JP2008308521A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition having excellent adhesiveness and elongation characteristic. <P>SOLUTION: This curable composition contains: a polymer (P) obtained by converting some or all of hydroxy groups to a group (S1) having a hydrolytic silicon radical by modifying polyoxyalkylene poly(mono)ol (p), the hydroxy group number of which is one or more; a chemical compound (A), which has an aliphatic heterocycle containing two nitrogen atoms, a univalent radical containing primary amino group or a univalent radical containing secondary amino bond being coupled to one of the two nitrogen atoms constituting the aliphatic heterocycle; and a chemical compound (B), which has a radical reacting with the primary amino group or the secondary amino bond in the chemical compound (A) and has a hydrolytic silicon radical. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition that is cured by hydrolysis and crosslinking reaction of a hydrolyzable silicon group in the presence of moisture.

A polymer having a hydrolyzable silicon group at the terminal of a polyoxyalkylene chain has a moisture curable property, a cured product has rubber elasticity, and the like, and therefore, an adhesive composition, a coating composition, and a sealing composition. It is used for curable compositions such as products (see Patent Document 1).
In particular, a polymer using trialkoxysilyl groups as the hydrolyzable silicon groups has a fast curing speed and a high crosslinking density, so that it is a fast-curing adhesive composition, coating composition, sealing material composition, etc. (See Patent Document 2).
In a curable composition used for a sealing material, an adhesive, and the like, it is known to add an adhesiveness imparting agent together with a curing catalyst in order to improve adhesiveness. In general, amino group-substituted alkoxysilanes (hereinafter sometimes referred to as “aminosilanes”) are known as adhesion-imparting agents suitable for curable compositions containing a polymer having a hydrolyzable silicon group. (For example, the following patent documents 3 to 5).
In addition, addition of a tin-based catalyst such as dibutyltin laurate to a polymer in which a trialkoxysilyl group is bonded to the polyoxyalkylene chain end via a urethane bond adds amino group-substituted alkoxysilanes to provide storage stability. Is described as being improved. (See Patent Document 6).
Japanese Patent Laid-Open No. 03-072527 Japanese Unexamined Patent Publication No. 03-047825 Japanese Patent No. 3161545 International Publication No. 00/56818 Pamphlet Japanese Patent Publication No. 5-40782 Japanese Patent No. 334604 (Japanese Patent Laid-Open No. 10-245482)

When aminosilane is added to a curable composition containing a polymer in which a hydrolyzable silicon group is bonded to a polyoxyalkylene chain via a urethane bond, adhesion occurs as described in Patent Documents 3 to 5. Although the properties are improved, the elongation properties, which are mechanical properties, are lowered.
This invention is made | formed in view of the said situation, and it aims at providing the curable composition excellent in the elongation characteristic while having favorable adhesiveness.

In the curable composition of the present invention, a part or all of the hydroxyl groups are represented by the following formula (1) by modifying the polyoxyalkylene poly (mono) ol (p) having 1 or more hydroxyl groups. A polymer (P) converted into a hydrolyzable silicon group (S1), an aliphatic heterocyclic ring containing two nitrogen atoms, and the two nitrogen atoms constituting the aliphatic heterocyclic ring And a compound (A) in which a hydrogen atom is bonded to one of them, and a monovalent group containing a primary amino group or a monovalent group containing a secondary amino bond is bonded to the other; A) a compound having a group that reacts with a primary amino group or a secondary amino bond in A) and a hydrolyzable silicon group represented by the following formula (1): To do.
-SiX _a R ¹ _3-a (1)
(In the formula, X represents an alkoxy group having 1 to 6 carbon atoms, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding an alkoxy group), and a It represents an integer of 1-3. However, may be different or a plurality of R ¹ is each independently when R ¹ there are a plurality, the plurality of X may be the same or different when X there are multiple .)

  According to the curable composition of the present invention, a cured product having good adhesiveness and excellent elongation characteristics can be obtained.

In the present invention, the number average molecular weight (Mn) means a number average molecular weight (Mn) converted on the basis of standard polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase. Moreover, a mass average molecular weight (Mw) means the mass average molecular weight (Mw) measured by the same GPC <Curable composition>
The curable composition of the present invention comprises a polymer (P), a compound (A) and a compound (B), and if necessary, a curing catalyst (C) and other additives (plasticizer, dehydrating agent, filling) Agent, anti-aging agent, coloring agent, thixotropic agent, etc.).
[Polymer (P)]
In the polymer (P), a part or all of the hydroxyl groups are hydrolyzable by modifying polyoxyalkylene poly (mono) ol having 1 or more hydroxyl groups (hereinafter referred to as polyol (p)). It is a polymer converted into a group (S1) having a silicon group. In the present specification, “poly (mono) ol” represents “monool or polyol”.
The polymer (P) may have a hydroxyl group that is not converted to the group (S1). A polymer (P) may be used individually by 1 type, and may use 2 or more types together.

[Group having hydrolyzable silicon group (S1)]
The hydrolyzable silicon group in the group (S1) is a group represented by the above formula (1).
X in the formula (1) represents an alkoxy group having 1 to 6 carbon atoms. Specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, or a hexyloxy group is preferable, and a methoxy group is more preferable. preferable.
R ¹ in Formula (1) represents a monovalent organic group having 1 to 20 carbon atoms which may have a substituent. However, R ¹ is not an alkoxy group. R ¹ is preferably an alkyl group having 8 or less carbon atoms, a fluoroalkyl group having 8 or less carbon atoms, or a phenyl group, and is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, or a phenyl group. It is more preferable.
A in formula (1) represents an integer of 1 to 3. In the group represented by formula (1), when a plurality of Xs are present, the plurality of Xs may be the same as or different from each other. Further, a plurality of R ¹ may be the same or different from each other when R ¹ there are a plurality.

In the above formula (1), it is preferable that a is 3 in terms of fast curing of the curable composition. That is, a group represented by the following formula (1-1) is more preferable.
-SiX ₃ (1-1).
Three Xs in the above formula (1-1) are synonymous with X in the above formula (1), including preferred embodiments thereof. The three Xs in the formula (1-1) may be the same group or different groups. It is preferable that they are the same groups.

Hereinafter, the group represented by the formula (S10) is referred to as a group (S10). Groups represented by other formulas are also described in the same manner. Moreover, the compound represented by a formula (S11) is described as a compound (S11). The compounds represented by other formulas are also described in the same manner.
The group (S1) having a hydrolyzable silicon group is, for example, the following groups (S10), (S20), and (S30) according to the modification method described later.
^{-O-A 1 -R 11 -CH (} R 12) CH (R 13) -A 2 -R 01 -SiX a R 1 3-a ··· (S10),
—O—C (O) NH—R ⁰² —SiX _a R ¹ _3-a (S20),
—O—C (O) NH—R ³¹ —A ³ —R ⁰³ —SiX _a R ¹ _3-a (S30).

X, R ¹ and a are the same as those in formula (1) including preferred embodiments.
A ¹ is a single bond, —C (O) —, —C (O) O—, or —C (O) NH—.
R ¹¹ is a single bond or a divalent organic group (—CH ₂ —, —CH ₂ CH ₂ —OC (O) —, etc.).
R ¹² and R ¹³ are a hydrogen atom or a monovalent organic group (such as —CH ₃ ).
A ² is a single bond or —S—.
R ⁰¹ is a single bond or a divalent organic group. The divalent organic group is preferably a divalent organic group having 1 to 17 carbon _atoms, -CH 2 _CH 2 CH ₂ - is more preferable.
R ⁰² and R ⁰³ are a divalent organic group, preferably a C 1-17 divalent organic group, more preferably —CH ₂ — or —CH ₂ CH ₂ CH ₂ —. In particular, when a is 2, it is preferable that R ⁰² is a methylene group from the viewpoint of fast curing of the curable composition.
R ³¹ is a divalent organic group (an alkylene group, a cycloalkylene group, an arylene group, etc.).
A ³ represents —NHC (O) O—, —NHC (O) NH—, —NHC (O) N (R ³² ) —, —NHC (O) OC (O) — or —NHC (O) S—. It is.
R ³² is a monovalent organic group (an alkyl group, a cycloalkyl group, an aryl group, etc.).

[Polyol (p)]
The polyol (p) used for the production of the polymer (P) is a poly (mono) ol having a polyoxyalkylene chain in the main chain. The polyol (p) may have a structure other than the polyoxyalkylene chain (for example, a structure derived from an initiator). The proportion of the total of the polyoxyalkylene chains in the entire polymer (P) is preferably 50% by mass or more, and more preferably 80% by mass or more.
The number of hydroxyl groups in the polyol (p) is 1 or more, preferably 2-8. When the number of hydroxyl groups is 2 to 8, the adhesiveness and curability to the adherend in the curable composition are good. As the polyol (p), one type may be used, or two or more types may be used. In order to obtain a balance between elongation and strength of the cured product, it is preferable to use polyoxypropylene diol and / or polyoxypropylene triol as the polyol (p). When the number of hydroxyl groups is 1, the viscosity of the curable composition and the elastic modulus of mechanical properties can be lowered. Therefore, it is preferably used in combination with a polyol having 2 to 8 hydroxyl groups.
The number average molecular weight (Mn) per hydroxyl group of the polyol (p) is preferably 1000 to 30000, more preferably 3000 to 20000.
The hydroxyl value of the polyol (p) is preferably 1 to 30 mgKOH / g, more preferably 5 to 20 mgKOH / g.

As the polyol (p), poly (mono) ol obtained by ring-opening polymerization reaction of a cyclic ether using a polymerization catalyst in the presence of an initiator is preferable.
(Initiator)
Examples of the initiator include compounds having one or more active hydrogen atoms in one molecule.
The compound having an active hydrogen atom is preferably an organic compound having an active hydrogen atom, more preferably a compound having a hydroxyl group or an amino group, and particularly preferably a compound having 2 to 8 hydroxyl groups.

Examples of the initiator include ethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, allyl alcohol, and methallyl alcohol. , Glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol and other alcohols; polyoxypropylene monool, polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene monool, polyoxyethylene diol, and polyoxyethylene triol The number average molecular weight (Mn) per hydroxyl group selected from the group consisting of 300 to 300 It includes 500 polymeric alcohol.
In addition, polyoxytetramethylene polyol, polyester polyol, polycarbonate polyol, and the like having a hydroxyl value converted molecular weight per hydroxyl group of 150 to 1500 (hydroxyl value 37 to 374 mgKOH / g) can also be used as the initiator. Examples of the polyester polyol include those obtained by condensation reaction of polyhydric alcohols and polycarboxylic acids, and those obtained by ring-opening polymerization of lactone monomers using polyhydric alcohols as initiators.
In addition, polyamines such as ethylenediamine and hexamethylenediamine: alkylene oxide adducts of the polyamines can also be used.
An initiator may be used individually by 1 type and may be used in combination of 2 or more type. It is preferable to use a polymeric alcohol having two hydroxyl groups and / or a polymeric alcohol having three hydroxyl groups.

(Cyclic ether)
Examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran and the like, and propylene oxide is preferable. A cyclic ether may be used individually by 1 type, and may be used in combination of 2 or more type.
When two or more kinds of cyclic ethers are used, the arrangement of two or more kinds of oxyalkylene polymer units in the polyoxyalkylene chain of the polyol (p) may be a block shape or a random shape.

(Compounds other than cyclic ether)
While the cyclic ether is ring-opening polymerized to the initiator, a compound other than the cyclic ether may be polymerized.
Examples of compounds other than the cyclic ether include cyclic esters such as β-propiolactone, δ-valerolactone, and ε-caprolactone; aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, and the like. Examples include acid anhydrides; aliphatic polycarboxylic acids such as succinic acid, maleic acid, and adipic acid and acid anhydrides thereof; and aromatic polycarboxylic acids mixed with some aliphatic carboxylic acids.
Of these, aromatic polycarboxylic acid anhydrides are preferable because they have a very high cohesive force and polarity and thus greatly contribute to adhesion to various adherends. The cyclic ester may be a monomer, a dimer, or a trimer, but is preferably a monomer from the viewpoint of reactivity. These compounds may be used alone or in combination of two or more.
The use ratio of the compound other than the cyclic ether is preferably 1000% by mass or less, and more preferably 500% by mass or less, when the amount of the initiator used for the synthesis of the polyol (p) is 100%. The viscosity of the polyol (p) obtained as it is 1000 mass% or less is restrained low. 5 mass% or more is preferable and, as for the lower limit of this use rate, 50 mass% or more is preferable. When it is 5% by mass or more, the effect of improving the mechanical strength and adhesiveness can be obtained satisfactorily.

<Polymerization catalyst>
Examples of the polymerization catalyst include alkali metal compounds, double metal cyanide complexes, metal porphyrin complexes, and compounds having a P = N bond. Examples of the alkali metal compound include potassium compounds (potassium hydroxide, potassium methoxide, etc.) and cesium compounds (cesium hydroxide, etc.).
As the polymerization catalyst, a double metal cyanide complex, a cesium compound, or a compound having a P═N bond is preferable because a polyol (p) having a large molecular weight is obtained. When a polyol (p) having a large molecular weight is used, a polymer (P) having a large molecular weight is obtained. The polymer (P) having a large molecular weight is excellent in curability, and the cured product is excellent in mechanical properties such as elongation.

As the double metal cyanide complex, a complex mainly composed of zinc hexacyanocobaltate is preferable from the viewpoint of high polymerization activity, and an ether and / or alcohol complex of zinc hexacyanocobaltate is more preferable from the viewpoint of high activity. .
As the ether, ethylene glycol dimethyl ether (hereinafter referred to as glyme) or diethylene glycol dimethyl ether (hereinafter referred to as diglyme) is preferable, and glyme is more preferable from the viewpoint of easy handling of the complex during production.
As the alcohol, tert-butyl alcohol is preferable because a highly active polymerization catalyst can be obtained.
The amount of the double metal cyanide complex used is preferably 0.0001 to 0.1% by mass when the obtained polyol (p) is 100% by mass, which is excellent in storage stability of the product and economically advantageous. From the point, 0.001 to 0.03 mass% is more preferable.
If the amount of the composite metal cyanide complex catalyst remaining in the polyol (p) is large, an operation of removing the composite metal cyanide complex catalyst may be performed before the next modification step. The denaturing step may be performed as it is without removing.
On the other hand, when the amount of the composite metal cyanide complex catalyst remaining in the polyol (p) is small (for example, 300 ppm or less) and does not adversely affect thereafter, the step of removing the composite metal cyanide complex catalyst is not performed. Proceed to the next step.

Examples of the cesium compound include cesium metal, cesium hydroxide, cesium carbonate, cesium alkoxide (such as cesium methoxide), and cesium hydroxide is preferable from the viewpoint of availability.
The amount of the cesium compound used is preferably 0.05 to 1.5% by mass and more preferably 0.1 to 1.0% by mass when the obtained polyol (p) is 100% by mass.

  Examples of the compound having a P = N bond include a phosphazenium compound, a phosphazene compound, or a phosphine oxide compound, and a phosphazenium compound or a phosphine oxide compound is preferable from the viewpoint of availability.

<Modification of polyol (p)>
Examples of the method for modifying the polyol (p) include the following methods (i), (ii), and (iii).
(I) The hydroxyl group of polyol (p), or -OM (where M is an alkali metal) converted to hydroxyl group by reacting the hydroxyl group with an alkali metal alkoxide (such as sodium methoxide). S11) is reacted to convert the hydroxyl group of the polyol (p) to the group (S12), and then the compound (S13) is allowed to act on the group (S12) to convert the group (S12) to the above group (S10). how to.
W ¹ −R ¹¹ −C (R ¹² ) = CH (R ¹³ ) (S11),
^{-O-A 1 -R 11 -C (} R 12) = CH (R 13) ··· (S12),
_{^{W 2 -R 01 -SiX a R 1}} 3-a ··· (S13).
W ¹ is a halogen atom, —COOH, —COX ′ (where X ′ is a halogen atom), a hydroxyl group such as —NCO or a group capable of reacting with —OM, and W ² is R ⁰¹ When is a single bond, it is a hydrogen atom, and when R ⁰¹ is a divalent organic group, it is —SH. X, R ¹ and a are the same as those in formula (1) including preferred embodiments. R ¹¹ , R ¹² , R ¹³ , A ¹ , R ⁰¹ are the same as those described for the group (S10).

(Ii) A method in which the hydroxyl group of the polyol (p) is urethanated with a compound (S21), which is a silane compound containing an isocyanate group, to convert the hydroxyl group into the above group (S20).
_{^{OCN-R 02 -SiX a R 1}} 3-a ··· (S21).
However, R ⁰² is the same as that described for the group (S20). X, R ¹ and a are the same as those in formula (1) including preferred embodiments.

(Iii) The compound (S31) having two isocyanate groups is allowed to act on the hydroxyl group of the polyol (p) to convert the hydroxyl group of the polyol (p) into the group (S32), and then the compound ( A method of converting the group (S32) into the above group (S30) by acting S33).
OCN-R ³¹ -NCO (S31),
—O—C (O) NH—R ³¹ —NCO (S32),
_{^{W 3 -R 03 -SiX a R 1}} 3-a ··· (S33).
^{However, W} 3 ^{_{are, -OH, -NH 2, -NHR 32}} , it is -COOH or -SH,. X, R ¹ and a are the same as those in formula (1) including preferred embodiments. R ³¹ and R ⁰³ are the same as those described for the group (S30).

Method (i):
Examples of the compound (S11) include allyl chloride, acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate.
As the compound (S13), the following compounds may be mentioned.
H-SiX _a R ¹ _3- (S13-1),
HS-R ⁰¹ -SiX _a R ¹ _3-a (S13-2).

The reaction (hydrosilylation reaction) between the group (S12) and the compound (S13-1) is performed in the presence of a catalyst.
Examples of the catalyst include platinum catalysts (chloroplatinic acid, platinum metal, platinum chloride, platinum olefin complexes, etc.), rhodium catalysts, cobalt catalysts, palladium catalysts, or nickel catalysts, and platinum catalysts are preferred. .
30-150 degreeC is preferable and the temperature of hydrosilylation reaction has more preferable 60-120 degreeC. The time for the hydrosilylation reaction is usually several hours.

Examples of the compound (S13-2) include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
The reaction between the group (S12) and the compound (S13-2) may be performed using a radical polymerization initiator, or may be performed by radiation or heat without using a radical polymerization initiator.
Examples of radical polymerization initiators include peroxide polymerization initiators, azo polymerization initiators, redox polymerization initiators, metal compound catalysts, and the like. Specifically, 2,2′-azobisisobutyronitrile, Examples include 2,2′-azobis-2-methylbutyronitrile, benzoyl peroxide, tert-alkyl peroxyester, acetyl peroxide, diisopropyl peroxycarbonate, and the like.
The reaction temperature in the case of using a radical polymerization initiator varies depending on the decomposition temperature (half-life temperature) of the radical polymerization initiator, and is usually 20 to 200 ° C, preferably 50 to 150 ° C. The reaction time is preferably about several hours to several tens of hours.

Method (ii):
As the isocyanate group-containing silane compound (S21), 1-isocyanate methyltrimethoxysilane, 1-isocyanatemethyldimethoxymethylsilane, 2-isocyanateethyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatebutyltrimethoxysilane 3-isocyanatopentyltrimethoxysilane, 1-isocyanatomethyltriethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatobutyltriethoxysilane, 3-isocyanatepentyltriethoxysilane, 1 -Isocyanatopropyltrimethoxysilane, 1-isocyanatopropyltriethoxysilane. Of these, 1-isocyanatomethyltrimethoxysilane or 3-isocyanatopropyltrimethoxysilane is preferable, and 3-isocyanatopropyl is preferred because the curable composition has a high curing rate and the cured product has good elongation. Trimethoxysilane is particularly preferred. A compound (S21) may be used individually by 1 type, and may be used in combination of 2 or more type.

The ratio (NCO / OH) of the isocyanate group (NCO) of the compound (S21) to the hydroxyl group (OH) of the polyol (p) is preferably 0.80 to 1.10 (molar ratio), 0.85 to 1. 05 (molar ratio) is more preferable, and 0.95 to 1.05 (molar ratio) is particularly preferable.
When NCO / OH is 0.80 (molar ratio) or more, the reaction between the unreacted hydroxyl group and the hydrolyzable silyl group hardly occurs in the curable composition, and the storage stability of the resulting curable composition. Becomes better. It is preferable to reduce the unreacted hydroxyl group by reacting with the compound (S21) or the monoisocyanate compound.
If NCO / OH is 1.10 (molar ratio) or less, the cured product is soft and foaming is unlikely to occur due to the reaction between unreacted isocyanate groups and water. Unreacted isocyanate groups are preferably reduced by reacting with alcohols.

The reaction between the hydroxyl group of the polyol (p) and the compound (S21) may be performed using a urethanization catalyst.
Examples of the urethanization catalyst include organotin compounds (dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, etc.), metal catalysts such as bismuth compounds, and base catalysts such as organic amines.
1-100 ppm is preferable and, as for the quantity of a urethanization catalyst, 10-50 ppm is more preferable. If the amount of the urethanization catalyst is 100 ppm or less, the storage stability of the curable composition will be good. If the amount of the urethanization catalyst is 1 ppm or more, the urethanization reaction proceeds in a short time.

The reaction temperature varies depending on the presence or absence of the urethanization catalyst and the amount thereof, and is usually 50 to 200 ° C, preferably 70 to 150 ° C.
The reaction time is preferably about several hours.
Since the method (ii) has a small number of steps, the manufacturing time can be greatly shortened. Moreover, since there are no impurities by-produced during the process, complicated operations such as purification are unnecessary, and the obtained curable composition is very excellent in storage stability.

Method (iii):
Examples of the compound having two isocyanate groups (S31) include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like.
The amount of the compound (S31) is set so that the isocyanate group becomes excessive with respect to the hydroxyl group of the polyol (p).

  As the compound (S33), aminosilane compounds (N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane) Etc.) and mercaptosilane compounds (3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.).

The reaction between the isocyanate group of the group (S32) and the compound (S33) may or may not be performed using a urethanization catalyst.
The reaction temperature varies depending on the presence or absence of the urethanization catalyst and the amount thereof, and is usually 20 to 200 ° C., preferably 50 to 150 ° C.
The reaction time is preferably about several hours.

<Polymer (P)>
A polymer (P) may be used individually by 1 type, and may be used combining 2 or more types from which molecular weight, molecular weight distribution, the number of hydroxyl groups of the raw material polyol (p), etc. differ.
The number average molecular weight (Mn) of the polymer (P) is preferably 1000 to 30000, more preferably 3000 to 20000 per end group. The terminal group of the polymer (P) here means a hydroxyl group derived from the polyol (p) used as a raw material.
When the number average molecular weight (Mn) of the polymer (P) is at least the lower limit of the above range, the curability of the composition will be good, and the resulting cured product will not be brittle. On the other hand, when it is not more than the upper limit of the above range, the viscosity of the polymer (P) becomes low, and the workability and handleability during construction of the curable composition become good.

The molecular weight distribution of the polymer (P) is preferably 3.0 or less, more preferably 1.6 or less, and even more preferably 1.5 or less.
If the molecular weight distribution of the polymer (P) is in the above range, the elongation at break of the cured product can be improved and the strength can be improved while maintaining the elastic modulus of the cured product. The lower limit of the molecular weight distribution of the polymer (P) is 1.0.
The molecular weight distribution of the polymer (P) is represented by the following formula as the ratio of the mass average molecular weight (Mw) to the number average molecular weight (Mn) of the whole polymer.
Molecular weight distribution = mass average molecular weight (Mw) / number average molecular weight (Mn)

In addition, when comparing a curable composition containing a polymer having a narrow molecular weight distribution and a curable composition containing a polymer having the same number average molecular weight and a wide molecular weight distribution, the former is a ratio of a polymer having a small molecular weight. Therefore, the elongation at break and the maximum stress of the cured product are larger than those of the latter, and the viscosity of the curable composition is low, so that the handleability is excellent.
A polymer (P) having a narrow molecular weight distribution can be stably produced by modifying a polyol (p) obtained by using a double metal cyanide complex as a polymerization catalyst and converting a hydroxyl group to a group (S1). .
The molecular weight distribution of the polymer (P) can be adjusted by the following method.
(I) A method for adjusting the type and amount of the polymerization catalyst used in the production of the polyol (p).
(Ii) A method for optimizing the polymerization conditions of the cyclic ether.
(Iii) A method of combining two or more kinds of polymers (P) having different molecular weights and molecular weight distributions.

<Compound (A)>
The compound (A) has an aliphatic heterocyclic ring containing two nitrogen atoms, and a primary amino group (—NH ₂ ) is attached to one of the two nitrogen atoms constituting the aliphatic heterocyclic ring. It is a compound in which a monovalent group (a2) containing a monovalent group (a1) or a secondary amino bond (—NH—) is bonded. The monovalent group (a1) containing one or more primary amino groups (—NH ₂ ) is more preferable in that the adhesiveness can be further improved. In the compound (A), it is preferable that a hydrogen atom is bonded to the other of the two nitrogen atoms constituting the aliphatic heterocyclic ring.
Examples of the aliphatic heterocyclic ring containing two nitrogen atoms include a piperazine ring, an imidazolidine ring and a pyrazolidine ring. A piperazine ring is preferred.
The monovalent group (a1) is a group containing one or more primary amino groups (—NH ₂ ), and a group in which a primary amino group is bonded to the terminal or side chain of a divalent organic group. Is preferred. The divalent organic group is preferably an alkylene group having 1 to 8 carbon atoms which may have an ether bond. The alkylene group is preferably linear. The monovalent group (a1) preferably has one or more primary amino groups from the viewpoint that the adhesiveness can be further improved. Specific examples of the monovalent group (a1) include an aminomethyl group, an aminoethyl group, and an aminopropyl group.
The monovalent group (a2) is a group containing one or more secondary amino bonds (—NH—). Specific examples include N- (β-aminoethyl) -γ-aminopropyl group.
Examples of the compound (A) include 1- (2-aminoethyl) piperazine, 1- (2-aminopropyl) piperazine and the like. Of these, 1- (2-aminoethyl) piperazine is particularly preferred. Compound (A) may be used alone or in combination of two or more.

  The content of the compound (A) in the curable composition of the present invention is preferably in the range of 0.1 parts by mass or more and less than 3 parts by mass with respect to 100 parts by mass of the polymer (P), and 0.5 parts by mass. The range of 2.0 parts by mass or less is more preferable. When the content of the compound (A) is 0.1 parts by mass or more, a good effect of improving adhesiveness is obtained, and when it is less than 3 parts by mass, good mechanical properties are obtained.

<Compound (B)>
The compound (B) has a group (b1) that reacts with a primary amino group or a secondary amino bond in the compound (A), and also has a hydrolyzable silicon group represented by the above formula (1). A compound.
The hydrolyzable silicon group of the polymer (P) and the hydrolyzable silicon group of the compound (B), which are present simultaneously in the curable composition, may be the same or different.
The primary amino group in the compound (A) is the primary amino group in the monovalent group (a1). In addition to the secondary amino bond in the monovalent group (a2), the secondary amino bond in the compound (A) has a hydrogen atom bonded to the nitrogen atom constituting the aliphatic heterocyclic ring. -NH- is also included.
Examples of the group (b1) that reacts with the primary amino group or secondary amino bond in the compound (A) include an epoxy group, a (meth) acryloyl group, and an isocyanate group. An epoxy group is preferable in terms of good reactivity with the compound (A).
Specific examples of the compound (B) having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane.
Specific examples of the compound (B) having a (meth) acryloyl group include γ-methacryloxypropyltrimethoxysilane.
Specific examples of the compound (B) having an isocyanate group include γ-isocyanatopropyltrimethoxysilane.

  The content of the compound (B) in the curable composition of the present invention is preferably in a range of 0.1 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the polymer (P), and 0.5 parts by mass. The range of 5 parts by mass or less is more preferable. When the content of the compound (B) is 0.1 parts by mass or more, a good adhesive improvement effect is obtained, and when it is less than 10 parts by mass, good mechanical properties are obtained.

  The ratio of the compound (A) and the compound (B) contained in the curable composition of the present invention is the total amount of primary amino groups or secondary amino bonds in the compound (A) (a, unit: mole). And the ratio (a / b) of the total amount (b, unit: mol) of the group (b1) that reacts with the primary amino group or the secondary amino bond in the compound (B) is 0.1 / The range of 1.0 to 10 / 1.0 is preferable, and the range of 0.5 / 1.0 to 7.5 / 1.0 is more preferable. If the ratio of (a) is less than 0.1 with respect to 1.0 of (b) above, it is not preferred in that the effect of improving adhesiveness tends to be insufficient and the cost is increased. When the ratio of (a) is more than 10 with respect to 1.0 of (b), the component (A) tends to bleed out in the cured product, which is not preferable in terms of performance.

<Curing catalyst (C)>
It is preferable to further contain a curing catalyst (C) in the curable composition of the present invention. Specific examples of the curing catalyst (C) include organotin compounds, organometallic compounds containing metals other than tin, metal organic alkoxides, complexes containing metals other than tin, organic amines (excluding compound (A)), and others. The catalyst is mentioned.

Specific examples of organotin compounds include
Dibutyltin diacetate, dibutyltin dilaurate, dioctyltin _{dilaurate, (n-C 4 H 9} ) 2 Sn (OCOCH = CHCOOCH 3) 2, (n-C 4 H 9) 2 Sn (OCOCH = CHCOO (n-C 4 H 9 _{)) 2, (n-C} 8 H 17) 2 Sn (OCOCH = CHCOOCH 3) 2, (n-C 8 H 17) 2 Sn (OCOCH = CHCOO (n-C 4 H 9)) 2, (n- organic stannous carboxylates of _{C 8 H 17) 2 Sn (} OCOCH = CHCOO (iso-C 8 H 17)) 2 and the like;
_{(N-C 4 H 9)} 2 Sn (SCH 2 COO), (n-C 8 H 17) 2 Sn (SCH 2 COO), (n-C 8 H 17) 2 Sn (SCH 2 CH 2 COO), _{(n-C 8 H 17)} 2 Sn (SCH 2 COOCH 2 CH 2 OCOCH 2 S), (n-C 4 H 9) 2 Sn (SCH 2 COO (iso-C 8 H 17)) 2, (n- _{C 8 H 17) 2 Sn (} SCH 2 COO (iso-C 8 H 17)) 2, (n-C 8 H 17) 2 Sn (SCH 2 COO (n-C 8 H 17)) 2, (n- Organotin compounds containing sulfur atoms such as C ₄ H ₉ ) ₂ SnS, (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ ;
_{(N-C 4 H 9)} 2 SnO, (n-C 8 H 17) an organic tin oxide compound such as 2 SnO;
A reaction product obtained by reacting an organotin oxide with an ester (ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, etc.);
_{(N-C 4 H 9)} 2 Sn (acac) 2, (n-C 8 H 17) 2 Sn (acac) 2, (n-C 4 H 9) 2 Sn (OC 8 H 17) (acac), _{(n-C 4 H 9)} 2 Sn (etac) 2, (n-C 8 H 17) 2 Sn (etac) 2, (n-C 4 H 9) 2 Sn (OC 8 H 17) (etac), Chelates of organotin compounds such as bisacetylacetonatotin;
A reaction product obtained by reacting an organotin compound chelate with an alkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc.);
_{(N-C 4 H 9)} 2 (CH 3 COO) SnOSn (OCOCH 3) (n-C 4 H 9) 2, (n-C 4 H 9) 2 (CH 3 O) SnOSn (OCH 3) (n An organotin compound having a —SnOSn— bond, such as —C ₄ H ₉ ) ₂ ;
Examples thereof include divalent tin carboxylates such as tin 2-ethylhexanoate, tin n-octylate, tin naphthenate and tin stearate. However, acac represents an acetylacetonate ligand and etac represents an ethylacetoacetate ligand (the same applies hereinafter).

  Specific examples of organometallic compounds containing metals other than tin include calcium carboxylate, zirconium carboxylate, iron carboxylate, vanadium carboxylate, bismuth carboxylate such as bismuth tris-2-ethylhexoate, lead carboxylate, Examples thereof include titanium carboxylate and nickel carboxylate.

  Specific examples of organometallic alkoxides include titanium alkoxides such as tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate, tetra (2-ethylhexyl titanate); aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, etc. Aluminum alkoxides; zirconium alkoxides such as zirconium-n-propylate and zirconium-n-butyrate; titanium alkoxides such as titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium octylene glycolate and titanium lactate.

  Specific examples of complexes containing metals other than tin include aluminum chelates such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, zirconium bisacetylacetonate, zirconium Zirconium chelates such as acetylacetonate bisethylacetoacetate and zirconium acetate can be mentioned.

  Specific examples of organic amines include aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, and laurylamine; aliphatic diamines such as ethylenediamine and hexanediamine; triethylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and the like. Aliphatic polyamines; heterocyclic amines such as piperidine and piperazine; aromatic amines such as metaphenylenediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; various modified amines used for curing epoxy resins It is done.

Specific examples of other catalysts include phosphoric acid, p-toluenesulfonic acid, and phthalic acid.
The curing catalyst (C) is preferably an organotin compound from the viewpoint of curability. From rapid curability _{viewpoint, (n-C 4 H 9} ) 2 Sn (acac) 2, (n-C 8 H 17) 2 Sn (acac) 2, (n-C 4 H 9) 2 Sn (OC ₈ H ₁₇ ) (acac), (nC ₄ H ₉ ) ₂ Sn (etac) ₂ , or (nC ₈ H ₁₇ ) ₂ Sn (etac) ₂ is particularly preferred. Moreover, dibutyltin dilaurate and dioctyltin dilaurate are preferable from the viewpoint of storage stability as the curable composition.

It is also possible to appropriately select the curing catalyst (C) and control the curing rate of the curable composition. For example, the curing rate of the curable composition of the present invention can be decreased by selecting a catalyst having low activity as the curing catalyst (C).
Specific examples of the low activity catalyst include specific organotin compounds containing a sulfur atom in the ligand (trade name UL-29 manufactured by Crompton, trade name Neostan U-860 manufactured by Nitto Kasei Co., Ltd.). It is done.

One type of curing catalyst (C) may be used, or two or more types may be used in combination. When two or more kinds of curing catalysts (C) are included, it is preferable to combine an organic tin compound and an organic amine in terms of excellent curability.
When adding a curing catalyst (C) to the curable composition of the present invention, the content of the curing catalyst (C) with respect to 100 parts by mass of the polymer (P) is preferably 0.001 to 10 parts by mass, 0.05-5.0 mass parts is more preferable. If content of a curing catalyst (C) is said range, the performance outstanding in both sclerosis | hardenability and mechanical properties can be expressed.

<Other ingredients>
In addition to the polymer (P), the compound (A), the compound (B), and the curing catalyst (C), the curable composition may contain, as necessary, a filler, a plasticizer, a dehydrating agent, It may contain a thixotropic agent and an anti-aging agent. Moreover, you may contain an adhesive imparting agent other than a compound (A) and a compound (B).
Further, a surface modifier; a solvent; a modulus modifier such as a compound that generates trimethylsilanol upon hydrolysis (eg, phenoxytrimethylsilane); a compound that cures by air (eg, tung oil); a compound that cures by light (eg, tung oil) Trimethylolpropane triacrylate); inorganic pigments such as iron oxide, chromium oxide and titanium oxide; organic pigments such as phthalocyanine blue and phthalocyanine green; flame retardants; fungicides; matting agents used for paint You may do it. The use of the pigment is effective not only for coloring but also for improving the weather resistance.
The curable composition is not limited to these, and may contain other additives as necessary.

(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; activated zinc white; Shirasu balloon, pearlite, 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 fillers, calcium carbonate is preferable, and it is particularly preferable to use heavy calcium carbonate and colloidal calcium carbonate in combination.
From the viewpoint of reducing the weight of the curable composition and the cured product, it is preferable to use a hollow body as a filler. 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.
1000 mass parts or less are preferable with respect to 100 mass parts of polymers (P), and, as for the addition amount in the case of adding a filler, 50-250 mass parts is more preferable.

(Plasticizer)
Plasticizers include phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, isononyl phthalate, di (2-ethylhexyl) phthalate; dioctyl adipate, diisodecyl succinate, dibutyl sebacate, olein Aliphatic carboxylic acid esters such as butyl acid; Alcohol esters such as pentaerythritol ester; Phosphate esters such as trioctyl phosphate and tricresyl phosphate; Epoxidized soybean oil, Dioctyl 4,5-epoxyhexahydrophthalate, Epoxy Epoxy plasticizers such as benzyl stearate; Chlorinated paraffins; Polyester plasticizers such as polyesters obtained by reacting dibasic acids with dihydric alcohols; Polyoxypropylene glycol and its derivatives such as polyoxypropylene Polyethers in which the hydroxyl group of the recall is sealed with alkyl ether, poly-α-methylstyrene, polystyrene oligomers such as polystyrene, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated Examples thereof include polymer plasticizers such as oligomers such as polybutene and epoxidized polybutadiene. These plasticizers can be used in combination of two or more different types such as phthalate ester and epoxy plasticizer.
1-100 mass parts is preferable with respect to 100 mass parts of polymers (P), and, as for the addition amount in the case of adding a plasticizer, 1-50 mass parts is more preferable.

(Dehydrating agent)
In order to further improve the storage stability of the curable composition, a small amount of a dehydrating agent can be added within a range that 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, tetraethoxysilane and the like. Examples include hydrolyzable organic silicon compounds; hydrolyzable organotitanium compounds. Among these, vinyltrimethoxysilane and tetraethoxysilane are particularly preferable from the viewpoint of cost and effect. In particular, it is effective to use a dehydrating agent when the curable composition is handled as a one-component blended type product contained in a moisture-proof container in a state containing a curing catalyst.
When the dehydrating agent is added, the amount added is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer (P).

(Thixotropic agent)
By including the thixotropic agent, the sagging property of the curable composition is improved. Specific examples of the thixotropic agent include hydrogenated castor oil, fatty acid amide and the like, and any amount thereof is used.
(Anti-aging agent)
As antioxidants, generally used antioxidants, ultraviolet absorbers, and light stabilizers can be appropriately used. Specifically, hindered amine, benzotriazole, benzophenone, benzoate, cyanoacrylate, acrylate, hindered phenol, phosphorus, and sulfur compounds can be appropriately used as the antioxidant. In particular, it is preferable to use a combination of two or all selected from light stabilizers, antioxidants, and ultraviolet absorbers. Specifically, it is preferable to combine a tertiary or secondary hindered amine light stabilizer, a benzotriazole ultraviolet absorber, and a hindered phenol-based and / or phosphite-based antioxidant.

(Adhesiveness imparting agent)
In the present invention, the adhesiveness is improved by containing the compound (A) and the compound (B), but other adhesion imparting agents (compounds (A) and (B) are not included) other than these are further added. May be.
As the other adhesion-imparting agent, a reaction product obtained by reacting two or more silane coupling agents may be used. As the reactant, a reactant obtained by reacting a silane having an amino group and a silane having an epoxy group, a reactant obtained by reacting a silane having an amino group and a silane having a (meth) acryloyloxy group, Examples include a reaction product obtained by reacting a silane having an epoxy group and a silane having a mercapto group, and a reaction product of a silane having a different mercapto group.

  In the case where another adhesiveness-imparting agent is added to the curable composition separately from the compound (A) and the compound (B), the addition amount is more than 0 to 10 with respect to 100 parts by mass of the polymer (P). It is preferably a part by mass, more preferably more than 0 to 5.0 parts by mass.

According to the present invention, by containing the compound (A) and the compound (B) in the curable composition containing the polymer (P), a cured product having good adhesiveness and excellent elongation characteristics can be obtained. Obtainable.
The reaction between compound (A) and compound (B) proceeds even at room temperature. Therefore, in a curable composition, it is estimated that a part or all of compound (A) and a part or all of compound (B) are reacting.
As shown in Examples and Comparative Examples described later, even when an oxypropylene adduct of 1- (2-aminoethyl) piperazine is used in place of the component (A), no improvement in adhesiveness and elongation characteristics is observed. (Comparative Example 5). This oxypropylene adduct is considered not to react with the compound (B) because the primary amino group and secondary amino bond of 1- (2-aminoethyl) piperazine have already reacted with oxypropylene. From this, it is considered that the reaction product of the compound (A) and the compound (B) contributes to the improvement of elongation characteristics and adhesiveness.
Therefore, the curable composition of the present invention preferably contains at least a reaction product of the compound (A) and the compound (B), and a reaction in which the compound (A) and the compound (B) are reacted in advance. The same effect can be obtained by adding the product to the polymer (P).
Further, if the compound (A) is contained and the compound (B) is not contained, sufficient adhesiveness cannot be obtained (Comparative Example 7). This is considered because the hydrolyzable silicon group in the reaction product of the compound (A) and the compound (B) strongly interacts with the adherend interface and the cured compound and contributes to the improvement in adhesion. It is done.
Further, in place of the compound (A), Example 1 is particularly excellent in adhesiveness (breaking state) as compared with Comparative Example 6 using aminomethylpiperidine in which the aliphatic heterocycle has only one nitrogen atom. ing. From this, it is considered that the structure of the aliphatic heterocyclic ring containing two nitrogen atoms in the compound (A) contributes to the effect of the present invention.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
[Preparation Example 1] Preparation of polymer (P1) In a stainless steel pressure-resistant reactor with a stirrer made of 10000 ml, 300 g of polyoxypropylenediol (Mn = 1000) as an initiator, glyme as a polymerization catalyst and a ligand 1000 mg of the zinc hexacyanocobaltate complex catalyst (8.0 mg as the amount of metal) was added. After the reactor was purged with nitrogen, the temperature was raised to 140 ° C., and 50 g of propylene oxide was fed into the reactor for reaction. After the pressure in the reactor dropped, 4500 g of propylene oxide was fed into the reactor at a rate of about 80 g / hr. The supply of propylene oxide was completed over 6 hours and 20 minutes, and stirring was continued for another hour. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 140 ° C. and the stirring speed at 500 rpm. The number average molecular weight (Mn) of the polyoxypropylene diol (p1) obtained by this reaction was 16000 (hydroxyl value 7.7 mgKOH / g). The residual metal amount of the zinc hexacyanocobaltate complex catalyst was about 40 ppm.

Subsequently, the polyoxypropylene diol (p1) obtained above was modified by the method (ii) above.
That is, 3000 g of polyoxypropylene diol (p1) was put into a 5000 ml pressure-resistant reactor, heated to 110 ° C., and vacuum dehydrated. Thereafter, the temperature of the reactor was lowered to 50 ° C. after nitrogen substitution, 86.1 g of 3-isocyanatopropyltrimethoxysilane (purity 95%) was added, and the mixture was heated to 80 ° C. and reacted for 8 hours. The molar ratio of isocyanate group / hydroxyl group was 0.97 / 1.00.
After confirming the disappearance of the isocyanate peak by FT-IR, the mixture was cooled to room temperature. As a result of analyzing the reactor contents, it was confirmed that a polymer (P1) having an oxypropylene chain and a substituent represented by “(Si (—OCH ₃ ) ₃ ) —CH ₂ CH ₂ CH ₂ NHCOO—” was confirmed. It was done. Mn of the obtained polymer (P1) was 16000 (Mn per terminal group was 8000), and Mw / Mn was 1.44.

[Preparation Example 2] Preparation of polymer (P2) Polyoxypropylene diol (p1) obtained in the same manner as Preparation Example 1 was modified by the method (i) above.
That is, 90 g of a methanol solution of sodium methoxide was added to 3000 g of polyoxypropylene diol (p1), and methanol was removed under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene diol into an -ONa group.
Next, after adding and reacting 40 g of allyl chloride, unreacted allyl chloride is removed under reduced pressure, and further, by-product salts are removed by purification, and a polyoxypropylene polymer having an allyl group at the terminal ( p2) was obtained. 2000 g of the polymer (p2) was reacted with 21.8 g of methyldimethoxysilane in the presence of a platinum catalyst to obtain a polymer (P2) having a methyldimethoxysilyl group at the molecular end. Mn of the obtained polymer (P2) was 16200 (Mn per terminal group was 8100), and Mw / Mn was 1.24.

[Example]
Using the polymers (P1) and (P2) obtained in the above preparation examples, curable compositions were prepared according to the formulation shown in Table 1, and the characteristics were evaluated. The unit of the blending ratio in Table 1 is “part by mass”.
Each component shown in Table 1 is as follows.
・ Surface treatment calcium carbonate: Shiraishi Kogyo Co., Ltd., Shiraka Hana CCR
-Heavy calcium carbonate: White Son SB (product name) manufactured by Shiraishi Calcium.
Phthalate ester: Di (2-ethylhexyl) phthalate, reagent.
-Hydrogenated castor oil: Disparon 6500 (product name) manufactured by Enomoto Kasei Co., Ltd.
Aminoethylpiperazine: 1- (2-aminoethyl) piperazine, reagent.
Aminosilane: N-aminoethyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM603 (product name).
Diethanolamine: Reagent.
Triethylamine: reagent.
-AEP PO adduct: 1- (2-aminoethyl) piperazine oxypropylene adduct (hydroxyl value 550).
Vinyltrimethoxysilane (dehydrating agent): Shin-Etsu Chemical Co., Ltd. KBM-1003 (product name).
Epoxy group-containing silane compound: 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403 (product name).
DBTDL: dibutyltin dilaurate, reagent.

Example 1
For 100 parts by mass of the oxyalkylene polymer (P1) obtained in Preparation Example 1, 75 parts by mass of surface-treated calcium carbonate and 75 parts by mass of heavy calcium carbonate as fillers, 40 parts by mass of plasticizer, Then, 3 parts by mass of a thixotropic agent was added 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.
Thereafter, 3 parts by mass of the dehydrating agent and 1 part by mass of the compound (B) were added and stirred, and then 1 part by mass of 1- (2-aminoethyl) piperazine was added and stirred as the compound (A). . Thereafter, 1 part by mass of dibutyltin dilaurate was added as a curing catalyst (C) and stirred to obtain a curable composition.

(Examples 2 and 3)
A curable composition was obtained in the same manner as in Example 1 except that the formulation was changed as shown in Table 1.
(Comparative Example 1)
A curable composition was obtained in the same manner as in Example 1 except that aminosilane known as an adhesion-imparting agent was used instead of the compound (A).
(Comparative Example 2)
A curable composition was obtained in the same manner as in Example 1 except that the compound (A) was not used.
(Comparative Examples 3-6)
A curable composition was obtained in the same manner as in Example 1 except that the comparative compound shown in Table 1 was used in place of the compound (A).
(Comparative Example 7)
A curable composition was obtained in the same manner as in Example 1 except that the compound (B) was not used.

[Evaluation]
(Tensile adhesion test)
Using each curable composition obtained in the above Examples and Comparative Examples, two H-type test specimens were prepared in accordance with the test method of JIS A5758. As the adherend, surface anodized aluminum was used.
The H-shaped specimen was cured and cured at 23 ° C. and 50% humidity for 7 days, and then cured at 50 ° C. and 65% humidity for 7 days, and each specimen was taken out from the curing apparatus. Further, a tensile adhesion test was conducted using a Tensilon tester on a test specimen that was left for 1 day under conditions of 23 ° C. and 50% humidity. The test is performed at a tensile speed of 50 mm / min, and stress at 50% tension (described as “M50” in the table. Unit: N / mm ² ), maximum elongation (unit:%), and maximum tensile stress (in the table). It is described as “Tmax.” (Unit: N / mm ² ) was measured. The measurement results are shown in Table 1.
In addition, the fractured form of the cured product in the tensile test of the above H-shaped specimen was visually observed, and the specimen was subjected to material destruction of the cured product without peeling at the interface between the cured product and the adherend. The CF ratio representing the ratio was obtained. When material failure occurs in both of the two specimens, the CF rate is 100%. When one material breaks down, and when one of the remaining specimens undergoes interface peeling, the CF rate is 50%. In the case where interfacial peeling occurs in FIG. The higher the CF ratio, the better the adhesion with the adherend. From these results, the evaluation results of the adhesive properties are shown in Table 1, with a CH ratio of 80% or more as ◯, a CF ratio of 30% to less than 80% as Δ, and a CF ratio of less than 30% as x.

(Evaluation of bleeding out)
The specimen prepared in the same manner as in the tensile adhesion test was cured and cured at 23 ° C. and 50% humidity for 7 days, then cured at 50 ° C. and 65% humidity for 7 days, and each specimen was taken out from the curing device. It was. Furthermore, the bleed-out property of the surface of the cured product was evaluated by touching the surface of the cured product in a state of being left for 1 day under conditions of 23 ° C. and 50% humidity. Table 1 shows the case where there is a liquid on the surface of the cured product as x and the case where there is no liquid as ◯.

From the results of Table 1, the cured products of the curable compositions of Examples 1 to 3 have a larger elongation and a smaller measured value of M50 compared to Comparative Examples 1 to 7, and the elasticity is well maintained. I can see that Moreover, adhesive evaluation was also favorable.
On the other hand, in Comparative Example 1 using aminosilane instead of compound (A), the adhesiveness was good, but the elongation was small and the measured value of M50 was large. Comparative Examples 2 to 6 using other comparative compounds were inferior in both adhesion and elongation. In Comparative Example 7 in which the compound (B) was not contained, the maximum elongation was large, but both M50 and Tmax were low, and the adhesiveness was insufficient.
In addition, in Comparative Example 7 in which the compounding amount of the compound (B) is 0 (zero) with respect to 1 part by mass of the compound (A), the bleedout of the component (A) was not recognized. This is probably because the content of the component (A) in the entire composition is small.

  The curable composition of the present invention is useful as a coating composition / sealing composition such as a sealant, a waterproof material, an adhesive, and a coating agent.

Claims (12)

By modifying polyoxyalkylene poly (mono) ol (p) having 1 or more hydroxyl groups, a group having a hydrolyzable silicon group represented by the following formula (1) can be obtained by modifying part or all of the hydroxyl groups ( A polymer (P) converted to S1);
A monovalent group containing a primary amino group or a secondary amino bond is bonded to one of the two nitrogen atoms constituting the aliphatic heterocycle having an aliphatic heterocycle containing two nitrogen atoms. A compound (A) to which a monovalent group is bonded;
A compound (B) having a hydrolyzable silicon group represented by the following formula (1) having a group that reacts with a primary amino group or a secondary amino bond in the compound (A). A curable composition characterized by the above.
-SiX _a R ¹ _3-a (1)
(In the formula, X represents an alkoxy group having 1 to 6 carbon atoms, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding an alkoxy group), and 1 It represents an -3 integer. However, may be different or a plurality of R ¹ is each independently when R ¹ there are a plurality, the plurality of X may be the same or different when X there are multiple.)   The curable composition according to claim 1, wherein the group (S1) of the polymer (P) has a urethane bond. The polymer (P) is a urethanization reaction between a polyoxyalkylene poly (mono) ol (p) having 1 or more hydroxyl groups and an isocyanate group-containing silane compound (S21) represented by the following formula (S21). The curable composition according to claim 2, which is a polymer obtained in this way.
OCN-R ⁰² -SiX _a R ¹ _3-a (S21)
(In the formula, X represents an alkoxy group having 1 to 6 carbon atoms, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding an alkoxy group), and R ⁰² represents a divalent organic group having 1 to 17 carbon atoms, a is an integer of 1-3. However, a plurality of R ¹ when R ¹ there are a plurality may be the same or different from each other, X A plurality of X may be the same or different from each other.)   The molar ratio (isocyanate group / hydroxyl group) of the total number of isocyanate groups of the isocyanate group-containing silane compound (S21) to the total number of hydroxyl groups of the polyoxyalkylene poly (mono) ol (p) is 0.80 to 1.10. The curable composition according to claim 3.   The curable composition as described in any one of Claims 1-4 whose number average molecular weights of the said polymer (P) are 1000-30000 per terminal group.   The curable composition as described in any one of Claims 1-5 whose aliphatic heterocyclic ring in the said compound (A) is a piperazine ring.   The curable composition according to claim 6, wherein the compound (A) is 1- (2-aminoethyl) piperazine.   Curing as described in any one of Claims 1-7 which contains the said compound (A) in 0.1 to 3 mass parts with respect to 100 mass parts of the said polymers (P). Sex composition.   Curability as described in any one of Claims 1-8 in which the said compound (B) has an epoxy group as a group which reacts with the primary amino group or the secondary amino bond in the said compound (A). Composition.   The compound (B) is at least one selected from the group consisting of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane. Curable composition.   Curing as described in any one of Claims 1-10 which contains the said compound (B) in 0.1 to 10 mass parts with respect to 100 mass parts of the said polymers (P). Sex composition.   Furthermore, 0.001-10 mass parts of hardening catalysts (C) are contained with respect to 100 mass parts of the said polymers (P), The curable composition as described in any one of Claims 1-11.