) is preferred because it has excellent adhesion and fast curability when it has a urethane bond in the molecule.

  The number average molecular weight (Mn) of the oxyalkylene polymer (A) in the present invention is preferably from 2,000 to 50,000, from the viewpoint that physical properties such as breaking stress and breaking elongation of the cured product can be further enhanced. 4,000 to 30,000 are particularly preferred. Here, in the present invention, the number average molecular weight means a number average molecular weight (Mn) in terms of standard polystyrene measured using tetrahydrofuran as a mobile phase by gel permeation chromatography (GPC), and the weight average molecular weight is the same as described above. It means the weight average molecular weight (Mw) when GPC measurement is performed. Furthermore, molecular weight distribution represents weight average molecular weight (Mw) / number average molecular weight (Mn). Moreover, Mn of an oxyalkylene polymer (A) means Mn before hardening. When the Mn of the oxyalkylene polymer (A) is 50,000 or less, the extrudability becomes good. For example, workability becomes good when the curable composition is used as a sealant or an elastic adhesive. On the other hand, if the Mn of the oxyalkylene polymer (A) is 2,000 or more, the curability of the composition will be good.

  Further, as a method for controlling the physical characteristics of the curable composition, there is a method for adjusting Mw / Mn (molecular weight distribution) of the oxyalkylene polymer (A). The Mw / Mn of the oxyalkylene polymer (A) is determined by adjusting the type and amount of the polymerization catalyst used in obtaining the polyoxyalkylene chain-containing polymer (P) as the raw material, and by optimizing the polymerization conditions of the cyclic ether. Can be adjusted. Moreover, it can adjust also by mixing and using 2 or more types of oxyalkylene polymers (A).

  When importance is attached to the strength of the cured product of the curable composition, the Mw / Mn of the oxyalkylene polymer (A) is preferably small. Thereby, even if the elasticity modulus of hardened | cured material is comparable, the fracture elongation is larger and it becomes higher intensity | strength. In particular, the polymer preferably has Mw / Mn of less than 1.6. In comparison between oxyalkylene polymers (A) having the same Mn, those having Mw / Mn of less than 1.6 are those having a smaller molecular weight than those having Mw / Mn of 1.6 or more. Accordingly, the elongation at break and the maximum stress of the cured product become larger, and the viscosity of the polymer itself becomes lower, and the handleability of the curable composition is excellent. For the same reason, Mw / Mn is more preferably 1.5 or less, and even more preferably 1.4 or less.

  As described above, the oxyalkylene polymer (A) having a small Mw / Mn has a desired Mw / Mn by a method in which a cyclic ether is polymerized in the presence of an initiator using a double metal cyanide complex as a catalyst. It is preferable that the polymer be obtained by a method in which a polyoxyalkylene chain-containing polymer is obtained and the terminal of this polymer is modified to introduce a reactive silicon group.

  On the other hand, when it is important to reduce the slump property of the curable composition to obtain a curable composition having good workability, the Mw / Mn of the oxyalkylene polymer (A) is 1.6 or more. It is preferable.

<Quaternary ammonium salt (B)>
In the present invention, the quaternary ammonium salt (B) (hereinafter sometimes referred to as the component (B)) is-(RO) _m R ¹⁰ group (R is an alkylene group having 2 to 4 carbon atoms, and m is 1 or more. An integer of R ¹⁰ represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, provided that when m is 2 or more, Rs may be the same or different from each other) and hydroxylated It consists of an anion derived from a product ion or a weak acid. The quaternary ammonium salt (B) in the present invention acts as a catalyst in the curable composition of the present invention.

(Quaternary ammonium cation)
Here, the quaternary ammonium cation refers to a cation having a tetravalent cationic nitrogen atom in the molecule and having no hydrogen atom directly bonded to the cationic nitrogen atom.

The quaternary ammonium cation has 1 to 3 cationic nitrogen atoms and one or more — (RO) _m R ¹⁰ groups bonded to at least one of the cationic nitrogen atoms. The cationic nitrogen atom may have a group that does not contain the (RO) group other than the — (RO) _m R ¹⁰ group.

R is an alkylene group having 2 to 4 carbon atoms. When the number of carbon atoms is 2 or more, the adhesiveness is good, and the number of carbon atoms is preferably 4 or less from the viewpoint of easy availability. R is more preferably an alkylene group having 2 or 3 carbon atoms, particularly preferably an alkylene group having 3 carbon atoms. When R is an alkylene group having 2 or 3 carbon atoms, in the m RO _group, the ratio of C 2 _{H 4} O groups and _C 3 _{H 6} O groups, in a molar ratio of 1: 99-50: 50 Preferably, 5: 95-30: 70 is more preferable.

The m is an integer of 1 or more. M is preferably an integer of 40 or less. When the quaternary ammonium salt (B) has two or more-(RO) _m R ¹⁰ groups in one molecule, the total m of-(RO) _m R ¹⁰ contained in one molecule is 40 or less. Preferably there is. When m is 1 or more, the adhesive property of the resulting curable composition is good, and when it is 40 or less, the curing rate is fast, so the curability is good.

R ¹⁰ is a hydrogen atom or an alkyl group having 6 or less carbon atoms. When R ¹⁰ is an alkyl group, the number of carbon atoms is preferably 1 to 4, and more preferably 1 or 2. R ¹⁰ is particularly preferably a hydrogen atom.

When m is 1, — (RO) _m R ¹⁰ group is preferably a 2-hydroxyethyl group or a 2-hydroxypropyl group, and more preferably a 2-hydroxyethyl group. When m is 2 or more (RO) _m is preferably a polyoxyethylene group, a polyoxypropylene group or a poly (oxyethylene / oxypropylene) group, and the ratio of the polyoxypropylene group or the oxypropylene group is 60 mol%. The above poly (oxyethylene / oxypropylene) group is more preferable.

  The quaternary ammonium cation preferably has 1 or 2 cationic nitrogen atoms. That is, the quaternary ammonium salt (B) preferably has 1 or 2 cationic nitrogen atoms.

When the quaternary ammonium salt (B) is a compound having one cationic nitrogen atom (hereinafter also referred to as a quaternary ammonium salt (B-1)), the cationic nitrogen atom has p (p Represents an integer of 1 to 3) at least one selected from the group consisting of an alkyl group and an aryl group (when p is 2 or 3, the groups selected from the group consisting of the alkyl group and the aryl group are the same as each other) And (4-p)-(RO) _m R ¹⁰ groups (when p is 1 or 2, the groups may be the same or different from each other). . p is preferably 2 or 3, more preferably 2 in that the resulting curable composition has good adhesion. The alkyl group preferably has 1 to 24 carbon atoms. The aryl group is preferably an aryl group which may have a substituent composed of a hydrocarbon having 1 to 6 carbon atoms, and more preferably a benzyl group. The group selected from the group consisting of an alkyl group and an aryl group is preferably an alkyl group. In particular, it is preferable that p is 2, one of the two alkyl groups is an alkyl group having 6 to 24 carbon atoms, and the other is an alkyl group having 5 or less carbon atoms.

When the quaternary ammonium salt (B) is a compound having two cationic nitrogen atoms (hereinafter also referred to as quaternary ammonium salt (B-2)), the two cationic nitrogen atoms are alkylene Bonding via a group is preferred. The cationic nitrogen atom is at least one selected from the group consisting of q alkyl groups (where q represents 1 or 2) and an aryl group (when q is 2, it is selected from the group consisting of the alkyl group and aryl group). Groups may be the same or different from each other) and (3-q)-(RO) _m R ¹⁰ groups (when q is 1, the groups may be the same or different from each other). They are bonded (however, two of the cationic nitrogen atoms to which the three groups are bonded may be the same or different from each other). q is preferably 1 in that the resulting curable composition has good adhesiveness. The alkyl group preferably has 1 to 24 carbon atoms, and more preferably 1 to 10 carbon atoms. The aryl group is preferably an aryl group which may have a substituent composed of a hydrocarbon having 1 to 6 carbon atoms, and more preferably a benzyl group. The group selected from the group consisting of an alkyl group and an aryl group is preferably an alkyl group. In particular, q is 1 and an alkyl group having 1 to 24 carbon atoms is preferable.

(Weak acid)
The weak acid in the present invention preferably has a kPa of 1 to 10. Examples of the weak acid having a pKa of 1 to 10 include organic acids or inorganic acids of weak acids. Specific examples of the weak acid in the present invention include the following compounds.

  Examples of the organic acid include aliphatic monocarboxylic acids (formic acid, acetic acid, octylic acid, 2-ethylhexanoic acid, etc.); aliphatic polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, etc.); aromatic Aromatic monocarboxylic acids (benzoic acid, toluic acid, ethylbenzoic acid, etc.); aromatic polycarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid, trimellitic acid, etc.); phenolic compounds (phenol, resorcinic, etc.); Sulfonic acid compounds (alkyl benzene sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, etc.); and organic phosphoric acid compounds.

  If the acid dissociation constant (pKa) is 1-10, the weak acid inorganic acid is preferable in terms of fast curability, and 9-10 is more preferable in terms of quick curability. Carbon dioxide is mentioned as an inorganic acid of a weak acid.

  Of the above weak acids, organic acids are preferable, carboxylic acids are more preferable in terms of fast curing speed, and octylic acid is more preferable in terms of faster curing speed.

In a preferred embodiment of the quaternary ammonium salt (B-1) in the present invention, the anion derived from the weak acid is a carbonium ion, and the groups bonded to the quaternary ammonium cation are the following (i) to (v): Can be mentioned.
(I):
— (RO) _m R ¹⁰ is an alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 40, and R ¹⁰ is a hydrogen atom. — (RO) _m R ¹⁰ groups are (4-p) A compound having p alkyl groups having 1 to 24 carbon atoms, wherein p is an integer of 1 to 3;
(Ii):
— (RO) _m R ¹⁰ is an alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 40, and R ¹⁰ is a hydrogen atom. — (RO) _m R ¹⁰ groups are (4-p) A compound having p alkyl groups having 1 to 24 carbon atoms and p is 2.
(Iii):
- _(RO) ^m m pieces of RO group in ^{R 10} is the ratio of the _C 2 _{H 4} O and _{C 3 H 6 O 1: 99~50} : 50 group, m is from 1 to 40 integer and ^{R 10,} Is a hydrogen atom, a compound having (4-p) (RO) _m R ¹⁰ groups, p alkyl groups having 1 to 24 carbon atoms, and p is 1 to 3.
(Iv):
- _(RO) ^m m pieces of RO group in ^{R 10} is the ratio of the _C 2 _{H 4} O and _{C 3 H 6 O 1: 99~50} : 50 group, m is from 1 to 40 integer and ^{R 10,} Is a hydrogen atom-(RO) _m R ¹⁰ A compound having 2 groups, an alkyl group having 6 to 24 carbon atoms, and an alkyl group having 5 or less carbon atoms.
(V):
-(RO) _m R ¹⁰ in which R is an alkylene group having 3 carbon atoms, m is an integer of 1 to 40, and R ¹⁰ is a hydrogen atom-(4-p) number of (RO) _m R ¹⁰ groups A compound having p alkyl groups having 1 to 24 carbon atoms, and p is 1 to 3;

In a preferred embodiment of the quaternary ammonium salt (B-2) in the present invention, the anion derived from the weak acid is a carbonium ion, and the groups bonded to the quaternary ammonium cation are the following (i) to (iii): Can be mentioned.
(I):
— (RO) _m R ¹⁰ in which R is an alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 40, and R ¹⁰ is a hydrogen atom. — (RO) _m R ¹⁰ group is a single nitrogen atom. A compound having (2-q) per group, q alkyl groups having 1 to 24 carbon atoms, and q being 1 or 2.
(Ii):
— (RO) _m R ¹⁰ in which R is an alkylene group having 3 carbon atoms, m is an integer of 1 to 40, and R ¹⁰ is a hydrogen atom. — (RO) _m R ¹⁰ groups per nitrogen atom ( 2-q) A compound having q alkyl groups having 1 to 24 carbon atoms and q being 1 or 2.
(Iii):
- _(RO) ^m m pieces of RO group in ^{R 10} is the ratio of the _C 2 _{H 4} O and _{C 3 H 6 O 1: 99~50} : 50 group, m is from 1 to 40 integer and ^{R 10,} Is a hydrogen atom — (RO) _m R having ¹⁰ groups (2-q) per nitrogen atom, q alkyl groups having 1 to 24 carbon atoms, and q being 1 or 2 A compound that is

(Method for producing quaternary ammonium salt (B))
Among the components (B), a quaternary ammonium salt (B-1) that is a salt with an anion derived from a weak acid is, for example, a production method (a): a method of reacting a quaternary ammonium hydroxide and a weak acid. , Production method (b):-(RO) _m R ^{10 A} tertiary amine having ¹⁰ groups is reacted with a carbonic acid diester to form a quaternary ammonium carbonate, and the resulting quaternary ammonium carbonate and a weak acid Obtained by a method of anion exchange reaction. The production method (b) is preferred in that there is no halogen element or alkali (earth) metal mixed in the reaction step.

  Examples of the carbonic acid diester used in the production method (b) include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate, and particularly preferred is dimethyl carbonate.

  When the acid used in the production method (b) is a weak acid, when a quaternary ammonium salt is used as a curing catalyst for a polymer having a reactive silicon group, the binding energy of the ionic bond of the quaternary ammonium salt is low. The quaternary ammonium salt using a weak acid having a low binding energy of ionic bond is considered to be fast in curability because the catalyst tends to have high activity and fast curability.

  In the present invention, the weak acid may be used alone or as a mixture of two or more.

  The equivalent ratio of ammonia, primary amine or secondary amine and carbonic acid diester in the production method (b) is usually 1: 0.3 to 1: 6. If necessary, a reaction solvent (methanol, ethanol, etc.) may be used. The reaction temperature is usually 30 to 150 ° C, preferably 50 to 130 ° C.

  The anion exchange reaction between the quaternary ammonium carbonate and the acid in the production method (b) can be performed in the presence or absence of a solvent. By appropriately removing carbon dioxide produced as a by-product and, if necessary, alcohol from the reaction system, the quaternary ammonium salt (B-1) in which the anion derived from the weak acid is an organic acid ion or an inorganic acid ion of the weak acid is quantitatively obtained. can get. After the reaction, if necessary, the reaction solvent can be distilled off and used as it is, or it can be used as an aqueous solution or an organic solvent solution. As the organic solvent, methanol, ethanol, acetone, (poly) ethylene glycol, (poly) propylene glycol, γ-butyrolactone, N-methylpyrrolidone and the like can be used.

  In the anion exchange reaction between the quaternary ammonium carbonate and the acid, the amount of the acid used is preferably 0.5 to 4.0 moles with respect to 1 mole of the quaternary ammonium carbonate. It is particularly preferable to carry out the anion exchange reaction at a blending ratio such that the pH in the aqueous solution or organic solvent solution of the ammonium salt (B-1) is 6.5 to 7.5.

  In the production method (b), when the tertiary amine has one cationic nitrogen atom, the compound having p = 1 is N-polyoxyethylene-N, N-dialkylamine (alkyl is C1-24). N-polyoxypropylene-N, N-dialkylamine (alkyl is C1-24), N-polyoxyethylene-polyoxypropylene-N, N-dialkylamine (alkyl is C1-24), N-polyoxybutylene -N, N-dialkylamine (alkyl is C1-24), N-polyoxyethylene-N-alkyl-N-arylamine (alkyl is C1-24), N-polyoxypropylene-N-alkyl-N-aryl Amine (alkyl is C1-24), N-polyoxyethylene-polyoxypropylene-N-alkyl-N-arylamine ( Alkyl is C1-24), N-polyoxybutylene-N-alkyl-N-arylamine (alkyl is C1-24), N-polyoxyethylene-N, N-diarylamine (alkyl is C1-24), N -Polyoxyethylene / polyoxypropylene-N, N-diarylamine (alkyl is C1-24), N-polyoxypropylene-N, N-diarylamine (alkyl is C1-24), N-polyoxybutylene-N , N-diarylamine (alkyl is C1-24) and the like. Specifically, N-polyoxyethylene-N, N-dimethylamine, N-polyoxypropylene-N, N-dimethylamine, N-polyoxypropylene-N, N-diethylamine, N-polyoxypropylene-N , N-didodecylamine, N-polyoxypropylene-N-benzyl-N-dodecylamine, N-polyoxybutylene-N, N-dimethylamine, N-polyoxyalkylene (copolymer of ethylene and propylene)- N, N-dimethylamine, N-polyoxyethylene / polyoxypropylene-N, N-didodecylamine, N-polyoxyethylene / polyoxypropylene-N-benzyl-N-dodecylamine, N, N-dipoly Oxyethylene / polyoxypropylene-N-alkylamine (alkyl is C8-8, trade name: Esopropo Down C / 18-18, Lion Akzo Co., Ltd.), and the like.

  Examples of the compound in which p is 2 include N, N-dipolyoxyethylene-N-alkylamine (alkyl is C1-24), N, N-dipolyoxypropylene-N-alkylamine (alkyl is C1-24), N, N-di (polyoxyethylene / polyoxypropylene) -N-alkylamine (alkyl is C1-24), N, N-dipolyoxybutylene-N-alkylamine (alkyl is C1-24), N, N-dipolyoxyethylene-N-arylamine, N, N-dipolyoxypropylene-N-arylamine, N, N-di (polyoxyethylene / polyoxypropylene) -N-arylamine, N, N- Dipolyoxybutylene-N-arylamine and the like, specifically, N, N-dipolyoxyethylene-N-methylamine, N, N-dipolyoxypro Len-N-methylamine, N, N-dipolyoxypropylene-N-dodecylamine, N, N-dipolyoxypropylene-N-benzylamine, N-polyoxyethylene-N-polyoxypropylene-N-methyl Amine, N, N-dipolyoxybutylene-N-methylamine, N, N-di (polyoxyethylene / polyoxypropylene) -N-methylamine, N, N-di (polyoxyethylene / polyoxypropylene) -N-dodecylamine, N, N-di (polyoxyethylene / polyoxypropylene) -N-benzylamine and the like.

  The compound having p of 3 is N, N, N-tripolyoxyalkyleneamine (alkylene is C2-4), specifically, N, N, N-tripolyoxyethyleneamine, N, N, N-tripoly Examples thereof include oxypropyleneamine, N, N, N-tripolyoxybutyleneamine, N-polyoxyethylene-N, N-dipolyoxypropyleneamine, N, N, N-tripoly (oxyethylene / polyoxypropylene) amine and the like. It is done.

  In the production method (b), when the tertiary amine has two cationic nitrogen atoms, q is 2, and dipolyoxyalkylene dialkyl-alkylene diamine, dipolyoxyalkylene monoalkyl monoaryl-alkylene Examples thereof include diamines and dipolyoxyalkylene diaryl-alkylene diamines.

  Examples of q = 1 include tetrapolyoxyalkylene-alkylenediamine, specifically, N, N, N ′, N′-tetrapolyoxyethylene-ethylenediamine, N, N, N ′, N′—. And tetrapolyoxypropylene-ethylenediamine (trade name: Exenol FD-550 or Exenol EL-750, manufactured by Asahi Glass Co., Ltd.).

  As the quaternary ammonium salt (B-1), specifically, octylate of N, N-dipolyoxyalkylene (copolymer of ethylene and propylene) -N-methyl-N-dodecylammonium, Examples include N, N, N ′, N′-tetrapolyoxyethylene-N, N′-methyl-ethylenediammonium octylate.

  Specific examples of the quaternary ammonium salt (B-2) include N, N-dipolyoxyalkylene (copolymer of ethylene and propylene) -N-methyl-N-dodecylammonium hydroxide. It is done.

  In this invention, (B) component may be 1 type and may use 2 or more types together. Either a quaternary ammonium salt (B-1) which is a salt with an anion derived from a weak acid or a quaternary ammonium salt (B-2) which is a salt with a hydroxide ion may be used. May be used in combination.

  In the curable composition of the present invention, when the component (B) is used as a curing catalyst, the hardness of the curable composition in the initial stage after application using the curable composition is large and the composition hardens quickly. This is presumed to be because the component (B) is composed of a quaternary ammonium cation and an anion derived from a hydroxide ion or a weak acid, so that the catalytic action is high.

The cured product after curing is excellent in surface smoothness and durability. Further, the component (B) of the present invention suppresses interfacial peeling between the adherend and the curable composition. The reason why the interfacial peeling is suppressed, (B) the component - _(RO) for having ^{m R 10} group, - _(RO) as compared to the curing catalyst having no ^{m R 10} group, a curable composition This is presumably because the compatibility of the catalyst is improved, and the catalyst component is less likely to migrate from the cured product of the curable composition to the adherend interface.

  The amount of the component (B) used in the curable composition of the present invention is 100 parts by weight of the component (A). When the component (C) described later is contained, the components (A) and (C) 0.1-10 mass parts is preferable with respect to 100 mass parts of total amounts, and 0.5-5 mass parts is more preferable. When the amount of component (B) used is 0.1 parts by mass or more, curing proceeds sufficiently, and when it is 10 parts by mass or less, the strength of the curable composition is unlikely to decrease.

  When preparing the curable composition of this invention, an oxyalkylene polymer (A), (B) component and the other component as needed can be mixed.

  Or when preparing the curable composition of this invention, you may use the mixture of an oxyalkylene polymer (A) and another polymer other than that. Examples of the other polymer include an acrylic polymer (C) described later.

<Acrylic polymer (C)>
The curable composition of the present invention comprises an acrylic polymer (C) having a reactive silicon group and containing a (meth) acrylic acid alkyl ester monomer unit (hereinafter sometimes referred to as component (C)). May be included. By including the acrylic polymer (C), the adhesion to the adherend becomes better. As the reactive silicon group, those used in the oxyalkylene polymer (A) are preferably used.

Specifically, the acrylic polymer (C) preferably contains a (meth) acrylic acid alkyl ester monomer represented by the following general formula (2) as a monomer unit.
-CH = CR ²¹ OOR ²² (2)
In the formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group which may be substituted with “a hydrocarbon group other than an alkyl group”. R ²² may be a linear or branched alkyl group or an alkyl group having a cyclic structure such as a cycloalkylalkyl group. R ²² may be an alkyl group in which one or more hydrogen atoms of the alkyl group are substituted with “a hydrocarbon group other than an alkyl group” such as an aryl group.

  One or two or more types of monomers may be used as a monomer unit, or one or more types of unsaturated group-containing monomers other than the monomer may be further used as a single unit. It may be included as a body unit. The ratio of the monomer unit derived from the (meth) acrylic acid alkyl ester monomer represented by the formula (2) is preferably 50% by mass or more with respect to the entire acrylic polymer (C). It is more preferable that it is 70 mass% or more.

  Specific examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) Isobutyl acrylate, (meth) acrylic acid-tert-butyl (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid isoheptyl, (meth) acrylic acid-n-octyl 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, ( (Meth) acrylic acid dodecyl, (meth) acrylic acid tetradecyl, (meth) acrylic acid hexadecyl, (meth) a Octadecyl acrylic acid, (meth) eicosanyl acrylate, (meth) docosanyl acrylate, and (meth) Hekisakosaniru acrylate.

  The number average molecular weight Mn of the acrylic polymer (C) is preferably 500 to 100,000, more preferably 1,000 to 100,000. When the Mn of the acrylic polymer (C) exceeds 100,000, the workability tends to decrease, and when the Mn is less than 500, the physical properties after curing tend to decrease.

  When the acrylic polymer (C) is contained in the curable composition of the present invention, the content thereof is 5 to 70 with respect to 100 parts by mass of the total amount of the oxyalkylene polymer (A) and the acrylic polymer (C). It is preferable to contain a mass part, and it is more preferable to contain 20-60 mass parts. When the content ratio of the acrylic polymer (C) is 5 parts by mass or more, the effect of adding the component (C) is sufficiently obtained, and when it is 70 parts by mass or less, an appropriate viscosity of the curable composition is obtained. Is obtained and workability is good.

<Other ingredients>
In addition to the components (A) to (C) described above, the curable composition is, as necessary, an adhesion imparting agent, a curability improver, a curing accelerator, a filler, a plasticizer, and a dehydrating agent. , A thixotropic agent, and an anti-aging agent may be contained.

  Furthermore, in addition to these, the curable composition includes a surface modifier, a solvent, a modulus regulator such as a compound that generates trimethylsilanol by hydrolysis such as phenoxytrimethylsilane, a compound that cures by air such as tung oil, A compound curable by light such as methylolpropane triacrylate, an inorganic pigment such as iron oxide, chromium oxide, and titanium oxide, or an organic pigment such as phthalocyanine blue and phthalocyanine green may be contained. The use of the pigment is effective not only for coloring but also for improving the weather resistance. In addition, known flame retardants and fungicides can be added to the curable composition. It is also possible to add a matting agent used in paint applications. The curable composition is not limited to these, and may contain other additives as necessary.

(Adhesiveness imparting agent)
Specific examples of the adhesiveness-imparting agent include organic silane coupling agents such as silane having a (meth) acryloyloxy group, silane having an amino group, silane having an epoxy group, and silane having a carboxyl group; Organometallic coupling agents such as aminoethyl-aminoethyl) titanate and 3-mercaptopropyltrimethotitanate; and epoxy resins. These adhesiveness-imparting agents also have the effect of improving curability.

  Specific examples of the silane having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy. Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N- (N-vinyl) Benzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane or 3-anilinopropyltrimethoxysilane.

  Specific examples of the epoxy resin include bisphenol A-diglycidyl ether type epoxy resin, bisphenol F-diglycidyl ether type epoxy resin, tetrabromobisphenol A-glycidyl ether type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy. Resin, glycidyl ether type epoxy resin of bisphenol A-propylene oxide adduct, glycidyl 4-glycidyloxybenzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl ester epoxy resin, m-aminophenol Epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, N, N-diglycidylaniline, N, N-diglycidyl-o- Toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols (glycerin.), Hydantoin type epoxy resin or an unsaturated polymer (petroleum resin.) Epoxy resin.

  When adding the said silane coupling agent to a curable composition, the addition amount is 0.01-30 mass parts with respect to 100 mass parts of total amounts of an oxyalkylene polymer (A) and an acrylic polymer (C). Preferably there is.

  When adding the said epoxy resin to a curable composition, the addition amount is 100 mass parts or less with respect to 100 mass parts of total amounts of an oxyalkylene polymer (A) and an acrylic polymer (C), and 10-80 Part by mass is more preferable.

(Curability improver)
In the present invention, if necessary, a curability improving agent can be used in combination. As the curability improving agent, a germanium compound described in Japanese Patent No. 4481105 and a fluorinating agent described in Japanese Patent Application Laid-Open No. 2010-65073 can be used.

(filler)
Specific examples of the filler include heavy calcium carbonate having an average particle diameter of 1 to 20 μm, light calcium carbonate having an average particle diameter of 1 to 3 μm manufactured by a precipitation method, and colloidal carbonate whose surface is treated with a fatty acid or a resin acid organic material. Calcium carbonate such as calcium and light calcium carbonate; fumed silica; precipitated silica; surface silicone-treated silica fine powder; anhydrous silicic acid; hydrous silicic acid; carbon black; magnesium carbonate; diatomaceous earth; Titanium oxide; Bentonite; Ferric oxide; Zinc oxide; Active zinc white; Shirasu balloon, Perlite, Glass balloon, Silica balloon, Fly ash balloon, Alumina balloon, Zirconia balloon, Carbon balloon and other inorganic hollow bodies; Phenol resin balloon , Epoxy resin balloon, urea resin balloon Organic resin hollow bodies such as plastics, polyvinylidene chloride resin balloons, polyvinylidene chloride-acrylic resin balloons, polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, styrene-acrylic resin balloons, polyacrylonitrile balloons; resin beads, wood powder Powder fillers such as pulp, cotton chips, mica, walnut flour, rice flour, graphite, fine aluminum powder, flint powder; fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber, polyethylene fiber Is mentioned. These fillers may be used alone or in combination of two or more.

  Among these, calcium carbonate is preferable, and it is particularly preferable to use heavy calcium carbonate and colloidal calcium carbonate in combination.

  Moreover, it is preferable to use a hollow body as a filler from the point which can lighten a curable composition and its hardened | cured material. In addition, by using a hollow body, it is possible to improve the workability by improving the stringiness of the composition. The hollow body may be used alone or in combination with other fillers such as calcium carbonate.

  Silica is preferred when it is desired to have transparency, thixotropy and moderate viscosity. Although the curable composition of the present invention is a composition that does not use a tin-based catalyst, since it has little coloration that has been a problem with conventional non-tin catalysts, it is a non-tin catalyst and a filler for applications that require transparency. As silica, silica is effective. Silica includes hydrophilic silica and hydrophobic silica in which the number of silanol groups on the surface of the silica is adjusted by surface treatment.

  In order to maintain good workability and storage stability, it is preferable to use hydrophilic silica.

  Although the usage-amount of a silica is not specifically limited, When (A) component and a plasticizer and (C) component are used, it is 10 mass parts or more and 50 mass parts with respect to 100 mass parts of total amounts which further added (C) component. It is preferably contained in the following proportion, more preferably 20 parts by mass or more and 40 parts by mass or less. Less than 10 parts by mass is not preferable because the reinforcing effect is small and the thixotropy is also poor. If it exceeds 50 parts by mass, the viscosity is high and the extrusion property is poor, which is not preferable.

  Hydrophobic silica can be used as long as good workability and storage stability are maintained. The amount of hydrophobic silica that can be used safely is less than 30 parts by weight per 100 parts by weight of the oxyalkylene polymer (A). It is preferably 15 parts by weight or less, more preferably 5 parts by weight or less, and most preferably not used. If it is used in an amount of 30 parts by weight or more, the viscosity of the curable composition will increase significantly during storage, such being undesirable.

  In addition, silica described in JP 2010-65073 A can also be used.

(Curing accelerator)
The curable composition of the present invention does not contain a curing accelerator, and a good curing rate can be obtained. Therefore, the curing composition may be substantially free of a curing accelerator. When used, the curing rate can be further improved.

  As a hardening accelerator, a tin compound is mentioned, for example. As tin compounds, divalent tin compounds such as tin 2-ethylhexanoate, tin naphthenate and tin stearate; dialkyltin dicarboxylates and dialkoxy such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin monoacetate and dibutyltin malate Organotin carboxylates such as tin monocarboxylate, tin chelate compounds such as dialkyltin bisacetylacetonate and dialkyltin monoacetylacetonate monoalkoxide, reaction products of dialkyltin oxide and ester compounds, dialkyltin oxide and alkoxysilane compounds And tetravalent tin compounds such as dialkyltin dialkyl sulfide.

  Examples of tin chelate compounds include dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, dibutyltin monoacetylacetonate monoalkoxide, and the like.

  Examples of the reaction product of the dialkyltin oxide and the ester compound include tin compounds in which dibutyltin oxide and a phthalic acid ester such as dioctyl phthalate or diisononyl phthalate are mixed by heating and reacted to form a liquid. In this case, as the ester compound, aliphatic and aromatic carboxylic acid esters other than phthalic acid esters, tetraethyl silicate and partial hydrolysis condensates thereof can be used. Further, compounds obtained by reacting or mixing these tin compounds with low-molecular alkoxysilanes or the like can also be preferably used.

  In addition to tin compounds, curing accelerators include acidic compounds such as phosphoric acid, p-toluenesulfonic acid, phthalic acid, di-2-ethylhexyl phosphate; butylamine, hexylamine, octylamine, decylamine, laurylamine, N, Aliphatic monoamines such as N-dimethyl-octylamine, aliphatic polyamine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, amine compounds such as aromatic amine compounds and alkanolamines, organic titanate compounds Is mentioned.

  In addition to the compounds described above, a carboxylic acid may be used in combination as a catalyst within a range that does not affect the quaternary ammonium salt of the present application. As the carboxylic acid, carboxylic acids described in WO2006 / 070673 and JP-A-2007-131798 can be used.

  Furthermore, carboxylic acid metal salts can also be used.

  Examples of the carboxylic acid metal salt include compounds described in WO 2006/07070637 and bismuth carboxylate.

  Examples of the carboxylic acid having an acid group of the carboxylic acid metal salt include various carboxylic acids exemplified in the above carboxylic acid.

(Plasticizer)
Plasticizers include phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate and isononyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate Alcohol esters such as pentaerythritol esters; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxy stearate; Chlorinated paraffins; polyester plasticizers such as polyesters obtained by reacting dibasic acids with dihydric alcohols; polyoxypropylene glycol and its derivatives, such as the hydroxyl group of polyoxypropylene glycol Polyethers such as those sealed with poly, α-methylstyrene, polystyrene oligomers such as polystyrene, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, epoxidized polybutadiene, etc. And high molecular plasticizers such as oligomers. These plasticizers can be used in combination of two or more different types such as phthalate ester and epoxy plasticizer.

(Dehydrating agent)
In order to further improve the storage stability, a small amount of a dehydrating agent can be added to the curable composition as long as it does not adversely affect the curability and flexibility. Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate and ethyl orthoformate, alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane and tetraethoxysilane. Examples include hydrolyzable organic silicon compounds and hydrolyzable organic titanium compounds. Among these, vinyltrimethoxysilane or tetraethoxysilane is particularly preferable from the viewpoint of cost and effect. In particular, when the curable composition is handled as a product known as a one-component combination type filled in a moisture-proof container in a state containing a curing accelerator, it is effective to use this dehydrating agent.

(Thixotropic agent)
By including the thixotropic agent, the sagging property of the curable composition is improved. Examples of the thixotropic agent include hydrogenated castor oil and fatty acid amide, and any amount thereof is used.

(Anti-aging agent)
As the anti-aging agent, generally used antioxidants, ultraviolet absorbers or light stabilizers can be appropriately used. Specifically, hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus, or sulfur compounds can be appropriately used as the antioxidant. In particular, it is preferable to use a combination of two or all selected from the group consisting of a light stabilizer, an antioxidant, and an ultraviolet absorber because they are effective as a whole taking advantage of their respective characteristics. Specifically, it is preferable to combine a tertiary or secondary hindered amine light stabilizer, a benzotriazole ultraviolet absorber, a hindered phenol type and / or a phosphite type antioxidant.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[Production example]
An oxyalkylene polymer, a quaternary ammonium salt having a — (RO) _m R ¹⁰ group, and an acrylic polymer were prepared as follows. In the following production examples, the synthesis reaction was performed using a pressure-resistant reaction vessel equipped with a nitrogen introduction tube and a stirring device and capable of adjusting the internal temperature.

(Production of quaternary ammonium salt Q1)
Chemical formula in a stirring autoclave:

(R ′ is an alkyl group having 8 to 18 carbon atoms, x, y, z, and w are each a positive integer, x + y + z + w = 16) N, N-di (polyoxyethylene / polyoxypropylene) -N— Alkylamine (trade name: Esopropomine C / 18-18, manufactured by Lion Akzo, the total number of moles of oxyethylene / oxypropylene added is 16 per molecule, alkyl is C8-18 alkyl) (1 mole), carbonic acid Dimethyl (4 mol) and methanol (4 mol) as a solvent were added, and reacted at a reaction temperature of 120 ° C. for 30 hours, and N, N-dipolyoxyalkylene (copolymer of ethylene and propylene) -N-alkyl-N— A methanol solution of methylammonium methyl carbonate was obtained.

  N, N-dipolyoxyalkylene (copolymer of ethylene and propylene) -N-alkyl-N-methylammonium · by adding octylic acid (1 mol) to this product and removing by-product carbon dioxide and methanol Octylate (quaternary ammonium salt (Q1)) was obtained.

(Production of quaternary ammonium salt Q2)
N, N, N ′, N′-tetrapolyoxypropylene-ethylenediamine (trade name: FD-550 / Asahi Glass Co., Ltd.) (1 mol), dimethyl carbonate (12 mol) obtained by adding 12 PO to ethylenediamine in a stirring autoclave 4 mol) and methanol (5 mol) as a solvent, and reacted at a reaction temperature of 120 ° C. for 30 hours, followed by N, N, N ′, N′-tetrapolyoxypropylene-N, N′-methyl-ethylenediammonium A methanol solution of dimethyl carbonate was obtained.

  N, N, N ′, N′-tetrapolyoxypropylene-N, N′-methyl-ethylenediammonium octyl is prepared by adding octylic acid (2 mol) to this product and removing the by-product carbon dioxide and methanol. An acid salt (quaternary ammonium salt (Q2)) was obtained.

(Production of quaternary ammonium salt Q3)
N, N, N ′, N′-tetrapolyoxypropylene-ethylenediamine (trade name: 750ED / manufactured by Asahi Glass Co., Ltd.) (1 mol), dimethyl carbonate (4 mol) in which 4 POs are added to ethylenediamine in a stirring autoclave ) And methanol (5 mol) as a solvent, and reacted for 30 hours at a reaction temperature of 120 ° C. N, N, N ′, N′-tetrapolyoxypropylene-N, N′-methyl-ethylenediammonium dimethyl carbonate A methanol solution was obtained.

  N, N, N ′, N′-tetrapolyoxypropylene-N, N′-methyl-ethylenediammonium octyl is prepared by adding octylic acid (2 mol) to this product and removing the by-product carbon dioxide and methanol. An acid salt (quaternary ammonium salt (Q3)) was obtained.

(Production of quaternary ammonium salt Q4)
A stirred autoclave was charged with didecylmethylamine (1 mol), dimethyl carbonate (2 mol) and methanol (2.0 mol) as a solvent and reacted at a reaction temperature of 120 ° C. for 12 hours to give N-dimethyldidecylammonium methyl carbonate. A methanol solution was obtained. Octyl acid (1 mol) was charged into this product, and by-product carbon dioxide gas and methanol were removed to obtain dimethyldidecylammonium octylate (quaternary ammonium salt (Q4)).

(Production of quaternary ammonium salt Q5)
Dialkylmethylamine having an alkyl group having 14 to 18 carbon atoms (trade name: Armin M2O, manufactured by Lion Akzo) (1 mol), dimethyl carbonate (2 mol) and methanol (2.0 mol) as a solvent in a stirring autoclave. Mol) was prepared and reacted at a reaction temperature of 120 ° C. for 12 hours to obtain a methanol solution of N-dimethyldialkyl (C = 14-18) ammonium methyl carbonate. Octylic acid (1 mol) was added to this product, and by-product carbon dioxide and methanol were removed to obtain dimethyldialkyl (C = 14-18) ammonium octylate (quaternary ammonium salt (Q5)). .

  Table 1 shows the curing catalysts used in the examples. Q1 to Q3 correspond to the quaternary ammonium salt (B) in the present invention, but Q4 and Q5 do not correspond.

(Production Example 1: Production of polymer (A1))
Polyoxypropylene triol (Mn1000) is used as an initiator, and propylene oxide (hereinafter referred to as “PO”) is reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to give Mn of 17000 and Mw / Mn of 1. 4 polyoxypropylene triol (polymer (pP-1)) was obtained. To this polyoxypropylene triol (polymer (pP-1)), a methanol solution containing sodium methoxide in an amount of 1.05 mol per mol of hydroxyl group in polyoxypropylene triol was added. After heating to 120 ° C. under reduced pressure to distill off methanol, the polyoxypropylene triol hydroxyl group was changed to sodium alkoxide, and then 1.05 moles of allyl chloride was added to the added sodium methoxide. And reacted.

After removing unreacted allyl chloride, the by-produced inorganic salt was removed to obtain an allyl group-terminated oxypropylene polymer having a viscosity of 7.0 Pa · s (25 ° C.).
Further, this oxypropylene polymer having an allyl group terminal is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 75 mol% of the allyl group to a methyldimethoxysilyl group terminal (A). (Hereinafter referred to as “oxyalkylene polymer (A1)”).

  The viscosity of the obtained oxyalkylene polymer (A1) was 9.0 Pa · s (25 ° C.), Mn was 17000, and Mw / Mn was 1.4.

(Production Example 2: Production of polymer (A2))
In this example, a polymer (A2) was produced by a method in which an isocyanate compound was urethanized with a polymer having a polyoxyalkylene chain and a hydroxyl group.

  PO is reacted with propylene glycol in the presence of a zinc hexacyanocobaltate-tertiary butyl alcohol complex catalyst to give a number average molecular weight (Mn) of 15000 and a molecular weight distribution (Mw / Mn) of 1.2. Of polyoxypropylene diol (polymer (pP-2)) was obtained.

  The polymer (pP-2) was placed in a pressure-resistant reactor (internal volume 5 L) and dehydrated under reduced pressure while maintaining the internal temperature at 110 ° C. Next, while replacing the atmosphere in the reactor with nitrogen gas and maintaining the internal temperature at 50 ° C., the organotin compound catalyst Neostan U-860 containing a sulfur atom in the ligand as a urethanization catalyst (manufactured by Nitto Kasei Co., Ltd.) ) Was added at about 80 ppm with respect to pP-2 and stirred, and then 3-isocyanatopropyltrimethoxysilane (purity 95%) was added so that NCO / OH was 0.97. Next, the internal temperature is maintained at 80 ° C. for 8 hours, the polymer (pP-2) and 3-isocyanatopropyltrimethoxysilane are urethanated, and the isocyanate peak disappears in FT-IR. After confirmation, the mixture was cooled to room temperature to obtain an oxypropylene polymer having a trimethoxysilyl group at the terminal (hereinafter referred to as “polymer (A2)”).

  Mn of the obtained polymer (A2) was 15,500, and Mw / Mn was 1.2.

(Production Example 3: Production of polymer mixture (A1 · C1))
In this example, an unsaturated group-containing monomer constituting the acrylic polymer (C) is polymerized in the presence of the polymer (A1) obtained in Production Example 1, and the polymer (A1) and the acrylic polymer are polymerized. A polymer mixture (A1 · C1) containing the coalescence (C1) was produced.

  140 g of the polymer (A1) was put in a pressure-resistant reactor equipped with a stirrer, and the temperature was raised to about 67 ° C. While maintaining the internal temperature of the reaction vessel at about 67 ° C. and stirring in a nitrogen atmosphere, 72 g of methyl methacrylate, 6.5 g of acrylate-n-butyl, 29.0 g of methacrylic acid-n-butyl, 3-methacryloyloxypropyltri A predetermined amount of a monomer selected from 15.0 g of ethoxysilane and 14.0 g of normal dodecyl mercaptan, and 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name: V65, manufactured by Wako Pure Chemical Industries, Ltd.) Polymerization is performed by dropping 2.5 g of the mixed solution into the polymer (A1) over 8 hours, and in the presence of the polymer (A1), the polymer (A1) has a triethoxysilyl group as a reactive silicon group (meta ) An acrylate copolymer (hereinafter referred to as “acrylic polymer (C1)”) was synthesized. The “polymer mixture (A1 · C1) containing polymer (A1) and acrylic polymer (C1)” thus obtained was dissolved in hexane, centrifuged, extracted, and the acrylic polymer ( The number average molecular weight (Mn) of C1) was measured and found to be 4,000.

[Examples 1-8 and Comparative Examples 1-7]
Using each of the components produced in the above production examples and the following commercially available components, curable compositions were prepared with the formulations shown in Tables 2 to 4, and the characteristics were evaluated. The unit of the blending ratio shown in the table is “part by mass”. Moreover, in Example 8 and Comparative Example 7, the blending amount of the polymer mixture (A1 · C1) is 100 parts by mass, and the total amount of the polymer A1 and the acrylic polymer C1 is 100 parts by mass.

<Filler>
・ White gloss flower CCR (product name), surface treated calcium carbonate, manufactured by Shiroishi Kogyo Co., Ltd.
・ Whiteon SB (product name), heavy calcium carbonate, manufactured by Shiraishi Calcium.
・ R820 (product name), titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.
<Plasticizer>
-Exenol 3020 (EL3020) (product name), polypropylene glycol, manufactured by Asahi Glass Co., Ltd.
<Thixotropic agent>
・ Dispalon 6500 (product name), hydrogenated castor oil, manufactured by Enomoto Kasei Co., Ltd.
<Toner>
・ HAMATITE Super II Dark Gray (product name), manufactured by Yokohama Rubber Co., Ltd.
<Stabilizer>
・ Irganox 1010 (product name), hindered phenol antioxidant, manufactured by BASF Corporation.
-Tinuvin 326 (product name), benzotriazole ultraviolet absorber, manufactured by BASF.
-Tinuvin 765 (product name), hindered amine light stabilizer, manufactured by BASF.
<Dehydrating agent>
-KBM-1003 (product name), vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
<Adhesive agent>
* KBM-603 (product name), N-aminoethyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
-KBM-403 (product name), 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
<Catalyst>
Organic tin catalyst: EXCESTAR C10 (product name), dibutyltin monoacetate, manufactured by Asahi Glass Co., Ltd.

(Examples 1-5, Comparative Examples 1-7)
One-component curable composition with the composition shown in Tables 2 and 3, using the polymers (A1 to A2) or (A1 · C1), the compounds (Q1) to (Q5), ethylenediamine and organotin catalyst as the curing catalyst The thing was manufactured. The blending amount of the polymer mixture (A1 · C1) in Tables 1 and 2 is the total amount of the polymer (A1) and the acrylic polymer (A1).

  First, a filler, a plasticizer, a thixotropic agent, a toner and a stabilizer were added to the polymer and stirred with a planetary stirrer (manufactured by Kurabo Industries). The temperature of the mixture was lowered to room temperature to obtain a more uniform mixture with three rolls.

  Next, a dehydrating agent and an adhesion-imparting agent were added and stirred. Then, the quantity shown in Tables 2-4 was added and stirred for the curing catalyst, and the curable composition was obtained.

[Evaluation]
(H type test / standard curing)
In order to confirm the adhesiveness with the adherend, an H-type test specimen was prepared by a method based on JIS A5758 using the curable composition obtained in each example. As the adherend, surface anodized aluminum was used. After preparing the specimen, it was cured for 7 days at 23 ° C. and 50% humidity, and then cured for 7 days at 50 ° C. and 65% humidity. Furthermore, it was left to stand for 24 hours or more at 23 ° C. and 50% humidity to obtain a cured product.

The obtained test piece (cured product) has a stress (M50, unit: N / mm ² ) and a maximum tensile stress (maximum point cohesive force, unit: N / mm) when stretched by 50% using a Tensilon tester. ² ), the amount of elongation at break (maximum point elongation, unit:%) was measured. After the test, the fracture form of the test piece (cured product) was visually confirmed. It means that adhesiveness with a to-be-adhered body is so favorable that there are few interface peeling of hardened | cured material and a to-be-adhered body, and the cohesive failure rate of hardened | cured material is high.
The results are shown in Tables 2-4.
As a method for determining adhesiveness in standard curing, A: the cohesive failure rate was 70% or more, and B: the cohesive failure rate was less than 70%.

(H type test / water resistant curing)
In order to confirm the adhesiveness with the adherend, an H-type test specimen was prepared by a method based on JIS A5758 using the curable composition obtained in each example. As the adherend, surface anodized aluminum was used. After preparing the specimen, it was cured for 7 days at 23 ° C. and 50% humidity, and then cured for 7 days at 50 ° C. and 65% humidity. Further, it was cured in water (23 ° C.) for 7 days to obtain a cured product.

The obtained test piece (cured product) has a stress (M50, unit: N / mm ² ) and a maximum tensile stress (maximum point cohesive force, unit: N / mm) when stretched by 50% using a Tensilon tester. ² ), the amount of elongation at break (maximum point elongation, unit:%) was measured. After the test, the fracture form of the test piece (cured product) was visually confirmed. It means that adhesiveness with a to-be-adhered body is so favorable that there are few interface peeling of hardened | cured material and a to-be-adhered body, and the cohesive failure rate of hardened | cured material is high.
The results are shown in Tables 2-4.

  As a method for determining adhesiveness in water-resistant curing, A: the cohesive failure rate was 50% or more, and B: the cohesive failure rate was less than 50%.

(Dumbell test / standard curing)
A test piece made of a cured product of the curable composition obtained in each example was prepared, and a tensile test was performed. The tensile test was performed according to JIS K6251.

Specifically, the curable composition was formed into a sheet having a thickness of 2 mm, cured for 7 days at 23 ° C. and 50% humidity, and then cured for 7 days at 50 ° C. and 65% humidity. Furthermore, it was left to stand for 24 hours or more at 23 ° C. and 50% humidity to obtain a cured product. The obtained sheet-like cured product was punched into a No. 3 dumbbell shape to obtain a test piece. After measuring the thickness of the test piece, using a Tensilon tester, the stress at 50% elongation (M50, unit: N / mm ² ), maximum tensile stress (Tmax, unit: N / mm ² ), fracture The amount of elongation at the time (E, unit:%) was measured. The results are shown in Tables 2-4.

As shown in Table 2, the curable composition using the quaternary ammonium salt of the present invention has a standard curing and a maximum point cohesive force of 1.0 N / mm ² or more by the H-type test, and a cohesive failure rate of 70. %, The adhesiveness is good. Moreover, also in water-resistant curing, a cohesive failure rate is 50% or more, and adhesiveness is favorable.

As shown in Table 3, the curable compositions of Comparative Examples 1 to 4 using a curing catalyst containing no-(RO) _m R ¹⁰ groups have a standard curing and a maximum point cohesion of 1.0 N according to the H-type test. / Mm ² and the cohesive failure rate is 50% or less, and the adhesiveness is poor.

The curable composition of Comparative Example 5 has a standard curing and a maximum point cohesion force of 1.2 N / mm ² in the H-type test, but the maximum point cohesion force is lower than that of Example 8 and the cohesive failure rate is 50% or less. And poor adhesion.

As shown in Table 4, Comparative Examples 6 to 7 are standard curing, the maximum point cohesive force by the H-type test is 1.0 N / mm ² or more, and the cohesive failure rate is 100%, but an organotin catalyst is used. Therefore, it contains organotin, which is not preferable in terms of the environment.

  According to the present invention, it contains a polymer having a reactive silicon group as a curing component, does not contain an organometallic compound that is expensive and requires strict management regarding discharge and disposal, and adheres to an adherend. Can be used as an adhesive or a sealing agent.

Claims (14)

An oxyalkylene polymer (A) having a reactive silicon group in which a hydroxyl group or a hydrolyzable group is bonded to a silicon atom, and
-(RO) _m R ¹⁰ group (R is an alkylene group having 2 to 4 carbon atoms, m is an integer of 1 or more, R ¹⁰ represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, provided that m is 2 or more. In which case R may be the same or different from each other), and a quaternary ammonium salt (B) comprising a quaternary ammonium cation having a hydroxide ion or an anion derived from a weak acid,
A curable composition comprising: The quaternary ammonium cation in the quaternary ammonium salt (B) has 1 to 3 cationic nitrogen atoms and — (RO) _m R ¹⁰ group bonded to at least one of the cationic nitrogen atoms. The curable composition according to claim 1. The quaternary ammonium salt (B) has one cationic nitrogen atom, and the cationic nitrogen atom is selected from the group consisting of p (p represents an integer of 1 to 3) alkyl group and aryl group. At least one (when p is 2 or 3, the groups selected from the group consisting of the alkyl group and aryl group may be the same or different from each other), and (4-p)-(RO) _m The curable composition according to claim 1 or 2, which is bonded to an R ¹⁰ group (when p is 1 or 2, the groups may be the same or different from each other). Two alkyl groups are bonded to the cationic nitrogen atom, one of the two alkyl groups is an alkyl group having 6 to 24 carbon atoms, the other is an alkyl group having 5 or less carbon atoms, and m is 1 The curable composition according to claim 3, which is an integer of ˜40 and R ¹⁰ is a hydrogen atom. The quaternary ammonium salt (B) has two cationic nitrogen atoms bonded via an alkylene group, and q (q represents an integer of 1 or 2) each of the cationic nitrogen atoms. At least one selected from the group consisting of an alkyl group and an aryl group (when q is 2, the alkyl group may be the same or different from each other) and (3-q)-(RO) _m R ¹⁰ groups (When q is 1, the groups may be the same or different from each other) are bonded to each other (provided that two of the cationic nitrogen atoms to which the three groups are bonded are the same or different from each other). The curable composition according to claim 1 or 2. The alkylene group is an ethylene group, q is 1, the alkyl group is an alkyl group having 5 or less carbon atoms, m is an integer of 1 to 40, and R ¹⁰ is a hydrogen atom. Curable composition. When m is 1 — (RO) _m R ¹⁰ group is a 2-hydroxyethyl group or 2-hydroxypropyl group, and when m is 2 or more (RO) _m is a polyoxyethylene group, a polyoxypropylene group or a polyoxyethylene group The curable composition according to any one of claims 1 to 6, which is an (oxyethylene-oxypropylene) group. When m is 1 — (RO) _m R ¹⁰ group is a 2-hydroxypropyl group, and when m is 2 or more (RO) _m is a polyoxypropylene group or a polyoxypropylene group having a proportion of 60 mol% or more. The curable composition according to any one of claims 1 to 6, which is an (oxyethylene-oxypropylene) group.   The curable composition according to any one of claims 1 to 8, wherein the weak acid providing an anion in the quaternary ammonium salt (B) is an acid having an acid dissociation constant pKa of 1 to 10.   The curable composition according to claim 9, wherein the weak acid that gives an anion in the quaternary ammonium salt (B) is a carboxylic acid. The reactive silicon group is a group represented by the following formula (1) (provided that the silicon atom of the group is bonded to the carbon atom of the oxyalkylene polymer (A)). The curable composition according to item 1.
-SiX ¹ _a (R ¹¹ ) _3-a (1)
[R ^{11 is a} monovalent hydrocarbon group having 1 to 20 carbon atoms, X ¹ is a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3. However, R ¹¹ when (3-a) is 2 may be the same or different, and X ¹ when a is 2 or 3 may be the same or different. ]   The curable composition according to any one of claims 1 to 11, wherein the polymer (A) has a urethane bond.   The usage method which uses the curable composition of any one of Claims 1-12 as an adhesive agent or a sealing agent.   The adhesive agent or sealing agent containing the curable composition of any one of Claims 1-12.