JP5757106B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing a polymer having a reactive silicon group and curable at room temperature by moisture in the air.

  The polymer having a reactive silicon group is crosslinked by the hydrolysis and condensation reaction of the reactive silicon group to form a siloxane bond. Therefore, it can be cured by moisture in the air at room temperature, and becomes a cured product having rubber elasticity after curing. Since the obtained cured product has excellent characteristics for various adherends, it is widely used as a base material for sealing materials, adhesives, coatings or sealing compositions.

In general, a curable composition used for a sealing material, an adhesive or the like is preferably a cured product that is flexible and stretches well. For this purpose, a plasticizer is blended in the curable composition.
As the plasticizer, aromatic carboxylic acid esters, aliphatic carboxylic acid esters, glycol esters, phosphate esters, epoxy plasticizers, chlorinated paraffins and the like are generally used.
It is also known to use an acrylic polymer or a polyether polymer as a plasticizer (Patent Document 1).
However, since these plasticizers have migratory properties, they easily flow out of the cured product, and there are problems such as contamination around the sealing portion, adverse effects on adhesion, contamination on the surface coating, and poor adhesion.

On the other hand, it has been proposed to use a low molecular weight polymer having a reactive silicon group as a plasticizer having low migration.
For example, in Patent Document 2, a high molecular weight polymer (I) having a molecular weight of 8,000 to 50,000 having an average of 1 to 1.5 reactive silicon groups per molecule and an average of 0.5 to 1 per molecule. A curable composition is described in combination with a low molecular weight polymer (II) having 300 reactive molecular groups and a molecular weight of 300 to 8,000.
Further, in Example 18 (Comparative Example) of Patent Document 2, high molecular weight polymer E having an average of 2.4 methyldimethoxysilylpropyl groups per molecule and a molecular weight of about 30,000, and 95 of the terminal hydroxyl groups of monool. % Is an allyloxy group, and a curable composition is described in combination with a low molecular weight polymer a having a molecular weight of about 5,000 reacted with 80% equivalent of methyldimethoxysilane. The viscosity at 25 ° C. of this curable composition is 28000 cP (= 28 Pa · s). However, Patent Document 2 does not disclose a high molecular weight polymer having a molecular weight exceeding 30,000, nor does it disclose a weight average molecular weight or a molecular weight distribution. Predicting from the disclosed viscosity, it becomes difficult to produce when the viscosity increases from the high molecular weight polymer E having a molecular weight of about 30,000. Therefore, a high molecular weight polymer having a molecular weight exceeding 30,000 is produced by the technique of Patent Document 2. Was probably difficult.

Japanese Patent Laid-Open No. 10-60253 JP-A-9-95619

By the way, in order to develop excellent elongation properties, a high molecular weight polymer having a reactive silicon group is preferably a polymer having a high molecular weight. However, a high molecular weight polymer having a high molecular weight has a high viscosity, and workability is impaired when the cured product is used as a sealing material or an adhesive. Therefore, a curable composition for a sealing material or an adhesive using a high molecular weight polymer requires a larger amount of plasticizer, but as described above, a plastic having migration properties. In the case of the agent, problems such as contamination around the sealing portion, adverse effect on adhesiveness, contamination on the surface coating and lowering of adhesion, etc., have appeared remarkably, so improvement has been particularly demanded.
Further, according to the knowledge of the present inventors, even in a method using a low molecular weight polymer having a reactive silicon group as a plasticizer having low migration property, the cured product may be inferior in elongation, paint film contamination, or durability. Yes, it was found that improvement was necessary.
In Example 18 (Comparative Example) of Patent Document 2, a high molecular weight polymer having a molecular weight of about 30,000 is used, but the flexibility is poor. According to the knowledge of the present inventors, it is considered that the high molecular weight polymer has a wide molecular weight distribution and contains a large amount of low molecular weight polymer components.

  This invention is made | formed in view of the said situation, and it aims at providing the curable composition which the softness | flexibility of a hardened | cured material, elongation, and durability are favorable, and can reduce coating-film pollution property.

The present invention is the following [1] to [6].
[1] It has a functional group capable of introducing a reactive silicon group at all main chain terminals, and the functional group is at least one selected from the group consisting of a group having an active hydrogen and an unsaturated group, A polymer obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (A ′) having an average functional group number of more than 2.0 and not more than 3.0 at the end of the main chain. A polymer (A) having a number average molecular weight of 25,000 or more and 50,000 or less and a molecular weight distribution of 1.01 to 1.20 , and linear, reactive silicon at one end A polymer obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (B ′) into which a group can be introduced, having a number average molecular weight of 5,000 or more and 20,000 The following polymer (B) is contained, and the precursor polymer (A ′) is a precursor polymer having three main chain terminal functional groups per molecule ( A′11), and the precursor polymer (A′11) is prepared by subjecting an initiator having three active hydrogens to ring-opening addition polymerization of an alkylene oxide in the presence of a catalyst (A′11). 11-a), and the mass ratio (A / B) of the content of the polymer (A) and the content of the polymer (B) is 90/10 to 40/60. Curable composition.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]
[2] It has a functional group capable of introducing a reactive silicon group at all main chain terminals, and the functional group is at least one selected from the group consisting of a group having active hydrogen and an unsaturated group, A polymer obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (A ′) having an average functional group number of more than 2.0 and not more than 3.0 at the end of the main chain. A polymer (A) having a number average molecular weight of 25,000 or more and 50,000 or less and a molecular weight distribution of 1.01 to 1.20 , and linear, reactive silicon at one end A polymer obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (B ′) into which a group can be introduced, having a number average molecular weight of 5,000 or more and 20,000 The following polymer (B) is contained, and the precursor polymer (A ′) is a precursor polymer having three main chain terminal functional groups per molecule ( A precursor polymer (A′11) comprising a ring-opening addition polymerized alkylene oxide with an initiator having three active hydrogens in the presence of a catalyst. It is a precursor polymer (A′11-b) produced by a method in which a hydroxyl group of a coalescence is converted into —OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon. The curable composition characterized by mass ratio (A / B) of content of (A) and content of said polymer (B) being 90/10 to 40/60.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]

[3] The curability of [1] or [2], wherein the precursor polymer (A ′) further includes a precursor polymer (A′12) having two main chain terminal functional groups per molecule. Composition.
[ 4 ] The curable composition according to any one of [1] to [3], wherein the polymer (B) has a molecular weight distribution of 1.01 to 1.30 .
[ 5 ] In the polymer (A), a functional group substituted with a group containing the reactive silicon group among functional groups at the main chain terminals capable of introducing the reactive silicon group of the precursor polymer (A ′). The curable composition according to any one of [1] to [ 4 ], wherein the ratio is from 45 to 100 mol%.
[ 6 ] The curable composition according to any one of [1] to [ 5 ], which is used for a sealing material or an adhesive.

  According to the curable composition of the present invention, it is possible to obtain a cured product having good flexibility, elongation and durability in the cured product and capable of reducing coating film contamination.

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

The mass average molecular weight (Mw, hereinafter also referred to as “Mw”) and the number average molecular weight (Mn, hereinafter also referred to as “Mn”) in the present specification are molecular weights in terms of polystyrene measured by gel permeation chromatography (GPC). . The molecular weight distribution in the present specification (hereinafter also referred to as “Mw / Mn”) is a value calculated from Mw and Mn measured by the above-described method, and is a mass average molecular weight (Mw) with respect to the number average molecular weight (Mn). The ratio (Mw / Mn).
In the present specification, the molecular weight converted from the hydroxyl value is referred to as “hydroxyl converted molecular weight MW (OH)”. That is, the relationship between the hydroxyl value and the hydroxyl equivalent molecular weight MW (OH) is represented by the following formula.
Hydroxyl equivalent molecular weight MW (OH) = number of hydroxyl groups × 56,100 / hydroxyl value The hydroxyl value in the present specification is a value measured by a method based on JIS K1557-1.
The viscosity value (unit: mPa · s or Pa · s) in this specification is determined using an E-type viscometer at 25 ° C. 4 rotor (cone rotor: 3 ° × R14), or No. It is a value measured using one rotor (cone rotor: 1 ° 34 ′ × R24).

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

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

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

In the present invention, the average functional group number of the polymer (A) is more than 2.0 to 3.0. When the average functional group number of the polymer (A) is more than 2.0, when the average functional group number of the polymer (A) is 2.0, that is, the main chain of the polymer (A) is linear. Since more reactive silicon groups can be introduced than in the case, it is preferable in that a curable composition that exhibits higher strength is obtained. Moreover, even if the introduction rate of the reactive silicon group is low, a curable composition that exhibits high strength can be obtained.
On the other hand, when the average functional group number of the polymer (A) is 3.0 or less, the flexibility of the cured product is improved.
When the average functional group number of the polymer (A) is 3.0, the polymer (A) is preferably composed of one or more kinds of the polymer (A11) having three functional groups at the main chain ends. A polymer having three functional groups at the end of the main chain (A11) has three functional groups at the end of the main chain per molecule, and has a number of functional groups at the end of all main chain ends of the branched precursor polymer (A′11). It is a polymer in which part or all of the functional group is substituted with a group containing a reactive silicon group.

When the polymer (A) is a mixture, (i) polymers having different numbers of functional groups at the main chain ends may be mixed, and (ii) a mixture of precursor polymers having different numbers of functional groups at the main chain ends. You may use and manufacture a polymer (A).
In the case of (i), the polymer (A) is a polymer having 2 to 4 functional groups at the end of the main chain mixed so that the average number of functional groups at the end of the main chain is within the above range. Mixtures are preferred. In the case of (i), the polymer (A) was prepared by mixing a polymer having 2 to 3 functional groups at the end of the main chain so that the average number of functional groups at the end of the main chain was within the above range. A mixture is more preferred. In particular, it is preferable that the polymer (A) includes at least a polymer (A11) having 3 functional groups at the main chain terminals, and 2 of the polymer (A11) having 3 functional groups at the main chain terminals. A mixture of two or more species, or a mixture of a polymer (A12) having two functional groups at the main chain ends and a polymer (A11) having three functional groups at the main chain ends is more preferable.
The polymer (A12) having two functional groups at the main chain ends is a linear precursor polymer (A′12) having two main chain terminal functional groups per molecule. A polymer in which a part or all of the functional groups at the ends of the main chain are substituted with groups containing reactive silicon groups.

  In the case of (ii), the polymer (A) is a precursor polymer having 2 to 4 main chain end groups per molecule, and the average number of functional groups at the main chain ends is more than 2.0. What introduce | transduced the reactive silicon group into the precursor polymer (A ') which consists of a mixture mixed so that it may become 3.0 is preferable. In the case of (ii), the polymer (A) is a precursor polymer having 2 to 3 main chain end groups per molecule, and the average number of functional groups at the main chain ends is more than 2.0. It is more preferable to introduce a reactive silicon group into the precursor polymer (A ′) composed of a mixture mixed so as to be 3.0. In particular, the precursor polymer (A ′) preferably contains at least the precursor polymer (A′11) having 3 main chain terminal functional groups per molecule, and the main chain terminal functional group number is 3. A mixture of two or more precursor polymers (A′11), or a precursor polymer (A′12) having two main chain terminal functional groups and three main chain terminal functional groups A mixture of the precursor polymer (A′11) is more preferable.

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

The polymer (A) has an alkylene oxide monomer and / or (meth) acrylic as an initiator having 2 or 3 terminal functional groups per molecule and all terminal groups are reactive functional groups. What is obtained through the process of addition-polymerizing an acid alkyl ester monomer is preferable.
That is, it is preferable that the repeating unit in the precursor polymer (A ′) and the polymer (A) includes an alkylene oxide monomer unit and / or a (meth) acrylic acid alkyl ester monomer unit. It is preferable to have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
When the polymer (A) has a polyoxyalkylene chain, there are advantages such as low temperature dependence, easy flexibility of the cured product, and excellent price.
The reactive functional group in the initiator is a group having active hydrogen, and preferably a hydroxyl group. The average functional group number of the initiator, the average functional group number of the main chain terminal of the precursor polymer (A ′), and the average functional group number of the main chain terminal of the polymer (A) are the same.

Alternatively, as a part or all of the polymer (A), the repeating unit in the precursor polymer (A ′) and the polymer (A) includes a (meth) acrylic acid alkyl ester monomer unit, and a polyoxyalkylene chain. You may use the acrylic polymer which does not have. Such a polymer contributes to improving the mechanical strength of the cured product and improving the weather resistance of the curable composition and the cured product.
In this specification, the (meth) acrylic acid alkyl ester monomer unit means a repeating unit derived from a (meth) acrylic acid alkyl ester. (Meth) acrylic acid alkyl ester means acrylic acid alkyl ester, methacrylic acid alkyl ester or a mixture of both.

As the precursor polymer (A ′), a linear or branched precursor polymer (A′-a) having a polyoxyalkylene chain and having all main chain ends being hydroxyl groups; or a polyoxyalkylene chain A linear or branched precursor polymer (A′-b) having an unsaturated group at all main chain ends is preferred.
The precursor polymer (A′-a) is preferably produced by ring-opening addition polymerization of alkylene oxide to an initiator having 2 or 3 active hydrogens in the presence of a catalyst.
As the initiator, a compound having 2 or 3 hydroxyl groups is preferable. Specific examples of the compound having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Of these, propylene glycol and dipropylene glycol are more preferable. Specific examples of the initiator having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane and the like. Of these, glycerin is particularly preferable.
Further, polyoxyalkylene diols or polyoxyalkylenes having a hydroxyl equivalent molecular weight MW (OH) of 190 to 20,000 obtained by ring-opening addition polymerization of alkylene oxide to these compounds having 2 or 3 hydroxyl groups It is also preferred to use triol as an initiator. An initiator may be used individually by 1 type and may use 2 or more types together.

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

Examples of the double metal cyanide catalyst include compounds represented by the following formula (i).
M ¹ _a [M ² _b (CN) _c ] _de (M ³ _f X _g ) h (H ₂ O) i (L) (i)
(In formula (i), M ^{1 to} M ³ are metals, X is a halogen atom, L is an organic ligand, a, b, c, d, e, f, g, h, i are metals. the number may vary due coordination number of valences and organic ligands, that is .M ¹ and M ³ respectively showing the same preferred.)

In the above formula (i), the metal represented by M ¹ or M ³ is Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), V (V), Sr (II), W (IV), W (VI), Mn (II), Cr (III), Cu (II), Sn (II) and Pb A metal selected from the group consisting of (II) is preferred, and Zn (II) or Fe (II) is more preferred. Zn (II) is particularly preferable in that the molecular weight distribution can be narrowed.

In the above formula (1), the metal represented by M ² includes Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II) , Mn (III), Ni (II), V (IV) and V (V) are preferred, and Co (III) or Fe (III) is more preferred. Note that Roman numerals such as II, III, IV, and V in parentheses following the metal element symbol indicate the valence of the metal. Co (III) is particularly preferable in that the molecular weight distribution can be made narrower.

  In the above formula (1), L representing an organic ligand is preferably at least one compound selected from the group consisting of alcohol, ether, ketone, ester, amine and amide. In the production method of the present invention, among these, the organic ligand L is preferably water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol. , Tert-pentyl alcohol, iso-pentyl alcohol, N, N-dimethylacetamide, glyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), ethylene glycol mono-tert-butyl ether, iso-propyl One type or two or more types of compounds selected from alcohol and dioxane may be mentioned. Dioxane may be 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferred.

  In the double metal cyanide complex catalyst used in the production method of the present invention, a more preferable organic ligand L is tert-butyl alcohol alone or a combination of tert-butyl alcohol and the compounds exemplified above. Among these, tert-butyl alcohol alone or a combination of tert-butyl alcohol and ethylene glycol mono-tert-butyl ether is particularly preferable because the molecular weight distribution can be narrowed.

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

  As described above, it is preferable that the precursor polymer (A ′) includes at least the precursor polymer (A′11) having 3 functional groups at the end of the main chain per molecule. Accordingly, as the precursor polymer (A ′), among the precursor polymers (A′-a), it was produced by ring-opening addition polymerization of alkylene oxide to an initiator having three active hydrogens in the presence of a catalyst. It is preferable to use a precursor polymer (A′11-a). Alternatively, among the precursor polymers (A′-b), a hydroxyl group of a polymer in which an alkylene oxide is subjected to ring-opening addition polymerization to an initiator having three active hydrogens in the presence of a catalyst, and the main chain terminal is a hydroxyl group. It is preferable to use a precursor polymer (A′11-b) produced by a method in which an alcoholate is converted into —OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon.

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

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

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

In the polymer (A), the functional group at the end of the main chain substituted with the group containing the reactive silicon group among the functional groups at the main chain end of the precursor polymer (A ′) into which the reactive silicon group can be introduced. The ratio (hereinafter sometimes referred to as “silylation rate”) is preferably 45 to 100 mol%, more preferably 50 to 84 mol%, and still more preferably 63 to 84 mol%.
The value of the silylation rate in this specification can be measured by NMR analysis. Or, since the reaction rate between the precursor polymer (A ′) produced using methallyl chloride and the silylating agent can be regarded as almost 100%, silylation with respect to the charged amount of the precursor polymer (A ′). You may use the value calculated from the preparation amount of an agent. In the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent, a side reaction occurs. Approximately 10 mol% of the allyl group of the precursor polymer (A ′) produced using allyl chloride is isomerized and not silylated, so that 100% silylation is difficult. However, in a silylation with a silylation rate of up to 90%, the reaction rate can be regarded as almost 100%. Therefore, when the silylation rate of the polymer (A) to be obtained by the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent is less than 90%, the polymer ( As the value of the silylation rate in A), a value calculated from the charged amount of the silylating agent with respect to the charged amount of the precursor polymer (A ′) may be used.
When two or more kinds of polymers corresponding to the polymer (A) are mixed and used, the silylation rate in the mixture after mixing may be within the above range, and one of the polymers (A) before mixing. A part having a silylation rate of less than 70% may be used.
The same applies to the polymer (B) described later.

In the curable composition of the present invention, the higher the amount of the polymer (B), the lower the viscosity. On the other hand, when the polymer (B) is blended with the polymer (A) and cured, the polymers (A) are cross-linked and a part of the polymer (A) reacts with the polymer (B). Since the polymer (B) has a reactive silicon group only at one end, the polymer (A) reacts with the polymer (B) to inhibit the crosslinking of the polymer (A). Therefore, when there are too many compounding quantities of a polymer (B), it will be hardened | cured and may become uncured.
That is, in order to make the curable composition have a lower viscosity and not to cause poor curing, it is advantageous that the amount of the polymer (B) is large and the silylation rate of the polymer (A) is high. The higher the silylation rate of the polymer (A), the more the polymer (B) is blended, the more difficult the crosslinking is due to the quantitative ratio, and the harder it becomes uncured.
Therefore, the silylation rate of the polymer (A) needs to be in a range where good curability can be obtained in the curable composition in which the polymer (B) is blended, and the higher silylation rate is. The amount of the polymer (B) added can be increased. Since the one where there is much blending quantity of a polymer (B) becomes lower viscosity, workability | operativity becomes better as a curable composition for sealing materials and adhesives.

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

The number average molecular weight (Mn) of the polymer (A) is 25,000 or more and 50,000 or less, exceeds 30,000, preferably 50,000 or less, more preferably 30,000 or more and 40,000 or less. If it is 25,000 or more, in addition to good elongation properties and flexibility of the cured product, the polymer (B) is favorably suppressed from flowing out of the cured product. If it is 50,000 or less, the curable composition tends to have a low viscosity, which is preferable for obtaining good workability. In particular, 31,000 to 36,000 is preferable because of low viscosity and excellent elongation properties.
The molecular weight distribution (Mw / Mn) of the polymer (A) is 1.01-1.40. Within this range, the flexibility is good and the viscosity is low. When the number average molecular weight is the same, the narrower the molecular weight distribution, the lower the viscosity. The reason is that when the molecular weight distribution is wide, a large number of high molecular weight substances are present, which causes high viscosity. Alternatively, as shown in the examples described later, when the flexibility is the same, the stretched physical properties are good. The reason is considered to be that when the molecular weight distribution exceeds 1.40, the amount of low molecular weight polymer components increases, so that the distance between cross-linking points becomes short and it becomes difficult to extend. Therefore, the molecular weight distribution is preferably narrower, more preferably 1.01-1.30, and still more preferably 1.01-1.20. The molecular weight distribution (Mw / Mn) of the polymer (A) can be controlled by the type of catalyst and the polymerization conditions (temperature, stirring conditions, pressure, etc.).
In the present invention, when the polymer (A) is a mixture, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) after mixing are respectively in the above ranges.
The same applies to the polymer (B) described later.

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

<Polymer (B)>
The polymer (B) has a reactive silicon group represented by the above formula (1).
The reactive silicon group of the polymer (A) coexisting in the curable composition and the reactive silicon group of the polymer (B) may be the same or different from each other.

The polymer (B) is a polymer obtained by introducing a reactive silicon group into a precursor polymer (B ′) that is linear and capable of introducing a reactive silicon group at one end.
Specifically, one main chain end group of both ends of the main chain of the precursor polymer (B ′) is a reactive group, preferably a hydroxyl group or an unsaturated group, It is preferable to introduce a reactive silicon group by reacting a reactive group and a compound having a reactive silicon group with the precursor polymer (B ′). The other main chain terminal group of the precursor polymer (B ′) is preferably an inert organic group that does not have reactivity with the compound having the reactive silicon group.

The polymer (B) is preferably obtained through a step of addition polymerization of an alkylene oxide monomer and / or a (meth) acrylic acid alkyl ester monomer to an initiator having one functional group.
That is, the repeating unit in the precursor polymer (B ′) and the polymer (B) preferably includes an alkylene oxide monomer unit and / or a (meth) acrylic acid alkyl ester monomer unit. It is preferable to have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
It is preferable that the polymer (B) has a polyoxyalkylene chain because the compatibility with the polymer (A) is good and the storage stability is good.
Alternatively, as a part or all of the polymer (B), the repeating unit in the heavy precursor polymer (B ′) and the polymer (B) includes a (meth) acrylic acid alkyl ester monomer unit, You may use the acrylic polymer which does not have. Such a polymer contributes to the weather resistance of the cured product, the adhesion between the cured product surface and the coating material, and the reduction of contamination.

As the precursor polymer (B ′), a linear precursor polymer (B′1) having a polyoxyalkylene chain and one end being a hydroxyl group; having a polyoxyalkylene chain and having one end not A linear precursor polymer (B′2) which is a saturated group is preferred.
The linear precursor polymer (B'1), which has a polyoxyalkylene chain and one end is a hydroxyl group, undergoes ring-opening addition of alkylene oxide to an initiator having one active hydrogen in the presence of a catalyst. It can be produced by polymerization.
Specific examples of the initiator include an aliphatic monool having 1 to 20 carbon atoms, an alicyclic monool having 1 to 20 carbon atoms, an aromatic monool having 1 to 20 carbon atoms, a thiol, a secondary amine, and a carboxylic acid. Or a polyoxyalkylene monool having a hydroxyl equivalent molecular weight MW (OH) of 300 to 5,000 obtained by ring-opening addition polymerization of alkylene oxide to the monool. More preferred is a polyoxyalkylene monool having a hydroxyl equivalent molecular weight MW (OH) of 300 to 3,300. An unsaturated group-containing monohydroxy compound such as allyl alcohol can also be used. An initiator may be used individually by 1 type and may use 2 or more types together.
The alkylene oxide and catalyst used for the synthesis of the precursor polymer (B′1) or the initiator are the same as the alkylene oxide and catalyst used for the synthesis of the precursor polymer (A′-a) described above, including preferred embodiments. It is.
The precursor polymer (B′1) is preferably a polyoxypropylene monool.

The linear precursor polymer (B′2) having a polyoxyalkylene chain and one end being an unsaturated group is a hydroxyl group (—OH) of the precursor polymer (B′1) having one end being a hydroxyl group. ) Is converted to -OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride. This method is preferable because it is general and the raw materials are easily available and the reaction yield is high.
Alternatively, a method in which a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated group is reacted with the precursor polymer (B′1) to introduce an unsaturated group via an ester bond, a urethane bond, a carbonate bond, or the like. can get.

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

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

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

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

The curable composition of this invention contains a polymer (A) and a polymer (B). The mass ratio (A / B) of the content of the polymer (A) and the content of the polymer (B) is 90/10 to 40/60.
When the polymer (B) is 10% by mass or more of the total of 100% by mass of the polymer (A) and the polymer (B), the viscosity of the curable composition is lowered and workability is improved. When the content is less than or equal to mass%, the number of crosslinking points increases, and the cured product obtained by curing the curable composition has excellent flexibility and elongation.
In particular, 80/20 to 40/60 is more preferable in that good viscosity, flexibility and elongation are easily obtained.

<Other ingredients>
The curable composition of this invention can contain a well-known component in a curable composition other than a polymer (A) and (B). Specifically, a curing catalyst, a filler, an additive, a solvent, a plasticizer, and the like. In addition, as an optional component, a polymer other than the polymers (A) and (B) is an acrylic or polyisobutylene having a reactive silicon group in order to improve the weather resistance and adhesion as long as the physical properties are not impaired. , Silicon or polyurethane polymers can be used.

<Curing catalyst>
The following compounds can be used as the curing catalyst.
Metal salts such as alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexoate; acidic compounds such as phosphoric acid, p-toluenesulfonic acid, phthalic acid; butylamine, hexylamine, octylamine, decylamine Aliphatic diamines such as ethylenediamine and hexanediamine; aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine; heterocyclic amines such as piperidine and piperazine; metaphenylene Amine compounds such as aromatic amines such as diamines; ethanolamines; various modified amines used as curing agents for triethylamine and epoxy resins.
A mixture of divalent tin such as tin dioctylate (bis (2-ethylhexanoate) tin), tin dinaphthenate and tin distearate and the above amines as a co-catalyst.

Dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate and the following carboxylic acid type organic tin compounds; a mixture of these carboxylic acid type organic tin compounds and the above amines.
_{(N-C 4 H 9)} 2 Sn (OCOCH = CHCOOCH 3) 2,
_{(N-C 4 H 9)} 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOOCH 3) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOOC 8 H 17 -iso) 2.

The following sulfur-containing organotin compounds.
_{(N-C 4 H 9)} 2 Sn (SCH 2 COO),
_{(N-C 8 H 17)} 2 Sn (SCH 2 COO),
_{(N-C 8 H 17)} 2 Sn (SCH 2 CH 2 COO),
_{(N-C 8 H 17)} 2 Sn (SCH 2 COOCH 2 CH 2 OCOCH 2 S),
_{(N-C 4 H 9)} 2 Sn (SCH 2 COOC 8 H 17 -iso) 2,
_{(N-C 8 H 17)} 2 Sn (SCH2COOC 8 H 17 -iso) 2,
_{(N-C 8 H 17)} 2 Sn (SCH2COOC 8 H 17 -n) 2,
_{(N-C 4 H 9)} 2 SnS.

_{(N-C 4 H 9)} 2 SnO, (n-C 8 H 17) 2 organotin oxide SnO or the like; and these organic tin oxide and ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, phthalic Reaction products with ester compounds such as dimethyl acid, diethyl phthalate and dioctyl phthalate.

The following chelated tin compounds and reaction products of these tin compounds and alkoxysilanes (where acac is an acetylacetonato ligand).
_{(N-C 4 H 9)} 2 Sn (acac) 2,
_{(N-C 8 H 17)} 2 Sn (acac) 2,
_{(N-C 4 H 9)} 2 (C 8 H 17 O) Sn (acac).

The following tin compounds.
_{(N-C 4 H 9)} 2 (CH 3 COO) SnOSn (OCOCH 3) (n-C 4 H 9) 2,
_{(N-C 4 H 9)} 2 (CH 3 O) SnOSn (OCH 3) (n-C 4 H 9) 2.

<Filler>
As the filler, for example, the following fillers can be used.
Calcium carbonate whose surface is treated with a fatty acid or resin acid organic substance, finely powdered colloidal calcium carbonate having an average particle size of 1 μm or less, light calcium carbonate having an average particle size of 1 to 3 μm and an average particle produced by a precipitation method Calcium carbonate such as heavy calcium carbonate having a diameter of 1 to 20 μm, fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, Organic bentonite, organic resin balloon, ferric oxide, zinc oxide, activated zinc white, shirasu balloon, wood flour, pulp, cotton chip, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, etc. Filler. Fibrous fillers such as asbestos, glass fiber, glass filament, carbon fiber, Kevlar fiber, polyethylene fiber.

  The amount of the filler used is preferably 1 to 1,000 parts by mass and more preferably 50 to 250 parts by mass with respect to 100 parts by mass in total of the polymer (A) and the polymer (B). These fillers may be used alone or in combination of two or more.

<Plasticizer>
A plasticizer may be contained in addition to the polymer (B).
Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, diisononyl phthalate (diisononyl phthalate), phthalic acid alkyl esters such as butyl benzyl phthalate; dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, etc. Aliphatic carboxylic acid alkyl esters; glycol esters such as pentaerythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; Paraffin; etc. can be used alone or in a mixture of two or more.
However, among such plasticizers, there is a problem that a low molecular weight plasticizer tends to bleed out after curing of the curable composition of the present invention. Therefore, it is preferable not to use a low molecular weight plasticizer. That is, when the curable composition of the present invention further contains a plasticizer, it is preferable not to contain a low molecular weight plasticizer as the plasticizer. The low molecular weight plasticizer refers to a plasticizer whose compound itself has a low molecular weight and does not have a reactive group. For example, alkyl phthalates.
Polyoxyalkylene polyols such as polypropylene polyol can also be used as a plasticizer. The number average molecular weight (Mn) of the polyoxyalkylene polyol is preferably 1,000 to 20,000, more preferably 3,000 to 15,000.

<Dehydrating agent>
In order to further improve the storage stability, a small amount of a dehydrating agent can be added to the curable composition as long as it does not adversely affect the curability and flexibility. Examples of the dehydrating agent include alkyl orthoformate such as methyl orthoformate and ethyl orthoformate, alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate, methyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane and tetraethoxysilane. Examples include hydrolyzable organic silicon compounds and hydrolyzable organic titanium compounds. Among these, vinyltrimethoxysilane and tetraethoxysilane are particularly preferable from the viewpoint of cost and effect. In particular, it is effective to use a one-pack type agent in which the curable composition contains a curing catalyst and is filled in a moisture-proof container.

<Adhesive agent>
Specific examples of the adhesion-imparting agent include organosilane coupling agents such as silane having a vinyl group, silane having an epoxy group, silane having an amino group, and silane having a carboxy group; isopropyltri (N-aminoethyl-amino) Organometallic coupling agents such as ethyl) propyltrimethoxytitanate, 3-mercaptopropyltrimethotitanate; and epoxy resins.
Specific examples of the silane having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane.
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- Vinylbenzyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and the like.

<Other additives>
In the curable composition of the present invention, a reactive silicon group-containing compound having a molecular weight of less than 300 may be optionally added for the purpose of adjusting the physical properties and curability of the cured product. Specific examples of such a compound include tetramethyl silicate, vinyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, and trimethylmethoxysilane, and compounds in which these methoxy groups are substituted with ethoxy groups.
Examples of other additives include a thixotropic agent; a pigment; various stabilizers; a photocurable compound for the purpose of surface modification such as an oligoester acrylate, and the like. A solvent can also be used for the purpose of adjusting the viscosity.

<Modulus modifier>
As other additives, a modulus adjusting agent may be used. The modulus modifier refers to a compound that can generate trimethylsilanol by hydrolysis. For example, a compound containing a trimethylsilyloxy group in the molecule. Trimethylsilanol generated by hydrolysis of the modulus modifier reacts with the polymer (A) or the polymer (B), and therefore the mechanical properties of the curable composition can be changed.
Specific examples of the modulus modifier include phenoxytrimethylsilane, 2,2-bis [(trimethylsiloxy) methyl] -1- (trimethylsiloxy) butane, and the like. 1 type may be used independently and 2 or more types may be used together.
The modulus modifier is not particularly limited as long as it has a functional group capable of generating trimethylsilanol, such as a trimethylsilyloxy group, but a compound having a molecular weight of 2,000 or less is preferable, and a compound having a molecular weight of 500 or less is more preferable. In addition, the average number of functional groups capable of generating trimethylsilanol is preferably 0.5 to 8.0 or less, and more preferably 0.9 to 4.0 on average.

Examples of the modulus regulator include monohydric alcohols such as methanol, ethanol, 2-ethylhexanol, and phenol; polyhydric alcohols such as ethylene glycol, propanediol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol; A compound obtained by trimethylsilyloxylation of is preferred. Examples of the compound to be trimethylsilyloxylated include 1,1,1,3,3,3-hexamethyldisilazane and trimethylchlorosilane.
Although the trimethylsilyloxylation rate in all the hydroxyl groups of a polyhydric alcohol can be adjusted arbitrarily, 50% or more is preferable and 80% or more is more preferable. Most preferably, substantially all hydroxyl groups are trimethylsilyloxylated.
The usage-amount of a modulus regulator is not specifically limited, A usage-amount can be freely set according to the physical property of the target hardened | cured material. Usually, 0.1-10.0 mass parts is preferable with respect to 100 mass parts of a polymer (A), and 0.1-5.0 mass parts is more preferable. In addition, for the purpose of adjusting the curing speed, several types of modulus adjusting agents may be used in combination.
Further, the modulus adjusting agent may be added in advance to one or both of the polymer A and the polymer B, or may be added when producing the curable composition.

<Curable composition>
The curable composition of the present invention can be prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after construction. Polymers (A) and (B) In addition to the main component containing, a curing agent composition is prepared as a two-component type in which components such as a curing catalyst, a filler, and water are blended, and the curing agent composition and the main component are mixed before use. You can also.

In the case of the one-component type, since all the blended components are blended in advance, it is preferable that the blended components containing moisture be used after being dehydrated and dried in advance or dehydrated under reduced pressure during blending and kneading.
In the case of the two-component type, since there is no need to blend a curing catalyst in the main agent containing a polymer having a reactive silicon group, there is little concern about gelation even if some moisture is contained in the main agent, When long-term storage stability is required, it is preferable to perform dehydration drying.
As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.
The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20.0 mass per 100 mass parts of the total amount of the polymer (A) and the polymer (B). Part is preferable, and 0.5 to 10.0 parts by mass is more preferable.

  The curable composition of the present invention comprises a sealant (elastic sealant for building, sealant for multi-layer glass, etc.), sealant (anti-rust / waterproof sealant for glass edge, solar cell back surface seal It is useful as an adhesive used in the fields of electrical insulating materials (insulating coatings for electric wires and cables). Moreover, the curable composition of this invention can be used also for uses, such as an adhesive, a coating material, a film material, a gasket material, a casting material.

  The present invention will be specifically described below, but the present invention is not limited to the examples. Examples 2 to 5, 8 to 11, 21 to 24, 26 to 29, 31 to 37, 41 to 48, 51 to 53 are examples, and examples 1, 6, 7, 25, 30, 38, 49, and 50 are compared. It is an example.

<Production Example 1: Production of polymer (A-1)>
Polyoxypropylene triol obtained by ring-opening addition polymerization of propylene oxide to glycerin (hydroxyl equivalent molecular weight MW (OH) 1,000) was used as an initiator (referred to as initiator A).
In the presence of a zinc hexacyanocobaltate t-butanol complex catalyst (0.03 g), propylene oxide (1,731 g) is added to initiator A (64.1 g) at 120 ° C. until the pressure of the reaction system does not drop. Reacted. As a result, a polymer (h1) having a polyoxypropylene chain and having three hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the polymer (h1) at 25 ° C. was 29.8 Pa · s. Mn measured by GPC was 34,000, Mw was 42,000, and thus Mw / Mn was 1.20.

  To the obtained polymer (h1), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polymer (h1) was added to alcoholate the polymer (h1). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl groups in the polymer (h1). As a result, a polymer (v1) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.

Next, in the presence of chloroplatinic acid hexahydrate, 0.5 times mole of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the polymer (v1) obtained, Reacted for hours. Thus, a polymer (A-1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained. The polymer (A-1) had a viscosity at 25 ° C. of 30.0 Pa · s. Mn measured by GPC was 34,000, Mw was 42,000, and thus Mw / Mn was 1.20. The polymer (A-1) was a polymer in which a dimethoxymethylsilyl group was introduced into 50% of the allyl group at the end of the main chain of the polymer (v1).
The average number of functional groups at the end of the main chain, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the obtained polymer (A-1) are shown in Table 1 (the same applies hereinafter).

<Production Examples 2 to 7: Production of polymers (A-2) to (A-7)>
Except having adjusted the preparation amount of dimethoxymethylsilane, it carried out similarly to synthesize | combining a polymer (A-1), and obtained the polymer (A-2)-(A-7).

<Production Example 8: Production of polymer (A-8)>
Polyoxypropylene diol (hydroxyl equivalent molecular weight MW (OH) 2,000) 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 a zinc hexacyanocobaltate t-butanol complex catalyst (0.03 g), initiator B (64.1 g) was reacted with propylene oxide (641 g) at 120 ° C. until the pressure of the reaction system was not lowered. It was. As a result, a polymer (h1 ′) having a polyoxypropylene chain and having two hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the polymer (h1 ′) at 25 ° C. was 28.5 Pa · s. Mn measured by GPC was 27,000, Mw was 30,000, and thus Mw / Mn was 1.11.

  To the obtained polymer (h1 ′), a methanol solution containing 1.05 times moles of sodium methoxide is added to the polymer (h1 ′) to form an alcoholate. did. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl groups in the polymer (h1 '). As a result, a polymer (v1 ') having a polyoxypropylene chain and having an allyl group at the end of the main chain was obtained.

  Next, in the presence of chloroplatinic acid hexahydrate, 0.84 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the obtained polymer (v1 ′) at 70 ° C. The reaction was allowed for 5 hours. As a result, a polymer (A-8) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at 84% of the ends of the main chain was obtained.

<Production Example 11: Production of polymer (B-1)>
Polyoxypropylene monool obtained by ring-opening addition polymerization of propylene oxide to t-butanol (hydroxyl equivalent molecular weight MW (OH) 2,000) was used as an initiator (referred to as initiator C).
In the presence of a t-butanol complex catalyst (0.03 g) of zinc hexacyanocobaltate, propylene oxide (249.6 g) was reacted with initiator C (384 g) at 120 ° C. until the pressure of the reaction system was not lowered. It was. As a result, a polymer (h2) having a polyoxypropylene chain and having one hydroxyl group per molecule at the end of the main chain was obtained. The viscosity of the polymer (h2) at 25 ° C. was 0.45 Pa · s. Mn measured by GPC was 5,200, Mw was 5,700, and thus Mw / Mn was 1.09.

To the obtained polymer (h2), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polymer (h2) was added to alcoholate the polymer (h2). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the polymer (h2). As a result, a polymer (v2) having a polyoxypropylene chain and having one allyl group per molecule at the end of the main chain was obtained.
Next, the obtained polymer (v2) and dimethoxymethylsilane were reacted at 70 ° C. for 5 hours in the presence of chloroplatinic acid hexahydrate. Thus, a polymer (B-1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained. The viscosity, Mn, Mw / Mn, viscosity and silylation rate (Si conversion rate) of the obtained polymer (B-1) are shown in Table 2 (the same applies hereinafter).

<Production Example 12: Production of polymer (B-2)>
In the presence of zinc hexacyanocobaltate t-butanol complex catalyst (0.05 g), initiator C (384 g) was reacted with propylene oxide (576 g) at 120 ° C. until the pressure of the reaction system was not lowered. As a result, a polymer (h3) having a polyoxypropylene chain and having one hydroxyl group per molecule at the end of the main chain was obtained. The viscosity of the polymer (h3) at 25 ° C. was 1.20 Pa · s. Mn measured by GPC was 7,300, Mw was 8,100, and thus Mw / Mn was 1.11.

To the obtained polymer (h3), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl group of the polymer (h3) was added to alcoholate the polymer (h3). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl groups in the polymer (h3). As a result, a polymer (v3) having a polyoxypropylene chain and having one allyl group per molecule at the end of the main chain was obtained.
Next, the obtained polymer (v3) and dimethoxymethylsilane were reacted at 70 ° C. for 5 hours in the presence of chloroplatinic acid hexahydrate. Thus, a polymer (B-2) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

<Production Example 13: Production of polymer (B-3)>
In the presence of a zinc hexacyanocobaltate t-butanol complex catalyst (0.07 g), initiator C (384 g) was reacted with propylene oxide (960 g) at 120 ° C. until the pressure of the reaction system was not reduced. As a result, a polymer (h4) having a polyoxypropylene chain and having one hydroxyl group per molecule at the end of the main chain was obtained. The viscosity of the polymer (h4) at 25 ° C. was 3.3 Pa · s. Mn measured by GPC was 12,900, Mw was 14,400, and thus Mw / Mn was 1.12.

To the obtained polymer (h4), a methanol solution containing 1.05 times moles of sodium methoxide was added to the amount of hydroxyl groups of the polymer (h4) to alcoholate the polymer (h4). Next, after removing methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the polymer (h4). As a result, a polymer (v4) having a polyoxypropylene chain and having one allyl group per molecule at the end of the main chain was obtained.
Next, the obtained polymer (v4) and dimethoxymethylsilane were reacted at 70 ° C. for 5 hours in the presence of chloroplatinic acid hexahydrate. Thus, a polymer (B-3) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

<Production Example 14: Production of polymer (B-4)>
In the presence of a zinc hexacyanocobaltate t-butanol complex catalyst (0.09 g), initiator C (384 g) was reacted with propylene oxide (1440 g) at 120 ° C. until the pressure of the reaction system was not reduced. As a result, a polymer (h5) having a polyoxypropylene chain and having one hydroxyl group per molecule at the end of the main chain was obtained. The viscosity of the polymer (h5) at 25 ° C. was 4.6 Pa · s. Mn measured by GPC was 15,300, Mw was 17,400, and thus Mw / Mn was 1.14.

To the obtained polymer (h5), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polymer (h5) was added to alcoholate the polymer (h5). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added to the amount of hydroxyl group of the polymer (h5). As a result, a polymer (v5) having a polyoxypropylene chain and having one allyl group per molecule at the end of the main chain was obtained.
Next, the obtained polymer (v5) and dimethoxymethylsilane were reacted at 70 ° C. for 5 hours in the presence of chloroplatinic acid hexahydrate. Thereby, a polymer (B-4) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained.

<Comparative Production Example 1: Production of Comparative Polymer (C-1)>
Comparative polymer (C-1) is a polyoxypropylene triol obtained by ring-opening addition polymerization of propylene oxide to glycerin (hydroxyl equivalent molecular weight MW (OH) 5,000) (referred to as initiator D). Used as an agent.
In the presence of zinc hexacyanocobaltate glyme complex catalyst (0.23 g), initiator D (64.1 g) was reacted with propylene oxide (449.1 g) at 120 ° C. until the pressure of the reaction system was not lowered. It was. As a result, a polymer (h6) 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 polymer (h6) at 25 ° C. was 37.2 Pa · s. Mn measured by GPC was 34,000, Mw was 49,000, and thus Mw / Mn was 1.45.

To the obtained polymer (h6), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polymer (h6) was added to alcoholate the polymer (h6). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl groups in the polymer (h6). As a result, a polymer (v6) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.
Next, in the presence of 1,1,3,3-tetramethyldivinylsiloxane platinum complex, 0.84 times moles of dimethoxymethylsilane with respect to the amount of allyl group at the end of the main chain of the obtained polymer (v6) was added. The mixture was added and reacted at 70 ° C. for 5 hours. Thereby, a polymer (C-1) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained. Table 3 shows the average number of functional groups at the end of the main chain, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the comparative polymer (C-1) obtained.

When the polymer (A-5) in Table 1 and the comparative polymer (C-1) in Table 3 are compared, the average number of functional groups at the end of the main chain, Mn, and the silylation rate (Si conversion rate) are equivalent. However, the comparative polymer (C-1) has a wider molecular weight distribution (Mw / Mn) and a higher viscosity at 25 ° C. From this, it can be seen that the comparative polymer (C-1) contains more high molecular weight.
Paying attention to the difference between the two production methods, the organic ligand of the double metal cyanide complex catalyst used for the production of the polymer is that the polymer (A-5) is t-butanol, and the comparative polymer (C- 1) is grime. It is considered that the difference in the molecular weight distribution in the polymer was caused by the difference in the organic ligand of such a double metal cyanide complex catalyst.

<Other additives>
The additives used in the following examples are as follows.
[Plasticizer (1)] Diisononyl phthalate (abbreviation: DINP) (trade name: Vinicizer 90, manufactured by Kao Corporation).
[Plasticizer (2)] Polypropylene glycol (manufactured by Asahi Glass Co., Ltd., trade name: PREMINOL S-4011, Mn = 14,000).
[Filler (1)] Colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Baiyinhua CCR)
[Filler (2)] Heavy calcium carbonate (manufactured by Shiroishi Calcium Industry Co., Ltd., trade name: Whiten SB, average particle size 1.78 μm)
[Filler (3)] A mixture of the filler (1) / the filler (2) = 1/1 (mass ratio).
[Filler (4)] Organic balloon (manufactured by Matsumoto Yushi Co., Ltd., trade name: 80-GCA)
[Filler (5)] Kaolin clay (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Glomax LL)
[Filler (6)] Titanium oxide (Ishihara Sangyo Co., Ltd., trade name: R820). Weathering agent.
[Thixotropic agent (1)] Fatty acid amide type thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 6500).
[Thixotropic agent (2)] Hydrogenated castor oil-based thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon # 305).
[Modulus Modifier] Tristrimethylsilyl derivative of trimethylolpropane.
[Stabilizer (1)] Benzotriazole UV absorber (Ciba Specialty Chemicals, trade name: Tinuvin 326) / Hindered phenol antioxidant (Ciba Specialty Chemicals, product) Name: Irganox 1010) = 1/1 (mass ratio).
[Stabilizer (2)] A mixture of ultraviolet absorber, hindered amine and antioxidant (Ciba Specialty Chemicals, trade name: Tinuvin B75).
[Adhesiveness imparting agent] Vinyl group-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM1003 / amino group-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM603) / Epoxy group-containing silane cup Ring agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM403) = 3/1/1 (mass ratio).
[Photo-curable compound] Polyfunctional acrylic group-containing compound (trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd., trade name: Aronix M-309).
[One-component curing agent] Tetravalent organotin compound (Asahi Glass Co., Ltd .: EXCESTAR C201)
[Two-component curing agent composition] Mixtures (a) to (d) below.
(A) Mass ratio of bis (2-ethylhexanoic acid) tin (manufactured by API Corporation) as a curing catalyst and laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.) as a cocatalyst (curing catalyst: cocatalyst) 4 parts by weight of 6: 1 mixture.
(B) 6 parts by mass of diisononyl phthalate (abbreviation: DINP, plasticizer (1)).
(C) 15 parts by mass of heavy calcium carbonate (trade name: Whiten SB, the filler (2)).
(D) 5 parts by mass of kaolin clay (trade name: Glomax LL, filler (5) above).

[Examples 1 to 11]
Using the polymer obtained in the above production example, each component was mixed according to the formulation shown in Table 4, and the viscosity at 25 ° C. of the obtained mixture was measured. The results are shown in Table 4.
In addition, the polymer (A) in Examples 7-11 is a mixture, and the average functional group number and number average molecular weight of the main chain terminal after mixing are shown in Table 4.

  As shown in the results in Table 4, the viscosity of the mixture of the polymer (A) and the polymer (B) is lower than the viscosity of the polymer (A). The viscosity of Examples 2-5 is lower than the viscosity of Example 1, and the viscosity of Examples 8-11 is lower than the viscosity of Examples 6 and 7. That is, it can be confirmed that the polymer (B) works as a plasticizer.

[Examples 21-30, 31-38]
Using the polymers obtained in the above production examples, the components shown in Tables 5 and 6 were mixed to produce a one-component curable composition. Measured with The results are shown in Tables 5 and 6.
In addition, the polymer (A) in Examples 26-30 is a mixture, and Table 5 shows the average number of functional groups and the number average molecular weight at the main chain ends after mixing.

(Workability)
The spatability and ease of handling when a test piece of a cured product was prepared using each curable composition were evaluated. Spatility refers to the property when the paste-like curable composition before curing is handled with a spatula. If the curable composition easily pulls the yarn, it is difficult to handle and the workability is poor. . The ease of handling refers to the ease of handling when a paste-like curable composition before curing is kneaded with a spatula, and is affected by the viscosity and thixotropy of the curable composition. “◎ (excellent)” indicates that spatability and ease of handling are particularly good, “○ (good)” indicates that both are good, and “△ (possible)” indicates that one is good. Those that were not good in all were defined as “x (defect)”.

(Tensile properties)
A test piece made of a cured product of the curable composition obtained in each example was prepared, and a tensile test was performed. The tensile test was performed according to JIS K 6251.
Specifically, the curable composition was formed into a sheet having a thickness of 2 mm, cured for 7 days at 23 ° C. and 50% humidity, and then cured for 7 days at 50 ° C. and 65% humidity. Furthermore, it was left to stand for 24 hours or more at 23 ° C. and 50% humidity to obtain a cured product. The obtained sheet-like cured product was punched into a No. 3 dumbbell shape to obtain a test piece. After measuring the thickness of the test piece, using a Tensilon tester, the stress at 50% elongation (M50, unit: N / mm ² ), maximum tensile stress (Tmax, unit: N / mm ² ), fracture The amount of elongation at the time (E, unit:%) was measured.
The lower the M50, the higher the flexibility, the higher the Tmax, the higher the tensile bond strength, and the higher the E, the better the elongation. The results are shown in Tables 5 and 6.

As shown in Table 5, Examples 21 to 24, in which the curable composition contains a polymer (A) and a polymer (B), and their mass ratio (A / B) is within the scope of the present invention, In Examples 26 to 29, it was confirmed that the workability of the curable composition was good, and the tensile properties (flexibility (M50) and elongation (E)) of the cured product obtained by curing the curable composition were also good. It was done. In particular, M50 was low and elongation (E) was high. On the other hand, Example 25 which does not contain a polymer (B) has insufficient workability | operativity compared with Examples 21-24, M50 is high, and elongation (E) is low. In addition, Example 30 also has insufficient workability, and has higher M50 and lower elongation (E) than Examples 26 to 29.
As Table 6 shows, in Examples 31-37 in which a curable composition contains a polymer (A) and a polymer (B), workability | operativity of a curable composition is favorable, and curable composition is It was confirmed that the cured cured product also had good tensile properties (flexibility and elongation).
On the other hand, Example 38 which does not contain a polymer (B) is inferior in workability | operativity compared with Example 37, respectively, especially M50 is high and elongation (E) is low.

[Examples 41 to 46]
Using the polymer obtained in the above production example, the components shown in Table 7 were mixed to produce a two-component curable composition (main agent). About 100 parts by mass of the main agent and 10 parts by mass of the two-component curing agent composition, and curing the mixture, the H-type physical properties / tensile properties, coating film contamination, durability, surface The stickiness was evaluated by the following method. Moreover, workability | operativity was evaluated by the same method as Examples 21-38. The results are shown in Table 7.
(H type physical properties and tensile properties)
Aluminum was used as the adherend, and a tensile property test was performed in accordance with the test method for architectural sealant of JIS A 1439.
In the tensile property test, using a Tensilon tester, the stress at 50% elongation (M50, unit: N / mm ² ), the maximum tensile stress (Tmax, unit: N / mm ² ), and the elongation at break (E, unit:%) was measured.

(Coating contamination)
When using the hardened | cured material of the curable composition of this invention as a sealing material, a coating material may be applied on top. Along with the adhesion between the cured product and the paint, it is necessary that the cured product does not deteriorate the curing performance of the paint. The coating film contamination property represents the influence of the cured product on the curing performance of the paint. A curable composition was applied to an aluminum plate in a shape of 50 mm in length, 50 mm in width, and 10 mm in thickness, and cured and cured at 23 ° C. and 50% humidity for 48 hours. A one-component aqueous reaction-curable silicone resin paint (manufactured by Nippon Paint Co., Ltd., trade name: Odefresh Si100II) was applied thereon. Thereafter, after curing at 50 ° C. for 1 week, the sample was left for 1 day under the condition of 23 ° C., then the well-dried contaminated powder was sprinkled on the entire surface and allowed to stand for 10 minutes, and then the contaminated powder that did not adhere was screened off. “◎ (excellent)” indicates that the color of the curable composition is maintained with little adhesion of the contaminated powder, and “A (excellent)” indicates that the color of the curable composition is maintained even though the contaminated powder is slightly adhered. “Good (good)” means that a large amount of contaminating powder is adhered and the color of the curable composition is impaired. In addition, JIS test powders 1 and 8 (Kanto Loam) (manufactured by Japan Powder Industrial Technology Association) were used as contaminated powder.

(durability)
An endurance test was conducted in accordance with JIS A 1439 architectural sealing material test method using aluminum as the adherend. The stretch test was performed 2,000 times or 4,000 times. “X (defect)” indicates that a crack occurred between the adherend and the cured curable composition after the stretch test. “Good (good)” means that no cracks occurred but slight dents occurred. No cracks or dents were generated, and a good one was designated as “◎ (excellent)”.

(Surface stickiness)
A curable composition is applied to a polyethylene terephthalate film in a shape of approximately 150 mm in length, 50 mm in width, and 5 mm in thickness, cured and cured for 8 hours at 23 ° C. and 50% humidity, and the surface stickiness is evaluated by touch. did. The non-sticky product was designated as “◯ (good)”, and the sticky product was designated as “x (defective)”.

From the results of Table 7, in Examples 41 to 48 in which the curable composition contains the polymer (A) and the polymer (B), the H-type physical properties / tensile properties, coating film contamination properties, durability, and surface stickiness Both were good. Moreover, since the viscosity and thixotropy were good, workability was excellent. Among these, in Examples 43 and 44 using the polymers (B-3) and (B-4) having a high molecular weight of the polymer (B), it was particularly difficult for the contaminated powder to adhere to the coating film.
On the other hand, Examples 49 and 50 using the comparative polymer (C-1) having a molecular weight distribution (Mw / Mn) wider than 1.40 instead of using the polymer (A), E) was low, coating film contamination and surface stickiness were poor, and durability was inferior. In addition, workability was good because the viscosity increased.

<Production Example 15: Production of polymer (A-9)>
The same initiator A as in Production Example 1 was used.
In the presence of zinc hexacyanocobaltate t-butanol complex catalyst (0.03 g), propylene oxide (1,538 g) was added to initiator A (64.1 g) at 120 ° C. until the pressure of the reaction system did not drop. Reacted. As a result, a polymer (h7) having a polyoxypropylene chain and having 3 hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the polymer (h7) at 25 ° C. was 24.1 Pa · s. Mn measured by GPC was 31,000, Mw was 37,000, and thus Mw / Mn was 1.19.

  To the obtained polymer (h7), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl groups of the polymer (h7) was added to alcoholate the polymer (h7). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the polymer (h7). As a result, a polymer (v7) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.

Next, in the presence of chloroplatinic acid hexahydrate, 0.84 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the polymer (v7) obtained, Reacted for hours. As a result, a polymer (A-9) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained. The polymer (A-9) had a viscosity at 25 ° C. of 24.0 Pa · s. Mn measured by GPC was 31,000, Mw was 37,000, and thus Mw / Mn was 1.19. The polymer (A-9) was a polymer in which a dimethoxymethylsilyl group was introduced into 75% of the allyl group at the end of the main chain of the polymer (v7).
Table 8 shows the average number of functional groups at the ends of the main chain, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the obtained polymer (A-9).

<Production Example 16: Production of polymer (A-10)>
The same initiator A as in Production Example 1 was used.
In the presence of a t-butanol complex catalyst (0.03 g) of zinc hexacyanocobaltate, propylene oxide (1,410 g) was added to initiator A (64.1 g) at 120 ° C. until the pressure of the reaction system did not decrease. Reacted. As a result, a polymer (h8) having a polyoxypropylene chain and having three hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the polymer (h8) at 25 ° C. was 19.1 Pa · s. Mn measured by GPC was 29,000, Mw was 34,000, and thus Mw / Mn was 1.17.

  To the obtained polymer (h8), a methanol solution containing 1.05 times moles of sodium methoxide was added to the polymer (h8) to form an alcoholate. Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl groups in the polymer (h8). As a result, a polymer (v8) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.

Next, in the presence of chloroplatinic acid hexahydrate, 0.84 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the polymer (v8) obtained, Reacted for hours. Thus, a polymer (A-10) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained. The viscosity of the polymer (A-10) at 25 ° C. was 19.1 Pa · s. Mn measured by GPC was 29,000, Mw was 34,000, and thus Mw / Mn was 1.17. The polymer (A-10) was a polymer in which a dimethoxymethylsilyl group was introduced into 75% of the allyl group at the end of the main chain of the polymer (v8).
Table 8 shows the average number of functional groups at the end of the main chain, Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C. of the obtained polymer (A-10).

<Production Example 17: Production of polymer (A-11)>
The same initiator A as in Production Example 1 was used.
In the presence of a zinc hexacyanocobaltate t-butanol complex catalyst (0.03 g), propylene oxide (1,218 g) is added to initiator A (64.1 g) at 120 ° C. until the pressure of the reaction system does not drop. Reacted. As a result, a polymer (h9) having a polyoxypropylene chain and having three hydroxyl groups per molecule at the end of the main chain was obtained. The viscosity of the polymer (h9) at 25 ° C. was 17.1 Pa · s. Mn measured by GPC was 26,000, Mw was 30,000, and thus Mw / Mn was 1.15.

  To the obtained polymer (h9), a methanol solution containing 1.05 times moles of sodium methoxide with respect to the amount of hydroxyl group of the polymer (h9) was added to alcoholate the polymer (h9). Next, after distilling off methanol by heating under reduced pressure, an excessive amount of allyl chloride was added relative to the amount of hydroxyl group in the polymer (h9). As a result, a polymer (v9) having a polyoxypropylene chain and having an allyl group at the end of the entire main chain was obtained.

Next, in the presence of chloroplatinic acid hexahydrate, 0.84 moles of dimethoxymethylsilane was added to the allyl group at the end of the main chain of the polymer (v9) obtained, Reacted for hours. Thus, a polymer (A-11) having a polyoxypropylene chain and having a dimethoxymethylsilyl group at the end of the main chain was obtained. The viscosity of the polymer (A-11) at 25 ° C. was 17.1 Pa · s. Mn measured by GPC was 26,000, Mw was 30,000, and thus Mw / Mn was 1.15. Further, the polymer (A-11) was a polymer in which a dimethoxymethylsilyl group was introduced into 75% of the allyl group at the end of the main chain of the polymer (v9).
Table 8 shows the average number of functional groups at the end of the main chain of the obtained polymer (A-11), Mn, Mw / Mn, silylation rate (Si conversion rate), and viscosity at 25 ° C.

As shown in Table 8, the polymer (A-9) has an Mn of about 30,000, and the polymer has a viscosity at 25 ° C. of 24.0 Pa · s.
On the other hand, the high molecular weight polymer E having a molecular weight of about 30,000 described in Example 18 of Patent Document 2 has a viscosity in the state of a curable composition containing the low molecular weight polymer a in addition to the high molecular weight polymer E. However, it is 28000 cP (= 28 Pa · s) at 25 ° C. When the low molecular weight polymer a is included, the viscosity of the composition is lowered, so that the viscosity of the high molecular weight polymer E itself having a molecular weight of about 30,000 at 25 ° C. is at least higher than 28 Pa · s.
Thus, the high molecular weight polymer E described in Example 18 of Patent Document 2 has a viscosity higher than that of the high molecular weight polymer E while the polymer (A-9) and Mn are substantially equivalent. From this, it is estimated that the high molecular weight polymer E of patent document 2 contains many high molecular weight bodies compared with a polymer (A-9), and molecular weight distribution is wide.

[Examples 51 to 53]
Using the polymer obtained in the above production example, the components shown in Table 9 were mixed to produce a two-component curable composition (main agent). About 100 parts by mass of the main agent and 10 parts by mass of the two-component curing agent composition, and curing the mixture, the H-type physical properties / tensile properties, coating film contamination, durability, surface Stickiness was evaluated in the same manner as in Examples 41-50. The results are shown in Table 9.

  From the results of Table 9, in Examples 51 to 53 in which the curable composition contains the polymer (A) and the polymer (B), the H-type physical properties / tensile properties, the film contamination property, the durability, and the surface stickiness Both were good.

Claims (6)

It has a functional group capable of introducing a reactive silicon group at all main chain ends, and the functional group is at least one selected from the group consisting of a group having an active hydrogen and an unsaturated group, In the precursor polymer (A ′) having an average functional group number of more than 2.0 and 3.0 or less,
A polymer obtained by introducing a reactive silicon group represented by the following formula (1), having a number average molecular weight of 25,000 or more and 50,000 or less, and a molecular weight distribution of 1.01 to 1. 20 and the polymer (A) which is linear, and a precursor polymer (B ′) which is linear and can introduce a reactive silicon group at one end, has a reactive silicon group represented by the following formula (1): A polymer obtained by introduction, containing a polymer (B) having a number average molecular weight of 5,000 or more and 20,000 or less,
The precursor polymer (A ′) includes a precursor polymer (A′11) having 3 functional groups at the end of the main chain per molecule,
The precursor polymer (A′11) is a precursor polymer (A′11-a) produced by ring-opening addition polymerization of alkylene oxide to an initiator having three active hydrogens in the presence of a catalyst,
A curable composition, wherein a mass ratio (A / B) of the content of the polymer (A) and the content of the polymer (B) is 90/10 to 40/60.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ] It has a functional group capable of introducing a reactive silicon group at all main chain ends, and the functional group is at least one selected from the group consisting of a group having an active hydrogen and an unsaturated group, In the precursor polymer (A ′) having an average functional group number of more than 2.0 and 3.0 or less,
A polymer obtained by introducing a reactive silicon group represented by the following formula (1), having a number average molecular weight of 25,000 or more and 50,000 or less, and a molecular weight distribution of 1.01 to 1. The reactive silicon group represented by the following formula (1) is introduced into the polymer (A) which is 20 and the precursor polymer (B ′) which is linear and can introduce a reactive silicon group at one end. And a polymer (B) having a number average molecular weight of 5,000 or more and 20,000 or less,
The precursor polymer (A ′) includes a precursor polymer (A′11) having 3 functional groups at the end of the main chain per molecule,
In the presence of a catalyst, the precursor polymer (A'11) is obtained by subjecting an alkylene oxide to ring-opening addition polymerization to an initiator having three active hydrogens, and alcoholating the hydroxyl group of a polymer having a hydroxyl group at the main chain end. -OM (M is an alkali metal) and then a precursor polymer (A'11-b) produced by a method of reacting with an unsaturated group-containing halogenated hydrocarbon,
A curable composition, wherein a mass ratio (A / B) of the content of the polymer (A) and the content of the polymer (B) is 90/10 to 40/60.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]   The curable composition according to claim 1 or 2, wherein the precursor polymer (A ') further comprises a precursor polymer (A'12) having two main chain terminal functional groups per molecule.   The curable composition as described in any one of Claims 1-3 whose molecular weight distribution of the said polymer (B) is 1.01-1.30.   In the polymer (A), the ratio of the functional group substituted with the group containing the reactive silicon group out of the functional groups at the main chain terminals capable of introducing the reactive silicon group of the precursor polymer (A ′) is The curable composition as described in any one of Claims 1-4 which is 45-100 mol%.   The curable composition according to any one of claims 1 to 5, which is used for a sealing material or an adhesive.