JP7073167B2 - Curable composition - Google Patents

Description

The present invention is a polyoxyalkylene-based polymer containing a terminal having two or more reactive silicon groups, a reactive silicon group-containing polyoxyalkylene-based polymer having three ends, and reactive only at one end. The present invention relates to a curable composition containing a polyoxyalkylene polymer having a silicon group and a plasticizer having an epoxy group.

Reactive silicon group-containing polymers are known as moisture-reactive polymers. Reactive silicon group-containing polymers are contained in many industrial products such as adhesives, sealing materials, coating materials, paints, and adhesives, and are used in a wide range of fields.

As such a reactive silicon group-containing polymer, a polymer having a main chain skeleton composed of a polyoxyalkylene-based polymer is known. The range of application of such a polymer is wide because it has a relatively low viscosity at room temperature and is easy to handle, and the cured product obtained after the reaction also exhibits good elasticity.

As the reactive silicon group of the polyoxyalkylene-based polymer containing a reactive silicon group, one having one at the terminal is often used. On the other hand, a polyoxyalkylene polymer having a plurality of reactive silicon groups at one terminal is also known (Patent Document 1). Since this polymer has a plurality of reactive silicon groups at one terminal, when this polymer is used, a curable composition that gives a cured product having improved strength can be obtained. It is also known to blend a polymer as described in Patent Document 1 with a polyoxyalkylene-based polymer having one or less reactive silicon groups on average at one terminal (Patent Document 1). 2). However, not only strength but also flexibility is an important requirement for improving the durability required for use as a sealing material, and the conventional curable composition may not be sufficient.

International Publication No. 2013/180203 International Publication No. 2015/080067

It is an object of the present invention to provide a curable composition that gives a cured product having improved durability, which is particularly required for a building sealant, and a cured product obtained from the curable composition.

（式中、Ｒ^１、およびＲ^３は、それぞれ独立に２価の炭素原子数１～６の連結基であり、Ｒ^１、およびＲ^３がそれぞれ有する２つの結合手は、それぞれ、連結基内の炭素原子、酸素原子、窒素原子、または硫黄原子に結合しており、Ｒ^２、およびＲ^４は、それぞれ独立に水素、または炭素原子数１～１０の炭化水素基であり、ｎは１～１０の整数であり、Ｒ^５は、それぞれ独立に、炭素原子数１～２０の炭化水素基であり、Ｒ^５としての炭化水素基は、置換されていてもよく、且つヘテロ含有基を有してもよく、Ｘは、それぞれ独立に水酸基または加水分解性基であり、ａは１、２、または３である。）
で表される、［１］に記載の硬化性組成物に関する。
［３］．反応性ケイ素基含有ポリオキシアルキレン系重合体（Ａ）の２個以上の反応性ケイ素基を有している末端が、１分子中に平均して０．１～２．０個である、［１］または［２］に記載の硬化性組成物に関する。
［４］．反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｂ）、および／または、反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｃ）が有する反応性ケイ素基が一般式（２）：
－Ｓｉ（Ｒ^６）_３－ｂ（Ｙ）_ｂ （２）
（式中、Ｒ^６はそれぞれ独立に、炭素原子数１～２０の炭化水素基であり、Ｒ^６としての炭化水素基は、置換されていてもよく、且つヘテロ含有基を有してもよく、Ｙは、それぞれ独立に水酸基または加水分解性基であり、ｂは１，２または３である。）
である、［１］～［３］のいずれか１つに記載の硬化性組成物に関する。
［５］．エポキシ基を有する可塑剤（Ｄ）がビス（２－エチルヘキシル）－４，５－エポキシシクロヘキサン－１，２－ジカーボキシレートである、［１］～［４］のいずれかに１つに記載の硬化性組成物に関する。
［６］．反応性ケイ素基含有ポリオキシアルキレン系重合体（Ａ）と反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｂ）との合計１００重量部に対して、反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｃ）５～１５０重量部と、エポキシ基を有する可塑剤（Ｄ）２～１００重量部と、を含有する、［１］～［５］のいずれか１つに記載の硬化性組成物に関する。
［７］．反応性ケイ素基含有ポリオキシアルキレン系重合体（Ａ）の重量と反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｂ）の重量との比が、反応性ケイ素基含有ポリオキシアルキレン系重合体（Ａ）／反応性ケイ素基含有ポリオキシアルキレン系重合体（Ｂ）として、７０／３０～３０／７０である、［１］～［６］のいずれか１つに記載の硬化性組成物に関する。
［８］．［１］～［７］のいずれか１つに記載の硬化性組成物を硬化させて得られる硬化物に関する。
［９］．［１］～［７］のいずれか１つに記載の硬化性組成物からなる、建築用シーリング材。
［１０］．［１］～［７］のいずれか１つに記載の硬化性組成物からなる、ダイレクトグレージング用シーリング材、ＳＳＧ工法用シーリング材、または建築物のワーキングジョイント用シーリング材。 As a result of diligent studies to solve the above problems, the present inventors have completed the following inventions.
That is, the present invention
[1]. A reactive silicon group-containing polyoxyalkylene polymer (A) having two ends and having two or more reactive silicon groups and having three ends per one end. The reactive silicon group-containing polyoxyalkylene polymer (B) having 0.3 to 1.0 reactive silicon groups and having two terminals, only one of which has a reactive silicon group. Reactive silicon group-containing polyoxyalkylene containing 0.3 to 1.0 reactive silicon groups per molecule and having two or more reactive silicon groups and not containing a terminal. The present invention relates to a curable composition containing a system polymer (C) and a plasticizer (D) having an epoxy group.
[2]. The terminal having two or more reactive silicon groups of the reactive silicon group-containing polyoxyalkylene polymer (A) is the general formula (1):

(In the formula, R ¹ and R ³ are independently divalent linking groups having 1 to 6 carbon atoms, and the two bonding hands of R ¹ and R ³ are in the linking group, respectively. It is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and R ² and R ⁴ are independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is 1 to 1. It is an integer of 10, and R ⁵ is an independently hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁵ may be substituted and has a hetero-containing group. X may be a hydroxyl group or a hydrolyzable group, respectively, and a may be 1, 2, or 3).
The curable composition according to [1], which is represented by.
[3]. The reactive silicon group-containing polyoxyalkylene polymer (A) has an average of 0.1 to 2.0 terminals having two or more reactive silicon groups in one molecule. 1] or [2] with respect to the curable composition.
[4]. The reactive silicon group contained in the reactive silicon group-containing polyoxyalkylene polymer (B) and / or the reactive silicon group-containing polyoxyalkylene polymer (C) is the general formula (2):
-Si (R ⁶ ) _3-b (Y) _b (2)
(In the formula, R ⁶ is independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁶ may be substituted or may have a hetero-containing group. , Y are independently hydroxyl groups or hydrolyzable groups, and b is 1, 2, or 3.)
The curable composition according to any one of [1] to [3].
[5]. The plasticizer (D) having an epoxy group is bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate, according to any one of [1] to [4]. With respect to the curable composition of.
[6]. Reactive silicon group-containing polyoxyalkylene-based polymer with respect to a total of 100 parts by weight of the reactive silicon group-containing polyoxyalkylene-based polymer (A) and the reactive silicon group-containing polyoxyalkylene-based polymer (B). (C) The curable composition according to any one of [1] to [5], which contains 5 to 150 parts by weight and 2 to 100 parts by weight of a plasticizer (D) having an epoxy group. ..
[7]. The ratio of the weight of the reactive silicon group-containing polyoxyalkylene polymer (A) to the weight of the reactive silicon group-containing polyoxyalkylene polymer (B) is the ratio of the reactive silicon group-containing polyoxyalkylene polymer (B). A) / The curable composition according to any one of [1] to [6], which is 70/30 to 30/70 as the reactive silicon group-containing polyoxyalkylene polymer (B).
[8]. The present invention relates to a cured product obtained by curing the curable composition according to any one of [1] to [7].
[9]. A building sealant comprising the curable composition according to any one of [1] to [7].
[10]. A sealing material for direct glazing, a sealing material for SSG method, or a sealing material for working joints of buildings, which comprises the curable composition according to any one of [1] to [7].

According to the present invention, it is possible to provide a curable composition that gives a cured product having improved durability, which is particularly required for a building sealant, and a cured product obtained by curing the curable composition.

<< Curable composition >>
The curable composition has a reactive silicon group-containing polyoxyalkylene polymer (A) having two ends and containing two or more reactive silicon groups, and three ends. It has a reactive silicon group-containing polyoxyalkylene polymer (B) having 0.3 to 1.0 reactive silicon groups per terminal and two terminals, one of which has two ends. Only reactive silicon groups are contained, the number of reactive silicon groups per molecule is 0.3 to 1.0, and the reactivity does not include a terminal having two or more reactive silicon groups. It contains a silicon group-containing polyoxyalkylene polymer (C) and a plasticizer (D) having an epoxy group.

In the present specification, the terminal includes the chain end in the polymer molecular chain and its neighboring structure. More specifically, it may be defined as a group to be substituted on the number of atoms constituting the polymer molecular chain, which is 20%, more preferably 10% from the end. Further, expressed by the number of bonded atoms, the terminal site may be defined as the terminal site from the end of the polymer molecular chain to 30 atoms, more preferably 20 atoms.

<Reactive silicon group-containing polyoxyalkylene polymer (A)>
The reactive silicon group-containing polyoxyalkylene polymer (A) (hereinafter, also referred to as polymer (A)) has two ends, and the end having two or more reactive silicon groups is used. Includes.
Having two ends means that the main chain structure of the polymer is linear.

The polymer (A) has a polymer having two or more reactive silicon groups at two ends and / or a terminal having two or more reactive silicon groups at one end. It suffices to contain a polymer, which is contained only in silicon. The polymer (A) may contain a polymer having at least one of the above two polymers and having two or more reactive silicon groups and having no terminal.

The number of terminals having two or more reactive silicon groups contained in one molecule is preferably 0.1 to 2.0 on average, preferably 0.1 to 1.5. Is more preferable, and 0.2 to 1.0 is more preferable because the balance between strength and flexibility is better.

（式中、Ｒ^１、およびＲ^３は、それぞれ独立に２価の炭素原子数１～６の連結基であり、Ｒ^１、およびＲ^３がそれぞれ有する２つの結合手は、それぞれ、連結基内の炭素原子、酸素原子、窒素原子、または硫黄原子に結合しており、Ｒ^２、およびＲ^４は、それぞれ独立に水素、または炭素原子数１～１０の炭化水素基であり、ｎは１～１０の整数であり、Ｒ^５は、それぞれ独立に、炭素原子数１～２０の炭化水素基であり、Ｒ^５としての炭化水素基は、置換されていてもよく、且つヘテロ含有基を有してもよく、Ｘは、それぞれ独立に水酸基または加水分解性基であり、ａは１、２、または３である。）
で表される構造が好ましい。 As the terminal having two or more reactive silicon groups, the general formula (1):

(In the formula, R ¹ and R ³ are independently divalent linking groups having 1 to 6 carbon atoms, and the two bonding hands of R ¹ and R ³ are in the linking group, respectively. It is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and R ² and R ⁴ are independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is 1 to 1. It is an integer of 10, and R ⁵ is an independently hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁵ may be substituted and has a hetero-containing group. X may be a hydroxyl group or a hydrolyzable group, respectively, and a may be 1, 2, or 3).
The structure represented by is preferable.

Examples of R ¹ in the general formula (1) include -CH ₂ OCH _2- , -CH ₂ O-, and -CH _2- . R ¹ is preferably −CH ₂ OCH _2- .

Examples of R ² and R ⁴ in the general formula (1) include a hydrogen atom, a methyl group, and an ethyl group. ^R2 and ^R4 are preferably hydrogen atoms and methyl groups.

Examples of R ³ in the general formula (1) include -CH _2- and -CH ₂ CH _2- , and more preferably -CH _2- .

N in the general formula (1) is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 2, and even more preferably 1.

Examples of R5 in the general formula ( ¹ ) include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group. Among these, a methyl group, an ethyl group, a chloromethyl group, and a methoxymethyl group are preferable, and a methyl group and an ethyl group are more preferable.

Examples of the X in the general formula (1) include a hydroxyl group, a hydrogen, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Be done. Among these, an alkoxy group such as a methoxy group and an ethoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable, because they are mildly hydrolyzable and easy to handle.

A in the general formula (1) is 1, 2, or 3, preferably 2 or 3.

Specific examples of the reactive silicon group (SiR ⁵ _{3-a Xa} ) in the polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, and a triacetoxysilyl group. Dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, Examples thereof include a (N, N-diethylaminomethyl) dimethoxysilyl group and a (N, N-diethylaminomethyl) diethoxysilyl group. Reactive silicon groups are not limited to these. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, and (methoxymethyl) diethoxysilyl group show high activity. , It is preferable because a cured product having good mechanical properties can be obtained. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are particularly preferable. From the viewpoint of stability, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group are particularly preferable. From the viewpoint of safety, a methyldiethoxysilyl group and a triethoxysilyl group are particularly preferable. The trimethoxysilyl group, triethoxysilyl group, and dimethoxymethylsilyl group are particularly preferable because they are easy to produce.

The average number of reactive silicon groups contained in one molecule of the polymer (A) is preferably 0.5 or more, and more preferably 0.8 or more. The upper limit is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less.

By containing the reactive silicon group-containing polyoxyalkylene polymer (A) containing a terminal having two or more reactive silicon groups in the curable composition, the strength and restoration rate of the cured product are improved. However, it improves durability.

Further, the reactive silicon group-containing polyoxyalkylene polymer (A) has a terminal having two or more reactive silicon groups, and is excellent in chemical resistance to acids, alkalis, solvents and the like. ing.

[Main chain structure]
The main chain skeleton of the polymer (A) is not particularly limited. Examples of the main chain skeleton include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer and the like. Be done. Among these, polyoxyethylene and polyoxypropylene are preferable, and polyoxypropylene is more preferable.

As the number average molecular weight of the polymer (A), the number average molecular weight obtained by GPC measurement is used. The polystyrene-equivalent molecular weight in the GPC is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is within the above range, the amount of the reactive silicon group introduced is appropriate, so that the polymer has a viscosity that is easy to handle and is excellent in workability while keeping the production cost within an appropriate range. A) is easy to obtain.

Regarding the molecular weight of the polymer (A), the principle of the method for measuring the hydroxyl value of JIS K 1557 and the method for measuring the raw material as specified in JIS K 0070 for the organic polymer precursor before the introduction of the reactive silicon group. It is also possible to directly measure the end group concentration by the titration analysis based on the above, and show it as the end group equivalent molecular weight obtained in consideration of the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). For the terminal group equivalent molecular weight of the reactive silicon group-containing polyoxyalkylene polymer (A), prepare a calibration line of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the terminal group equivalent molecular weight. It is also possible to convert the number average molecular weight of the reactive silicon group-containing polyoxyalkylene polymer (A) obtained by GPC into the terminal group equivalent molecular weight.

The molecular weight distribution (Mw / Mn) of the polymer (A) is not particularly limited. The molecular weight distribution is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. The molecular weight distribution of the polymer (A) can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

[Method for synthesizing polymer (A)]
Next, a method for synthesizing the polymer (A) will be described. The polymer (A) reacts with a carbon-carbon unsaturated bond after introducing two or more carbon-carbon unsaturated bonds into one terminal of the linear hydroxyl group terminal polymer obtained by the polymerization. It is preferably obtained by reacting a reactive silicon group-containing compound.
The preferred synthesis method described above will be described below.

(polymerization)
As a polymerization method in the production of the polymer (A), a method of polymerizing an epoxy compound with an initiator having two hydroxyl groups by using a composite metal cyanide complex catalyst such as a zinc hexacyanocovalent glyme complex is preferable.

Examples of the initiator having two hydroxyl groups include ethylene glycol, propylene glycol, and low molecular weight polypropylene glycol.

Examples of the epoxy compound include ethylene oxide and alkylene oxides such as propylene oxide, methyl glycidyl ether, and glycidyl ethers such as allyl glycidyl ether. Of these, propylene oxide is preferable.

(Introduction of carbon-carbon unsaturated bond)
As a method of introducing two or more carbon-carbon unsaturated bonds at one terminal, an alkali metal salt is allowed to act on a polyoxyalkylene-based polymer containing a hydroxyl group terminal, and then a carbon-carbon unsaturated bond is first introduced. It is preferable to use a method in which an epoxy compound having a carbon-carbon unsaturated bond is reacted, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. By using this method, it becomes possible to efficiently and stably introduce a reactive group while controlling the molecular weight and the molecular weight distribution of the polymer backbone according to the polymerization conditions.

By using an alkali metal salt when reacting an epoxy compound having a carbon-carbon unsaturated bond with a hydroxyl group terminal-containing polyoxyalkylene polymer, a carbon-carbon unsaturated bond is uniformly bonded to the terminal sites of all the polymers. The epoxy compound having the above can be reacted.
When a composite metal cyanide complex catalyst is used instead of an alkali metal salt, an epoxy compound having a carbon-carbon unsaturated bond selectively reacts with a polymer having a small molecular weight, and some of the polymers have a carbon-carbon unsaturated bond. It is not preferable because a carbon-carbon unsaturated bond is locally introduced into the terminal site.

Examples of the alkali metal salt include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, cesium alkoxide and the like. Sodium hydroxide, sodium methoxide, sodium methoxide, potassium hydroxide, potassium methoxide, and potassium methoxide are preferable, and sodium methoxide and potassium methoxide are more preferable, because of ease of handling and solubility. Sodium methoxide is particularly preferred in terms of availability. The alkali metal salt may be used in a state of being dissolved in a solvent.

（式中のＲ^１、およびＲ^２は上記と同じである。）
で表される化合物が好適に使用できる。具体的には、アリルグリシジルエーテル、メタリルグリシジルエーテル、グリシジルアクリレート、グリシジルメタクリレート、ブタジエンモノオキシド、および１，４－シクロペンタジエンモノエポキシドが反応活性の点から好ましく、アリルグリシジルエーテルが特に好ましい。 As an epoxy compound having a carbon-carbon unsaturated bond, the general formula (3):

(R ¹ and R ² in the equation are the same as above.)
The compound represented by is preferably used. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferable.

Hydrocarbon compounds having a carbon-carbon unsaturated bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Can be mentioned. Allyl chloride and methallyl chloride are more preferred because of their ease of handling.

(Introduction of reactive silicon group)
The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.
(I) A method for adding a hydrosilane compound to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.
(Ii) A polymer having a carbon-carbon unsaturated bond and a compound having both a group capable of reacting with a carbon-carbon unsaturated bond to form a bond and a reactive silicon group (also referred to as a silane coupling agent). How to react. Examples of the silane coupling agent that reacts with a carbon-carbon unsaturated bond to form a bond include, but are not limited to, a silane coupling agent having a mercapto group.

The method (i) is preferable because the reaction is simple, the amount of the reactive silicon group introduced is adjusted, and the physical properties of the obtained polymer (A) are stable.

Preferred specific examples of the hydrosilane compound used in the method (i) are trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl) dichlorosilane, (dichloromethyl) dichlorosilane, and bis (chloromethyl). ) Chlorosilanes, and halogenated silanes such as (methoxymethyl) dichlorosilanes; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (Chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, bis (chloromethyl) methoxysilane, (methoxymethyl) methylmethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) Diethoxysilane, (ethoxymethyl) diethoxysilane, (3,3,3-trifluoropropyl) dimethoxysilane, (N, N-diethylaminomethyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane, [ (Chloromethyl) dimethoxysilyloxy] dimethylsilane, [(chloromethyl) diethoxysilyloxy] dimethylsilane, [(methoxymethyl) dimethoxysilyloxy] dimethylsilane, [(diethylaminomethyl) dimethoxysilyloxy] dimethylsilane, and [ (3,3,3-trifluoropropyl) Dimethoxysilyloxy] Ekalkylsilanes such as dimethylsilane; Asyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; Bis (dimethylketoximate) methylsilane, and Ketoximate silanes such as bis (cyclohexylketoximate) methylsilanes; isopropeniroxysilanes such as triisopropeniroxysilanes, (chloromethyl) diisopropeniroxysilanes, and (methoxymethyl) diisopropeniroxysilanes. Deacelatin type) and the like.

<Reactive silicon group-containing polyoxyalkylene polymer (B)>
The reactive silicon group-containing polyoxyalkylene-based polymer (B) (hereinafter, also referred to as polymer (B)) has three terminals, and the number of reactive silicon groups per terminal is 0.3 to 1. It is 0.0.
Having three ends means that the backbone structure of the polymer contains branches. A backbone structure with three ends can be obtained, for example, by polymerizing with an initiator having three hydroxyl groups.

It is preferable that the terminal structure of the polymer (B) does not include a terminal having two or more reactive silicon groups.

By adding the polymer (B) to the curable composition together with the above-mentioned polymer (A), the strength of the cured product is further improved, thereby improving the durability.

[Reactive silicon group]
The reactive silicon group of the polymer (B) has a general formula (2) :.
-Si (R ⁶ ) _3-b (Y) _b (2)
(In the formula, R ⁶ is independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁶ may be substituted or has a hetero-containing group. Often, Y is a hydroxyl group or a hydrolyzable group, respectively, and b is 1, 2, or 3).
It is preferably a group represented by.

Preferred specific examples of R ⁶ include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group. Of these, a methyl group, an ethyl group, a chloromethyl group, and a methoxymethyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.

Preferred specific examples of Y include a hydroxyl group, a hydrogen, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, an alkoxy group such as a methoxy group and an ethoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable, because they are mildly hydrolyzable and easy to handle.

b is 1, 2, or 3. As b, 2 or 3 is preferable.

Specific examples of the reactive silicon group in the polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group and a diethoxymethylsilyl group. Group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxy Examples thereof include, but are not limited to, a silyl group and a (N, N-diethylaminomethyl) diethoxysilyl group. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, and (methoxymethyl) diethoxysilyl group show high activity. , It is preferable because a cured product having good mechanical properties can be obtained. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are particularly preferable. From the viewpoint of stability, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group are particularly preferable. From the viewpoint of safety, a methyldiethoxysilyl group and a triethoxysilyl group are particularly preferable, and a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable because they are easy to produce.

The number of reactive silicon groups in the polymer (B) is 0.3 to 1.0 on average per terminal, preferably 0.5 to 1.0.
Since the reactive silicon group-containing polyoxyalkylene polymer (B) has three terminals, the number of reactive silicon groups per molecule is preferably 0.9 to 3.0, preferably 1.0 to 2.5. Is more preferable.

[Main chain structure]
The main chain skeleton of the polymer (B) is not particularly limited, and is, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene. -Examples include polyoxybutylene copolymers. Among these, polyoxyethylene and polyoxypropylene are preferable, and polyoxypropylene is more preferable.

As the number average molecular weight of the polymer (B), the number average molecular weight obtained by GPC measurement is used. The polystyrene-equivalent molecular weight in the GPC is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is within the above range, the amount of the reactive silicon group introduced is appropriate, so that the polymer has a viscosity that is easy to handle and is excellent in workability while keeping the production cost within an appropriate range. B) is easy to obtain.

The molecular weight distribution (Mw / Mn) of the polymer (B) is not particularly limited. The molecular weight distribution is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. The molecular weight and molecular weight distribution of the polymer (B) can be determined by the same method as that of the reactive silicon group-containing polyoxyalkylene polymer (A).

[Method for synthesizing polymer (B)]
Next, a method for synthesizing the polymer (B) will be described.
The polymer (B) is a reaction that reacts with a carbon-carbon unsaturated bond after introducing one carbon-carbon unsaturated bond into the terminal of a polyoxyalkylene-based polymer having three hydroxyl group terminals obtained by the polymerization. It is preferably obtained by reacting a sex silicon group-containing compound.
The preferred synthesis method described above will be described below.

(polymerization)
As a polymerization method in the production of the polymer (B), a method of polymerizing an epoxy compound with an initiator having three hydroxyl groups by using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable.

Examples of the initiator having three hydroxyl groups include glycerin and polyoxypropylene triol.
Examples of the epoxy compound include ethylene oxide and alkylene oxides such as propylene oxide, methyl glycidyl ether, and glycidyl ethers such as allyl glycidyl ether. Of these, propylene oxide is preferable.

(Introduction of reactive silicon group)
In the polymer (B), a polyoxyalkylene-based polymer having three hydroxyl groups is obtained, and then (i) a carbon-carbon unsaturated group is introduced into the hydroxyl group of the obtained hydroxyl group-terminated polyoxyalkylene-based polymer. After that, a method of adding a silane compound by a hydrosilylation reaction, (ii) a method of reacting the obtained hydroxyl group-terminated polyoxyalkylene polymer with a compound having both a group that reacts with a hydroxyl group and a reactive silicon group. , (Iii) A hydroxyl group-terminated polyoxyalkylene-based polymer is reacted with an excess polyisocyanate compound to form a polymer having an isocyanate group at the terminal, and then both a group that reacts with the isocyanate group and a hydrolyzable silyl group are added. It is preferably obtained by a method of reacting a compound having the same. Of the above three methods, the method (i) is the method (i) because the reaction is simple, the amount of the reactive silicon group introduced is adjusted, and the physical properties of the obtained reactive silicon group-containing polyoxyalkylene polymer are stable. More preferred.

Examples of the carbon-carbon unsaturated group used in the method (i) include a vinyl group, an allyl group, and a metallicyl group. Of these, the allyl group is preferable.

As a method for introducing a carbon-carbon unsaturated group into the hydroxyl group of (i), an alkali metal salt is allowed to act on the hydroxyl group terminal-containing polymer, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. It is preferable to use the method of causing.

Examples of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond used in the method (i) include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, and iodide. Examples include allyl, and metalyl iodide.

As the hydrosilane compound used in the method (i), the same hydrosilane compound as the suitable hydrosilane compound exemplified for the method for producing the polymer (A) can be used.

As a compound having both a group that reacts with a hydroxyl group and a reactive silicon group that can be used in the method (ii), for example, 3-isoxapropyltrimethoxysilane, 3-isoxapropyldimethoxymethylsilane, 3-isocyandiapropyltriethoxysilane. , Isoisylsilanes such as isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, 3-isocyanatepropyl (chloromethyl) dimethoxysilane, and 3-isocyanatepropyl (methoxymethyl) dimethoxysilane; 3-mercapto Mercaptosilanes such as propyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyl (methoxymethyl) dimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, And epoxy silanes such as 3-glycidoxypropyl (methoxymethyl) dimethoxysilane can be used.

Examples of the polyisocyanate compound that can be used in the method (iii) include aromatic polyisocyanates such as toluene (tolylen) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. And so on.

Examples of the compound having both a group that reacts with an isocyanate group and a hydrolyzable silyl group that can be used in the method (iii) include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, and γ-aminopropyltriethoxy. Silane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyldimethoxymethylsilane, N- (β-aminoethyl) -γ-aminopropyltri Ethoxysilane, γ- (N-phenyl) aminopropyltrimethoxysilane, γ- (N-phenyl) aminopropyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexyl Amino group-containing silanes such as aminomethyltrimethoxysilane and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; γ-mercapto Examples thereof include propyltrimethoxysilanes and mercapto group-containing silanes such as γ-mercaptopropyldimethoxymethylsilane; and the like.

[Ratio of reactive silicon group-containing polyoxyalkylene polymer (A) to reactive silicon group-containing polyoxyalkylene polymer (B)]
The weight ratio of the polymer (A) to the polymer (B) is not particularly limited. The weight ratio of the polymer (A) to the polymer (B) is preferably 70/30 to 30/70, more preferably 60/40 to 40/60, as the polymer (A) / polymer (B). ..

<Reactive silicon group-containing polyoxyalkylene polymer (C)>
The reactive silicon group-containing polyoxyalkylene-based polymer (C) (hereinafter, also referred to as polymer (C)) has two terminals, and only one of them contains a reactive silicon group, and per molecule. The number of reactive silicon groups is 0.3 to 1.0, and the terminal having two or more reactive silicon groups is not included.

Having two ends and containing a reactive silicon group in only one of them means that the main chain structure of the polymer is linear and only one of the two ends has a reactive silicon group. That is.

The fact that the number of reactive silicon groups per molecule is 0.3 to 1.0 means that not only the polymer having a reactive silicon group at only one of both ends but also the reactive silicon at both ends. It means that it may contain a polymer having no group.

The number of reactive silicon groups in the polymer (C) is 0.3 to 1.0 per molecule, preferably 0.5 to 1.0.

A reactive silicon group-containing polyoxyalkylene polymer having two ends, wherein only one of them contains a reactive silicon group and does not contain a terminal having two or more reactive silicon groups. By adding the polymer (C) to the curable composition, the flexibility (elongation) of the cured product is improved, and by balancing the strength and the flexibility, the durability is further improved.

[Reactive silicon group]
As the reactive silicon group of the polymer (C), the same reaction-formed silicon group as the reactive silicon group described for the polymer (B) can be used.

[Main chain structure]
The main chain skeleton of the polymer (C) is not particularly limited, and is, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene. -Examples include polyoxybutylene copolymers. Among these, polyoxyethylene and polyoxypropylene are preferable, and polyoxypropylene is more preferable.

As the number average molecular weight of the polymer (C), the number average molecular weight obtained by GPC measurement is used. The polystyrene-equivalent molecular weight in the GPC is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000.

The molecular weight distribution (Mw / Mn) of the polymer (C) is not particularly limited. The molecular weight distribution is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.

The molecular weight and molecular weight distribution of the polymer (C) can be obtained by the same method as that of the polymer (A).

The reactive silicon group-containing polyoxyalkylene polymer (C) has two ends, and only one end has a reactive silicon group. The reactive silicon group-containing polyoxyalkylene polymer (C) can be obtained by carrying out polymerization using an initiator having one hydroxyl group.

[Method for synthesizing reactive silicon group-containing polyoxyalkylene polymer (C)]
Next, a method for synthesizing the polymer (C) will be described.
The polymer (C) is a reactive silicon group-containing compound that reacts with a carbon-carbon unsaturated bond after introducing a carbon-carbon unsaturated bond into the terminal of the polymer having one hydroxyl group terminal obtained by the polymerization. It is preferably obtained by reacting.
The preferred synthesis method described above will be described below.

(polymerization)
As the polymer (C), a method of polymerizing an epoxy compound with an initiator having one hydroxyl group using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable.

Examples of the initiator having one hydroxyl group include allyl alcohol, polypropylene monoallyl ether, polypropylene monoalkyl ether and the like.

Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.

(Introduction of reactive silicon group)
The reactive silicon group in the polymer (C) can be introduced by the same method as described for the polymer (B).

[Amount of reactive silicon group-containing polyoxyalkylene polymer (C) added]
The amount of the polymer (C) added is preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).
When the polymer (C) is added in an amount within the above range, flexibility in an appropriate range can be imparted to the cured product, and it is easy to balance the flexibility and strength of the cured product.

<Plasticizer (D) having an epoxy group>
The curable composition contains a plasticizer (D) having an epoxy group (hereinafter, also referred to as a component (D)).
By containing the plasticizer (D) having an epoxy group in the curable composition, the durability of the cured product derived from the polymer (A), the polymer (B), and the polymer (C) is improved. .. On the other hand, when the curable composition does not contain the plasticizer (D) having an epoxy group, the durability of the cured product derived from the polymer (A), the polymer (B), and the polymer (C) is increased. There is room for improvement.

Examples of the plasticizer (D) having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate. , And epoxy butyl stearate and the like. Of these, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate is particularly preferred.

The amount of the plasticizer (D) having an epoxy group to be used is preferably 2 to 100 parts by weight, more preferably 4 to 70 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B). ..

<Other additives>
The curable composition may contain various additives in addition to the polymer (A), the polymer (B), the polymer (C), and the plasticizer (D) having an epoxy group. Additives include silanol condensation catalysts, fillers, adhesives, plasticizers other than the component (D), solvents, diluents, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, and physical property modifiers. , Adhesive-imparting resin, photocurable substance, oxygen-curable substance, epoxy resin other than the component (D), and other resins. These additives may be used alone or in combination of two or more.

Further, other additives may be added to the curable composition, if necessary, for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include surface improvers, foaming agents, curability modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxides. Examples include decomposing agents, lubricants, pigments, and fungicides.

[Silanol condensation catalyst]
The curable composition has the purpose of promoting the reaction of hydrolyzing and condensing the reactive silicon groups of the polymer (A), the polymer (B), and the polymer (C), and extending or cross-linking the polymer. It may also contain a silanol condensation catalyst.

Examples of the silanol condensation catalyst include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.

Specific examples of the organic tin compound include dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin bis (butyl maleate), dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), and dioctyl tin bis (acetylacetate). Nart), a reaction product of dibutyl tin oxide and a silicate compound, a reaction product of dioctyl tin oxide and a silicate compound, and a reaction product of dibutyl tin oxide and a phthalate ester.

Specific examples of the metal carboxylate salt include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, and iron carboxylate. Further, as the carboxylic acid metal salt, a salt in which the following carboxylic acid and various metals are combined can be used.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), and 1. , 5-Diazabicyclo [4,3,0] Nonen-5 (DBN) and other nitrogen-containing heterocyclic compounds; guanidines such as guanidine, phenylguanidine, and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide, and Viguanides such as 1-phenylbiguanide; amino group-containing silane coupling agents; ketimine compounds and the like can be mentioned.

Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of the alkoxy metal include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethyl. Examples thereof include aluminum compounds such as acetoacetate and zirconium compounds such as zirconium tetrakis (acetylacetonate).

As other silanol condensation catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.

The silanol condensation catalyst may be used in combination with two or more different catalysts.
The amount of the silanol condensation catalyst used is 0.001 with respect to 100 parts by weight of the total of the reactive silicon group-containing polyoxyalkylene polymer (A) and the reactive silicon group-containing polyoxyalkylene polymer (B). ~ 20 parts by weight is preferable, 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable.

[filler]
Various fillers can be added to the curable composition. As fillers, heavy calcium carbonate, glued calcium carbonate, magnesium carbonate, silica soil, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, molten silica, silicon dioxide, hydrous silicic acid, Examples thereof include carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc flower, PVC powder, PMMA powder, glass fiber and filament.

The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 250 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).

A balloon (hollow filler) such as an organic balloon and an inorganic balloon may be added for the purpose of reducing the weight (reducing the specific gravity) of the cured product formed by using the curable composition. The balloon is a spherical filler with a hollow inside. Examples of the material of the balloon include inorganic materials such as glass, silas, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran.

The amount of the balloon used is preferably 0.1 to 100 parts by weight, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).

[Adhesive imparting agent]
An adhesiveness-imparting agent can be added to the curable composition. As the adhesiveness-imparting agent, a silane coupling agent and a reaction product of the silane coupling agent can be added.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, and N-β-aminoethyl-γ-. Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl) aminomethyltrimethoxysilane; γ-isocyanapropyltrimethoxysilane, γ-isocyanapropyl Silanes containing isocyanate groups such as triethoxysilane, γ-isocyanapropylmethyldimethoxysilane, α-isocyanammethyltrimethoxysilane, and α-isocyanatemethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy. Silanes and mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilanes and epoxy group-containing silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilanes. , Can be mentioned.

The adhesive-imparting agent may be used alone or in combination of two or more. Further, reactants of various silane coupling agents can also be used as an adhesive-imparting agent.

The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B). ..

[Plasticizer]
A plasticizer other than the component (D) can be added to the curable composition. Specific examples of the plasticizer include phthalate ester compounds such as dibutylphthalate, diisononylphthalate (DINP), diheptylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate (DIDP), and butylbenzylphthalate; bis (2-). Ethylhexyl) -1,4-benzenedicarboxylate and other terephthalate ester compounds; 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalate ester compounds; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate , And aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyllithinolate; alkyl sulfonic acid phenyl esters; phosphoric acid ester compounds; trimellitic acid ester compounds. Examples include chlorinated paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated ester phenyls; process oils and the like.

Moreover, a polymer plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers; polyester plasticizers; polyethylene glycols having a number average molecular weight of 500 or more, and polyether polyols such as polypropylene glycols, and the hydroxy groups of these polyether polyols are ester groups and ethers. Examples thereof include polyethers such as derivatives converted into groups; polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.

The amount of the plasticizer used is preferably 3 to 150 parts by weight, more preferably 5 to 120 parts by weight, and 10 to 100 parts by weight with respect to 100 parts by weight of the total of the polymer (A) and the polymer (B). Is particularly preferable. When a plasticizer is used within the above range, it is easy to obtain a curable composition capable of forming a cured product having excellent mechanical strength while obtaining the desired effect as the plasticizer. The plasticizer may be used alone or in combination of two or more.

[Solvent, diluent]
Solvents or diluents can be added to the curable composition. The solvent and the diluent are not particularly limited. As the solvent and diluent, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers and the like can be used. Due to the problem of air pollution when the curable composition is used indoors, the boiling point of the solvent or diluent under atmospheric pressure is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher. preferable. The above solvent or diluent may be used alone or in combination of two or more.

[Sauce preventive agent]
An anti-sauce agent may be added to the curable composition, if necessary, in order to prevent sagging and improve workability. The sagging preventive agent is not particularly limited. Examples of the anti-sagging agent include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sauce agents may be used alone or in combination of two or more.

The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of the polymer (A) and the polymer (B).

[Antioxidant]
Antioxidants (antioxidants) can be used in the curable composition. The use of antioxidants can increase the weather resistance of the cured product. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of the antioxidant are described in, for example, JP-A-4-283259 and JP-A-9-194731.

The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).

[Light stabilizer]
A light stabilizer can be used in the curable composition. The use of a light stabilizer can prevent photooxidation deterioration of the cured product. Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds. As the light stabilizer, a hindered amine type is particularly preferable.

The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).

[UV absorber]
An ultraviolet absorber can be used for the curable composition. The use of UV absorbers can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based compounds, and metal chelate-based compounds. As the ultraviolet absorber, a benzotriazole type is particularly preferable. Preferable specific examples of the benzotriazole-based UV absorber include the commercially available names Chinubin P, Chinubi 213, Chinubi 234, Tinubin 326, Tinubin 327, Tinubin 328, Tinubin 329, and Tinubin 571 (all manufactured by BASF). ..

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).

[Physical characteristic adjuster]
A physical characteristic adjusting agent for adjusting the tensile properties of the produced cured product may be added to the curable composition, if necessary. The physical property adjusting agent is not particularly limited. Examples of the physical property adjusting agent include alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, and phenyltrimethoxysilane. Arylalkoxysilanes; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, and tris (triethyl). Examples thereof include trialkylsilylborates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical characteristic adjusting agent, the hardness of the cured product of the curable composition can be increased, or conversely, the hardness can be decreased to obtain elongation at break. The physical property adjusting agent may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has an action of lowering the modulus of the cured product without aggravating the stickiness of the surface of the cured product. Particularly, a compound that produces trimethylsilanol is preferable. Compounds that produce compounds having a monovalent silanol group in the molecule by hydrolysis are derivatives of alcohols such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, and are silanes by hydrolysis. Examples include silicon compounds that produce monools. Specific examples thereof include phenoxytrimethylsilane and tris ((trimethylsiloxy) methyl) propane.

The amount of the physical property adjusting agent used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B).

[Adhesive-imparting resin]
A tackifier resin can be added to the curable composition for the purpose of enhancing the adhesiveness and adhesion to the substrate, or if necessary. The tackifier resin is not particularly limited, and a resin usually used as a tackifier resin can be used.

Specific examples of the tackifier resin include terpene-based resin, aromatic-modified terpene resin, hydrogenated terpene resin, terpene-phenol resin, phenol resin, modified phenol resin, xylene-phenol resin, cyclopentadiene-phenol resin, and kumaron inden. Resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogenated additives, petroleum resins (eg, C5 carbonized). Hydrogen resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

The amount of the tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and 5 to 30 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B). More preferred. When the tackifier resin is used within the above range, it is easy to achieve both the adhesion and adhesion effect of the cured product to the substrate and the appropriate viscosity of the curable composition which is easy to handle.

[Photocurable substance]
A photocurable substance can be used in the curable composition. When a photocurable material is used, a film of a photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many substances of this type are known, such as organic monomers, oligomers, resins, and compositions containing them. As a typical substance, a monomer having one or several acrylic or methacrylic unsaturated groups, an unsaturated acrylic compound which is an oligomer or a mixture thereof, vinyl polysilicate dermatates, an azide resin and the like can be used.

The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B). stomach. When a photocurable substance is used within the above range, it is easy to obtain a curable composition that gives a cured product having excellent weather resistance, flexibility, and less cracking.

[Oxygen curable substance]
Oxygen curable substances can be used in the curable composition. An unsaturated compound that can react with oxygen in the air can be exemplified as an oxygen-curable substance. It reacts with oxygen in the air to form a cured film near the surface of the cured product, and the surface is sticky or dust on the surface of the cured product. It has the effect of preventing the adhesion of dust and dirt.

Specific examples of the oxygen-curable substance include dry oils such as drilling oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers, epoxy resins, silicon resins and the like. Modifications of the resin by dry oil; 1,2-polybutadiene, 1,4-polybutadiene, and C5 to obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. Examples thereof include a liquid polymer such as a polymer of C8 diene. These may be used alone or in combination of two or more.

The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polymer (A) and the polymer (B). .. When the amount of the oxygen-curable substance used is within the above range, it is easy to obtain a sufficient effect of improving the contamination property, and the tensile properties of the cured product are not easily impaired. As described in Japanese Patent Application Laid-Open No. 3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.

[Epoxy resin]
An epoxy resin can be used in combination with the composition of the present invention. The composition to which the epoxy resin is added is particularly preferable as an adhesive, particularly an adhesive for outer wall tiles. Examples of the epoxy resin include bisphenol A type epoxy resins and novolak type epoxy resins.

The ratio of these epoxy resins to the polymer (A) and the polymer (B) is the weight ratio (polymer (A) + polymer (B)) / epoxy resin = 100/1 to 1/1. It is in the range of 100. When the ratio of (polymer (A) + polymer (B)) / epoxy resin is within the above range, it is easy to obtain the effect of improving the impact strength and toughness of the cured product.

When the epoxy resin is added, a curing agent that cures the epoxy resin can be used in combination with the curable composition. The epoxy resin curing agent that can be used is not particularly limited, and a generally used epoxy resin curing agent can be used.

When a curing agent for an epoxy resin is used, the amount of the curing agent used is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

<Preparation of curable composition>
The curable composition described above can be prepared as a one-component type in which all the compounding components are previously compounded and sealed and stored, and then cured by the humidity in the air after construction. Further, it is also possible to separately blend components such as a curing catalyst, a filler, a plasticizer, and water as a curing agent, and prepare a two-component type in which the compounding material and the organic polymer composition are mixed before use. .. From the viewpoint of storage stability, the two-component type is preferable.

<Use>
The curable composition described above includes sealing materials for buildings, ships, automobiles, roads, adhesives, adhesives, waterproof materials, waterproof coating materials, molding agents, vibration-proofing materials, vibration-damping materials, and soundproofing materials. Can be used in applications such as foaming materials, paints, and spraying materials. Since the cured product obtained by curing the curable composition described above is excellent in flexibility and adhesiveness, it is more preferable to use it as a sealing material or an adhesive, and it is excellent in durability. Therefore, it is more preferable to use it as a sealing material.
Specific uses as a sealing material include a sealing material for direct glazing, a sealing material for the SSG method, and a sealing material for a working joint of a building, and these uses are applications that require durability.

Hereinafter, the present invention will be specifically described with reference to examples. The present embodiment does not limit the present invention in any way.

The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid transfer system: Tosoh HLC-8120GPC
Column: Tosoh TSK-GEL H type Solvent: THF
Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C

For the terminal group equivalent molecular weight in the examples, the hydroxyl value is determined by the measuring method of JIS K 1557 and the iodine value is determined by the measuring method of JIS K 0070, and the structure of the organic polymer (the degree of branching determined by the polymerization initiator used) is determined. It is the molecular weight obtained in consideration.
The average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer (Q) shown in the examples was calculated by the following formula.
(Average number of introductions) = [Unsaturated group concentration (mol / g) of polymer (Q) determined from iodine value-Unsaturated group concentration (mol / g) of precursor polymer (P) determined from iodine value] / [The hydroxyl group concentration (mol / g) of the precursor polymer (P) obtained from the hydroxyl value].

The average number of silyl groups introduced per terminal of the polymer (A), the polymer (B), and the polymer (C) shown in the examples was calculated by NMR measurement.

(Synthesis Example 1)
Using polyoxypropylene glycol having a number average molecular weight of about 2,000 as an initiator, propylene oxide is polymerized with a zinc hexacyanocovalent glyme complex catalyst, and the number average molecular weight is 20,900 (terminal group equivalent) having hydroxyl groups at both ends. Polyoxypropylene (P-1) having a molecular weight of 13,600) and a molecular weight distribution of Mw / Mn = 1.23 was obtained. Subsequently, 1.0 molar equivalent of sodium methoxide was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-1) as a 28% methanol solution. 0.3 mol equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-1), and the reaction was carried out at 130 ° C. for 2 hours. Then, 0.28 mol equivalent of a methanol solution of sodium methoxydo was added to remove the methanol, and 1.79 mol equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group, resulting in unreacted chloride. Allyl was removed by vacuum devolatile. After mixing and stirring n-hexane and water with respect to the obtained unpurified polyoxypropylene, water was removed by centrifugation, and hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-1) having a carbon-carbon unsaturated bond at the end was obtained. It was found that the polymer (Q-1) had an average of 1.29 carbon-carbon unsaturated bonds introduced at one terminal site.
To 500 g of the obtained (Q-1), 50 μL of a platinum divinyldisiloxane complex (2-propanol solution of 3% by weight in terms of platinum) was added, and 8.2 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to have a number average molecular weight of 22, including a terminal having two dimethoxymethylsilyl groups at one terminal. 000 reactive silicon group-containing polyoxypropylene (A-1) was obtained. It was found that the polymer (A-1) had an average of 1.0 dimethoxymethylsilyl groups at one terminal and an average of 2.0 in one molecule.

(Synthesis Example 2)
Starting with polyoxypropylene glycol having a number average molecular weight of about 3,000, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 18,000 (terminal group equivalent molecular weight 12500) having hydroxyl groups at both ends. ), Polyoxypropylene (P-2) having a molecular weight distribution Mw / Mn = 1.20 was obtained. 1.0 molar equivalent of sodium methoxide was added to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene (P-2) as a 28% methanol solution. After distilling off methanol by vacuum devolatile, 0.3 mol equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-2), and the reaction was carried out at 130 ° C. for 2 hours. Then, 0.28 mol equivalent of a methanol solution of sodium methoxide was added to remove methanol, and 0.79 mol equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. After that, the same purification operation as in Synthesis Example 1 was performed. From the above, polyoxypropylene (Q-2) having a carbon-carbon unsaturated bond was obtained. It was found that the polymer (Q-2) had an average of 1.30 carbon-carbon unsaturated bonds introduced into one terminal site.
To 500 g of the obtained carbon-carbon unsaturated bond (Q-2), 50 μL of a platinum divinyl disiloxane complex solution was added, and 8.1 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to have a number average molecular weight of 20000 including a terminal having two dimethoxymethylsilyl groups at one terminal. Polyoxypropylene (A-2) was obtained. It was found that the polymer (A-2) had an average of 0.9 dimethoxymethylsilyl groups at one terminal and an average of 1.8 in one molecule.

(Synthesis Example 3)
Starting with polyoxypropylene triol having a number average molecular weight of about 3,000, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 24,600 (terminal group) having hydroxyl groups at three ends. Polyoxypropylene (P-3) having a converted molecular weight of 17,400) and a molecular weight distribution of Mw / Mn = 1.31 was obtained. 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene (P-3). After distilling off methanol by vacuum devolatile, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-3), and the reaction was carried out at 130 ° C. for 2 hours. Then, 0.28 mol equivalent of a methanol solution of sodium methoxide was added to remove methanol, and 1.79 mol equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. After that, the same purification operation as in Synthesis Example 1 was performed. From the above, polyoxypropylene (Q-3) having a carbon-carbon unsaturated bond was obtained. It was found that the polymer (Q-3) had an average of 2.0 carbon-carbon unsaturated bonds introduced into one terminal site.
To 500 g of the obtained polyoxypropylene (Q-3) having a carbon-carbon unsaturated bond, 50 μL of a platinum divinyl disiloxane complex solution was added, and 12.6 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to have a number average molecular weight of 27, including a terminal having two dimethoxymethylsilyl groups at one terminal. 500 polyoxypropylene (A'-1) was obtained. It was found that the polymer (A'-1) had an average of 1.6 dimethoxymethylsilyl groups at one terminal and an average of 4.8 in one molecule.

(Synthesis Example 4)
Starting with polyoxypropylene triol having a number average molecular weight of about 3,000, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 26,200 (terminal group) having hydroxyl groups at three ends. Polyoxypropylene (P-4) having a converted molecular weight of 17,400) and a molecular weight distribution of Mw / Mn = 1.34 was obtained. To the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene (P-4), 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution. After methanol was distilled off by vacuum devolatile, 1.5 mol equivalent of allyl chloride was further added to the hydroxyl group of the polymer (P-4) to convert the terminal hydroxyl group into an allyl group. After that, the same purification operation as in Synthesis Example 1 was performed. From the above, polyoxypropylene (Q-4) having a carbon-carbon unsaturated bond at the terminal site was obtained. To 500 g of this polymer (Q-4), 50 μL of a platinum divinyldisiloxane complex solution was added, and 5.5 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 100 ° C. for 6 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (B-1) having a dimethoxymethylsilyl group at the terminal and having a number average molecular weight of about 27,500. Obtained. It was found that the polymer (B-1) had an average of 0.7 dimethoxymethylsilyl groups at one terminal and an average of 2.1 in one molecule.

(Synthesis Example 5)
1.1 molar equivalents of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl group-terminated polyoxyalkylene (P-1) obtained in Synthesis Example 1. After methanol was distilled off by vacuum devolatile, 1.4 mol equivalent of allyl chloride was further added to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group into an allyl group. After that, the same purification operation as in Synthesis Example 1 was performed. From the above, polyoxypropylene (Q-5) having a carbon-carbon unsaturated bond at the terminal site was obtained. To 500 g of this polymer (Q-5), 50 μL of a platinum divinyldisiloxane complex solution was added, and 5.8 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 100 ° C. for 6 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (B'-1) having a dimethoxymethylsilyl group at the terminal and having a number average molecular weight of about 21100. rice field. It was found that the polymer (B'-1) had an average of 0.7 dimethoxymethylsilyl groups at one terminal and an average of 1.5 in one molecule.

(Synthesis Example 6)
Polypropylene oxide is polymerized using butanol as an initiator with a zinc hexacyanocobaltate glyme complex catalyst, and has a number average molecular weight of 7800 (terminal group equivalent molecular weight of 5000) having a hydroxyl group at one end, and a molecular weight distribution of Mw / Mn = 1.48. Polyoxypropylene (P-6) was obtained. Subsequently, 1.2 molar equivalents of sodium methoxide was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-6) as a 28% methanol solution. After distilling off methanol by vacuum devolatilization, 2.0 molar equivalent of allyl chloride was added to the hydroxyl group of the polymer (P-6) to convert the terminal hydroxyl group into an allyl group, resulting in unreacted chloride. Allyl was removed by vacuum devolatile. After that, the same purification operation as in Synthesis Example 1 was performed. From the above, polyoxypropylene (Q-6) having a carbon-carbon unsaturated bond at only one end was obtained. It was found that the polymer (Q-6) had a butyloxy group at one end and an average of 1.0 carbon-carbon unsaturated bonds introduced at the other end.
To 500 g of the obtained (Q-6), 50 μL of a platinum divinyldisiloxane complex (2-propanol solution of 3 wt% in platinum equivalent) was added, and 9.5 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxypropylene (C-) having a dimethoxymethylsilyl group only at one end. 1) was obtained. It was found that the polymer (C-1) had an average of 0.8 dimethoxymethylsilyl groups at only one end.

(Examples 1 to 4 and Comparative Examples 1 to 9)
Polymers and plasticizers shown in Tables 1 and 2 [Sunsosizer E-PS (Shin Nihon Rika: Di2-ethylhexyl epoxyhexahydrophthalate), DINP (J-Plus Co., Ltd .: Diisononyl phthalate) ], Further, 120 parts by weight of Shiro Gloss Flower CCR (manufactured by Shiraishi Calcium Co., Ltd .: precipitated calcium carbonate), 20 parts by weight of Whiten SB (manufactured by Shiraishi Kogyo Co., Ltd .: heavy calcium carbonate), Disparon # 308 (Kusumoto Chemical Co., Ltd.) Made by: Hydrate Epoxy Oil) 3 parts by weight, Tinubin 326 (BASF made: 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol) 1 part by weight, Sanol LS770 (Ciba Specialty) Chemicals: 1 part by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 3 parts by weight of Aronix M309 (Toa Synthetic: 1,1,1-trimethylol propanetriacrylic acid ester) , Phenoxytrimethylsilane in the amounts shown in Tables 1 and 2, and tris ((trimethylsiloxy) methyl) propane in the amounts shown in Tables 1 and 2, Neostan U-28 3.0 parts by weight, as the main ingredient. Using 0.5 parts by weight of laurylamine, 6.4 parts by weight of DINP, 15 parts by weight of Whiten SB, and 5 parts by weight of ASP170 (BASF: Kaolin) as a curing agent, 4 parts by weight of DINP, and Typake R820 (manufactured by Ishihara Sangyo Co., Ltd.) : Titanium oxide) 5 parts by weight was mixed and defoamed as a collar.

(Durability evaluation)
After mixing the obtained main agent, curing agent, and color, an H-type test piece having a joint width of 12 mm was prepared, cured at 23 ° C. for 7 days + 50 ° C. for 7 days, and then subjected to JIS A1439: 2016 fatigue resistance test (CR90). ) Was carried out. That is, the test piece obtained by curing was fixed at a compression deformation rate of 30% using a spacer for compression fixation, allowed to stand at 90 ° C. for 24 hours, and then the joint width was released from fixation to 23 ° C. It was allowed to stand for 24 hours. After that, the test piece was installed in a repeated fatigue tester, the joint width was fixed to 12 mm at 23 ° C., and the joint was expanded / reduced by ± 30% 6,000 times for judgment. The durability was judged according to the following criteria.

(Durability judgment)
6: No cracks at 4 sealant interfaces 5: Cracks at 4 sealant interfaces with a depth of 1 mm or less and a length of 2 cm or less 4: Cracks at 4 sealant interfaces with a depth of 1 mm or less and a length of 2 to 10 cm
3: The cracks at the four sealant interfaces have a depth of 1 mm or less and a length of 10 to 20 cm.
2: Cracks at 4 sealant interfaces have a depth of 1 mm or more and a length of 10 cm or less 1: Cracks at 4 sealant interfaces have a depth of 1 mm or more and a length of 10 to 20 cm

According to Tables 1 and 2, the durability evaluation of Examples 1 to 4 is 5 or more, whereas the polymer (A) is changed to A'-1 having a branch, which is Comparative Example 1 and the polymer. In Comparative Example 2 in which (B) was changed to linear B'-1, Comparative Example 3 in which the polymer (C) was changed to DINP, and Comparative Example 4 in which the component (D) was changed to DINP, the durability evaluation was performed. It turns out to be low.
Further, Comparative Example 5 not containing the polymer (A), Comparative Example 6 not containing the polymer (B), Comparative Example 7 not containing the polymer (A), and the polymer (C) also have low durability evaluations. ..
Further, from Comparative Examples 8 and 9, when the curable composition does not contain the component (D), the branched A'-1 is changed to the straight chain A-1 which is the polymer (A). However, it can be seen that the durability does not improve. On the other hand, from Example 2 and Comparative Example 1, when the curable composition contains the component (D), the durability can be greatly improved by changing A'-1 to the linear A-1. I understand.

Claims (10)

A reactive silicon group-containing polyoxyalkylene polymer (A) having two ends and having two or more reactive silicon groups and having three ends per one end. The reactive silicon group-containing polyoxyalkylene polymer (B) having 0.3 to 1.0 reactive silicon groups and having two terminals, only one of which has a reactive silicon group. Reactive silicon group-containing polyoxyalkylene containing 0.3 to 1.0 reactive silicon groups per molecule and having two or more reactive silicon groups and not containing a terminal. It contains a system polymer (C) and a plasticizer (D) having an epoxy group.
A curable composition in which the number of reactive silicon groups contained in one molecule of the polymer (A) is 0.5 or more and 4.0 or less . The terminal having two or more reactive silicon groups of the reactive silicon group-containing polyoxyalkylene polymer (A) is the general formula (1):.

(In the formula, R ¹ and R ³ are independently divalent linking groups having 1 to 6 carbon atoms, and the two bonding hands of R ¹ and R ³ are in the linking group, respectively. It is bonded to a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and R ² and R ⁴ are independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is 1 to 1. It is an integer of 10, and R ⁵ is an independently hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁵ may be substituted and has a hetero-containing group. X may be independently a hydroxyl group or a hydrolyzable group, and a may be 1, 2, or 3).
The curable composition according to claim 1. The reactive silicon group-containing polyoxyalkylene-based polymer (A) has an average of 0.1 to 2.0 terminals having two or more reactive silicon groups in one molecule. The curable composition according to claim 1 or 2. The reactive silicon group contained in the reactive silicon group-containing polyoxyalkylene polymer (B) and / or the reactive silicon group-containing polyoxyalkylene polymer (C) is the general formula (2):.
-Si (R ⁶ ) _3-b (Y) _b (2)
(In the formula, R ⁶ is independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁶ may be substituted and has a hetero-containing group. Often, Y is a hydroxyl group or a hydrolyzable group, respectively, and b is 1, 2, or 3).
The curable composition according to any one of claims 1 to 3. The one according to any one of claims 1 to 4, wherein the plasticizer (D) having an epoxy group is bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate. Curable composition. The reactive silicon group-containing polyoxyalkylene based on a total of 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer (A) and the reactive silicon group-containing polyoxyalkylene polymer (B). The curable composition according to any one of claims 1 to 5, which contains 5 to 150 parts by weight of the system polymer (C) and 2 to 100 parts by weight of the plasticizer (D) having an epoxy group. .. The ratio of the weight of the reactive silicon group-containing polyoxyalkylene polymer (A) to the weight of the reactive silicon group-containing polyoxyalkylene polymer (B) is the weight of the reactive silicon group-containing polyoxyalkylene-based polymer. The curable composition according to any one of claims 1 to 6, wherein the combined (A) / reactive silicon group-containing polyoxyalkylene polymer (B) is 70/30 to 30/70. A cured product obtained by curing the curable composition according to any one of claims 1 to 7. A building sealant comprising the curable composition according to any one of claims 1 to 7. A sealing material for direct glazing, a sealing material for an SSG method, or a sealing material for a working joint of a building, which comprises the curable composition according to any one of claims 1 to 7.