JP6508261B2 - 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 sealants, adhesives, coatings and the like.
When a curable composition containing a modified silicone polymer is used as a sealing material applied, for example, outdoors, the cured product has good weather resistance, and cracks appear on the surface even if it is exposed to the environment for a long time outdoors. It is required to be hard to occur.

As a method of improving the weather resistance of a curable composition containing a modified silicone polymer, for example, a method of containing a (meth) acrylic acid alkyl ester polymer having a reactive silicon group, a method of containing a photocurable compound However, it is difficult to balance the modulus (elastic modulus) of the cured product with the weather resistance (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 modifier.
For example, Example 8 of Patent Document 1 is a polyoxypropylene having a methyldimethoxysilyl group 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 of P3 and a toluene solution of an acrylic copolymer having a photocurable functional group, 100 parts of Pd, 0.4 parts of phenyloxytrimethylsilane as a modifier and tristrimethylsilyl form of trimethylolpropane Curable compositions containing 0.4 parts of (TMP-3TMS) are described.
In Tables 7 and 9 of Patent Document 2, the average number of functional groups at the main chain terminal 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, a polymer (A) into which a reactive silicon group has been introduced, and a polymer having a number average molecular weight of 5,200 to 15,300, which has a reactive silicon group at one end, which is linear and has a reactive silicon group at one end And a curable composition comprising a modulus modifier, tristrimethylsilyl form of trimethylolpropane (TMP-3TMS).

Patent No. 4815663 gazette JP, 2011-202157, A

However, in the conventional curable composition, it is necessary to simultaneously satisfy the requirements that the curing speed is good and the curability is excellent, the elongation and durability of the cured product are good, and the surface of the cured product is not sticky difficult.
According to the findings of the present inventors, it is effective to contain a modulus regulator in the curable composition to prevent the surface from sticking. However, even with the inclusion of a modulus modifier, in the case of the curable composition described in Patent Document 1, the elongation and durability of the cured product are not necessarily sufficient, and further improvement is required. Moreover, although the curable composition described in patent document 2 makes the elastic modulus of hardened | cured material low and achieves favorable elongation and durability, the elastic modulus in the point which prevents the surface stickiness of hardened | cured material Is preferable, and it is required to increase the elastic modulus without losing the durability.
For example, it is shown in Tables 7 and 9 of the example of Patent Document 2 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 although the curability is good and the elastic modulus is relatively high, the elongation and durability of the cured product are good, and the tackiness of the surface of the cured product It is an object of the present invention to provide a curable composition in which

The present invention is the following [1] to [7].
[1] The main chain has an alkylene oxide monomer unit, all the main chain terminals have a functional group capable of introducing a reactive silicon group, and the functional group is a group having an active hydrogen and an unsaturated group At least one functional group selected from the group consisting of: an average number of functional groups at the end of the main chain of 2.0 to 3.0, and a molecular weight of 7,000 to 20,000 per functional group; 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 It contains two or more kinds of compounds (B) capable of generating trimethylsilanol, and the total content of the compounds (B) is 0.4 to 2.0 with respect to 100 parts by mass of the polymer (A) A curable composition characterized by being in parts by mass.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents a C1-C20 monovalent organic group which may have a substituent (excluding hydrolysable groups), and X ¹ represents a hydroxyl group or a hydrolysable group] . The two X ^{1 s} may be the same or different. ]

[2] 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 in the presence of an alkylene oxide ring-opening polymerization catalyst. The curable composition as described in [1] which is a precursor polymer (A'-a) which consists of a ring-opening addition-polymerized oxyalkylene polymer.

[3] The curable composition according to [2], wherein the alkylene oxide ring-opening polymerization catalyst is a complex 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) contains phenoxytrimethylsilane and a tristrimethylsilyl form of trimethylolpropane.
[5] The curable composition according to [4], wherein the mass ratio of the two represented by tristrimethylsilyl form of phenoxytrimethylsilane / trimethylolpropane is 20/80 to 80/20.
[6] Further, any one of [1] to [5], which is linear, and contains a polymer (C) having an alkylene oxide monomer unit in the main chain and a reactive silicon group at one end thereof The curable composition as described in one term.
[7] The curable composition according to any one of [1] to [6], further comprising a (meth) acrylic acid ester copolymer (D) having a reactive silicon group.

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

In the present specification, the “main chain” of a polymer refers to a polymer chain formed by the connection of two or more monomers. The term "main chain end" means the end of each main chain, and there are two main chain ends in a polymer having a linear main chain. The "all main chain end" of the polymer refers to all of the main chain ends of the polymer. In addition, “straight, single end” of the polymer means one end of two main chain ends in which the polymer is linear.
In the present specification, the average number of functional groups at the main chain end of the precursor polymer (A ′) is the number of functional groups capable of introducing reactive silicon groups at all main chain ends of the precursor polymer (A ′) It is an average value per molecule.
In the present specification, the number of functional groups at the main chain terminal in the polymer (A) is the reactive silicon group introduced at the main chain terminal of the precursor polymer (A ′) and the reactive silicon group are not introduced. The average number of functional groups at the main chain terminal of the polymer (A) is the average value per molecule of the total number.
Accordingly, the average number of functional groups at the main chain end of the precursor polymer (A ') and the average number of functional groups at the main chain end of the polymer (A) are equal.
When the precursor polymer (A ′) or the polymer (A) is a mixture, the average of the functional group number at the main chain end after mixing per molecule is the precursor polymer (A ′) or the polymer (A) The average number of functional groups at the end of the main chain (hereinafter sometimes referred to simply as "average number of functional groups") of A).

The mass average molecular weight (Mw, hereinafter referred to as "Mw") and the number average molecular weight (Mn, hereinafter also referred to as "Mn") in the present specification are polystyrene equivalent molecular weights measured by gel permeation chromatography (GPC) . Further, the molecular weight distribution (hereinafter also referred to as “Mw / Mn”) in the present specification is a value calculated from Mw and Mn measured by the above method, and the mass average molecular weight (Mw) relative to the number average molecular weight (Mn) It is a ratio (Mw / Mn).
In the present 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 the value measured by the method based on JISK1557-1.
In the present 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 calibration curve is drawn with a polymer whose molecular weight per one functional group is known, and the molecular weight per one functional group is calculated by measuring an object to be measured.

<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 is a monovalent organic group having 1 to 20 carbon atoms that may have a substituent (excluding a hydrolyzable group.). R ¹ is preferably a hydrocarbon group having 8 or less carbon atoms. As a specific example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group etc. are mentioned. A methyl group and a phenyl group are more preferable, and a methyl group is particularly preferable.

In Formula (1), X ¹ represents a hydroxyl group or a hydrolyzable group. Two X ¹ present in one molecule may be the same or different.
The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or 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 carbon number thereof is preferably 6 or less, and more preferably 4 or less. As X ¹ , an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is particularly preferable. More specifically, X ¹ is particularly preferably a methoxy group or an ethoxy group.

The polymer (A) has a functional group capable of introducing a reactive silicon group at all main chain terminals, and a precursor polymer having an average functional group number of 2.0 or more and 3.0 or less at the main chain terminal It is a polymer formed by introducing a reactive silicon group to A '). At one main chain end of the precursor polymer (A ′), one functional group capable of introducing a reactive silicon group is present. The functional group capable of introducing a reactive silicon group is at least one selected from an active hydrogen-containing group 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 vinyl group, allyl group and isopropenyl group.
When the reactive silicon group is present at the main chain end of the polymer (A), the elongation properties, internal curability, and surface curability of the cured product tend 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 number of functional groups 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 end of the main chain is the main component of a linear precursor polymer (A'12) in which the number of functional groups at the main chain end is two It is a polymer in which some or all of the functional groups at 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 number of functional groups of the polymer (A) is 3.0, the polymer (A) is preferably made of one or more kinds of polymers (A11) having three functional groups at the end of the main chain. The polymer (A11) having 3 functional groups at the end of the main chain is the entire main chain end of the branched precursor polymer (A'11) having 3 functional groups at the main chain end per molecule. It is a polymer in which some or all of the functional groups are 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), in the polymer (A), polymers having 2 to 4 functional groups at the end of the main chain are mixed such 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 such that the average number of functional groups at the end of the main chain is within the above range Mixtures are more preferred. In particular, it is preferable that the polymer (A) contains a polymer (A11) in which at least the number of functional groups at the main chain terminal is three, and two of the polymers (A11) in which the number of functional groups at the main chain terminal is three. A mixture of a species or more, or a mixture of a polymer (A12) having two functional groups at the main chain end and a polymer (A11) having three functional groups at the main chain end is more preferable.

  In the case of (ii), the polymer (A) is a precursor polymer in which the number of main chain terminal groups per molecule is 2 to 4 and the average number of functional groups at the main chain terminals is 2.0 to 3 It is preferable to introduce a reactive silicon group into a precursor polymer (A ') composed of a mixture mixed to be .0. In the case of (ii), the polymer (A) is a precursor polymer in which the number of main chain end groups per molecule is 2 to 3 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 a precursor polymer (A ') consisting of a mixture mixed to be .0. In particular, the precursor polymer (A ′) preferably contains at least a precursor polymer (A′11) having 3 functional groups at the main chain end per molecule, and has 3 functional groups at the main chain end. A mixture of two or more types of precursor polymers (A'11) which are individual, or a precursor polymer (A'12) having two functional groups at the main chain terminal and three functional groups at the main chain terminal More preferred is a mixture of precursor polymers (A'11).

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

A polymer (A) is a polymer which has an alkylene oxide monomeric unit in a principal chain. The polymer (A) has a terminal functional group number of 2 or 3 per molecule, and through the step of addition-polymerizing an alkylene oxide monomer to an initiator in which all the terminal groups are functional groups having reactivity. What is obtained, or what is obtained through the step of addition polymerizing an alkylene oxide monomer and a (meth) acrylic acid alkyl ester monomer to the initiator is preferable.
That is, the main chains of the precursor polymer (A ′) and the polymer (A) may have (meth) acrylic acid alkyl ester monomer units in addition to the alkylene oxide monomer units.
In the present specification, the (meth) acrylic acid alkyl ester monomer unit means a repeating unit derived from the (meth) acrylic acid alkyl ester. The (meth) acrylic acid alkyl ester means acrylic acid alkyl ester, methacrylic acid alkyl ester or a mixture of both.

The repeating units in the precursor polymer (A ′) and the polymer (A) include alkylene oxide monomer units. It is preferable that the main chains of the precursor polymer (A ′) and the polymer (A) 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 small temperature dependence, easy flexibility of the cured product, and excellent price.
The reactive functional group in the initiator is a group having an active hydrogen, 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 of the main chain terminals as a hydroxyl group; or a polyoxyalkylene chain A linear or branched precursor polymer (A'-b) which is possessed and in which all the main chain ends are unsaturated groups is preferred.

Precursor Polymer (A'-a)>
The precursor polymer (A′-a) is an oxyalkylene polymer obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or three active hydrogens in the presence of an alkylene oxide ring-opening polymerization catalyst Is preferred.
The initiator is preferably a compound having two or three hydroxyl groups. 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. Among 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. Among these, glycerin is particularly preferred.
In addition, polyoxyalkylene diol or polyoxyalkylene triol having a molecular weight of 80 to 10,000, which is obtained by ring-opening addition polymerization of an alkylene oxide to a compound having 2 or 3 hydroxyl groups, It is also preferred to use as initiator. The initiator may be used alone or in combination of two or more.

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

The complex metal cyanide complex catalyst is a reaction product (hereinafter referred to as a catalyst skeleton) obtained by reacting a metal halide and an alkali metal cyanometalate in water (hereinafter referred to as a catalyst skeleton) and a formula ((t-butyl alcohol or t-butyl alcohol) What is manufactured by coordinating the organic ligand which consists of a compound shown by i) is preferable.
In particular, a complex metal cyanide complex catalyst in which t-butyl alcohol is coordinated to the catalyst skeleton as an organic ligand is preferable.

As metals of metal halide salts, Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), V 1 type selected from (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II), and Pb (II) or It is preferable to use 2 or more types. Zn (II) or Fe (II) is more preferable, and Zn (II) is particularly preferable in that the molecular weight distribution can be narrower.
Examples of metals constituting cyanometalates of alkali metal cyanometalates include Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II) It is preferable to use one or more selected from Mn (III), Ni (II), V (IV), and V (V). Co (III) or Fe (III) is more preferable, and Co (III) is particularly preferable in that the molecular weight distribution can be narrower.
Note that Roman numerals such as II, III, IV, V, etc. in parentheses following the elemental symbol of metal indicate the valence of the metal.

The synthesis reaction of the catalyst skeleton is preferably performed by mixing an aqueous solution of metal halide salt and an aqueous solution of alkali metal cyanometalate, and more preferably, the aqueous solution of alkali metal cyanometalate is dropped into the aqueous metal halide salt solution. The reaction temperature is preferably 0 ° C. or more and less than 70 ° C., and more preferably 30 ° C. or more and less than 70 ° C.
The metal halide salt is preferably a 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 preferred.
As the catalyst skeleton, Zn ₃ [Co (CN) ₆ ] ₂ (that is, zinc hexacyanocobaltate complex) is more preferable.

  Next, a compound serving as an organic ligand is coordinated to 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 the 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)
However, in 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, n is an integer of 1 to 3 .
The following compounds may be mentioned as compounds represented by formula (i).
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, 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 More preferred are t-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol mono-t-butyl ether and triethylene glycol mono-t-pentyl ether. Ethylene glycol mono-t-butyl ether, propylene glycol mono-t-butyl ether, ethylene glycol mono-t-pentyl ether, propylene glycol mono-t-pentyl ether are more preferable, and ethylene glycol mono-t in that molecular weight distribution can be narrowed more. -Butyl ether is most preferred.

When t-butyl alcohol and the compound represented by the formula (i) are used in combination, the mixing ratio is such that the mass ratio of t-butyl alcohol / the compound represented by the formula (i) is 20 to 95/80 to 5 preferable.
The mixed metal cyanide complex catalyst is a mixture of t-butyl alcohol or t-butyl alcohol and a compound represented by the formula (i) with a catalyst skeleton obtained by reacting a zinc halide with an alkali metal cyanocobaltate. The solution is heated and stirred (aging step) in an organic ligand solution containing the compound of formula I, and then filtered, washed and dried by a known method.

Precursor Polymer (A'-b)>
A linear or branched precursor polymer (A'-b) having a polyoxyalkylene chain and having unsaturated groups at all ends is a precursor polymer (A'-a) having hydroxyl groups at all ends The hydroxyl group (-OH) is alcoholated to form -OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride. This method is preferred in view of general availability of raw materials and high reaction yield.
Or a method of reacting a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group with a precursor polymer (A'-a) to introduce an unsaturated group via an ester bond, a urethane bond, a carbonate bond, etc. But you can get it.

  As described above, the precursor polymer (A ′) preferably includes a precursor polymer (A′11) in which the number of functional groups at the main chain end per molecule is at least three. Therefore, as the precursor polymer (A '), among the precursor polymers (A'-a), it was produced by ring-opening addition polymerization of an alkylene oxide with 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), hydroxyl groups of polymers having ring-opening addition polymerization of an alkylene oxide to an initiator having three active hydrogens in the presence of a catalyst, wherein the main chain terminal is a hydroxyl group It is preferable to use a precursor polymer (A′11-b) produced by a method of alcoholating to give —OM (M is an alkali metal) and then reacting it with an unsaturated group-containing halogenated hydrocarbon.

<Method of producing polymer (A)>
A known method can be used to introduce the reactive silicon group into the terminal unsaturated group of the precursor polymer (A'-b) to obtain the polymer (A). For example, the method of the following [1] or [2] can be used.
[1] A method of reacting a terminal unsaturated group and 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 the above formula (1). HSiX ¹ ₂ R ¹ (2)
[2] A method of reacting the terminal unsaturated group with the mercapto group of the 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 the above formula (1). R ² is a divalent organic group, and W ¹ is a mercapto group.

As a method for obtaining a polymer (A) by introducing a reactive silicon group to the terminal hydroxyl group of the precursor polymer (A'-a) without passing through the precursor polymer (A'-b), a known method may be used. It can be used. For example, the method of the following [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 subjected to a urethanization reaction. This reaction may be carried out 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 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-isocyanatomethyldimethoxymethylsilane, 1-isocyanatemethyldiethoxyethylsilane, 1-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyldiethoxy Ethylsilane etc. are mentioned.
The urethanization catalyst to be used is not particularly limited, and a known urethanization catalyst can be appropriately used. For example, metal catalysts such as organotin compounds (dibutyltin dilaurate, dioctyltin dilaurate, etc.), bismuth compounds, etc., and base catalysts such as organic amines are used. 20-200 degreeC is preferable and, as for reaction temperature, 50-150 degreeC is especially preferable. The urethanization reaction is preferably carried out under an inert gas (preferably nitrogen gas) atmosphere.

[4] After the hydroxyl group at the end is reacted with a polyisocyanate compound such as tolylene diisocyanate to convert the end to an isocyanate group, a group represented by W ² of the silicon compound represented by the following formula (5) in the 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 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), of the functional groups at the end of the main chain capable of introducing a reactive silicon group of the precursor polymer (A ′), of the functional groups at the end of the main chain substituted with a group containing a reactive silicon group The ratio (hereinafter sometimes referred to as “silylation ratio”) 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 ratio in the mixture after mixing may be within the above range, and one of the polymers (A) before mixing may be used. As a part, one having a silylation rate of less than 70% may be used.

The value of the degree of silylation in the present specification can be measured by NMR analysis. Or, since the reaction rate of the precursor polymer (A ') manufactured using methallyl chloride and the silylating agent can be regarded as almost 100%, the silylation with respect to the amount of the precursor polymer (A') is usually carried out. You may use the value calculated from the charge of the agent. Side reactions occur in the reaction of the precursor polymer (A ') prepared with allyl chloride and the silylating agent. The approximately 10 mole% of the allyl groups of the precursor polymer (A ′) prepared with allyl chloride is isomerized and is not silylated, so 100% silylation is difficult. However, in the silylation where the silylation rate is up to about 90%, the reaction rate can also be regarded as about 100%. Therefore, when the silylation ratio of the polymer (A) to be obtained by the reaction of the precursor polymer (A ′) manufactured using allyl chloride and the silylating agent is less than 90%, the polymer As the value of the degree of silylation in A), a value calculated from the amount of charge of the silylating agent relative to the amount of charge of the precursor polymer (A ′) may be used.
The same applies to the value of the silylation ratio of the polymer (C) described later.

As described later, in the curable composition of the present invention, the reactivity represented by the above formula (1) in the precursor polymer (C ′) which is linear and can introduce a reactive silicon group at one end thereof The polymer (C) obtained by introducing a silicon group can be contained.
By blending the polymer (C), the viscosity of the curable composition can be reduced. On the other hand, when the polymer (C) is blended with the polymer (A) and cured, the polymers (A) crosslink with each other, and a part of the polymer (A) reacts with the polymer (C). Since the polymer (C) has a reactive silicon group at only one end, the crosslinking of the polymer (A) is inhibited by the reaction of the polymer (A) with the polymer (C). Therefore, when the compounding quantity of a polymer (C) is too large, it may become curing failure and may become unhardened.
That is, in order to make the curable composition lower in viscosity and not cause curing failure, it is advantageous that the blending amount of the polymer (C) is large and the silylation ratio of the polymer (A) is high. As the silylation ratio of the polymer (A) is higher, even if the polymer (C) is compounded in a large amount, the crosslinking is less likely to be inhibited due to the relationship of the amount ratio, and it is hard to be uncured.
Therefore, in the curable composition in which the polymer (C) is blended, the silylation ratio of the polymer (A) needs to be a range in which good curability is obtained, and the higher the silylation ratio, The amount of polymer (C) added can be increased. The larger the blending amount of the polymer (C), the lower the viscosity, and hence the workability as a curable composition for a sealing material or an adhesive becomes better.

  When the precursor polymer (A ′) has a hydroxyl group as a functional group at the end of the main chain capable of introducing a reactive silicon group, the main chain terminal substituted with a group containing a reactive silicon group among all the hydroxyl groups 45 mol% or more is preferable and, as for the ratio (silylation ratio) of a functional group, 50 mol% or more is more preferable. A sealing material and an adhesive agent can be manufactured, without becoming a gel-like substance which does not harden | cure depending on compounding as it is 45 mol% or more. The silylation rate may be 100 mol%. When the precursor polymer (A ′) has an unsaturated group as a functional group at the end of the main chain to which a reactive silicon group can be introduced, the silylation ratio is preferably 45 mol% or more, for the same reason. More than mol% 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. If it is 7,000 or more, the elongation properties and flexibility of the cured product are good. The curable composition tends to have a low viscosity if it is 20,000 or less, which is preferable in order to obtain good workability.
The molecular weight distribution (Mw / Mn) of the polymer (A) is 1.01 to 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 amount of high molecular weight is present, which causes high viscosity. Alternatively, as shown in the examples described later, when the flexibility is equal, the elongation property is good. The reason is considered that when the molecular weight distribution exceeds 1.40, the amount of low molecular weight polymer components increases, so the distance between crosslinking points becomes short and it becomes difficult to stretch. Accordingly, the molecular weight distribution is preferably narrow, more preferably 1.01 to 1.30, and still more preferably 1.01 to 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 made to fall within the above ranges, respectively.
The same applies to the case where the polymer (C) described later is a mixture.

The polymer (A) may have a reactive silicon group other than the reactive silicon group represented by the formula (1), but the reaction of the polymer (A) from the viewpoint of excellent storage stability and elongation properties. The reactive silicon group is preferably only a 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 types 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 linear polymer having an alkylene oxide monomer unit in its main chain and 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 as a precursor polymer (C ′) capable of introducing a reactive silicon group at one end. It is obtained by introducing.
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 as or different from each other.
Specifically, one of the main chain terminal groups at both ends of the main chain of the precursor polymer (C ′) is a reactive group, preferably a hydroxyl group or an unsaturated group, and the main chain terminal group It is preferable to react a compound having a reactive group and a reactive silicon group with a precursor polymer (C ′) to introduce a reactive silicon group. The other main chain terminal group of the precursor polymer (C ′) is preferably an inert organic group having no reactivity with the compound having a reactive silicon group.

The polymer (C) is preferably obtained by subjecting an initiator having a functional group of 1 to addition polymerization of an alkylene oxide monomer.
The repeating units in the precursor polymer (C ′) and the polymer (C) include alkylene oxide monomer units. It is preferable that the main chains of the precursor polymer (C ′) and the polymer (C) 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 a precursor polymer (C '), the following precursor polymer (C'1) or a precursor polymer (C'2) is preferable.
Precursor polymer (C′1): inactive having a polyoxyalkylene chain, one end of which is a hydroxyl group, and the other main chain end group having no reactivity with the compound having a reactive silicon group Linear precursor polymers that are organic groups.
Precursor polymer (C′2): having polyoxyalkylene chain, unsaturated at one end, and the other main chain end group having no reactivity with the compound having the reactive silicon group, Linear precursor polymers that are inert organic groups.
The precursor polymer (C′1) can be produced by ring-opening addition polymerization of an alkylene oxide to an initiator having one active hydrogen in the presence of a catalyst.
Specific examples of the initiator include aliphatic monools having 1 to 20 carbon atoms, alicyclic monools having 1 to 20 carbon atoms, aromatic monools having 1 to 20 carbon atoms, thiols, secondary amines, and carboxylic acids. Or a polyoxyalkylene monool having a molecular weight of 300 to 5,000 per hydroxyl group obtained by subjecting the monool to ring-opening addition polymerization of an alkylene oxide. More preferable is a polyoxyalkylene monool having a molecular weight of 300 to 3,300 per hydroxyl group. Unsaturated group-containing monohydroxy compounds such as allyl alcohol can also be used. The initiator may be used alone or in combination of two or more.
The alkylene oxide and the alkylene oxide ring-opening polymerization catalyst used for the synthesis of the precursor polymer (C′1) or the initiator are the alkylene oxides and the alkylene oxides used for the synthesis of the precursor polymer (A′-a) described above. The same applies to the ring polymerization catalyst, including the preferred embodiments.
The precursor polymer (C'1) is preferably polyoxypropylene monool.

The precursor polymer (C′2) is formed by alcoholation of hydroxyl group (—OH) of precursor polymer (C′1) having a hydroxyl group at one end to form —OM (M is an alkali metal), and then allyl chloride or the like It can be produced by a method of reacting with unsaturated group-containing halogenated hydrocarbon. This method is preferred in view of general availability of raw materials and high reaction yield.
Alternatively, a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group is reacted with a precursor polymer (C'1) to introduce an unsaturated group via an ester bond, a urethane bond, a carbonate bond, etc. can get.

A known method can be used to introduce the reactive silicon group into the terminal unsaturated group of the precursor polymer (C'2) to obtain the polymer (C). For example, the method of the above [1] or [2] can be used.
The method of introduce | transducing a reactive silicon group to the terminal hydroxyl group of a precursor polymer (C'1), and obtaining a polymer (C) can use a well-known method. For example, the method of the above [3] or [4] can be used.

Proportion of main chain end group substituted by a group containing a reactive silicon group among main chain end groups capable of introducing a reactive silicon group in the precursor polymer (C ′) in the polymer (C) (silylation The ratio is preferably 60 to 100 mol%.
The silylation ratio in the polymer (C) is determined by reacting the terminal reactive group of the precursor polymer (C ′) with the terminal reactive compound when reacting a compound having a reactive silicon group. And reactive silicon groups can be controlled by the molar ratio.
When the silylation ratio at one end of the polymer (C) is 60 mol% or more, the transferability as a plasticizer is low, and the contamination around the sealing material portion and the adhesiveness are improved.
In particular, when the precursor polymer (C ') has a hydroxyl group as a main chain terminal group capable of introducing a reactive silicon group, a main chain terminal group substituted by a group containing a reactive silicon group among all the hydroxyl groups. 60 mol% or more is preferable from said point to the ratio (silylation ratio), and 75 mol% or more is more preferable.
Similarly, when the precursor polymer (C ′) has an unsaturated group as a main chain end group capable of introducing a reactive silicon group, the silylation ratio is preferably 60 mol% or more, for the same reason, 75 More than mol% 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, and more preferably 5,000 or more and 12,000. It is below. When the number average molecular weight (Mn) is 3,000 or more, there is no contamination around the sealing material portion even if the polymer (C) has a reactive silicon group, and the adhesiveness is improved, and the cured product is It has good physical properties. If it is less than 20,000, the viscosity of the polymer (C) is lowered, and it works effectively as a plasticizer.
2,000-15,000 are preferable and, as for the molecular weight per one functional group of a polymer (C), 2,000-12,000 are more preferable.
The molecular weight distribution (Mw / Mn) of the polymer (C) is preferably 1.01 to 1.30. Within this range, the viscosity of the polymer (C) tends to be lower. Mw / Mn is more preferably 1.01 to 1.20.
The molecular weight distribution (Mw / Mn) of the polymer (C) can be controlled by the type of catalyst and the polymerization conditions (temperature, stirring conditions, pressure, etc.).

Although the polymer (C) may have a reactive silicon group other than the reactive silicon group represented by the formula (1), the polymer (C) is a polymer (C) from the viewpoint of excellent storage stability and elongation properties. The reactive silicon group is preferably only the reactive silicon group represented by formula (1).
The polymer (C) may be used alone or in combination of two or more.
When two or more types 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 end 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 end group is a hydroxyl group and the other main chain end group is an unsaturated group ) Is obtained. When a reactive silicon group is introduced into the terminal unsaturated group to obtain the polymer (C), it is preferable to convert the terminal hydroxyl group into an inactive organic group by a method such as reacting with benzoyl chloride.

When the curable composition of the present invention contains the polymer (A) and the polymer (C), the ratio of the content of both is the polymer (C) relative to 100 parts by mass of the polymer (A) Is preferably at most 60 parts by mass, and more preferably at most 50 parts by mass.
When the polymer (C) is contained, the viscosity of the curable composition is reduced, and good workability can be easily obtained. When the content of the polymer (C) is not more than the upper limit value of the above range of the above range, the crosslinking point is sufficiently obtained, and 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)). May be. 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 the improvement of the mechanical strength of the cured product and the improvement of the weatherability of the curable composition and the cured product. For example, when applied to sealants and the like used outdoors, it is effective to suppress the occurrence of cracks (fine cracks) on the surface when the cured product is exposed to ultraviolet light for a long time.

A polymer (D) is a copolymer containing the structural unit derived from the (meth) acrylic-acid alkylester represented by following General formula (ii), Comprising: Reaction represented by said 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)
(Wherein, 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) simultaneously present in the curable composition may be the same as or different from each other.
The polymer (D) is a homopolymer or copolymer comprising a constitutional unit derived from one or two or more kinds of (meth) acrylic acid alkyl ester monomers represented by the above general formula (ii) Structural unit derived from one or two or more of (meth) acrylic acid alkyl ester monomers represented by the above general formula (ii), and unsaturated group-containing other than the monomers The copolymer which consists of a structural unit based on 1 type, or 2 or more types of a monomer may be sufficient.
500-50,000 are preferable, as for the number average molecular weight (Mn) of a polymer (D), 1,000-30,000 are more preferable, and 2,000-20,000 are more preferable. Alternatively, the mass average molecular weight (Mw) is preferably 600 to 100,000, more preferably 1,200 to 60,000, and still more preferably 2,400 to 40,000.

A polymer (D) can be manufactured by polymerizing the said monomer in presence of components other than a polymer (D) among the structural components of a curable composition. For example, it can be synthesized by polymerization in the presence of the polymer (A). Alternatively, after synthesizing by polymerizing the above-mentioned 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 above monomers may be polymerized in the absence of the components of the curable composition. In this case, it is possible to polymerize in an ester, a ketone or an aromatic organic solvent and mix it with the polymer (A) or the like. At this time, the solvent may be removed by vacuum degassing or the like before mixing, or may be removed after being mixed with the polymer (A) or the like before being mixed. Degassing after mixing is preferable in terms of ease of 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: ARUFON US-6000 series (for example, US-6120, US-6110, etc., all product names) manufactured by Toa Gosei Co., Ltd. can be used.

When the curable composition of the present invention contains the polymer (A) and the polymer (D), the ratio of the content of both is the polymer (D) relative to 100 parts by mass of the 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 value of the above range, the addition effect of the polymer (D) is easily obtained sufficiently. When it is not more than the upper limit value of the above range, it is possible to suppress the workability and the decrease in the elongation of the cured product obtained by curing the curable composition.

<Compound (B)>
The curable composition of the present invention contains two or more compounds (B) (also referred to simply as compound (B)) capable of generating trimethylsilanol by hydrolysis.
The compound (B) is also called a modulus modifier, and the trimethylsilanol generated by hydrolysis reacts with the polymer (A), (C) or (D) to cure the product while suppressing the decrease in elastic modulus. Can be improved, which can contribute to the prevention of surface tackiness of the cured product.
The compound (B) is, for example, a compound containing a trimethylsilyloxy group in the molecule. Specific examples thereof include phenoxytrimethylsilane, tristrimethylsilyl form of trimethylolpropane (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. Further, it is preferable that the number of functional groups capable of generating trimethylsilanol in one molecule is, on average, 0.5 to 8.0 or less, more preferably 0.9 to 4.0 on average.

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

In the present invention, two or more kinds of compounds (B) are used in combination. Two or more types of compounds (B) used in combination preferably have different hydrolysis rates.
When two or more compounds (B) are used in combination, the durability of the cured product is achieved by using compound (B) having a faster hydrolysis rate than the hydrolysis rate of the reactive silicon group in polymer (A). It is easy to obtain the effect of improving the quality. For this reason, it is preferable to use at least one compound (B) having a faster hydrolysis rate than the hydrolysis rate of the reactive silicon group in the polymer (A).
For example, phenoxytrimethylsilane is mentioned as a compound (B) whose hydrolysis rate is faster than the hydrolysis rate of the reactive silicon group in the polymer (A), and hydrolysis of the reactive silicon group in the polymer (A) The compound (B) having a slower hydrolysis rate than the degradation rate includes tristrimethylsilyl form of trimethylolpropane (TMP-3TMS).

It is particularly preferable to use, as the compound (B), for example, phenoxytrimethylsilane and tristrimethylsilyl form of trimethylolpropane (TMP-3TMS) in combination. TMP-3TMS has a slower hydrolysis rate than phenoxytrimethylsilane and a slower hydrolysis rate than that of reactive silicon groups in polymer (A). Therefore, when TMP-3TMS is used as the compound (B), the curing reaction of the polymer (A) is likely to proceed rapidly, which contributes to good curability. On the other hand, phenoxytrimethylsilane has a faster hydrolysis rate than TMP-3TMS and a faster hydrolysis rate than that of reactive silicon groups 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 using phenoxy trimethylsilane and TMP-3TMS together, 20 / 80-80 / 20 are preferable and, as for mass ratio of the usage-amount of both, 20 / 80-80 / 20, 30 / 70-70 / 30 are more preferable. When the mass ratio of the two used amounts 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. Is easy to obtain a good cured product.
It is preferable that the sum total of phenoxy trimethylsilane and TMP-3TMS is 60 mass% or more among the total amounts of the compound (B) contained in a curable composition, 80 mass% or more is more preferable, and 100 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), 0.4 to 1.5 parts by mass Is preferred. When the content of the compound (B) is at least the lower limit value of the above range, the addition effect of the compound (B) is easily obtained sufficiently. In addition, the surface tackiness of the cured product is easily prevented. Favorable curability 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 range of content, and the number of moles (b) of functional groups capable of generating trimethylsilanol of the compound (B) present in the curable composition is 1 When it is said that the molar ratio (a / b) of the sum (a) of the hydroxyl group of the polymer (A) and the hydrolysable group present in the curable composition (a sum of X ^{1 in} the formula (1)) is It is preferable that it is 0.5-7.2. When the molar ratio (a / b) is at least the lower limit of the above range, a sufficient curing rate of the polymer (A) is easily obtained, and when it is at the upper limit or less, the mechanical properties of the curable composition are improved. The effect of suppressing the surface tackiness of the cured product is easily obtained. The molar ratio (a / b) is more preferably 1.5 to 6.3, further preferably 1.8 to 5.0.
The compound (B) may be previously added to the component (for example, the polymer (A), (C), or (D)) of the curable composition, and is added when producing the curable composition. May be

<Other ingredients>
The curable composition of the present invention can contain, in addition to the above polymers (A), (C), (D) and the compound (B), components known in the curable composition. Specific examples thereof include additives such as a curing catalyst, cocatalyst, filler, plasticizer, thixotropic agent, air oxidation curing compound, stabilizer, adhesion promoter and the like.
The method for preparing a curable composition containing such additive components is not particularly limited, and the additive components may be added all at once or several times during or after the production of the curable composition. It may be divided and added. 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 the compound (B), and salts of metal (tin, bismuth etc.) and organic acid (octylic acid, octenoic acid, naphthene) Acids and the like); organic metal complexes and the like are preferable. The organic acid salt is preferably stannous octoate, bismuth tris (2-ethylhexanoic acid) and 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. One species may be used alone, or two or more species may be used in combination.

[Co-catalyst]
A curing catalyst and a cocatalyst may be used in combination. The cocatalyst is preferably an amine, a carboxylic acid or a phosphoric acid, and particularly preferably an amine from the viewpoint of the rapid curing property of the curable composition and the mechanical properties of the cured product.
The amine is not particularly limited, and a primary amine is preferred. Specific examples of the amine include aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, laurylamine and N, N-dimethyloctylamine; ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like Aliphatic polyamines; aromatic amines; alkanolamines; N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, amines having a hydrolyzable silyl group such as 3-aminopropyltrimethoxysilane and the like. The cocatalyst may be used alone or in combination of two or more. Among them, the combined use of a divalent tin compound and a primary amine compound is preferable, and the combined use of stannous octoate and laurylamine is more preferable.
It is preferable to use 0.01-15 mass parts with respect to 100 mass parts of a polymer (A), and, as for a co-catalyst, it is especially preferable to use 0.1-5 mass parts.

[Filling material]
As the filler, ground calcium carbonate having an average particle size of 1 to 20 μm, light calcium carbonate having an average particle size of 1 to 3 μm manufactured by a precipitation method, colloidal calcium carbonate whose surface is surface treated with fatty acid or resin acid organic substance, light Calcium carbonate such as calcium carbonate; fumed silica; precipitated silica; surface siliconized silica fine powder; anhydrous silicic acid; hydrous silicic acid; carbon black; magnesium carbonate; diatomaceous earth; calcined clay; clay; Bentonite; Ferric oxide; Zinc oxide; Active zinc flower; Shirasu balloon, pearlite, glass balloon, silica balloon, fly ash balloon, alumina balloon, zirconia balloon, inorganic hollow body such as carbon balloon, etc .; Phenolic resin balloon, epoxy resin Balloon, urea resin balloon, Organic resin hollow bodies such as orchid balloon, polystyrene balloon, polymethacrylate balloon, polyvinyl alcohol balloon, styrene-acrylic resin balloon, polyacrylonitrile balloon, etc .; resin beads, wood flour, pulp, cotton chip, mica, walnut flour, rice flour, Powdered fillers such as graphite, aluminum fine powder and flint powder; and fibrous fillers such as glass fibers, glass filaments, carbon fibers, kevlar fibers and polyethylene fibers.

  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 ground calcium carbonate and colloidal calcium carbonate in combination. By using a hollow body (balloon), the weight of the curable composition and the cured product thereof can be reduced. Moreover, by using a hollow body, the stringiness of the composition can be improved to improve the workability. The hollow bodies 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 polymer (A), and, as for the usage-amount of the filler in this invention, 50-250 mass parts is more preferable.

[Plasticizer]
As a plasticizer, phthalic acid esters such as di (2-ethylhexyl) phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate and the like; dioctyl adipate, bis (2-methylnonyl succinate), dibutyl sebacate, olein Aliphatic carboxylic acid esters such as butyl acid; alcohol esters such as pentaerythritol ester; phosphoric acid 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, epoxy benzyl stearate and the like; chlorinated paraffins; isoparaffins; polyester-based plasticizers such as polyesters obtained by reacting a dibasic acid and a dihydric alcohol; Polyether derivatives in which the hydroxyl group of polyoxypropylene glycol is sealed with alkyl ether; Oligomers of polystyrene such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, Oligomers such as polybutene, hydrogenated polybutene, epoxidized polybutadiene and the like can be mentioned.
A commercially available isoparaffinic solvent can be used as isoparaffin as a plasticizer. For example, product name: Isopar series (Isopar H, Isopar M, etc., all of which are product names) manufactured by ExxonMobil can be used.
In addition, paraffinic hydrocarbons can also be used as plasticizers, and are effective in improving the surface tackiness (tack) of the cured product. A paraffin hydrocarbon having preferably 6 or more carbon atoms, and more preferably 8 to 18 carbon atoms is preferable in that 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-dipropyl octane, 3-methyl tridecane, 6-methyl tridecane, n-hexadecane, n-heptadecane, n-octadecane and the like.

  Although relatively low molecular plasticizers such as phthalic acid esters have a large plasticizing effect and are effective in reducing the viscosity of the composition, they are most commonly used, but these low molecular plasticizers were used. In the cured product of the curable composition, the migration of the plasticizer to the surface is high, and when it is used as an adhesive, there may be a problem with reduced adhesion, and the cured product surface or around the cured product It may cause contamination of the adherend or adversely affect the weatherability of the cured product itself. Therefore, when using such a low molecular plasticizer, it is preferable to appropriately adjust the content in consideration of the compatibility with the curable composition and the like.

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

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 of a divalent tin carboxylate and a primary amine. Has the effect of obtaining a cured product having a large rate of return (compression recovery rate) after fixation in a compressed state under certain conditions and then releasing fixation. The above plasticizers may be used alone or in combination of two or more.
One plasticizer may be used alone, or two or more plasticizers may be used in combination. 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 addition of the thixotropic agent improves the sag of the curable composition. As the thixotropic agent, hydrogenated castor oil, fatty acid amide, calcium stearate, zinc stearate, finely powdered silica, organic acid-treated calcium carbonate and the like can be mentioned.
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]
The addition of the air oxidation curing compound to the curable composition improves the weatherability of the cured product and adhesion of dust.
Examples of air oxidation curable compounds include drying oils such as soy sauce and linseed oil, alkyd resins obtained by modifying drying oils, acrylic polymers modified with drying oils, silicone resins, polybutadiene, dienes having 5 to 8 carbon atoms These polymers and diene polymers such as copolymers, modified products of these polymers and copolymers (maleated modification, boiled oil modified, etc.), air-curable polyester compounds, etc. may be mentioned. These may be used alone or in combination.
As for the usage-amount of an air oxidation hardening compound, 0.1-50 mass parts is preferable with respect to 100 mass parts of a polymer (A).

[Stabilizer]
Examples of stabilizers (anti-aging agents) include antioxidants, ultraviolet light absorbers, light stabilizers and the like, and hindered amines, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, hindered phenols And phosphorus and sulfur compounds can be used. In particular, it is preferable to use two or more of a light stabilizer, an antioxidant, and an ultraviolet absorber in combination. According to such a method of use, it is possible to improve the anti-aging effect as a whole by making full use of each feature.
Specifically, it is particularly effective to combine two or more selected from tertiary and secondary hindered amine light stabilizers, benzotriazole ultraviolet light absorbers, hindered phenols, and phosphite antioxidants. is there.
Products marketed as antioxidants, ultraviolet light absorbers or light stabilizers can be used as appropriate.
The use amount of the antioxidant, the ultraviolet light absorber and the light stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A). If it is less than 0.1 part by mass, the antiaging 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 promoter may be used to improve adhesion. Specific examples of the adhesion promoter include organosilane coupling agents such as silanes having a (meth) acryloyloxy group, silanes having an amino group, silanes having an epoxy group, and silanes having a carboxyl group; isopropyltri (N- Organometallic coupling agents such as aminoethyl-aminoethyl) propyltrimethoxytitanate, 3-mercaptopropyltrimethoxitanate, etc .; 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) Examples include benzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane.

Specific examples of the epoxy resin include bisphenol A-diglycidyl ether epoxy resin, bisphenol F-diglycidyl ether epoxy resin, tetrabromobisphenol A-glycidyl ether epoxy resin, novolac epoxy resin, hydrogenated bisphenol A epoxy Resin, glycidyl ether type epoxy resin of bisphenol A-propylene oxide adduct, glycidyl 4-glycidyloxybenzoate, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl ester based epoxy resin, m-aminophenol Epoxy resin, diaminodiphenylmethane epoxy resin, urethane modified epoxy resin, N, N-diglycidyl aniline, 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 polymer (A) of (A) component.
When adding the said epoxy resin to a curable composition, 100 mass parts or less are preferable with respect to 100 mass parts of cured resin components, and, as for the addition amount, 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 compounding components are compounded and stored beforehand and cured by moisture in the air after application, and the polymer (A) and the compound (B) A) a curing agent composition, a curing catalyst, a filler, water and other components are prepared separately as a curing agent composition separately from the main agent containing a), and the curing agent composition and the main agent are mixed before use, to prepare a two-component type It can also be done. In the case of the two-component type, when mixing the main agent and the curing agent, a colorant such as toner may be added and 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% A cured product having a durability which is preferably 700 to 900% and which does not cause a crack in the bonding interface between the adherend and the cured product even after conducting 2000 times of stretching tests by the durability evaluation method described later Is obtained.

  The curable composition of the present invention comprises a sealant (elastic sealant for construction, sealant for double glazing, etc.), sealant (anticorrosive for waterproofing of glass edge, sealant for waterproofing, solar cell backside sealing) It is useful as an adhesive used in the fields of adhesives, etc., electrical insulating materials (insulation coating materials for electric wires and cables), etc. In particular, it is suitable for applications requiring stretch fatigue resistance, such as sealing materials applied outdoors.

EXAMPLES The present invention will be described in more detail using the following examples, but the present invention is not limited to these examples.
[Precursor polymer]
Precursor polymers used in the examples are shown in Table 1. Each precursor polymer is obtained by the following production example. The composite metal cyanide complex catalyst (alkylene oxide ring-opening polymerization catalyst) used in the production of the precursor polymer is one 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 one functional group.
In the following Reference Production Examples 1 and 2, as an aqueous solution of zinc chloride, 10 g of zinc chloride dissolved in 15 mL of water, and as an aqueous solution of potassium hexacyanocobaltate, 4 g of potassium hexacyanocobaltate dissolved in 80 mL of water, used.

(Reference Production Example 1: Production of mixed metal cyanide complex catalyst in which the ligand is t-butyl alcohol)
Aqueous potassium hexacyanocobaltate solution was added dropwise to the aqueous zinc chloride solution at 40 ° C. over 30 minutes. After the 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 at 60 ° C. for 1 hour for aging. After aging, the complex was filtered off.
To the obtained complex was added 40 mL of TBA and 80 mL of water, and the mixture was 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 until the weight became constant at 50 ° C., pulverization was performed to obtain a composite metal cyanide complex catalyst (t-butyl alcohol complex catalyst of zinc hexacyanocobaltate) whose ligand is t-butyl alcohol .

(Reference Production Example 2: Production of a mixed metal cyanide complex catalyst in which the ligand is glyme)
Aqueous potassium hexacyanocobaltate solution was added dropwise to the aqueous zinc chloride solution at 40 ° C. for 30 minutes. After completion of the dropwise addition, 80 mL of glyme and 80 mL of water were added, and after stirring for 1 hour at 60 ° C., the complex was separated by filtration.
To the obtained complex was added 80 mL of glyme and 80 mL of water, and the mixture was stirred for 30 minutes and filtered off, and 100 mL of glyme and 10 mL of water were added and filtered off after stirring. After drying at 80 ° C. for 4 hours, the resultant was pulverized to obtain a composite metal cyanide complex catalyst (glyme complex catalyst of zinc hexacyanocobaltate) whose ligand is glyme.

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).
Propylene oxide (1,522 g) was added to initiator A (64.1 g) in the presence of t-butyl alcohol complex catalyst (0.08 g) of zinc hexacyanocobaltate, and the pressure of the reaction system did not fall at 120 ° C. It was made to react. 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. The Mn measured by GPC was 30,000, the Mw was 35,100, and thus the Mw / Mn was 1.17.

Production Example 2: Production of Precursor Polymer (A'2)
The polyoxypropylene diol (molecular weight 1,000 per one 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 t-butyl alcohol complex catalyst (0.03 g) of zinc hexacyanocobaltate, initiator B (64.1 g) is reacted with propylene oxide (525 g) at 120 ° C. until the pressure of the reaction system does not fall. I did. Thus, 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 at 25 ° C. of the precursor polymer (A′2) was 20 Pa · s. The Mn measured by GPC was 22,000, the Mw was 23,800, and the Mw / Mn was 1.08.

Production Example 3: Production of Precursor Polymer (A'3)
Propylene oxide (858 g) was added to a mixture of initiator A (21.4 g) and initiator B (42.7 g) in the presence of t-butyl alcohol complex catalyst (0.05 g) of zinc hexacyanocobaltate, 120 The reaction was allowed to proceed until the pressure of the reaction system did not fall at ° C. 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. The Mn measured by GPC was 26,000, the Mw was 31,800, and the Mw / Mn was 1.22.

Production Example 4 Production of Precursor Polymer (A′4)
The polyoxypropylene triol (molecular weight of 330 per functional group, the initiator A) obtained by ring-opening addition polymerization of propylene oxide to glycerin was used as an initiator.
Propylene oxide (2,280 g) was added to initiator A (64.1 g) in the presence of t-butyl alcohol complex catalyst (0.08 g) of zinc hexacyanocobaltate, and the pressure of the reaction system did not fall at 120 ° C. It was made to react. Thus, 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. The Mn measured by GPC was 41,000, the Mw was 47,100, and the Mw / Mn was 1.15.

Production Example 5 Production of Precursor Polymer (E′1)
Polyoxypropylene triol (molecular weight: 1,000 per one functional group) (initiator C) obtained by ring-opening addition polymerization of propylene oxide to glycerin was used as an initiator.
In the presence of a glyme complex catalyst of zinc hexacyanocobaltate (0.09 g), initiator D (64.1 g) was reacted with propylene oxide (376 g) at 120 ° C. until the pressure of the reaction system did not fall. Thus, 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. The Mn measured by GPC was 25,000, and the Mw 35,500 was thus Mw / Mn 1.42.

Production Example 6: Production of Precursor Polymer (E'2)
In the presence of t-butyl alcohol complex catalyst (0.05 g) of zinc hexacyanocobaltate, initiator A (64.1 g) is reacted with propylene oxide (924 g) at 120 ° C. until the pressure of the reaction system does not fall. I did. 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 at 25 ° C. of the precursor polymer (E′2) was 6 Pa · s. The Mn measured by GPC was 19,000, the Mw 21,800 was thus Mw / Mn 1.15.

Production Example 7: Production of Precursor Polymer (C'1)
The polyoxypropylene monool (molecular weight 2,000 per one 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).
Propylene oxide (594 g) was reacted with initiator D (384 g) in the presence of t-butyl alcohol complex catalyst (0.05 g) of zinc hexacyanocobaltate at 120 ° C. until the pressure of the reaction system did not fall. . Thus, 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 precursor polymer (C'1) had a viscosity of 1.2 Pa · s at 25 ° C. The Mn measured by GPC was 7,800, the Mw was 8,600, and thus the Mw / Mn was 1.10.

[Polymer (A) (C) (E)]
The polymers (A) (C) (E) used in the examples are shown in Table 2. Each polymer is obtained by the following production example.
The 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 at the end of the precursor polymer, and a dimethoxymethylsilyl group was introduced at the main chain terminal of the precursor polymer by a method of reacting dimethoxymethylsilane with the allyl group. In such a 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 ratio in the table is a value calculated by measuring the amount of H in the methylene chain bound 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.
In the table, the content (unit: mmol / g) of reactive silicon group (dimethoxymethylsilyl group) in 1 g of polymer, and the content of hydrolysable group (methoxy group bonded to silicon atom) in 1 g of polymer The amount (unit: mmol / g) is shown.

Production Example 8 Production of Polymer (A1)
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide to the precursor polymer (A′1) obtained above with respect to the amount of hydroxyl groups of the precursor polymer (A′1). (A'1) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (A′1). Thus, a polymer (A′′1) having a polyoxypropylene chain and an allyl group at all of the main chain terminals was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.72 moles of dimethoxymethylsilane is added to the allyl group of the main chain terminal of the obtained polymer (A′′1), Reaction for 5 hours. Thus, a polymer (A1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal was obtained.

Production Example 9 Production of Polymer (A2)
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide to the precursor polymer (A′2) obtained above with respect to the amount of hydroxyl groups of the precursor polymer (A′2). (A'2) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (A′2). Thereby, thereby, the polymer (A''2) which has a polyoxypropylene chain and has an allyl group at all the principal chain terminal was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.77 moles of dimethoxymethylsilane is added to the allyl group of the main chain terminal of the obtained polymer (A ′ ′ 2), and the temperature is 70 ° C. Reaction for 5 hours. Thus, a polymer (A2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal was obtained.

Production Example 10 Production of Polymer (A3)
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide relative to the amount of hydroxyl groups of the precursor polymer (A'3) to the precursor polymer (A'3) obtained above. (A'3) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (A'3). Thereby, thereby, the polymer (A''3) which has a polyoxypropylene chain and has an allyl group at all the principal chain terminal was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.745 moles of dimethoxymethylsilane is added to the allyl group of the main chain terminal of the obtained polymer (A ′ ′ 3), and the temperature is 70 ° C. Reaction for 5 hours. Thus, a polymer (A3) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal 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 moles of dimethoxymethylsilane is added to the allyl group at the main chain end of the polymer (A′′1), and the reaction is allowed to proceed at 70 ° C. for 5 hours The Thus, a polymer (A4) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal 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 moles of dimethoxymethylsilane is added to the allyl group at the main chain end of the polymer (A′′1), and the reaction is allowed to proceed at 70 ° C. for 5 hours The Thus, a polymer (A5) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal was obtained.

Production Example 13 Production of Polymer (A6)
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide to the precursor polymer (A′4) obtained above with respect to the amount of hydroxyl groups of the precursor polymer (A′4). (A'4) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (A'4). Thus, a polymer (A′′4) having a polyoxypropylene chain and an allyl group at all of the main chain terminals was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.72 moles of dimethoxymethylsilane is added to the allyl group of the main chain terminal of the obtained polymer (A ′ ′ 4), and the temperature is 70 ° C. Reaction for 5 hours. Thus, a polymer (A6) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal was obtained.

Production Example 14 Production of Comparative Polymer (E1)
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide to the precursor polymer (E′1) obtained above with respect to the amount of hydroxyl groups of the precursor polymer (E′1). (E'1) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (E′1). Thereby, thereby, the polymer (E''1) which has a polyoxypropylene chain and has an allyl group at all the principal chain terminal was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.70 moles of dimethoxymethylsilane is added to the allyl group of the main chain terminal of the obtained polymer (E′′1), and the temperature is 70 ° C. Reaction for 5 hours. Thus, a polymer (E1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal was obtained.

Production Example 15 Production of Comparative Polymer (E2)
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide to the precursor polymer (E'2) obtained above with respect to the amount of hydroxyl groups of the precursor polymer (E'2). (E'2) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (E'2). Thereby, thereby, the polymer (E''2) which has a polyoxypropylene chain and has an allyl group in all the principal chain terminals was obtained.
Next, in the presence of chloroplatinic acid hexahydrate, 0.66 moles of dimethoxymethylsilane is added to the allyl group of the main chain terminal of the obtained polymer (E ′ ′ 2), and the temperature is 70 ° C. Reaction for 5 hours. Thus, a polymer (E2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal was obtained.

Production Example 16 Production of Polymer (C1) Having Reactive Silicon Group at One End
A precursor polymer is obtained by adding a methanol solution containing 1.05 moles of sodium methoxide relative to the amount of hydroxyl groups of the precursor polymer (C'1) to the precursor polymer (C'1) obtained above. (C'1) was alcoholated. Next, after distilling off methanol by heating and pressure reduction, an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer (C'1). As a result, a polymer (C′′1) having a polyoxypropylene chain and 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 is added to the allyl group of the main chain terminal of the obtained polymer (C′′1), Reaction for 5 hours. Thus, a polymer (C1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the main chain terminal 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) is obtained by the following production example. The polymer (D2) is ARUFON US-6120 (product name, Mw 2,400) manufactured by Toagosei Co., Ltd.
(Production Example 21: Production of Polymer (D1))
In this example, the polymer (D1) was produced by a method of polymerizing the unsaturated group-containing monomer constituting the polymer (D1) in the presence of a solvent.
In a pressure resistant reactor equipped with a stirrer, 200 g of ethyl acetate was charged, and the temperature was raised to about 67 ° C. While maintaining the internal temperature of the reaction vessel at about 67 ° C. and stirring under a nitrogen atmosphere, 72 g of methyl methacrylate, 6.5 g of n-butyl acrylate, 29.0 g of n-butyl methacrylate, 3-methacryloyloxypropyl tritri 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.) A mixed solution of 2.5 g is dropped into ethyl acetate over 5 hours to carry out polymerization, and a (meth) acrylate copolymer having a triethoxysilyl group as a reactive silicon group (hereinafter referred to as “polymer (D1) ") Was synthesized. The number average molecular weight (Mn) of the polymer (D1) was measured to be 4,000.

[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 1, 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 above polymers (A), (C), (D), comparative polymer (E) and 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 separately prepared, and the curing agent composition and the main agent composition are used before use A two-component curable composition was prepared for mixing.
The formulations of the main agent composition are shown in Tables 3 to 6, and the formulations of the curing agent composition are shown in Table 7. The additive components shown in the table are as follows.
In the table showing the composition of the main agent composition, the molar number a (relative value) of the total of the hydroxyl group and the hydrolysable group of the polymer (A) or the comparative polymer (E) present in the main agent composition The molar number b (relative value) of functional groups capable of generating trimethylsilanol of the compound (B) present in the main agent composition and the value of the molar ratio a / b thereof are shown.

[filler]
White matting CCR (product name): Colloidal calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.
Whiteton SB (product name): Heavy calcium carbonate, manufactured by Shiraishi Calcium Industry Co., Ltd., average particle diameter 1.78 μm.
Titanium oxide: manufactured by Ishihara Sangyo Co., Ltd., R820 (product name).
Balloon 80 GCA (product name): Organic balloon manufactured by Matsumoto Yushi Co., Ltd.
Gromax LL (product name): Calcined kaolin manufactured by Takehara Chemical Industry Co., Ltd.

[Plasticizer]
DINP (abbreviation): diisononyl phthalate, manufactured by Shin Nippon Rika Co., Ltd., product name: Sanssoizer DINP.
PMLS 4012 (product name): high molecular weight polyol, manufactured by Asahi Glass Co., Ltd., molecular weight 5,000 per hydroxyl group (PMLS 4012 has two hydroxyl groups in the molecule).
UP-1000 (product name): Touasei Co., Ltd. product ARUFON UP-1000 (product name, non-functional acrylic polymer, Mw 3,000).
Sanssoizer EPS (trade name): Shin Nippon Rika Co., Ltd., 4, 5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl.
Isopar H (product name): ExxonMobil, an isoparaffinic plasticizer.
Isopar M (product name): ExxonMobil, an isoparaffinic plasticizer.
Octane: manufactured by Wako Pure Chemical Industries, Ltd.
Undecane: manufactured by Wako Pure Chemical Industries, Ltd.
Tridecane: manufactured by Wako Pure Chemical Industries, Ltd.
N-12 (product name): Nippon Ore Oil Chemical Co., Ltd., normal paraffin (n-dodecane 99.0%).
YH-NP (product name): manufactured by Nippon Ore Oil Chemical Co., Ltd., normal paraffin (n-dodecane 18%, n-tridecane 59%, n-tetradecane 19%, n-heptadecane 4%).
SH-NP (product name): SH-NP is a natural ore oil chemical normal paraffin (55% of n-tetradecane, 37% of n-heptadecane, 8% of n-hexadecane).

[Thixotropic agent]
Disparon # 305 (product name): Hydrogenated castor oil-based thixotropic agent, manufactured by Kushimoto Chemical Co., Ltd.
[Air oxidation curable compound]
Soy sauce: Made by Kimura.
[Stabilizer]
(Antioxidant)
IRGANOX 1010 (product name): hindered phenolic antioxidant manufactured by BASF.
IRGANOX 245 (product name): Hindered phenolic antioxidant, manufactured by BASF.
(UV absorber)
TINUVIN 326: (product name): benzotriazole-based ultraviolet absorber manufactured by BASF.
CHIMASSORB 81 (product name): benzophenone based ultraviolet absorber, manufactured by BASF.
(Light stabilizer)
TINUVIN 765 (product name): hindered amine light stabilizer manufactured by BASF.
LA-63P (product name): hindered amine light stabilizer, manufactured by ADEKA, molecular weight 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 / cocatalyst mixture: mass ratio of stannous octoate (made by Yoshitomi Pharmaceutical Co., Ltd., trade name: stanoct) as a curing catalyst and laurylamine (n-dodecylamine, reagent) as a cocatalyst (Curing catalyst: co-catalyst) 6: 1 mixed mixture.

[Preparation of Hardener Composition]
(Examples 1 to 31)
In the formulations shown in Tables 3 to 6, the respective components were mixed by a planetary stirrer to prepare a main agent composition. Examples 15 to 18 are Examples of the present invention, examples 1～14,19～25 for illustrative purposes, Example 26 to 31 are Ru Comparative Example der. In Tables 3 to 6, a is the total (relative mole number) of the hydroxyl group of the polymer (A) or (E) and the hydrolyzable group, and b can generate the trimethylsilanol group of the compound (B) It is the total (relative number of moles) of functional groups.
Separately from this, in the formulation shown in Table 7, the following (a) to (d) were mixed to prepare a curing agent composition.
The weight ratio of main ingredient composition / hardener composition / dark gray toner (100/10 / 5.2) of the main ingredient composition of each example, the curing agent composition of the formulation of Table 7, and the toner as a colorant The mixture was mixed to obtain a curable composition.
The resulting curable composition was evaluated by the following method. The evaluation results are shown in Tables 8 and 9.
The curable compositions obtained in Examples 2 and 25 were subjected to 2000 expansion tests in the durability test described below, and then additionally 1000 expansion tests were performed 2000 times. The results are shown in Table 10.

<Evaluation of Curability (Consistency)>
450 g of the obtained curable composition was placed in a container (size: 10.5 cm long × 7.0 cm wide × 4.0 cm deep), and nitrogen gas was blown from the surface to remove air bubbles. After that, place the container horizontally in an atmosphere at 10 ° C, cure it for 40 hours, and use it as a sample to measure consistency using an automatic consistency / penetration tester (RPM-101). The
Ease of penetration: A stainless steel cone-shaped cone (0.38 mm in diameter) was introduced into the center of the surface of this sample under a load of 100 g, and the penetration length in 5 seconds (penetration depth, unit : Mm) was measured, and the penetration depth was multiplied by 10 to obtain the consistency value.
When the value of the consistency was 100 or less, the curability was good (○), and when it was more than 100, the curability was poor (x).

<Evaluation of tensile properties (H-type test)>
As an adherend, using surface anodized aluminum treated with a primer (product name: MP-2000, manufactured by Cemedine) on the surface and using the test method of JIS A 1439 for a sealing material for construction, H type test body Were tested for tensile properties.
Specifically, the prepared H-type test body was aged for 1 week at a temperature of 23 ° C. and a humidity of 65%, and further aged for 1 week at a temperature of 50 ° C. and a humidity of 65% to prepare a cured product of the H-type . The obtained cured product was subjected to tensile property measurement (H-type physical property) with a Tensilon tester, and the stress at 50% elongation (M50, unit: N / mm ² ), maximum point tensile stress (unit: N) / ^mm 2), the maximum elongation (unit: was measured%).
The smaller the value of M50, the higher the flexibility, the larger the value of the maximum point tensile stress, the higher the tensile strength, and the larger the value of the maximum point elongation, the better the elongation.

<Surface tackiness>
The curable composition is applied on a polyethylene terephthalate film in a shape of approximately 150 mm long, 50 mm wide and 5 mm thick, cured for 8 hours at 23 ° C., 50% humidity, and cured to indicate the presence or absence of surface tack It evaluated by.

<Durability>
The durability was measured in accordance with the durability category 9030 described in JIS A 5758 (2004 edition). As the adherend, a surface anodized aluminum having a primer (product name: MP-2000, manufactured by Cemedine) treated on the surface was used.
Cracks in the adhesion interface between the adherend and the cured product after 2000 elongation tests in the durability test are confirmed, and those without the cracks are marked as ((best) with some cracks A very small case of very shallow and less than about 0.5 mm is regarded as 優良 (excellent), and those having a shallow crack of about 1 mm over the entire surface are △ (good), a deep crack of 1 mm or more across the entire surface The thing was made into x (defect).
The fact that the durability in this durability test is good indicates that the resistance to stretch fatigue 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 types of compounds (B) in appropriate ratio, the composition is sufficiently cured at 10 ° C. for 40 hours Good curability was obtained. Although the elastic modulus (M50) of the cured product was relatively high at 0.18 to 0.23 N / mm ² , the elongation and the durability were good. There was no stickiness on the surface of the cured product.
On the other hand, Example 26 does not use the polymer (A), but instead uses the comparative polymer (E1) in which the molecular weight distribution (Mw / Mn) of the precursor polymer is larger than 1.40. is there. The modulus of elasticity and tensile strength of the cured product are almost the same as in Examples 1 to 24, but the elongation and the durability are inferior.
Example 27 is an example using the comparative polymer (E2) in which the molecular weight per functional group of the precursor polymer is less than 7,000 instead of using the polymer (A), and the cured product Modulus of elasticity is almost equal to that of Examples 1 to 25, but tensile strength, elongation and durability are inferior.
Example 28 is an example using only one type of phenoxytrimethylsilane (B1) as the compound (B). The curability was inferior to that of Example 2 and was not fully cured at 10 ° C. for 40 hours.
Example 29 is an example using only one kind of TMP-3TMS (B2) as the compound (B). Although the curability was good, compared with Example 2, the modulus of elasticity of the cured product was low, 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, although the value of elastic modulus was high, tensile strength and elongation were inferior and durability was insufficient. Also, tackiness was observed on the surface of the cured product.
Example 31 is an example in which the compound (B) is contained in more than 2 parts by mass with respect to 100 parts by mass of the polymer (A). The curability was inferior to that of Example 22 and the resin did not fully cure at 10 ° C. for 40 hours. Moreover, compared with Example 22, although the value of the elasticity modulus of hardened | cured material was small and elongation and durability were good, tensile strength was inferior.
Further, from the results of Table 10, in Examples 2 and 25 in which the curable composition contains the polymer (A) and the two types of compounds (B) in an appropriate amount ratio, and the molecular weight per one functional group is different, Although the elastic modulus of the product is almost the same, Example 25 having a high molecular weight is superior in tensile strength and elongation, and results in excellent durability when an additional expansion and contraction test is performed.

Claims (5)

A group having an alkylene oxide monomer unit in the main chain, a functional group capable of introducing a reactive silicon group at all of the main chain terminals, and the functional group comprising a group having active hydrogen and an unsaturated group It is 1 or more types selected, and introduce | transduces the reactive silicon group represented by the following Formula (1) to the precursor polymer (A ') which is the functional group number of a principal chain terminal is 2-4. A polymer having a molecular weight per one functional group of 7,000 to 20,000, and a molecular weight distribution selected from the group consisting of 1.01 to 1.40; A polymer (A) which is a mixture containing two or more kinds of groups different from each other and has an average of the number of functional groups at the main chain terminal of 2.0 to 3.0, and a compound capable of generating trimethylsilanol by hydrolysis (B) And the compound (B) contains phenoxytrimethylsilane and It is 2 or more types including tristrimethylsilyl body of methylol propane, and the total content of the compound (B) is 0.4 to 2.0 parts by mass with respect to 100 parts by mass of the polymer (A). Curable composition.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents a C1-C20 monovalent organic group which may have a substituent (excluding hydrolysable groups), and X ¹ represents a hydroxyl group or a hydrolysable group] . The two X ^{1 s} may be the same or different. ] The curable composition according to claim 1 , wherein a mass ratio of the two represented by tristrimethylsilyl form of phenoxytrimethylsilane / trimethylolpropane is 20/80 to 80/20. Furthermore, a linear main chain has an alkylene oxide monomer unit, polymers having a reactive silicon group at one end includes a (C), the curable composition according to claim 1 or 2. Furthermore, the curable composition as described in any one of Claims 1-3 containing the (meth) acrylic acid ester copolymer (D) which has a reactive silicon group. The curable composition is placed in a container measuring 10.5 cm long, 7.0 cm wide, and 4.0 cm deep, and the cured product cured at 10 ° C. for 40 hours has a value of the following consistency of 100 or less. The curable composition as described in any one of Claims 1-4.
  Consistency: A stainless steel conical cone with a tip of 0.38 mm is infiltrated into the center of the surface of the cured product under a load of 100 g, and the length (unit: mm) of penetration in 5 seconds Measured value multiplied by 10 times the length.