JP6163918B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing a polymer having a reactive silicon group.

A polyoxyalkylene polymer having a reactive silicon group (hereinafter sometimes referred to as a modified silicone polymer) is liquid at room temperature and is cured by a hydrolysis reaction to form a flexible rubber-like cured product.
Curable compositions containing such modified silicone polymers are widely used as sealing materials, adhesives, coating agents and the like.
When a curable composition containing a modified silicone polymer is used as, for example, a sealing material applied outdoors, the cured product has good weather resistance, and even if it is exposed to an outdoor environment for a long period of time, the surface is cracked. It is required to be difficult to occur.

Examples of a method for improving the weather resistance of a curable composition containing a modified silicone polymer include a method for containing a (meth) acrylic acid alkyl ester polymer having a reactive silicon group, and a method for containing a photocurable compound. However, it is difficult to balance the modulus (elastic modulus) and weather resistance of the cured product (for example, [0004] to [0007] of Patent Document 1).
It is also known that a curable composition contains a compound capable of generating trimethylsilanol by hydrolysis as a modulus regulator.
For example, in Example 8 of Patent Document 1, polyoxypropylene in which a methyldimethoxysilyl group is introduced into a precursor polymer having a number average molecular weight of 18,000, a molecular weight distribution of 2.1, and an average functional group number of 2.16. 100 parts of a mixture Pd obtained by mixing P3 with a toluene solution of an acrylic copolymer having a photocurable functional group, 0.4 parts of phenyloxytrimethylsilane which is a modulus regulator, and tristrimethylsilyl form of trimethylolpropane A curable composition containing 0.4 parts of (TMP-3TMS) is described.
In Tables 7 and 9 of Patent Document 2, the average number of functional groups at the end of the main chain of the polymer is 3, the number average molecular weight is 26,000 to 34,000, and the molecular weight distribution is 1.15 to 1. 20 and a polymer (A) having a reactive silicon group introduced, and a linear polymer having a reactive silicon group at one end and having a number average molecular weight of 5,200 to 15,300 (B ) And a tristrimethylsilyl form of trimethylolpropane (TMP-3TMS), which is a modulus regulator, is described.

Japanese Patent No. 4815663 JP 2011-202157 A

However, in the conventional curable composition, the curing rate is good and the curability is excellent, the elongation and durability of the cured product are good, and the requirement that the surface of the cured product is not sticky is simultaneously satisfied. difficult.
According to the knowledge of the present inventors, inclusion of a modulus regulator in the curable composition is effective in preventing surface stickiness. However, even if a modulus modifier is contained, the curable composition described in Patent Document 1 does not necessarily have sufficient elongation and durability of the cured product, and further improvement is required. Moreover, although the curable composition described in Patent Document 2 achieves good elongation and durability by lowering the elastic modulus of the cured product, it is elastic in terms of preventing surface stickiness of the cured product. Is preferable, and it is required to increase the elastic modulus without impairing the durability.
For example, Tables 7 and 9 in Examples of Patent Document 2 show that good durability was obtained when the elastic modulus of the cured product was as low as 0.10 to 0.13 N / mm ² .
The present invention has been made in view of the above circumstances, and the curability is good, the elongation and durability of the cured product are good despite the relatively high elastic modulus, and the surface of the cured product is sticky. An object of the present invention is to provide a curable composition in which the above is prevented.

The present invention includes the following [1] to [7].
[1] The main chain has an alkylene oxide monomer unit, has a functional group capable of introducing a reactive silicon group at the end of the main chain, and the functional group includes a group having an active hydrogen and an unsaturated group. 1 or more selected from the group consisting of: the average number of functional groups at the end of the main chain is 2.0 or more and 3.0 or less, and the molecular weight per functional group is 7,000 to 20,000 A polymer (A) obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (A ′) having a molecular weight distribution of 1.01 to 1.40, and hydrolysis. 2 or more compounds (B) capable of generating trimethylsilanol, and the total content of the compound (B) is 0.4 to 2.0 with respect to 100 parts by mass of the polymer (A). A curable composition characterized by being part by mass.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]

[2] In the presence of an alkylene oxide ring-opening polymerization catalyst, the precursor polymer (A ′) contains an alkylene oxide in one or both of an initiator having two active hydrogens and an initiator having three active hydrogens. The curable composition according to [1], which is a precursor polymer (A′-a) composed of an oxyalkylene polymer subjected to ring-opening addition polymerization.

[3] The curable composition according to [2], wherein the alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand.
[4] The curable composition according to any one of [1] to [3], wherein the compound (B) includes a tristrimethylsilyl form of phenoxytrimethylsilane and trimethylolpropane.
[5] The curable composition according to [4], wherein the mass ratio of the phenoxytrimethylsilane / trimethylolpropane tristrimethylsilyl compound is 20/80 to 80/20.
[6] Further, any one of [1] to [5], further comprising a polymer (C) which is linear, has a main chain having an alkylene oxide monomer unit, and has a reactive silicon group at one end. The curable composition according to one item.
[7] The curable composition according to any one of [1] to [6], further including a (meth) acrylic acid ester copolymer (D) having a reactive silicon group.

  According to the present invention, a curable composition having good curability, good elongation and durability of the cured product, and prevention of stickiness of the surface of the cured product, although the elastic modulus is relatively high. A thing is obtained.

In the present specification, the “main chain” of a polymer refers to a polymer chain formed by linking two or more monomers. The main chain end is the end of each main chain, and there are two main chain ends in a polymer in which the main chain is linear. The “total main chain end” of the polymer means all the main chain ends of the polymer. The term “linear and one end” of the polymer means that the polymer is linear and one end of two main chain ends.
In this specification, the average number of functional groups at the end of the main chain of the precursor polymer (A ′) is the number of functional groups capable of introducing reactive silicon groups at the end of the main chain of the precursor polymer (A ′). The average value per molecule.
In this specification, the number of functional groups at the end of the main chain in the polymer (A) is such that the reactive silicon group introduced into the main chain end of the precursor polymer (A ′) and the reactive silicon group are not introduced. The total number of functional groups at the ends of the main chain, and the average number of functional groups at the ends of the main chain of the polymer (A) is the average value per molecule of the total number.
Therefore, the average number of functional groups at the end of the main chain of the precursor polymer (A ′) is equal to the average number of functional groups at the end of the main chain of the polymer (A).
When the precursor polymer (A ′) or the polymer (A) is a mixture, the average number of functional groups at the end of the main chain after mixing per molecule is calculated as the precursor polymer (A ′) or the polymer ( A), the average number of functional groups at the end of the main chain (hereinafter sometimes simply referred to as “average number of functional groups”).

The mass average molecular weight (Mw, hereinafter also referred to as “Mw”) and the number average molecular weight (Mn, hereinafter also referred to as “Mn”) in the present specification are molecular weights in terms of polystyrene measured by gel permeation chromatography (GPC). . The molecular weight distribution in the present specification (hereinafter also referred to as “Mw / Mn”) is a value calculated from Mw and Mn measured by the above-described method, and is a mass average molecular weight (Mw) with respect to the number average molecular weight (Mn). The ratio (Mw / Mn).
In this specification, when the functional group is a hydroxyl group, the molecular weight per functional group is a value obtained by dividing 56,100 by the hydroxyl value.
The hydroxyl value in this specification is a value measured by a method based on JIS K1557-1.
In this specification, when the functional group is a group other than a hydroxyl group, the molecular weight per functional group is a value determined by gel permeation chromatography (GPC). Specifically, a molecular weight per functional group is calculated by drawing a calibration curve with a polymer whose molecular weight per functional group is known and measuring the measurement object.

<Polymer (A)>
The polymer (A) used in the present invention has a reactive silicon group represented by the above formula (1).
In Formula (1), R ¹ represents a monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group) which may have a substituent. R ¹ is preferably a hydrocarbon group having 8 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group. A methyl group and a phenyl group are more preferable, and a methyl group is particularly preferable.

In the formula (1), X ¹ represents a hydroxyl group or a hydrolyzable group. Two X ¹ existing in one molecule may be the same as or different from each other.
The hydrolyzable group 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 has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. X ¹ is particularly preferably an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms. More specifically, X ¹ is particularly preferably a methoxy group or an ethoxy group.

The polymer (A) has a functional group capable of introducing reactive silicon groups at all main chain ends, and a precursor polymer (average functional group number of main chain ends is 2.0 or more and 3.0 or less). A ′) is a polymer obtained by introducing a reactive silicon group. One functional group capable of introducing a reactive silicon group is present at one main chain end of the precursor polymer (A ′). The functional group capable of introducing a reactive silicon group is at least one selected from a group having an active hydrogen or an unsaturated group. The group having active hydrogen is preferably a hydroxyl group. An unsaturated group is a monovalent group containing an unsaturated double bond. Specific examples of the unsaturated group include a vinyl group, an allyl group, and an isopropenyl group.
When there is a reactive silicon group at the end of the main chain of the polymer (A), the elongation property, internal curability and surface curability of the cured product are likely to be good.

In the present invention, the average functional group number of the polymer (A) is 2.0 to 3.0. When the average functional group number of the polymer (A) is 2.0, the main chain of the polymer (A) is linear. When the average number of functional groups of the polymer (A) is 2.0 or more, good strength in the cured product is easily obtained.
The polymer (A12) having two functional groups at the main chain ends is the total main component of the linear precursor polymer (A'12) having two functional groups at the main chain ends per molecule. A polymer in which a part or all of the functional groups at the chain ends are substituted with a group containing a reactive silicon group.

  On the other hand, when the average functional group number of the polymer (A) is 3.0 or less, good flexibility in the cured product is easily obtained. When the average functional group number of the polymer (A) is 3.0, the polymer (A) is preferably composed of one or more kinds of the polymer (A11) having three functional groups at the main chain ends. A polymer having three functional groups at the end of the main chain (A11) has three functional groups at the end of the main chain per molecule. It is a polymer in which part or all of the functional group is substituted with a group containing a reactive silicon group.

When the polymer (A) is a mixture, (i) polymers having different numbers of functional groups at the main chain ends may be mixed, and (ii) a mixture of precursor polymers having different numbers of functional groups at the main chain ends. You may use and manufacture a polymer (A).
In the case of (i), the polymer (A) is a polymer having 2 to 4 functional groups at the end of the main chain mixed so that the average number of functional groups at the end of the main chain is within the above range. Mixtures are preferred. In the case of (i), the polymer (A) was prepared by mixing a polymer having 2 to 3 functional groups at the end of the main chain so that the average number of functional groups at the end of the main chain was within the above range. A mixture is more preferred. In particular, it is preferable that the polymer (A) includes at least a polymer (A11) having 3 functional groups at the main chain terminals, and 2 of the polymer (A11) having 3 functional groups at the main chain terminals. A mixture of two or more species, or a mixture of a polymer (A12) having two functional groups at the main chain ends and a polymer (A11) having three functional groups at the main chain ends is more preferable.

  In the case of (ii), the polymer (A) is a precursor polymer having 2 to 4 main chain end groups per molecule, and the average number of functional groups at the main chain ends is 2.0 to 3 It is preferable to introduce a reactive silicon group into the precursor polymer (A ′) composed of a mixture mixed so as to be 0.0. In the case of (ii), the polymer (A) is a precursor polymer having 2 to 3 main chain end groups per molecule, and the average number of functional groups at the main chain ends is 2.0 to 3 It is more preferable to introduce a reactive silicon group into the precursor polymer (A ′) composed of a mixture mixed so as to be 0.0. In particular, the precursor polymer (A ′) preferably contains at least the precursor polymer (A′11) having 3 main chain terminal functional groups per molecule, and the main chain terminal functional group number is 3. A mixture of two or more precursor polymers (A′11), or a precursor polymer (A′12) having two main chain terminal functional groups and three main chain terminal functional groups A mixture of the precursor polymer (A′11) is more preferable.

  The polymer (A) includes a compound (hereinafter also referred to as “silylating agent”) having both a group that reacts with a functional group at the terminal of the entire main chain of the precursor polymer (A ′) and a reactive silicon group. It can be obtained by a method in which a reactive silicon group is introduced by reacting the precursor polymer (A ′).

The polymer (A) is a polymer having an alkylene oxide monomer unit in the main chain. The polymer (A) undergoes a step of subjecting an alkylene oxide monomer to addition polymerization to an initiator having 2 or 3 terminal functional groups per molecule and having all reactive terminal functional groups. What is obtained or what is obtained through the process of addition-polymerizing an alkylene oxide monomer and a (meth) acrylic acid alkyl ester monomer to the initiator is preferred.
That is, the main chain of the precursor polymer (A ′) and the polymer (A) may have a (meth) acrylic acid alkyl ester monomer unit in addition to the alkylene oxide monomer unit.
In this specification, the (meth) acrylic acid alkyl ester monomer unit means a repeating unit derived from a (meth) acrylic acid alkyl ester. (Meth) acrylic acid alkyl ester means acrylic acid alkyl ester, methacrylic acid alkyl ester or a mixture of both.

The repeating unit in the precursor polymer (A ′) and the polymer (A) includes an alkylene oxide monomer unit. The main chains of the precursor polymer (A ′) and the polymer (A) preferably have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
When the polymer (A) has a polyoxyalkylene chain, there are advantages such as low temperature dependence, easy flexibility of the cured product, and excellent price.
The reactive functional group in the initiator is a group having active hydrogen, and preferably a hydroxyl group. The average functional group number of the initiator, the average functional group number of the main chain terminal of the precursor polymer (A ′), and the average functional group number of the main chain terminal of the polymer (A) are the same.
As the precursor polymer (A ′), a linear or branched precursor polymer (A′-a) having a polyoxyalkylene chain and having all main chain ends being hydroxyl groups; or a polyoxyalkylene chain A linear or branched precursor polymer (A′-b) having an unsaturated group at all main chain ends is preferred.

<Precursor polymer (A'-a)>
The precursor polymer (A′-a) is an oxyalkylene polymer obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or three active hydrogens in the presence of an alkylene oxide ring-opening polymerization catalyst. Is preferred.
As the initiator, a compound having 2 or 3 hydroxyl groups is preferable. Specific examples of the compound having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Of these, propylene glycol and dipropylene glycol are more preferable. Specific examples of the initiator having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane and the like. Of these, glycerin is particularly preferable.
Further, polyoxyalkylene diols or polyoxyalkylene triols having a molecular weight of 80 to 10,000 per hydroxyl group obtained by ring-opening addition polymerization of alkylene oxide to these compounds having 2 or 3 hydroxyl groups Is preferably used as an initiator. An initiator may be used individually by 1 type and may use 2 or more types together.

The alkylene oxide used for the synthesis of the precursor polymer (A′-a) or the initiator preferably has 2 to 20 carbon atoms, and specific examples thereof include propylene oxide, butylene oxide, and ethylene oxide. Propylene oxide is particularly preferred. An alkylene oxide may be used individually by 1 type, and may use 2 or more types together. When the polyoxyalkylene chain is composed of two or more oxyalkylene monomer units, the arrangement of the monomer units may be block or random.
Examples of the alkylene oxide ring-opening polymerization catalyst include an alkali metal catalyst, a double metal cyanide complex catalyst, and a metal porphyrin. In particular, a double metal cyanide complex catalyst is preferable in that the molecular weight distribution of the polymer (A) tends to be small, and a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand is more preferable.

The double metal cyanide complex catalyst is obtained by reacting a reaction product (hereinafter referred to as catalyst skeleton) obtained by reacting a metal halide salt with an alkali metal cyanometalate in water with t-butyl alcohol or t-butyl alcohol and a formula ( Those prepared by coordinating an organic ligand comprising the compound represented by i) are preferred.
In particular, a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand to the catalyst skeleton is preferable.

Examples of the metal halide metal include Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), V (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II), and Pb (II) Two or more are preferably used. Zn (II) or Fe (II) is more preferable, and Zn (II) is particularly preferable in that the molecular weight distribution can be narrowed.
As the metal constituting the cyanometalate of the alkali metal cyanometalate, Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II) , Mn (III), Ni (II), V (IV), and V (V) are preferably used alone or in combination. Co (III) or Fe (III) is more preferable, and Co (III) is particularly preferable in that the molecular weight distribution can be narrowed.
Note that Roman numerals such as II, III, IV, and V in parentheses following the metal element symbol indicate the valence of the metal.

The catalyst skeleton synthesis reaction is preferably carried out by mixing a metal halide aqueous solution and an alkali metal cyanometalate aqueous solution, more preferably by dropping the alkali metal cyanometalate aqueous solution into the metal halide aqueous solution. The reaction temperature is preferably 0 ° C. or higher and lower than 70 ° C., more preferably 30 ° C. or higher and lower than 70 ° C.
The metal halide salt is preferably zinc halide. The alkali metal cyanometalate is preferably Na ₃ [Co (CN) ₆ ] or K ₃ [Co (CN) ₆ ], and Na ₃ [Co (CN) ₆ ] or K ₃ [Co (CN) ₆ ] Is particularly preferable.
As the catalyst skeleton, Zn ₃ [Co (CN) ₆ ] ₂ (that is, zinc hexacyanocobaltate complex) is more preferable.

  Next, a compound to be an organic ligand is coordinated with the catalyst skeleton. The organic ligand is preferably at least one compound selected from the group consisting of alcohols, ethers, ketones, esters, amines and amides. It is preferable to use t-butyl alcohol or a mixture of t-butyl alcohol and a compound represented by formula (i) as an organic ligand in that the molecular weight distribution can be narrowed.

R ¹¹ —C (CH ₃ ) ₂ (OR ¹⁰ ) _n OH (i)
In the formula (i), R ¹¹ is a methyl group or an ethyl group, R ¹⁰ is an ethylene group or a group in which a hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, and n is an integer of 1 to 3. .
Examples of the compound represented by the formula (i) include the following compounds.
Ethylene glycol mono-t-butyl ether, propylene glycol mono-t-butyl ether, 1,2-butylene glycol mono-t-butyl ether, isobutylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether, propylene glycol mono-t -Pentyl ether, 1,2-butylene glycol mono-t-pentyl ether, isobutylene glycol mono-t-pentyl ether, diethylene glycol mono-t-butyl ether, dipropylene glycol mono-t-butyl ether, di-1,2-butylene glycol Mono-t-butyl ether, diisobutylene glycol mono-t-butyl ether, diethylene glycol mono-t-pentyl ether, dipropylene glycol mono-t Pentyl ether, di-1,2-butylene glycol mono-t-pentyl ether, diisobutylene glycol mono-t-pentyl ether, triethylene glycol mono-t-butyl ether, tripropylene glycol mono-t-butyl ether, tri-1, 2-butylene glycol mono-t-butyl ether, triisobutylene glycol mono-t-butyl ether, triethylene glycol mono-t-pentyl ether, tripropylene glycol mono-t-pentyl ether, tri-1,2-butylene glycol mono-t -Pentyl ether, triisobutylene glycol mono-t-pentyl ether.

  Among these, the compounds used in combination with t-butyl alcohol are ethylene glycol mono-t-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether, propylene glycol mono-t-pentyl ether, diethylene glycol mono -T-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol mono-t-butyl ether, and triethylene glycol mono-t-pentyl ether are more preferable. More preferred are ethylene glycol mono-t-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether, propylene glycol mono-t-pentyl ether, and ethylene glycol mono-t in that the molecular weight distribution can be narrower. -Butyl ether is most preferred.

Further, when t-butyl alcohol and the compound represented by formula (i) are used in combination, the mixing ratio is such that the mass ratio of t-butyl alcohol / compound represented by formula (i) is 20 to 95/80 to 5. preferable.
The composite metal cyanide complex catalyst comprises a catalyst skeleton obtained by reacting a zinc halide and an alkali metal cyanocobaltate with t-butyl alcohol or a mixture of t-butyl alcohol and a compound represented by formula (i). It is manufactured by heating and stirring in an organic ligand solution containing aging (aging step), followed by filtration, washing and drying by a known method.

<Precursor polymer (A′-b)>
A linear or branched precursor polymer (A′-b) having a polyoxyalkylene chain and all terminals being unsaturated groups is a precursor polymer (A′-a) having all terminals being hydroxyl groups. The hydroxyl group (—OH) of this compound is alcoholated to make —OM (M is an alkali metal), and then reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride. This method is preferable because it is general and the raw materials are easily available and the reaction yield is high.
Alternatively, a method in which a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group is reacted with the precursor polymer (A′-a) to introduce the unsaturated group via an ester bond, a urethane bond, a carbonate bond, or the like. But you can get it.

  As described above, it is preferable that the precursor polymer (A ′) includes the precursor polymer (A′11) having at least three functional groups at the main chain terminals per molecule. Accordingly, as the precursor polymer (A ′), among the precursor polymers (A′-a), it was produced by ring-opening addition polymerization of alkylene oxide to an initiator having three active hydrogens in the presence of a catalyst. It is preferable to use a precursor polymer (A′11-a). Alternatively, among the precursor polymers (A′-b), a hydroxyl group of a polymer in which an alkylene oxide is subjected to ring-opening addition polymerization to an initiator having three active hydrogens in the presence of a catalyst, and the main chain terminal is a hydroxyl group. It is preferable to use a precursor polymer (A′11-b) produced by a method in which an alcoholate is converted into —OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon.

<Method for producing polymer (A)>
As a method for obtaining the polymer (A) by introducing a reactive silicon group into the terminal unsaturated group of the precursor polymer (A′-b), a known method can be used. For example, the following method [1] or [2] can be used.
[1] A method of reacting a terminal unsaturated group with a silicon hydride compound represented by the following formula (2) in the presence of a catalyst. However, X ¹ and R ¹ in the formula (2) are the same as in the above formula (1).
HSiX ¹ ₂ R ¹ (2)
[2] A method of reacting a terminal unsaturated group with a mercapto group of a silicon compound represented by the following formula (3).
W ¹ R ² —SiX ¹ ₂ R ¹ (3)
X ¹ and R ¹ in the formula (3) are the same as those in the above formula (1). R ² is a divalent organic group, and W ¹ is a mercapto group.

The method for obtaining the polymer (A) by introducing a reactive silicon group into the terminal hydroxyl group of the precursor polymer (A′-a) without passing through the precursor polymer (A′-b) is a known method. Can be used. For example, the following method [3] or [4] can be used.
[3] A method in which a terminal hydroxyl group and an isocyanate silane compound (U) represented by the following formula (4) are urethanated. This reaction may be performed in the presence of a urethanization catalyst.
^{_{NCO- (CH 2) n -SiX 1}} 2 R 1 ... (4)
X ¹ and R ¹ in the formula (4) are the same as in the above formula (1). n is an integer of 1 to 8, preferably 1 to 3.
Preferred examples of the isocyanate silane compound (U) include 1-isocyanate methyldimethoxymethylsilane, 1-isocyanatemethyldiethoxyethylsilane, 1-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyldiethoxy. Examples include ethylsilane.
The urethanization catalyst to be used is not specifically limited, A well-known urethanization catalyst can be used suitably. For example, organic tin compounds (dibutyltin dilaurate, dioctyltin dilaurate, etc.), metal catalysts such as bismuth compounds, and base catalysts such as organic amines are used. The reaction temperature is preferably 20 to 200 ° C, particularly preferably 50 to 150 ° C. The urethanization reaction is preferably performed in an inert gas (nitrogen gas is preferred) atmosphere.

[4] A group represented by W ² of a silicon compound represented by the following formula (5) after reacting a terminal hydroxyl group with a polyisocyanate compound such as tolylene diisocyanate to convert the terminal to an isocyanate group. How to react.
_{^{W 2 R 3 -SiX 1 2 R}} 1 ... (5)
X ¹ and R ¹ in the formula (5) are the same as in the above formula (1). R ³ is a divalent organic group, and W ² is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary).

In the polymer (A), the functional group at the end of the main chain substituted with the group containing the reactive silicon group among the functional groups at the main chain end of the precursor polymer (A ′) into which the reactive silicon group can be introduced. The ratio (hereinafter sometimes referred to as “silylation rate”) is preferably 45 to 100 mol%, more preferably 50 to 84 mol%, and still more preferably 63 to 84 mol%.
When two or more kinds of polymers corresponding to the polymer (A) are mixed and used, the silylation rate in the mixture after mixing may be within the above range, and one of the polymers (A) before mixing. A part having a silylation rate of less than 70% may be used.

The value of the silylation rate in this specification can be measured by NMR analysis. Or, since the reaction rate between the precursor polymer (A ′) produced using methallyl chloride and the silylating agent can be regarded as almost 100%, silylation with respect to the charged amount of the precursor polymer (A ′). You may use the value calculated from the preparation amount of an agent. In the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent, a side reaction occurs. Approximately 10 mol% of the allyl group of the precursor polymer (A ′) produced using allyl chloride is isomerized and not silylated, so that 100% silylation is difficult. However, in a silylation with a silylation rate of up to 90%, the reaction rate can be regarded as almost 100%. Therefore, when the silylation rate of the polymer (A) to be obtained by the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent is less than 90%, the polymer ( As the value of the silylation rate in A), a value calculated from the charged amount of the silylating agent with respect to the charged amount of the precursor polymer (A ′) may be used.
The value of the silylation rate of the polymer (C) described later is also the same.

As described later, the reactivity represented by the above formula (1) is linear to the precursor polymer (C ′) capable of introducing a reactive silicon group at one end into the curable composition of the present invention. A polymer (C) obtained by introducing a silicon group can be contained.
By mix | blending a polymer (C), the viscosity of a curable composition can be reduced. On the other hand, when the polymer (C) is blended with the polymer (A) and cured, the polymers (A) are cross-linked and a part of the polymer (A) reacts with the polymer (C). Since the polymer (C) has a reactive silicon group only at one end, the polymer (A) reacts with the polymer (C) to inhibit crosslinking of the polymer (A). Therefore, when there are too many compounding quantities of a polymer (C), it will be hardened | cured and may become uncured.
That is, in order to make the curable composition have a lower viscosity and not to cause poor curing, it is advantageous that the amount of the polymer (C) is large and the silylation rate of the polymer (A) is high. The higher the silylation rate of the polymer (A), the more the polymer (C) is blended, the more difficult it is to crosslink from the relationship of the quantity ratio, and the harder it becomes to be uncured.
Therefore, the silylation rate of the polymer (A) needs to be in a range where good curability can be obtained in the curable composition containing the polymer (C), and the higher the silylation rate, the higher the silylation rate. The amount of the polymer (C) added can be increased. As the blending amount of the polymer (C) is larger, the viscosity becomes lower, so that workability becomes better as a curable composition for a sealing material or an adhesive.

When the precursor polymer (A ′) has a hydroxyl group as a functional group at the end of the main chain into which a reactive silicon group can be introduced, the main chain terminal of the hydroxyl group substituted with a group containing a reactive silicon group out of all the hydroxyl groups The functional group ratio (silylation rate) is preferably 45 mol% or more, and more preferably 50 mol% or more. When it is 45 mol% or more, a sealing material and an adhesive can be produced without becoming a gel-like material that does not harden depending on the formulation. The silylation rate may be 100 mol%.
Further, when the precursor polymer (A ′) has an unsaturated group as a functional group at the end of the main chain capable of introducing a reactive silicon group, the silylation rate is preferably 45 mol% or more for the same reason. Mole% or more is more preferable. The silylation rate may be 100 mol%.

The molecular weight per functional group of the polymer (A) is 7,000 to 20,000, preferably 7,000 to 18,500, and more preferably 7,500 to 17,000. When it is 7,000 or more, the elongation property and flexibility of the cured product are good. When it is 20,000 or less, the curable composition tends to have a low viscosity, which is preferable for obtaining good workability.
The molecular weight distribution (Mw / Mn) of the polymer (A) is 1.01-1.40. Within this range, the flexibility is good and the viscosity is low. When the number average molecular weight is the same, the narrower the molecular weight distribution, the lower the viscosity. The reason is that when the molecular weight distribution is wide, a large number of high molecular weight substances are present, which causes high viscosity. Alternatively, as shown in the examples described later, when the flexibility is the same, the stretched physical properties are good. The reason is considered to be that when the molecular weight distribution exceeds 1.40, the amount of low molecular weight polymer components increases, so that the distance between cross-linking points becomes short and it becomes difficult to extend. Therefore, the molecular weight distribution is preferably narrower, more preferably 1.01-1.30, and still more preferably 1.01-1.20. The molecular weight distribution (Mw / Mn) of the polymer (A) can be controlled by the type of catalyst and the polymerization conditions (temperature, stirring conditions, pressure, etc.).

In the present invention, when the polymer (A) is a mixture, the molecular weight and the molecular weight distribution (Mw / Mn) per functional group before mixing are within the above ranges.
The same applies when the polymer (C) described later is a mixture.

Although the polymer (A) may have a reactive silicon group other than the reactive silicon group represented by the formula (1), the reaction of the polymer (A) from the viewpoint of excellent storage stability and elongation property. The reactive silicon group is preferably only the reactive silicon group represented by the formula (1).
The polymer (A) may be used alone or in combination of two or more.
When two or more kinds of polymers corresponding to the polymer (A) coexist in the curable composition, their reactive silicon groups may be the same as or different from each other.

<Polymer (C)>
The curable composition of the present invention may contain a polymer (C) in addition to the polymer (A). The polymer (C) is a polymer that is linear, has an alkylene oxide monomer unit in the main chain, and has a reactive silicon group at one end. The reactive silicon group is preferably a group represented by the above formula (1).
The polymer (C) is linear, has an alkylene oxide monomer unit in the main chain, and has a reactive silicon group on the precursor polymer (C ′) capable of introducing a reactive silicon group at one end. Obtained by introduction.
The reactive silicon group of the polymer (A) coexisting in the curable composition and the reactive silicon group of the polymer (C) may be the same or different from each other.
Specifically, one main chain end group of both ends of the main chain of the precursor polymer (C ′) is a reactive group, preferably a hydroxyl group or an unsaturated group, It is preferable to introduce a reactive silicon group by reacting a compound having a reactive group and a reactive silicon group with the precursor polymer (C ′). The other main chain terminal group of the precursor polymer (C ′) is preferably an inert organic group that does not have reactivity with the compound having a reactive silicon group.

The polymer (C) is preferably obtained through a step of addition polymerization of an alkylene oxide monomer to an initiator having 1 functional group.
The repeating unit in the precursor polymer (C ′) and the polymer (C) includes an alkylene oxide monomer unit. The main chains of the precursor polymer (C ′) and the polymer (C) preferably have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
It is preferable that the polymer (C) has a polyoxyalkylene chain because the compatibility with the polymer (A) is good and the storage stability is good.

As the precursor polymer (C ′), the following precursor polymer (C′1) or precursor polymer (C′2) is preferable.
Precursor polymer (C′1): Polyoxyalkylene chain, one terminal is a hydroxyl group, and the other main chain terminal group is not reactive with the compound having a reactive silicon group, inert A linear precursor polymer, which is an organic group.
Precursor polymer (C′2): having a polyoxyalkylene chain, one terminal is an unsaturated group, and the other main chain terminal group is not reactive with the compound having the reactive silicon group, A linear precursor polymer which is an inert organic group.
The precursor polymer (C′1) can be produced by subjecting an alkylene oxide to ring-opening addition polymerization to an initiator having one active hydrogen in the presence of a catalyst.
Specific examples of the initiator include an aliphatic monool having 1 to 20 carbon atoms, an alicyclic monool having 1 to 20 carbon atoms, an aromatic monool having 1 to 20 carbon atoms, a thiol, a secondary amine, and a carboxylic acid. Or a polyoxyalkylene monool having a molecular weight of 300 to 5,000 per hydroxyl group obtained by ring-opening addition polymerization of alkylene oxide to the monool. More preferred is a polyoxyalkylene monool having a molecular weight of 300 to 3,300 per hydroxyl group. An unsaturated group-containing monohydroxy compound such as allyl alcohol can also be used. An initiator may be used individually by 1 type and may use 2 or more types together.
The alkylene oxide and alkylene oxide ring-opening polymerization catalyst used for the synthesis of the precursor polymer (C′1) or the initiator are the alkylene oxide and alkylene oxide used for the synthesis of the precursor polymer (A′-a) described above. The same applies to the ring polymerization catalyst and preferred embodiments.
The precursor polymer (C′1) is preferably polyoxypropylene monool.

The precursor polymer (C′2) is obtained by alcoholating the hydroxyl group (—OH) of the precursor polymer (C′1) whose one end is a hydroxyl group into -OM (M is an alkali metal), It can be produced by a method of reacting with an unsaturated group-containing halogenated hydrocarbon. This method is preferable because it is general and the raw materials are easily available and the reaction yield is high.
Alternatively, a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group is reacted with the precursor polymer (C′1) to introduce an unsaturated group via an ester bond, a urethane bond, a carbonate bond, or the like. can get.

As a method for obtaining the polymer (C) by introducing a reactive silicon group into the terminal unsaturated group of the precursor polymer (C′2), a known method can be used. For example, the above method [1] or [2] can be used.
As a method for obtaining a polymer (C) by introducing a reactive silicon group into the terminal hydroxyl group of the precursor polymer (C′1), a known method can be used. For example, the above method [3] or [4] can be used.

In the polymer (C), the proportion of the main chain end groups substituted with groups containing reactive silicon groups among the main chain end groups capable of introducing reactive silicon groups in the precursor polymer (C ′) (silylation) The ratio is preferably 60 to 100 mol%.
The silylation rate in the polymer (C) is determined by reacting the terminal reactive group of the precursor polymer (C ′) with a compound having a reactive silicon group. And the reactive silicon group and the molar ratio can be controlled.
When the silylation rate at one end of the polymer (C) is 60 mol% or more, the plasticizer has low transferability, and contamination around the sealing material part and adhesion are improved.
In particular, when the precursor polymer (C ′) has a hydroxyl group as a main chain end group capable of introducing a reactive silicon group, the main chain end group substituted with a group containing a reactive silicon group out of all the hydroxyl groups The ratio (silylation rate) is preferably 60 mol% or more, more preferably 75 mol% or more from the above point.
Similarly, when the precursor polymer (C ′) has an unsaturated group as a main chain terminal group capable of introducing a reactive silicon group, the silylation rate is preferably 60 mol% or more for the same reason. Mole% or more is more preferable. The silylation rate may be 100 mol%.

The number average molecular weight (Mn) of the polymer (C) is 3,000 or more and 20,000 or less, preferably 3,000 or more and 15,000 or less, more preferably 5,000 or more and 12,000. It is as follows. If the number average molecular weight (Mn) is 3,000 or more, even if the polymer (C) has a reactive silicon group, there is no contamination around the sealing material part, the adhesion is improved, and the cured product is Good physical properties. When it is 20,000 or less, the viscosity of the polymer (C) becomes low, and it works effectively as a plasticizer.
The molecular weight per functional group of the polymer (C) is preferably 2,000 to 15,000, more preferably 2,000 to 12,000.
The molecular weight distribution (Mw / Mn) of the polymer (C) is preferably from 1.01 to 1.30. Within this range, the viscosity of the polymer (C) tends to be lower. As for Mw / Mn, 1.01-1.20 is more preferable.
The molecular weight distribution (Mw / Mn) of the polymer (C) can be controlled by the type of catalyst and polymerization conditions (temperature, stirring conditions, pressure, etc.).

The polymer (C) may have a reactive silicon group other than the reactive silicon group represented by the formula (1), but from the viewpoint of excellent storage stability and elongation property, the polymer (C) The reactive silicon group is preferably only the reactive silicon group represented by the formula (1).
A polymer (C) may be used individually by 1 type, and may use 2 or more types together.
When two or more kinds of polymers corresponding to the polymer (C) coexist in the curable composition, their reactive silicon groups may be the same as or different from each other.
In the polymer (C), the main chain terminal group other than the reactive silicon group is preferably an inert organic group. For example, when an unsaturated group-containing monohydroxy compound such as allyl alcohol is used as an initiator, a precursor polymer (C′1) in which one main chain terminal group is a hydroxyl group and the other main chain terminal group is an unsaturated group. ) Is obtained. When a reactive silicon group is introduced into the terminal unsaturated group to obtain the polymer (C), the terminal hydroxyl group is preferably converted to an inert organic group by a method such as reacting with benzoyl chloride.

When the curable composition of this invention contains a polymer (A) and a polymer (C), the ratio of both content is a polymer (C) with respect to 100 mass parts of a polymer (A). Is preferably 60 parts by mass or less, and more preferably 50 parts by mass or less.
When the polymer (C) is contained, the viscosity of the curable composition is lowered and good workability is easily obtained. When the content of the polymer (C) is not more than the upper limit of the above range, the crosslinking point is sufficiently obtained, so that excellent flexibility and elongation are easily obtained in the cured product obtained by curing the curable composition. .

<Polymer (D)>
The curable composition of the present invention contains, in addition to the polymer (A), a (meth) acrylic acid ester copolymer (D) having a reactive silicon group (also simply referred to as a polymer (D)). But you can. The polymers (A), (C) and (D) may be included.
The repeating unit in the main chain of the polymer (D) contains a (meth) acrylic acid alkyl ester monomer unit and does not contain an alkylene oxide monomer unit. Such a polymer contributes to improving the mechanical strength of the cured product and improving the weather resistance of the curable composition and the cured product. For example, it is effective in suppressing the occurrence of cracks (fine cracks) on the surface when the cured product is exposed to ultraviolet rays for a long time, such as when applied to a sealant used outdoors.

The polymer (D) is a copolymer containing a structural unit derived from a (meth) acrylic acid alkyl ester represented by the following general formula (ii), and the reaction represented by the general formula (iii) It is a polymer having a functional silicon group at the main chain terminal or side chain.
CH ₂ = CR ¹² COOR ¹³ (ii)
(In the formula, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents an alkyl group having 1 to 30 carbon atoms.)
-SiX ¹ _a R ¹ _(3-a) (iii)
^R 1, ^{X 1} in the formula is the same meaning as ^R 1, ^{X 1} in the formula (1). a is an integer of 1 to 3.
The reactive silicon groups of the polymer (A) and the polymer (D) that are simultaneously present in the curable composition may be the same as or different from each other.
The polymer (D) is a homopolymer or copolymer composed of structural units derived from one or more of the (meth) acrylic acid alkyl ester monomers represented by the general formula (ii). There may be a structural unit derived from one or more of the (meth) acrylic acid alkyl ester monomers represented by the general formula (ii), and an unsaturated group other than the monomer. The copolymer which consists of a structural unit based on 1 type, or 2 or more types of a monomer may be sufficient.
The number average molecular weight (Mn) of the polymer (D) is preferably 500 to 50,000, more preferably 1,000 to 30,000, and still more preferably 2,000 to 20,000. Alternatively, the mass average molecular weight (Mw) is preferably 600 to 100,000, more preferably 1,200 to 60,000, and further preferably 2,400 to 40,000.

The polymer (D) can be produced by polymerizing the monomer in the presence of components other than the polymer (D) among the constituent components of the curable composition. For example, it can be synthesized by polymerization in the presence of the polymer (A). Or after polymerizing and synthesizing the above monomers in the presence of the components of the curable composition other than the polymers (A) and (D), they may be mixed with the polymer (A) or the like. The monomer may be polymerized in the absence of the constituent components of the curable composition. In this case, it can be polymerized in esters, ketones or aromatic organic solvents and mixed with the polymer (A) or the like. At that time, the solvent used in the synthesis may be removed by vacuum degassing or the like before mixing, or may be removed after mixing with the polymer (A) or the like. It is preferable to deaerate after mixing from the viewpoint of easy handling.
Moreover, the (meth) acrylic acid ester copolymer (D) which has a commercially available reactive silicon group can also be used. As such a commercial product, for example, product name: ARUFUON US-6000 series (for example, US-6120, US-6110, etc., both of which are product names) manufactured by Toa Gosei Co., Ltd. can be used.

When the curable composition of this invention contains a polymer (A) and a polymer (D), ratio of both content is a polymer (D) with respect to 100 mass parts of a polymer (A). Is preferably 5 to 100 parts by mass, and more preferably 5 to 50 parts by mass.
When the content of the polymer (D) is at least the lower limit of the above range, the effect of adding the polymer (D) can be sufficiently obtained. When it is at most the upper limit of the above range, workability and a decrease in elongation of the cured product obtained by curing the curable composition can be suppressed.

<Compound (B)>
The curable composition of the present invention contains two or more compounds (B) capable of generating trimethylsilanol by hydrolysis (also simply referred to as compound (B)).
Compound (B) is also called a modulus modifier, and trimethylsilanol generated by hydrolysis reacts with the polymer (A), (C), or (D) to suppress a decrease in elastic modulus, and a cured product. Can be improved, and can contribute to prevention of surface stickiness of the cured product.
Compound (B) is a compound containing, for example, a trimethylsilyloxy group in the molecule. Specific examples include phenoxytrimethylsilane, trimethylolpropane tristrimethylsilyl (TMP-3TMS), 2,2-bis [(trimethylsiloxy) methyl] -1- (trimethylsiloxy) butane, and the like.
The compound (B) is not particularly limited as long as it has a functional group capable of generating trimethylsilanol, such as a trimethylsilyloxy group, but a compound having a molecular weight of 2,000 or less is preferable, and a compound having a molecular weight of 500 or less is more preferable. In addition, the average number of functional groups capable of generating trimethylsilanol is preferably 0.5 to 8.0 or less, and more preferably 0.9 to 4.0 on average.

Compound (B) is, for example, a monovalent alcohol such as methanol, ethanol, 2-ethylhexanol, or phenol; a polyhydric alcohol such as ethylene glycol, propanediol, trimethylolpropane, glycerin, pentaerythritol, or sorbitol; Obtained by trimethylsilyloxylation of the hydroxyl group. Examples of the compound to be trimethylsilyloxylated include 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane.
Although the trimethylsilyloxylation rate in all the hydroxyl groups of a polyhydric alcohol can be adjusted arbitrarily, 50 mol% or more is preferable and 80 mol% or more is more preferable. Most preferably, substantially all hydroxyl groups are trimethylsilyloxylated.

In this invention, 2 or more types of compounds (B) are used together. The two or more compounds (B) used in combination are preferably different in hydrolysis rate.
Moreover, when using 2 or more types of compounds (B) together, durability of hardened | cured material is obtained by using the compound (B) whose hydrolysis rate is faster than the hydrolysis rate of the reactive silicon group in a polymer (A). It is easy to obtain a sufficient improvement effect. For this reason, it is preferable to use at least one compound (B) having a faster hydrolysis rate than the reactive silicon group in the polymer (A).
For example, the compound (B) having a faster hydrolysis rate than the reactive silicon group hydrolysis rate in the polymer (A) includes phenoxytrimethylsilane, and the reactive silicon group hydrolysis in the polymer (A). Examples of the compound (B) having a slower hydrolysis rate than the decomposition rate include tristrimethylsilyl form of trimethylolpropane (TMP-3TMS).

As the compound (B), it is particularly preferable to use, for example, phenoxytrimethylsilane and trimethylolpropane tristrimethylsilyl (TMP-3TMS) in combination. TMP-3TMS has a slower hydrolysis rate than phenoxytrimethylsilane and a slower hydrolysis rate than a reactive silicon group in the polymer (A). For this reason, when TMP-3TMS is used as the compound (B), the curing reaction of the polymer (A) tends to proceed quickly, and contributes to good curability. On the other hand, phenoxytrimethylsilane has a higher hydrolysis rate than TMP-3TMS, and has a higher hydrolysis rate than the hydrolysis rate of the reactive silicon group in the polymer (A). Therefore, when phenoxytrimethylsilane is used as the compound (B), the curing reaction of the polymer (A) is delayed, but the effect of improving the durability of the cured product is high.
When phenoxytrimethylsilane and TMP-3TMS are used in combination, phenoxytrimethylsilane / TMP-3TMS is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, as the mass ratio of the amounts used. If the mass ratio of the amounts used is within the above range, good curability and the effect of improving the durability of the cured product can be obtained in a well-balanced manner, and the durability is high despite the relatively high elastic modulus. However, it is easy to obtain a cured product.
Of the total amount of compound (B) contained in the curable composition, the total of phenoxytrimethylsilane and TMP-3TMS is preferably 60% by mass or more, more preferably 80% by mass or more, and 100% by mass. Particularly preferred.

The total content of the compound (B) in the curable composition is 0.4 to 2.0 parts by mass with respect to 100 parts by mass of the polymer (A), and 0.4 to 1.5 parts by mass. Is preferred. When the content of the compound (B) is at least the lower limit of the above range, the effect of adding the compound (B) can be sufficiently obtained. In addition, surface stickiness of the cured product is easily prevented. Good sclerosis | hardenability is easy to be obtained as it is below the upper limit of the said range.
The total amount of the compound (B) used satisfies the above content range, and the number of moles (b) of the functional group capable of generating trimethylsilanol of the compound (B) present in the curable composition is 1 When the molar ratio (a / b) of the sum of the hydroxyl groups and hydrolyzable groups (a) (sum of X ^{1 in} formula (1)) of the polymer (A) present in the curable composition is It is preferable that it is 0.5-7.2. When the molar ratio (a / b) is not less than the lower limit of the above range, a sufficient curing rate of the polymer (A) can be easily obtained, and if it is not more than the upper limit, the mechanical properties of the curable composition are improved. The effect of suppressing the surface stickiness of the cured product is easily obtained. The molar ratio (a / b) is more preferably 1.5 to 6.3, and even more preferably 1.8 to 5.0.
The compound (B) may be added in advance to the constituent components of the curable composition (for example, the polymer (A), (C), or (D)), and is added when producing the curable composition. May be.

<Other ingredients>
The curable composition of this invention can contain a well-known component in a curable composition other than said polymer (A), (C), (D), and a compound (B). Specific examples include additives such as a curing catalyst, a co-catalyst, a filler, a plasticizer, a thixotropic agent, an air oxidation curable compound, a stabilizer, and an adhesive agent.
The method for preparing such a curable composition containing an additive component is not particularly limited, and the additive component may be added once or several times at an appropriate time during or after the production of the curable composition. What is necessary is just to add separately. Hereinafter, these additive components will be described.

[Curing catalyst]
The curing catalyst is not particularly limited as long as it is a compound that catalyzes the hydrolysis reaction of the reactive silicon group and compound (B), and a salt (octylic acid, octenoic acid, naphthene) of a metal (tin, bismuth, etc.) and an organic acid. Acids, etc.); organometallic complexes and the like are preferred. The organic acid salt is preferably stannous octylate, bismuth tris (2-ethylhexanoate), or the like.
0.01-15.0 mass parts is preferable with respect to 100 mass parts of a polymer (A), and, as for the usage-amount of a curing catalyst, 0.1-10 mass parts is more preferable. 1 type may be used independently and may be used together 2 or more types.

[Cocatalyst]
A curing catalyst and a co-catalyst may be used in combination. The cocatalyst is preferably an amine, carboxylic acid, or phosphoric acid, and an amine is particularly preferable from the viewpoint of fast curability of the curable composition and mechanical properties of the cured product.
The amine is not particularly limited, and a primary amine is preferable. Specific examples of amines include aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, laurylamine, N, N-dimethyloctylamine; ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. An amine having a hydrolyzable silyl group, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane. A promoter may be used individually by 1 type, and may be used together 2 or more types. Especially, combined use of a bivalent tin compound and a primary amine compound is preferable, and combined use of stannous octylate and laurylamine is more preferable.
The cocatalyst is preferably used in an amount of 0.01 to 15 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymer (A).

[Filler]
As the filler, 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 produced by a precipitation method, colloidal calcium carbonate whose surface is treated with a fatty acid or a resin acid organic substance, Fumed silica; precipitated silica; surface silicone-treated silica fine powder; silicic anhydride; hydrous silicic acid; carbon black; magnesium carbonate; diatomaceous earth; calcined clay; clay; talc; 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, sa Organic resin hollow bodies such as orchid balloons, polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, styrene-acrylic resin balloons, polyacrylonitrile balloons; resin beads, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, Examples thereof include powdery fillers such as graphite, fine aluminum powder, and flint powder; and fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber, and polyethylene fiber.

  These fillers may be used alone or in combination of two or more. Among these, it is preferable to use calcium carbonate, and it is particularly preferable to use heavy calcium carbonate and colloidal calcium carbonate in combination. By using a hollow body (balloon), the curable composition and its cured product can be reduced in weight. 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. 1-1000 mass parts is preferable with respect to 100 mass parts of a polymer (A), and, as for the usage-amount of the filler in this invention, 50-250 mass parts is more preferable.

[Plasticizer]
Plasticizers include phthalate esters such as di (2-ethylhexyl) phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate; dioctyl adipate, bis (2-methylnonyl) 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, 4,5-epoxycyclohexane-1,2-dicarboxylic acid Epoxy plasticizers such as di-2-ethylhexyl and epoxy benzyl stearate; Chlorinated paraffins; Isoparaffins; Polyester plasticizers such as polyesters obtained by reacting dibasic acids with dihydric alcohols; Polyethers such as polyoxyalkylene polyols A polyether derivative in which the hydroxyl group of polyoxypropylene glycol is sealed with an alkyl ether; an oligomer of polystyrene such as poly-α-methylstyrene and polystyrene; a polybutadiene, a butadiene-acrylonitrile copolymer, a polychloroprene, a polyisoprene, Examples include oligomers such as polybutene, hydrogenated polybutene, and epoxidized polybutadiene.
As isoparaffin as a plasticizer, a commercially available isoparaffin solvent can be used. For example, the product name: Isopar series (Isopar H, Isopar M, etc., both of which are product names) manufactured by ExxonMobil can be used.
Paraffin hydrocarbons can also be used as a plasticizer and are effective in improving the surface stickiness (tack) of the cured product. Paraffinic hydrocarbons having 6 or more carbon atoms, more preferably 8 to 18 carbon atoms are preferred, because a remarkable effect can be easily obtained. Specifically, n-octane, 2-ethylheptane, 3-methylheptane, n-nonane, 2-methyloctane, 3-methyloctane, n-decane, 2-methylnonane, 3-methylnonane, n-undecane, n -Dodecane, n-tridecane, n-tetradecane, 4,5-dipropyloctane, 3-methyltridecane, 6-methyltridecane, n-hexadecane, n-heptadecane, n-octadecane and the like can be exemplified.

  Relatively low molecular weight plasticizers such as the above phthalates are most commonly used because they have a large plasticizing effect and are effective in reducing the viscosity of the composition, but these low molecular plasticizers were used. In the cured product of the curable composition, since the plasticizer has a high transferability to the surface, when used as an adhesive, there may be a problem of a decrease in adhesiveness. The adherend may be contaminated, and the weather resistance of the cured product itself may be adversely affected. Therefore, when such a low molecular plasticizer is used, it is preferable to appropriately adjust the content in consideration of compatibility with the curable composition.

In the present invention, among the plasticizers exemplified above, it is preferable to use a polymer plasticizer having Mn of 1,000 or more, Mw of 1,000 or more, or a molecular weight per hydroxyl group of 500 or more.
For example, a polyoxyalkylene polyol such as polypropylene polyol can be preferably used as a plasticizer. The molecular weight per hydroxyl group of the polyoxyalkylene polyol as a plasticizer is preferably 500 to 20,000, more preferably 1,000 to 12,000.
A solventless acrylic polymer can be preferably used as a plasticizer. The mass average molecular weight of the acrylic polymer as a plasticizer is preferably 1,000 to 10,000. For example, a commercially available solventless acrylic polymer can be used. As such a commercially available product, for example, product name: ARUFON UP series (for example, UP-1000, US-1110, etc., both of which are product names) manufactured by Toa Gosei Co., Ltd. can be used.
In this case, only a high molecular plasticizer may be used, or a high molecular plasticizer and a low molecular plasticizer may be used in combination. By using a polymeric plasticizer, the effects of reducing the surface contamination and surrounding contamination of the cured product, improving the drying property of the paint on the cured product, and reducing the contamination of the paint surface can be obtained. It contributes to the improvement.

In addition, when an epoxy plasticizer such as 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl is used as a curing accelerator, particularly in combination with a divalent tin carboxylate and a primary amine. Has an effect that a cured product having a large return ratio (compression restoration rate) when the fixation is released after being fixed in a compressed state under a certain condition can be obtained. Said plasticizer may be used independently or may use 2 or more types together.
A plasticizer may be used individually by 1 type and may use 2 or more types together. 0.1-150 mass parts is preferable with respect to 100 mass parts of a polymer (A), and, as for the usage-amount of the plasticizer in this invention, 10-120 mass parts is more preferable.

[Thixotropic agent]
The sagging property of the curable composition is improved by the addition of the thixotropic agent. Examples of the thixotropic agent include hydrogenated castor oil, fatty acid amide, calcium stearate, zinc stearate, fine powder silica, and organic acid-treated calcium carbonate.
The thixotropic agent is preferably added in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).

[Air oxidation curable compound]
By adding an air oxidation curable compound to the curable composition, the weather resistance of the cured product and the adhesion of dust are improved.
Examples of the air oxidative curable compound include drying oils such as tung oil and linseed oil, alkyd resins obtained by modifying drying oils, acrylic polymers modified with drying oils, silicone resins, polybutadiene, and dienes having 5 to 8 carbon atoms. And diene polymers such as polymers and copolymers, modified products of these polymers and copolymers (maleinization modification, boiled oil modification, etc.), air curable polyester compounds, and the like. These may be used alone or in combination.
As for the usage-amount of an air oxidation curable compound, 0.1-50 mass parts is preferable with respect to 100 mass parts of a polymer (A).

[Stabilizer]
Stabilizers (anti-aging agents) include antioxidants, UV absorbers, light stabilizers, and hindered amines, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, hindered phenols Phosphorus and sulfur compounds can be used. In particular, it is preferable to use a combination of two or more of light stabilizers, antioxidants, and ultraviolet absorbers. By using such a method, the anti-aging effect can be improved as a whole by making use of the respective characteristics.
Specifically, it is particularly effective to combine two or more selected from tertiary and secondary hindered amine light stabilizers, benzotriazole ultraviolet absorbers, hindered phenols, and phosphite antioxidants. is there.
Products commercially available as antioxidants, ultraviolet absorbers, or light stabilizers can be used as appropriate.
It is preferable that the usage-amount of antioxidant, a ultraviolet absorber, and a light stabilizer is 0.1-10 mass parts, respectively with respect to 100 mass parts of a polymer (A). If the amount is less than 0.1 parts by mass, the anti-aging effect is not sufficiently exhibited, and if it exceeds 10 parts by mass, it is economically disadvantageous.

[Adhesive agent]
In the present technology, an adhesion-imparting agent may be used to improve adhesion. 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) propyltrimethoxytitanate, 3-mercaptopropyltrimethotitanate; and epoxy resins.
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, 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 resins, unsaturated polymer (petroleum resin.) Epoxy resin.
When adding the said organosilane coupling agent to a curable composition, it is preferable that the addition amount is 0.1-30 mass parts with respect to 100 mass parts of the polymer (A) of (A) component.
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 a cured resin component, and 10-80 mass parts is more preferable.

<Curable composition>
The curable composition of the present invention can also be prepared as a one-component type in which all the ingredients are pre-blended and stored and cured by moisture in the air after construction. The polymer (A) and the compound (B In addition to the main component containing), the curing agent composition is prepared as a two-component type in which components such as a curing catalyst, a filler and water are blended and the curing agent composition and the main component are mixed before use. You can also. In the case of the two-component type, a colorant such as toner may be added and mixed when the main agent and the curing agent are mixed.
According to the curable composition of the present invention, a cured product having good elongation and good durability can be obtained while having a relatively high elastic modulus.
For example, the value of M50 according to the measurement method described later is 0.14 to 0.30 N / mm ² , preferably 0.16 to 0.24 N / mm ² , and the elongation value according to the measurement method described later is 670 to 900%. The cured product preferably has a durability of 700 to 900% and does not cause cracks at the adhesion interface between the adherend and the cured product even after 2000 stretching tests are performed by the durability evaluation method described later. Is obtained.

  The curable composition of the present invention comprises a sealant (elastic sealant for building, sealant for multi-layer glass, etc.), sealant (anti-rust / waterproof sealant for glass edge, solar cell back surface seal It is useful as an adhesive used in the fields of electrical insulating materials (insulating coatings for electric wires and cables). In particular, it is suitable for applications that require stretch fatigue resistance, such as a sealing material to be installed outdoors.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
[Precursor polymer]
The precursor polymers used in the examples are shown in Table 1. Each precursor polymer is obtained in the following production examples. The double metal cyanide complex catalyst (alkylene oxide ring-opening polymerization catalyst) used for the production of the precursor polymer was obtained in the following Reference Production Example.
The precursor polymer (E′1) is a comparative example having a small molecular weight distribution, and the precursor polymer (E′2) is a comparative example having a small molecular weight per functional group.
In the following Reference Production Examples 1 and 2, the zinc chloride aqueous solution was prepared by dissolving 10 g of zinc chloride in 15 mL of water, and the potassium hexacyanocobaltate aqueous solution was prepared by dissolving 4 g of potassium hexacyanocobaltate in 80 mL of water. used.

(Reference Production Example 1: Production of double metal cyanide complex catalyst whose ligand is t-butyl alcohol)
A potassium hexacyanocobaltate aqueous solution was added dropwise to the zinc chloride aqueous solution at 40 ° C. over 30 minutes. After dropwise addition, 80 mL of t-butyl alcohol (hereinafter referred to as TBA) and 80 mL of water were added, and the mixture was stirred and aged at 60 ° C. for 1 hour. After aging, the complex was filtered off.
To the resulting complex, 40 mL of TBA and 80 mL of water were added, stirred for 30 minutes, washed and filtered. Further, 100 mL of TBA was added, and the mixture was stirred for 30 minutes and filtered. After drying under reduced pressure at 50 ° C. until the weight becomes constant, pulverization was performed to obtain a double metal cyanide complex catalyst (z-hexacyanocobaltate t-butyl alcohol complex catalyst) whose ligand is t-butyl alcohol. .

(Reference Production Example 2: Production of double metal cyanide complex catalyst whose ligand is glyme)
A potassium hexacyanocobaltate aqueous solution was dropped into the zinc chloride aqueous solution at 40 ° C. over 30 minutes. After completion of the dropwise addition, 80 mL of glyme and 80 mL of water were added, and after stirring at 60 ° C. for 1 hour, the complex was filtered off.
To the resulting complex, 80 mL of glyme and 80 mL of water were added and stirred for 30 minutes, followed by filtration. Further, 100 mL of glyme and 10 mL of water were added and stirred, followed by filtration. After drying at 80 ° C. for 4 hours and pulverizing, a double metal cyanide complex catalyst (zinc hexacyanocobaltate glyme complex catalyst) having a ligand of glyme was obtained.

(Production Example 1: Production of precursor polymer (A′1))
Polyoxypropylene triol (molecular weight 330 per functional group) obtained by ring-opening addition polymerization of propylene oxide to glycerin was used as an initiator (referred to as initiator A).
In the presence of a zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.08 g), propylene oxide (1,522 g) is added to initiator A (64.1 g), and the pressure of the reaction system does not decrease at 120 ° C. Reacted until. As a result, a precursor polymer (A′1) having a polyoxypropylene chain and having three hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (A′1) at 25 ° C. was 24 Pa · s. Mn measured by GPC was 30,000, Mw was 35,100, and thus Mw / Mn was 1.17.

(Production Example 2: Production of precursor polymer (A′2))
Polyoxypropylene diol (molecular weight 1,000 per functional group) obtained by ring-opening addition polymerization of propylene oxide to propylene glycol was used as an initiator (referred to as initiator B).
In the presence of zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.03 g), initiator B (64.1 g) is reacted with propylene oxide (525 g) at 120 ° C. until the pressure of the reaction system does not drop. I let you. As a result, a precursor polymer (A′2) having a polyoxypropylene chain and having two hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (A′2) at 25 ° C. was 20 Pa · s. Mn measured by GPC was 22,000, Mw was 23,800, and thus Mw / Mn was 1.08.

(Production Example 3: Production of precursor polymer (A'3))
In the presence of a zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.05 g), propylene oxide (858 g) was added to a mixture of initiator A (21.4 g) and initiator B (42.7 g). The reaction was continued at 0 ° C. until the pressure of the reaction system did not drop. As a result, a precursor polymer (A′3) having a polyoxypropylene chain and having 2.5 hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (A′3) at 25 ° C. was 23 Pa · s. Mn measured by GPC was 26,000, Mw was 31,800, and thus Mw / Mn was 1.22.

(Production Example 4: Production of precursor polymer (A′4))
Polyoxypropylene triol obtained by ring-opening addition polymerization of propylene oxide to glycerin (molecular weight 330 per functional group, initiator A) was used as an initiator.
In the presence of a zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.08 g), propylene oxide (2,280 g) is added to initiator A (64.1 g), and the pressure of the reaction system does not decrease at 120 ° C. Reacted until. As a result, a precursor polymer (A′4) having a polyoxypropylene chain and having three hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (A′4) at 25 ° C. was 50 Pa · s. Mn measured by GPC was 41,000, Mw was 47,100, and thus Mw / Mn was 1.15.

(Production Example 5: Production of precursor polymer (E′1))
Polyoxypropylene triol obtained by ring-opening addition polymerization of propylene oxide to glycerin (molecular weight 1,000 per functional group) (referred to as initiator C) was used as an initiator.
In the presence of a glyme complex catalyst (0.09 g) of zinc hexacyanocobaltate, propylene oxide (376 g) was reacted with initiator D (64.1 g) at 120 ° C. until the pressure of the reaction system was not lowered. As a result, a precursor polymer (E′1) having a polyoxypropylene chain and having 3.0 hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (E′1) at 25 ° C. was 23 Pa · s. Mn measured by GPC was 25,000, Mw 35,500, and thus Mw / Mn was 1.42.

(Production Example 6: Production of precursor polymer (E′2))
In the presence of zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.05 g), initiator A (64.1 g) was reacted with propylene oxide (924 g) at 120 ° C. until the pressure of the reaction system was not lowered. I let you. As a result, a precursor polymer (E′2) having a polyoxypropylene chain and having three hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (E′2) at 25 ° C. was 6 Pa · s. Mn measured by GPC was 19,000, Mw21,800, and thus Mw / Mn was 1.15.

(Production Example 7: Production of precursor polymer (C′1))
Polyoxypropylene monool (molecular weight 2,000 per functional group) obtained by ring-opening addition polymerization of propylene oxide to t-butyl alcohol was used as an initiator (referred to as initiator D).
In the presence of a zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.05 g), initiator D (384 g) was reacted with propylene oxide (594 g) at 120 ° C. until the pressure of the reaction system did not drop. . As a result, a precursor polymer (C′1) having a polyoxypropylene chain and having one hydroxyl group per molecule at the end of the main chain was obtained. The viscosity of the precursor polymer (C′1) at 25 ° C. was 1.2 Pa · s. Mn measured by GPC was 7,800, Mw was 8,600, and thus Mw / Mn was 1.10.

[Polymer (A) (C) (E)]
Table 2 shows the polymers (A), (C) and (E) used in the examples. Each polymer was obtained in the following production examples.
Polymers (E1) and (E2) are comparative polymers. The polymer (C1) is a linear polymer having a reactive silicon group at one end.
In the following production examples, an allyl group was introduced to the end of the precursor polymer, and a dimethoxymethylsilyl group was introduced to the end of the main chain of the precursor polymer by a method of reacting the allyl group with dimethoxymethylsilane. In this method, a structure in which a reactive silicon group (dimethoxymethylsilyl group) is bonded to a methylene chain formed by cleavage of an allyl group is obtained. The silylation rate in the table is a value calculated by measuring the amount of H of the methylene chain bonded to the reactive silicon group by ¹ H-NMR.
The average number of functional groups in the table was determined as the average value of the number of hydroxyl groups of the initiator used for the synthesis of each polymer.
Table 1 shows content (unit: mmol / g) of reactive silicon group (dimethoxymethylsilyl group) in 1 g of polymer and content of hydrolyzable group (methoxy group bonded to silicon atom) in 1 g of polymer. Amount (unit: mmol / g) is shown.

(Production Example 8: Production of polymer (A1))
To the precursor polymer (A′1) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl group of the precursor polymer (A′1), and the precursor polymer is added. (A′1) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group of the precursor polymer (A′1). As a result, a polymer (A ″ 1) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.72 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (A ″ 1), and 70 ° C. For 5 hours. As a result, a polymer (A1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 9: Production of polymer (A2))
To the precursor polymer (A′2) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl group of the precursor polymer (A′2), and the precursor polymer is added. (A′2) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the precursor polymer (A′2). Thereby, a polymer (A ″ 2) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.77-fold mol of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (A ″ 2), and 70 ° C. For 5 hours. Thus, a polymer (A2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 10: Production of polymer (A3))
To the precursor polymer (A′3) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl group of the precursor polymer (A′3), and the precursor polymer is added. (A′3) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group of the precursor polymer (A′3). Thereby, a polymer (A ″ 3) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.745 times moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (A ″ 3), and 70 ° C. For 5 hours. Thus, a polymer (A3) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 11: Production of polymer (A4))
In the same manner as in Production Example 8, a polymer (A ″ 1) was obtained. In the presence of chloroplatinic acid hexahydrate, 0.67-fold moles of dimethoxymethylsilane is added to the allyl group at the end of the main chain of the polymer (A ″ 1) and reacted at 70 ° C. for 5 hours. It was. As a result, a polymer (A4) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 12: Production of polymer (A5))
In the same manner as in Production Example 8, a polymer (A ″ 1) was obtained. In the presence of chloroplatinic acid hexahydrate, 0.79-fold mol of dimethoxymethylsilane is added to the allyl group at the end of the main chain of the polymer (A ″ 1) and reacted at 70 ° C. for 5 hours. It was. Thus, a polymer (A5) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 13: Production of polymer (A6))
To the precursor polymer (A′4) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl groups of the precursor polymer (A′4), and the precursor polymer is added. (A′4) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added to the amount of hydroxyl group of the precursor polymer (A′4). As a result, a polymer (A ″ 4) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.72 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (A ″ 4), and 70 ° C. For 5 hours. As a result, a polymer (A6) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 14: Production of comparative polymer (E1))
To the precursor polymer (E′1) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl group of the precursor polymer (E′1) to obtain the precursor polymer. (E′1) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added to the amount of hydroxyl group of the precursor polymer (E′1). Thereby, a polymer (E ″ 1) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.70-fold mol of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (E ″ 1), and 70 ° C. For 5 hours. Thus, a polymer (E1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 15: Production of comparative polymer (E2))
To the precursor polymer (E′2) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl group of the precursor polymer (E′2), and the precursor polymer (E′2) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the precursor polymer (E′2). As a result, a polymer (E ″ 2) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.66 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the polymer (E ″ 2) obtained, For 5 hours. As a result, a polymer (E2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

(Production Example 16: Production of polymer (C1) having a reactive silicon group at one end)
To the precursor polymer (C′1) obtained above, a methanol solution containing 1.05 times moles of sodium methoxide is added to the amount of hydroxyl group of the precursor polymer (C′1), and the precursor polymer is added. (C′1) was alcoholated. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group of the precursor polymer (C′1). As a result, a polymer (C ″ 1) having a polyoxypropylene chain and having one allyl group per molecule at the end of the main chain was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.85 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (C ″ 1), and 70 ° C. For 5 hours. As a result, a polymer (C1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

[Polymer (D)]
The polymers (D1) and (D2) used in the examples are examples of the (meth) acrylic acid ester copolymer (D) having a reactive silicon group. The polymer (D1) was obtained in the following production examples. The polymer (D2) is ARUFON US-6120 (product name, Mw2,400) manufactured by Toa Gosei Co., Ltd.
(Production Example 21: Production of polymer (D1))
In this example, the polymer (D1) was produced by a method of polymerizing an unsaturated group-containing monomer constituting the polymer (D1) in the presence of a solvent.
200 g of ethyl acetate was put into 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 was performed by dropping 2.5 g of the mixed solution into ethyl acetate over 5 hours, and a (meth) acrylate copolymer having a triethoxysilyl group as a reactive silicon group (hereinafter referred to as “polymer (D1)”). )). It was 4,000 when the number average molecular weight (Mn) of the polymer (D1) was measured.

[Compound (B)]
The compounds (B) used in the examples are the following compounds (B1) and (B2).
Compound (B1): Phenoxytrimethylsilane. The number of functional groups capable of generating trimethylsilanol present in one molecule is one, and the functional group capable of generating trimethylsilanol present in 1 g is 0.060 mmol / g.
Compound (B2): Tristrimethylsilyl form of trimethylolpropane (TMP-3TMS). The number of functional groups capable of generating trimethylsilanol present in one molecule is 3, and the functional group capable of generating trimethylsilanol present in 1 g is 0.085 mmol / g.

<Curable composition>
A curable composition was prepared using the polymers (A), (C), (D), the comparative polymer (E) and the compound (B).
In the following examples, a main agent composition containing a polymer (A) and a compound (B) and a curing agent composition containing a curing catalyst are prepared separately, and the curing agent composition and the main agent composition are prepared before use. A two-component curable composition to be mixed was prepared.
Tables 3 to 6 show the composition of the main agent composition, and Table 7 shows the composition of the curing agent composition. The additive components shown in the table are as follows.
In the table showing the composition of the main agent composition, the total number of moles a (relative value) of the hydroxyl group and hydrolyzable group of the polymer (A) or the comparative polymer (E) present in the main agent composition, The number of moles b (relative value) of functional groups capable of generating trimethylsilanol of the compound (B) present in the main agent composition, and the value of these mole ratios a / b are shown.

[filler]
White gloss CCR (product name): Colloidal calcium carbonate, manufactured by Shiroishi Kogyo Co., Ltd.
Whiteon SB (product name): Heavy calcium carbonate, manufactured by Shiraishi Calcium Industry Co., Ltd., average particle size 1.78 μm.
Titanium oxide: R820 (product name) manufactured by Ishihara Sangyo Co., Ltd.
Balloon 80GCA (product name): Organic balloon, manufactured by Matsumoto Yushi Co., Ltd.
Glomax LL (product name): calcined kaolin, manufactured by Takehara Chemical Industries, Ltd.

[Plasticizer]
DINP (abbreviation): diisononyl phthalate, manufactured by Shin Nippon Chemical Co., Ltd., product name: Sansosizer DINP.
PMLS4012 (product name): high molecular weight polyol, manufactured by Asahi Glass Co., Ltd., molecular weight 5,000 per hydroxyl group (PMLS4012 has two hydroxyl groups in the molecule).
UP-1000 (product name): ARUFON UP-1000 (product name, non-functional acrylic polymer, Mw 3,000) manufactured by Toa Gosei Co., Ltd.
Sansosizer EPS (product name): 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl manufactured by Shin Nippon Chemical Co., Ltd.
Isopar H (product name): An isoparaffin plasticizer manufactured by ExxonMobil.
Isopar M (product name): An isoparaffin plasticizer manufactured by ExxonMobil.
Octane: manufactured by Wako Pure Chemical Industries.
Undecane: Wako Pure Chemical Industries, Ltd.
Tridecane: manufactured by Wako Pure Chemical Industries.
N-12 (product name): Normal paraffin (n-dodecane 99.0%) manufactured by Nikko Petrochemical Co., Ltd.
YH-NP (product name): manufactured by Nikko Petrochemical Co., Ltd., normal paraffin (n-dodecane 18%, n-tridecane 59%, n-tetradecane 19%, n-heptadecane 4%).
SH-NP (product name): SH-NP is Nippon Mining Petrochemical normal paraffin (n-tetradecane 55%, n-heptadecane 37%, n-hexadecane 8%).

[Thixotropic agent]
Disparon # 305 (product name): Hydrogenated castor oil-based thixotropic agent, manufactured by Enomoto Kasei Co., Ltd.
[Air oxidation curable compound]
Tung Oil: Made by Kimura
[Stabilizer]
(Antioxidant)
IRGANOX 1010 (product name): a hindered phenol antioxidant, manufactured by BASF.
IRGANOX 245 (product name): A hindered phenol antioxidant, manufactured by BASF.
(UV absorber)
TINUVIN 326: (Product name): Benzotriazole ultraviolet absorber, manufactured by BASF Corporation.
CHIMASSORB 81 (product name): Benzophenone ultraviolet absorber, manufactured by BASF Corporation.
(Light stabilizer)
TINUVIN 765 (product name): hindered amine light stabilizer, manufactured by BASF Corporation.
LA-63P (product name): hindered amine light stabilizer, manufactured by ADEKA, molecular weight of about 2,000, melting point 85-105 ° C.
[Adhesive agent]
KBM-403 (product name): 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
[Curing catalyst / co-catalyst]
(A) Curing catalyst / co-catalyst mixture: Mass ratio of stannous octylate (manufactured by Yoshitomi Pharmaceutical Co., Ltd., trade name: Stanocto) as a curing catalyst and laurylamine (n-dodecylamine, reagent) as a co-catalyst (Curing catalyst: cocatalyst) A mixture mixed at 6: 1.

[Preparation of curing agent composition]
(Examples 1-31)
With the formulations shown in Tables 3 to 6, each component was mixed with a planetary stirrer to prepare a main agent composition. Examples 1 to 25 are examples, and examples 26 to 31 are comparative examples. In Tables 3 to 6, a is the total (relative mole number) of the hydroxyl group and hydrolyzable group of the polymer (A) or (E), and b can generate the trimethylsilanol group of the compound (B). This is the sum of the functional groups (relative moles).
Separately, the curing agent composition was prepared by mixing the following (a) to (d) with the formulation shown in Table 7.
The main agent composition of each example, the curing agent composition having the formulation shown in Table 7, and the toner as the colorant were mixed at a mass ratio of main agent composition / curing agent composition / dark gray toner (100/10 / 5.2). The mixture was mixed to obtain a curable composition.
The obtained curable composition was evaluated by the following methods. The evaluation results are shown in Tables 8 and 9.
In addition, the curable compositions obtained in Examples 2 and 25 were subjected to 2000 times of expansion / contraction tests in the durability test described later, and then additionally 1000 times and 2000 times of expansion / contraction tests. The results are shown in Table 10.

<Evaluation of curability (consistency)>
450 g of the obtained curable composition was put into a container (size: length 10.5 cm × width 7.0 cm × depth 4.0 cm), and air bubbles were removed by blowing nitrogen gas from the surface. After that, place the container horizontally in an atmosphere of 10 ° C and cure it for 40 hours, and use it to measure the consistency using an automatic consistency / penetration tester (RPM-101 type). It was.
Consistency is the length (penetration depth, unit of penetration) in which a stainless steel cone (0.38 mm at the tip) penetrates into the center of the surface of this sample under a load of 100 g and penetrates in 5 seconds. : Mm), and the penetration depth was 10 times the penetration depth.
When the consistency value was 100 or less, the curability was judged as good (◯), and when it exceeded 100, the curability was judged as poor (x).

<Evaluation of tensile properties (H-type test)>
As an adherend, a surface anodized aluminum whose surface is treated with a primer (product name: MP-2000, manufactured by Cemedine Co., Ltd.) is used, and an H-type test body conforming to the test method for architectural sealing material of JIS A 1439 And a tensile property test was conducted.
Specifically, the prepared H-type specimen was cured at a temperature of 23 ° C. and a humidity of 65% for one week, and further cured at a temperature of 50 ° C. and a humidity of 65% for one week to prepare a cured product of the H-type specimen. . About the obtained hardened | cured material, a tensile physical property measurement (H-type physical property) is carried out with a Tensilon test machine, the stress (M50, unit: N / mm < ² >) when extended 50%, the maximum point tensile stress (unit: N) / Mm ² ) and maximum point elongation (unit:%) were measured.
The smaller the M50 value, the higher the flexibility, the higher the maximum point tensile stress value, the higher the tensile strength, and the higher the maximum point elongation value, the better the elongation.

<Surface stickiness>
A curable composition is applied to a polyethylene terephthalate film in a shape of approximately 150 mm in length, 50 mm in width, and 5 mm in thickness, and cured and cured for 8 hours at 23 ° C. and 50% humidity. It was evaluated with.

<Durability>
The durability was measured in accordance with the durability category 9030 described in JIS A5758 (2004 edition). As the adherend, surface anodized aluminum whose surface was treated with a primer (product name: MP-2000, manufactured by Cemedine) was used.
In the durability test, the cracks at the adhesion interface between the adherend and the cured product after 2000 stretching tests were confirmed, and those having no cracks were marked as ◎ (best), and some cracks Very small and very shallow, less than 0.5 mm, is marked as ◯ (excellent), and there is a shallow crack of about 1 mm over the entire surface, △ (good), and there is a deep crack of 1 mm or more over the entire surface. The thing was made into x (defect).
Good durability by this durability test indicates that the stretch fatigue resistance is good.

From the results of Tables 8 and 9, in Examples 1 to 25 in which the curable composition contains the polymer (A) and the two kinds of compounds (B) in an appropriate quantitative ratio, the composition was sufficiently cured at 10 ° C. for 40 hours. And good curability was obtained. Although the value of the elastic modulus (M50) of the cured product was relatively high at 0.18 to 0.23 N / mm ² , the elongation and durability were good. Further, there was no stickiness on the surface of the cured product.
On the other hand, Example 26 is an example in which the polymer (A) is not used, and instead, a comparative polymer (E1) in which the molecular weight distribution (Mw / Mn) of the precursor polymer is larger than 1.40 is used. is there. The elastic modulus and tensile strength of the cured product are almost the same as in Examples 1 to 24, but the elongation and durability are inferior.
Example 27 is an example in which the polymer (A) was not used, and a comparative polymer (E2) having a molecular weight per functional group of the precursor polymer smaller than 7,000 was used instead. The modulus of elasticity was almost the same as in Examples 1 to 25, but the tensile strength, elongation and durability were inferior.
Example 28 is an example in which only one kind of phenoxytrimethylsilane (B1) was used as the compound (B). Compared with Example 2, the curability was inferior and was not sufficiently cured at 10 ° C. for 40 hours.
Example 29 is an example in which only one kind of TMP-3TMS (B2) was used as the compound (B). Although the curability was good, the value of the elastic modulus of the cured product was lower than that of Example 2, but the tensile strength, elongation and durability were inferior.
Example 30 is an example in which the compound (B) was not contained. Compared with Example 21, the value of elastic modulus was high, but the tensile strength and elongation were inferior, and the durability was insufficient. Further, stickiness was observed on the surface of the cured product.
Example 31 is an example in which the compound (B) is contained more than 2 parts by mass with respect to 100 parts by mass of the polymer (A). Compared with Example 22, the curability was inferior and was not sufficiently cured at 10 ° C. for 40 hours. Moreover, although the value of the elasticity modulus of hardened | cured material was small compared with Example 22, elongation and durability were good, but the tensile strength was inferior.
In addition, from the results of Table 10, Examples 2 and 25 in which the curable composition contains the polymer (A) and the two kinds of compounds (B) in an appropriate quantitative ratio and the molecular weights per functional group are different are cured. Although the elastic modulus of the product was almost the same, Example 25 having a higher molecular weight was superior in tensile strength and elongation, and was superior in durability when an additional stretch test was conducted.

Claims (8)

The main chain has an alkylene oxide monomer unit, has a functional group capable of introducing a reactive silicon group at the end of the main chain, and the functional group includes a group having an active hydrogen and an unsaturated group More than one selected, the average number of functional groups at the end of the main chain is 2.0 or more and 3.0 or less, the molecular weight per functional group is 7,000 to 20,000, and the molecular weight distribution A polymer (A) obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (A ′) having a viscosity of 1.01-1.40, and trimethylsilanol by hydrolysis. A compound (B ) capable of being generated, wherein the compound (B) is at least two kinds including a phenoxytrimethylsilane and a tristrimethylsilyl form of trimethylolpropane, and the total content of the compound (B) is 100 parts by mass of coalesced (A) Curable composition characterized in that 0.4 to 2.0 parts by weight for.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]   The curable composition of Claim 1 whose molecular weight per functional group in the said polymer (A) is 7,000-20,000, and whose molecular weight distribution is 1.01-1.40. The precursor polymer (A ′) undergoes ring-opening addition of alkylene oxide to one or both of an initiator having two active hydrogens and an initiator having three active hydrogens in the presence of an alkylene oxide ring-opening polymerization catalyst. The curable composition according to claim 1 or 2 , which is a precursor polymer (A'-a) comprising a polymerized oxyalkylene polymer. In the tristrimethylsilyl form of phenoxytrimethylsilane and trimethylolpropane contained in the compound (B), the mass ratio of both represented by the tristrimethylsilyl form of phenoxytrimethylsilane / trimethylolpropane is 20/80 to 80/20. The curable composition as described in any one of Claims 1-3 . Furthermore, it is linear, the main chain has an alkylene oxide monomer unit, and includes a polymer (C) having a reactive silicon group at one end, according to any one of claims 1 to 4 . Curable composition. Furthermore, the curable composition as described in any one of Claims 1-5 containing the (meth) acrylic acid ester copolymer (D) which has a reactive silicon group.   A method for producing a curable composition according to claim 1, wherein an alkylene oxide is subjected to ring-opening addition polymerization to an initiator having two or three active hydrogens in the presence of an alkylene oxide ring-opening polymerization catalyst. The method for producing a curable composition, wherein the precursor polymer (A ′) is obtained, the reactive silicon group is introduced to obtain the polymer (A), and the compound (B) is added.   The method for producing a curable composition according to claim 7, wherein the alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand.