JP2019182885A - Curable composition - Google Patents

Abstract

To provide a curable composition providing a cured article with enhanced durability required for a sealant for building, and the cured article obtained from the curable composition.SOLUTION: A curable composition containing a reactive silicon group-containing polyoxyalkylene polymer (A) containing 2 terminals having 2 or more reactive silicon groups, a reactive silicon group-containing polyoxyalkylene polymer (B) containing 3 terminals with the number of reactive silicon group per 1 terminal of 0.3 to 1.0, and a reactive silicon group-containing polyoxyalkylene polymer (C) containing 2 terminals, containing a reactive silicon group only in one terminal, having the number of the reactive silicon group per one molecule of 0.3 to 1.0, and containing no terminal having 2 or more reactive silicon groups, and a plasticizer having an epoxy group (D), is used.SELECTED DRAWING: None

Description

  The present invention relates to a polyoxyalkylene polymer containing a terminal having two or more reactive silicon groups, a reactive silicon group-containing polyoxyalkylene polymer having three terminals, and reactive only at one terminal. The present invention relates to a curable composition comprising 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 included in many industrial products such as adhesives, sealing materials, coating materials, paints, and pressure-sensitive 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 polymer is known. Such polymers have a relatively low viscosity at room temperature, are easy to handle, and a cured product obtained after the reaction also exhibits good elasticity.

  A reactive silicon group-containing polyoxyalkylene polymer having one reactive silicon group 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 end, when this polymer is used, a curable composition giving 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 polymer having 1 or less reactive silicon groups on average at one end (Patent Document). 2). However, not only strength but also flexibility is an important requirement for improving durability required for use as a sealing material, and conventional curable compositions may not be sufficient.

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

  An object of this invention is to provide the curable composition which gives the hardened | cured material which the durability especially requested | required with the sealing material for construction improved, and the hardened | cured material obtained from this 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 intensive studies to solve the above problems, the present inventors have completed the following invention.
That is, the present invention
[1]. Reactive silicon group-containing polyoxyalkylene polymer (A) having two ends and having two or more reactive silicon groups, and three ends, per end A reactive silicon group-containing polyoxyalkylene polymer (B) having a number of reactive silicon groups of 0.3 to 1.0 and two terminals, and only one of them has a reactive silicon group Reactive silicon group-containing polyoxyalkylene containing no terminal, having a number of reactive silicon groups per molecule of 0.3 to 1.0 and having two or more reactive silicon groups The present invention relates to a curable composition containing a 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) has the general formula (1):

(In the formula, R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the two bonds that R ¹ and R ³ each have are each within the linking group. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is 1 to 10 carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms. And R ⁵ is independently a 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 is independently a hydroxyl group or a hydrolyzable group, and a is 1, 2, or 3.)
It is related with the curable composition as described in [1].
[3]. The average number of terminals having two or more reactive silicon groups in the reactive silicon group-containing polyoxyalkylene polymer (A) is 0.1 to 2.0 in one molecule. The curable composition according to [1] or [2].
[4]. The reactive silicon group-containing polyoxyalkylene polymer (B) and / or the reactive silicon group contained in the reactive silicon group-containing polyoxyalkylene polymer (C) has the general formula (2):
-Si (R ⁶ ) _3-b (Y) _b (2)
(In the formula, each R ⁶ is independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group as R ⁶ may be substituted and may have a hetero-containing group. Y and Y are each independently a hydroxyl group or a hydrolyzable group, and b is 1, 2 or 3.)
It is related with the curable composition as described in any one of [1]-[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] It relates to a curable composition.
[6]. Reactive silicon group-containing polyoxyalkylene polymer with respect to a total of 100 parts by weight of reactive silicon group-containing polyoxyalkylene polymer (A) and reactive silicon group-containing polyoxyalkylene polymer (B) (C) It relates to the curable composition as described in any one of [1]-[5] containing 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 such that the reactive silicon group-containing polyoxyalkylene polymer ( A) As the reactive silicon group-containing polyoxyalkylene polymer (B), the curable composition according to any one of [1] to [6], which is 70/30 to 30/70.
[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 sealing material comprising the curable composition according to any one of [1] to [7].
[10]. A sealing material for direct glazing, a sealing material for an SSG method, or a sealing material for a working joint of a building, comprising the curable composition according to any one of [1] to [7].

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which gives the hardened | cured material which the durability especially requested | required with the sealing material for buildings improved, and the hardened | cured material which hardened this curable composition can be provided.

≪Curable composition≫
The curable composition has a reactive silicon group-containing polyoxyalkylene polymer (A) having two ends and a terminal having two or more reactive silicon groups, and three ends. 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 Only reactive silicon groups, the number of reactive silicon groups per molecule is 0.3 to 1.0, and the terminal-free reactivity having two or more reactive silicon groups A silicon group-containing polyoxyalkylene polymer (C) and a plasticizer (D) having an epoxy group are included.

  In the present specification, the term “end” includes the chain end in the polymer molecular chain and its neighboring structure. More specifically, it may be defined as a group that substitutes on the number of atoms corresponding to 20%, more preferably 10% from the end of the bonding atoms constituting the polymer molecular chain. In terms of the number of bonded atoms, the terminal site may be defined as the terminal site of 30 atoms, more preferably 20 atoms from the end of the polymer molecular chain.

<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 ends having two or more reactive silicon groups. Contains.
Having two ends means that the main chain structure of the polymer is linear.

  The polymer (A) is a polymer having two terminals having two or more reactive silicon groups and / or one terminal having two or more reactive silicon groups. It is only necessary to contain a polymer contained only in The polymer (A) may contain a polymer having no terminal having two or more reactive silicon groups as long as it contains at least one of the two polymers.

  The number of terminals having two or more reactive silicon groups contained in one molecule is preferably 0.1 to 2.0 on average, and 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 becomes 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 each independently a divalent linking group having 1 to 6 carbon atoms, and the two bonds that R ¹ and R ³ each have are each within the linking group. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is 1 to 10 carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms. And R ⁵ is independently a 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 is independently a hydroxyl group or a hydrolyzable group, and a is 1, 2, or 3.)
The structure represented by these is preferable.

The ^{R 1} in the general formula (1), for _{example, -CH 2 OCH 2 -, -} CH 2 O-, and -CH ₂ - and the like. 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. R ² and R ⁴ are preferably a hydrogen atom and a methyl group.

The ^{R 3} in the general formula (1), for example, -CH ₂ -, and _-CH 2 CH ₂ - can be exemplified, more preferably, -CH ₂ - is.

  N in General formula (1) is an integer of 1-10, the integer of 1-5 is preferable, the integer of 1-2 is more preferable, and 1 is more preferable.

Examples of R ⁵ 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 X in the general formula (1) include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group. It is 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 the hydrolyzability is mild and easy to handle.

  A in general formula (1) is 1, 2, or 3, and 2 or 3 is preferable.

Specific examples of the reactive silicon group (SiR ⁵ _3-a X _a ) in the polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, Dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, Examples thereof include (N, N-diethylaminomethyl) dimethoxysilyl group and (N, N-diethylaminomethyl) diethoxysilyl group. The reactive silicon group is 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. Since a cured product having good mechanical properties can be obtained, it is preferable. 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. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are particularly preferable because of easy production.

  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.

  The curable composition contains a reactive silicon group-containing polyoxyalkylene polymer (A) containing a terminal having two or more reactive silicon groups, thereby improving the strength and restoration rate of the cured product. As a result, durability is improved.

  The reactive silicon group-containing polyoxyalkylene polymer (A) has a terminal having two or more reactive silicon groups, and is excellent in chemical resistance such as acid, alkali, and solvent. 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, and polyoxypropylene-polyoxybutylene copolymer. It is done. Among these, polyoxyethylene and polyoxypropylene are preferable, and polyoxypropylene is more preferable.

  The number average molecular weight obtained by GPC measurement is used as the number average molecular weight of the polymer (A). The polystyrene-equivalent molecular weight in 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 introduction amount of the reactive silicon group is moderate, so that a polymer having an easy-to-handle viscosity and excellent workability while keeping the production cost within an appropriate range ( A) is easy to obtain.

  Regarding the molecular weight of the polymer (A), the organic polymer precursor before introduction of the reactive silicon group is obtained by measuring the hydroxyl value of JIS K 1557 and the principle of the iodine value measuring method defined in JIS K 0070. The end group concentration can be directly measured by a titration analysis based on the above, and can be expressed by the end group converted molecular weight determined in consideration of the structure of the organic polymer (the degree of branching determined by the used polymerization initiator). For the reactive silicon group-containing polyoxyalkylene polymer (A), the end group equivalent molecular weight was determined by preparing a calibration curve of the number average molecular weight determined by general GPC measurement of the organic polymer precursor and the above end group equivalent molecular weight. The number average molecular weight determined by GPC of the reactive silicon group-containing polyoxyalkylene polymer (A) can also be determined by converting it to a 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 determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

[Synthesis Method of 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 at one end of a linear hydroxyl-terminated polymer obtained by polymerization. It is preferably obtained by reacting a reactive silicon group-containing compound.
The preferred synthesis method will be described below.

(polymerization)
As a polymerization method in the production of the polymer (A), a method in which an epoxy compound is polymerized to an initiator having two hydroxyl groups using a double metal cyanide complex catalyst such as zinc hexacyanocobaltate 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 alkylene oxides such as ethylene oxide and propylene oxide, glycidyl ethers such as methyl glycidyl ether, and allyl glycidyl ether. Among 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 hydroxyl group-containing polyoxyalkylene polymer, and then, first, a carbon-carbon unsaturated bond. It is preferable to use a method of reacting an epoxy compound having a hydrogen atom and then reacting a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond. By using this method, it is possible to efficiently and stably introduce reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain according to the polymerization conditions.

By using an alkali metal salt when an epoxy compound having a carbon-carbon unsaturated bond is reacted with a hydroxyl group-terminated polyoxyalkylene polymer, the carbon-carbon unsaturated bond is uniformly distributed at the terminal sites of all polymers. An epoxy compound having can be reacted.
When a double 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 low molecular weight. This is not preferable because a carbon-carbon unsaturated bond is locally introduced into the terminal portion.

  Examples of the alkali metal salt include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. In view of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferable, and sodium methoxide and potassium methoxide are more preferable. Sodium methoxide is particularly preferred from the standpoint of availability. You may use an alkali metal salt in the state melt | dissolved in the 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, in particular, the general formula (3):

(In the formula, R ¹ and R ² are the same as above.)
The compound represented by these can be used conveniently. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferable.

  Examples of the halogenated hydrocarbon compound 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. Is mentioned. From the viewpoint of ease of handling, allyl chloride and methallyl chloride are more preferable.

(Introduction of reactive silicon groups)
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 in which a hydrosilane compound is added 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 forming a bond by reacting with the carbon-carbon unsaturated 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 the 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 adjustment of the amount of reactive silicon groups introduced, and the physical properties of the resulting polymer (A) are stable.

  Preferable specific examples of the hydrosilane compound used in the method (i) include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl) dichlorosilane, (dichloromethyl) dichlorosilane, and bis (chloromethyl). ) Halogenated silanes such as chlorosilane and (methoxymethyl) dichlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (Chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, bis (chloromethyl) methoxysilane, (methoxymethyl) Rumethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (ethoxymethyl) diethoxysilane, (3,3,3-trifluoropropyl) dimethoxysilane, (N, N-diethylaminomethyl) dimethoxy Silane, (N, N-diethylaminomethyl) diethoxysilane, [(chloromethyl) dimethoxysilyloxy] dimethylsilane, [(chloromethyl) diethoxysilyloxy] dimethylsilane, [(methoxymethyl) dimethoxysilyloxy] dimethylsilane , [(Diethylaminomethyl) dimethoxysilyloxy] dimethylsilane, and alkoxysilanes such as [(3,3,3-trifluoropropyl) dimethoxysilyloxy] dimethylsilane; diacetoxymethylsilane, and di Acyloxysilanes such as cetoxyphenylsilane; ketoximate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane; triisopropenyloxysilane, (chloromethyl) diisopropeni Examples thereof include loxysilane and isopropenyloxysilanes (deacetone type) such as (methoxymethyl) diisopropenyloxysilane.

<Reactive silicon group-containing polyoxyalkylene polymer (B)>
The reactive silicon group-containing polyoxyalkylene 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. .0.
Having three ends means that the main chain structure of the polymer contains a branch. The main chain structure having three terminals can be obtained, for example, by performing polymerization using 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 a polymer (B) with the above-mentioned polymer (A) with respect to a curable composition, the intensity | strength of hardened | cured material improves further and thereby durability improves.

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

Preferable specific examples of R ⁶ 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 more preferable, and a methyl group and an ethyl group are particularly preferable.

  Preferable specific examples of Y include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group. 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 the hydrolyzability is mild and easy to handle.

  b is 1, 2 or 3; b is preferably 2 or 3.

  Specific examples of the reactive silicon group in the polymer (B) include trimethoxysilyl group, triethoxysilyl group, tris (2-propenyloxy) silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl. 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. Since a cured product having good mechanical properties can be obtained, it is preferable. 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 of easy production.

The number of reactive silicon groups in the polymer (B) is 0.3 to 1.0 on average per terminal, and 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, and 1.0 to 2.5. Is more preferable.

[Main chain structure]
The main chain skeleton of the polymer (B) is not particularly limited. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene -Polyoxybutylene copolymer etc. are mentioned. 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 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 introduction amount of the reactive silicon group is moderate, so that a polymer having an easy-to-handle viscosity and excellent 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 for the reactive silicon group-containing polyoxyalkylene polymer (A).

[Synthesis Method of 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 at the terminal of a polyoxyalkylene polymer having three hydroxyl terminals obtained by polymerization. It is preferable to obtain by reacting a functional silicon group-containing compound.
The preferred synthesis method will be described below.

(polymerization)
As a polymerization method in the production of the polymer (B), a method in which an epoxy compound is polymerized to an initiator having three hydroxyl groups using a double metal cyanide complex catalyst such as 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 alkylene oxides such as ethylene oxide and propylene oxide, glycidyl ethers such as methyl glycidyl ether, and allyl glycidyl ether. Among these, propylene oxide is preferable.

(Introduction of reactive silicon groups)
After the polymer (B) obtained a polyoxyalkylene polymer having three hydroxyl groups, (i) a carbon-carbon unsaturated group was introduced into the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene polymer. And (ii) a method of reacting the obtained hydroxyl-terminated polyoxyalkylene polymer with a compound having both a group capable of reacting with a hydroxyl group and a reactive silicon group. (Iii) A hydroxyl group-terminated polyoxyalkylene polymer and an excess polyisocyanate compound are reacted to form a polymer having an isocyanate group at the end, and then both the group that reacts with the isocyanate group and the hydrolyzable silyl group are removed. It is preferable to obtain by the method of making the compound which has it react. Among the above three methods, the reaction is simple, the adjustment of the introduction amount of the reactive silicon group, and the physical properties of the resulting 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 methallyl group. Among these, an 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 a hydroxyl-terminated polymer, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. It is preferable to use the method of making it.

  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 methallyl iodide.

  As the hydrosilane compound used in the method (i), a hydrosilane compound similar to the suitable hydrosilane compound exemplified for the production method of the polymer (A) can be used.

  Examples of the compound having both a hydroxyl group-reactive group and a reactive silicon group that can be used in the method (ii) include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, and 3-isocyanatepropyltriethoxysilane. , Isocyanate silanes such as isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, 3-isocyanatopropyl (chloromethyl) dimethoxysilane, and 3-isocyanatopropyl (methoxymethyl) dimethoxysilane; 3-mercapto Propyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyl (methoxymethyl) dimethoxy Mercaptosilanes such as orchid; epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropyl (methoxymethyl) dimethoxysilane can be used. is there.

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

  Examples of the compound having both an isocyanate group-reactive 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 Aminomethyltrimethoxy Silanes and amino group-containing silanes such as N-cyclohexylaminomethyldimethoxymethylsilane; γ-hydroxypropyltrimethoxysilane and hydroxy group-containing silanes such as γ-hydroxypropyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane , 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)]
There is no particular limitation on the weight ratio of the polymer (A) and the polymer (B). 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 polymer (C) (hereinafter also referred to as polymer (C)) has two ends, and only one of them contains a reactive silicon group, The number of reactive silicon groups is 0.3 to 1.0 and does not include a terminal having two or more reactive silicon groups.

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

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

  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 terminals, which contains a reactive silicon group only in one of them, and does not include a terminal having two or more reactive silicon groups, By adding a polymer (C) to a curable composition, the softness | flexibility (elongation) of hardened | cured material improves and durability improves further by balancing intensity | strength and a softness | flexibility.

[Reactive silicon group]
As a reactive silicon group which a polymer (C) has, the reactive silicon group similar to the reactive silicon group described about the polymer (B) can be used.

[Main chain structure]
The main chain skeleton of the polymer (C) is not particularly limited. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene -Polyoxybutylene copolymer etc. are mentioned. 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 molecular weight in terms of polystyrene in 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 determined by the same method as for the polymer (A).

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

[Synthesis Method of 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 at the terminal of the polymer having one hydroxyl terminal obtained by polymerization. It is preferable to obtain by reaction.
The preferred synthesis method will be described below.

(polymerization)
The polymer (C) is preferably a method in which an epoxy compound is polymerized to an initiator having one hydroxyl group using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex.

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

  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 groups)
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)]
The amount of the polymer (C) added is preferably 5 to 150 parts by weight and more preferably 10 to 100 parts by weight with respect to 100 parts by weight as the total of the polymer (A) and the polymer (B).
When the polymer (C) is used in an addition amount within the above range, an appropriate range of flexibility can be imparted to the cured product, and the flexibility and strength of the cured product can be easily balanced.

<Plasticizer having epoxy group (D)>
A curable composition contains the plasticizer (D) (henceforth (D) component) which has an epoxy group.
When the curable composition contains 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 improved. . On the other hand, when the curable composition does not contain a 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 improved. 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), epoxy octyl stearate And epoxybutyl stearate. Of these, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate is particularly preferred.

  The amount of the plasticizer (D) having an epoxy group 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, adhesion-imparting agents, plasticizers other than component (D), solvents, diluents, sagging inhibitors, antioxidants, light stabilizers, UV absorbers, and physical property modifiers. , Tackifying resins, photo-curing substances, oxygen-curing substances, epoxy resins other than the component (D), and other resins. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, you may add another additive to a curable composition as needed for the purpose of adjustment of various physical properties of a curable composition or hardened | cured material. Examples of such additives include, for example, surface property improvers, foaming agents, curability modifiers, flame retardants, silicates, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxides. Examples include decomposers, lubricants, pigments, and fungicides.

[Silanol condensation catalyst]
The curable composition promotes the reaction of hydrolyzing and condensing the reactive silicon group of the polymer (A), the polymer (B), and the polymer (C), and is intended to extend or crosslink the polymer. And may 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 dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis (butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis (acetylacetonate), dioctyltin bis (acetylacetate). Natto), a reaction product of dibutyltin oxide and a silicate compound, a reaction product of dioctyltin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalate, and the like.

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

  Specific examples of the amine compound 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] nonene-5 (DBN) and other heterocyclic compounds; guanidines such as guanidine, phenylguanidine, and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide, and Examples include biguanides such as 1-phenylbiguanide; amino group-containing silane coupling agents; ketimine compounds and the like.

  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 (ethylacetocetate), aluminum tris (acetylacetonate), and diisopropoxyaluminumethyl. 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.

As the silanol condensation catalyst, two or more different types of catalysts may be used in combination.
The amount of the silanol condensation catalyst used is 0.001 relative to 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). -20 parts by weight is preferable, 0.01-15 parts by weight is more preferable, and 0.01-10 parts by weight is particularly preferable.

[filler]
Various fillers can be mix | blended with a curable composition. Fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, Examples thereof include carbon black, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, 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).

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

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

[Adhesive agent]
An adhesiveness imparting agent can be added to the curable composition. As an adhesion 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, N-β-aminoethyl-γ-. Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and (2-aminoethyl) aminomethyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyl Isocyanate group-containing silanes such as triethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, and α-isocyanatemethyldimethoxymethylsilane; γ-mercaptopropyl Mercapto group-containing silanes such as limethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl And epoxy group-containing silanes such as trimethoxysilane.

  The adhesiveness-imparting agent may be used alone or in combination of two or more. Moreover, the reaction material of various silane coupling agents can also be used as an adhesive imparting agent.

  The amount of the silane coupling agent used is preferably from 0.1 to 20 parts by weight, particularly preferably from 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 plasticizers include phthalate compounds such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate; bis (2- Terephthalic acid ester compounds such as ethylhexyl) -1,4-benzenedicarboxylate; non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate And aliphatic polycarboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; Sulfonic acid phenyl ester; phosphoric acid ester compound; trimellitic acid ester compound; chlorinated paraffins, alkyl diphenyl, and hydrocarbon-based oils such as partially hydrogenated terphenyl; and the like process oil.

  Moreover, a polymeric plasticizer can be used. Specific examples of the polymer plasticizer include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol having a number average molecular weight of 500 or more, and polypropylene glycol, and hydroxy groups of these polyether polyols as ester groups and ethers. Polyethers such as derivatives converted into groups and the like; 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 more preferably 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 preferred. 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 a desired effect as a plasticizer. A plasticizer may be used independently and may use 2 or more types together.

[Solvent, Diluent]
A solvent or a diluent can be added to the curable composition. The solvent and 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. From the problem of air contamination 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 said solvent or diluent may be used independently and may be used together 2 or more types.

[Anti-sagging agent]
An anti-sagging agent may be added to the curable composition as necessary in order to prevent sagging and improve workability. The anti-sagging agent is not particularly limited. Examples of the sagging inhibitor include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sagging 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 as the total of the polymer (A) and the polymer (B).

[Antioxidant]
An antioxidant (antiaging agent) can be used for the curable composition. If an antioxidant is used, the weather resistance of the cured product can be increased. 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.

  0.1-10 weight part is preferable with respect to a total of 100 weight part of a polymer (A) and a polymer (B), and, as for the usage-amount of antioxidant, 0.2-5 weight part is especially preferable.

[Light stabilizer]
A light stabilizer can be used for the curable composition. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds. As the light stabilizer, a hindered amine system is particularly preferable.

  0.1-10 weight part is preferable with respect to a total of 100 weight part of a polymer (A) and a polymer (B), and, as for the usage-amount of a light stabilizer, 0.2-5 weight part is especially preferable.

[Ultraviolet absorber]
An ultraviolet absorber can be used for the curable composition. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds. As the ultraviolet absorber, a benzotriazole type is particularly preferable. Preferable specific examples of the benzotriazole ultraviolet absorber include commercially available names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (above, manufactured by BASF). .

  0.1-10 weight part is preferable with respect to a total of 100 weight part of a polymer (A) and a polymer (B), and, as for the usage-amount of a ultraviolet absorber, 0.2-5 weight part is especially preferable.

[Physical property modifier]
You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to a curable composition. It does not specifically limit as a physical property modifier. Examples of the physical property modifier 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) And trialkylsilyl borates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using a physical property modifier, the hardness of the cured product of the curable composition can be increased, or conversely, the hardness can be decreased and elongation at break can be produced. The physical property modifiers may be used alone or in combination of two or more.

  In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. Compounds that generate monovalent silanol groups in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol. Mention may be made of silicon compounds that produce monools. Specific examples include phenoxytrimethylsilane and tris ((trimethylsiloxy) methyl) propane.

  0.1-10 weight part is preferable with respect to a total of 100 weight part of a polymer (A) and a polymer (B), and, as for the usage-amount of a physical property modifier, 0.5-5 weight part is especially preferable.

[Tackifying resin]
A tackifying resin can be added to the curable composition for the purpose of enhancing the adhesion and adhesion to the substrate, or as necessary. There is no restriction | limiting in particular as tackifying resin, Usually, resin used as tackifying resin can be used.

  Specific examples of tackifying resins include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, coumarone indenes. Resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, styrene block copolymer and hydrogenated product thereof, petroleum resin (for example, C5 carbonization) Hydrogen resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, and DCPD resin. These may be used alone or in combination of two or more.

  The amount of the tackifying 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). Further preferred. When the tackifier resin is used within the above range, it is easy to achieve both the adhesion to the base material and the adhesion effect of the cured product and an appropriate viscosity that allows easy handling of the curable composition.

[Photo-curing substance]
A photocurable material can be used for the curable composition. When a photocurable material is used, a film of a photocurable material 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. As this kind of substance, many substances such as organic monomers, oligomers, resins or compositions containing them are known. As typical substances, there can be used unsaturated acrylic compounds, polyvinyl cinnamates or azide resins which are monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups.

  0.1-20 weight part is preferable with respect to a total of 100 weight part of a polymer (A) and a polymer (B), and, as for the usage-amount of a photocurable substance, 0.5-10 weight part is more preferable. Yes. When a photocurable substance is used within the above range, it is easy to obtain a curable composition that gives a cured product that is excellent in weather resistance, is flexible, and does not easily crack.

[Oxygen curable substances]
An oxygen curable substance can be used for the curable composition. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And acts to prevent adhesion of dust.

  Specific examples of the oxygen curable substance include drying oil typified by drill oil and linseed oil, and various alkyd resins obtained by modifying the compound; acrylic polymers, epoxy resins, silicone resins, etc. 1. A modified product of a resin with a drying oil; 1,2-polybutadiene, 1,4-polybutadiene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, and 1,3-pentadiene, and C5 Examples thereof include liquid polymers such as C8 diene polymers. 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 and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight as 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 it is difficult to impair the tensile properties of the cured product. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

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

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

  When adding an epoxy resin, the curable composition can be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used.

  When using the hardening | curing agent for epoxy resins, the usage-amount of a hardening | curing agent has preferable 0.1-300 weight part with respect to 100 weight part of epoxy resins.

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

<Application>
The curable compositions described above are sealing materials for buildings, ships, automobiles, roads, etc., adhesives, pressure-sensitive adhesives, waterproofing materials, waterproofing coating materials, mold preparations, vibration damping materials, vibration damping materials, and soundproofing materials. It can be used for applications such as foam materials, paints, and spray materials. Since the cured product obtained by curing the curable composition described above is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive, and it has excellent 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 an SSG method, and a sealing material for a working joint of a building, and these uses are required for durability.

  Hereinafter, the present invention will be specifically described with reference to examples. This embodiment does not limit the present invention.

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

The molecular weight in terms of end groups in the examples is determined by measuring the hydroxyl value by the measuring method of JIS K 1557 and the iodine value by the measuring method of JIS K 0070, and calculating the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). This is the molecular weight determined 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 of polymer (Q) determined from iodine value (mol / g) −Unsaturated group concentration of precursor polymer (P) determined from iodine value (mol / g)] / [Hydroxyl concentration of precursor polymer (P) determined from hydroxyl value (mol / g)].

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

(Synthesis Example 1)
Polyoxypropylene glycol having a number average molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight having a hydroxyl group at both ends is 20,900 (in terms of end group) Polyoxypropylene (P-1) having a molecular weight of 13,600) and a molecular weight distribution Mw / Mn = 1.23 was obtained. Subsequently, 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-1). 0.3 mol equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-1) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove the methanol, and 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl group to an allyl group. Allyl was removed by vacuum devolatilization. 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 devolatilization under reduced pressure. Thus, polyoxypropylene (Q-1) having a carbon-carbon unsaturated bond at the terminal was obtained. The polymer (Q-1) was found to have 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 platinum divinyldisiloxane complex (3-wt% 2-propanol solution in terms of platinum) was added, and 8.2 g of dimethoxymethylsilane was slowly added dropwise with stirring. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a number average molecular weight of 22, containing a terminal having two dimethoxymethylsilyl groups at one terminal. 000 reactive silicon group-containing polyoxypropylene (A-1) was obtained. The polymer (A-1) was found to have an average of 1.0 dimethoxymethylsilyl groups at one end and an average of 2.0 per molecule.

(Synthesis Example 2)
A polyoxypropylene glycol having a number average molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight 18000 having a hydroxyl group at both ends (terminal group equivalent molecular weight 12500) ), Polyoxypropylene (P-2) having a molecular weight distribution Mw / Mn = 1.20 was obtained. 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the obtained hydroxyl-terminated polyoxypropylene (P-2). After distilling off methanol by vacuum devolatilization, 0.3 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-2) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove methanol, and 0.79 molar equivalent of allyl chloride was further added to convert the terminal hydroxyl group into an allyl group. Thereafter, the same purification operation as in Synthesis Example 1 was performed. Thus, polyoxypropylene (Q-2) having a carbon-carbon unsaturated bond was obtained. The polymer (Q-2) was found to have an average of 1.30 carbon-carbon unsaturated bonds introduced at one terminal site.
To 500 g of the obtained polyoxypropylene (Q-2) having a carbon-carbon unsaturated bond, 50 μL of platinum divinyldisiloxane complex solution was added, and 8.1 g of dimethoxymethylsilane was slowly added dropwise with stirring. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby a number-average molecular weight of 20000 containing a terminal having two dimethoxymethylsilyl groups at one terminal. Polyoxypropylene (A-2) was obtained. The polymer (A-2) was found to have an average of 0.9 dimethoxymethylsilyl groups at one end and an average of 1.8 per molecule.

(Synthesis Example 3)
Polyoxypropylene triol having a number average molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight having a hydroxyl group at three terminals is 24,600 (terminal group Polyoxypropylene (P-3) having a converted molecular weight of 17,400) and a molecular weight distribution Mw / Mn = 1.31 was obtained. 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the obtained hydroxyl-terminated polyoxypropylene (P-3). After distilling off methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-3) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Thereafter, the same purification operation as in Synthesis Example 1 was performed. Thus, polyoxypropylene (Q-3) having a carbon-carbon unsaturated bond was obtained. The polymer (Q-3) was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.
To 500 g of the obtained polyoxypropylene (Q-3) having a carbon-carbon unsaturated bond, 50 μL of a platinum divinyldisiloxane complex solution was added, and 12.6 g of dimethoxymethylsilane was slowly added dropwise with stirring. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a number average molecular weight of 27, including a terminal having two dimethoxymethylsilyl groups at one terminal. 500 polyoxypropylenes (A′-1) were obtained. The polymer (A′-1) was found to have an average of 1.6 dimethoxymethylsilyl groups at one end and an average of 4.8 per molecule.

(Synthesis Example 4)
Polymerization of propylene oxide using a polyoxypropylene triol having a number average molecular weight of about 3,000 as an initiator, and a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 26,200 having three hydroxyl groups (terminal groups) Polyoxypropylene (P-4) having a converted molecular weight of 17,400) and a molecular weight distribution of Mw / Mn = 1.34 was obtained. 1.2 mole equivalent of sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the obtained hydroxyl-terminated polyoxypropylene (P-4). After distilling off methanol by vacuum devolatilization, 1.5 mol equivalent of allyl chloride was added to the hydroxyl group of the polymer (P-4) to convert the terminal hydroxyl group into an allyl group. Thereafter, the same purification operation as in Synthesis Example 1 was performed. Thus, 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 number average molecular weight of about 27,500 having a dimethoxymethylsilyl group at the terminal. Obtained. The polymer (B-1) was found to have an average of 0.7 dimethoxymethylsilyl groups at one end and an average of 2.1 per 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 distilling off methanol by vacuum devolatilization, 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. Thereafter, the same purification operation as in Synthesis Example 1 was performed. Thus, 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 is distilled off under reduced pressure to obtain polyoxypropylene (B′-1) having a number average molecular weight of about 21100 having a dimethoxymethylsilyl group at the terminal. It was. The polymer (B′-1) was found to have an average of 0.7 dimethoxymethylsilyl groups at one end and an average of 1.5 per molecule.

(Synthesis Example 6)
Polymerization of propylene oxide with butanol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, number average molecular weight 7800 having a hydroxyl group at one end (terminal group equivalent molecular weight 5000), molecular weight distribution Mw / Mn = 1.48 Of polyoxypropylene (P-6) was obtained. Subsequently, 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-6). After distilling off the methanol by vacuum devolatilization, 2.0 mol equivalent of allyl chloride is added to the hydroxyl group of the polymer (P-6) to convert the terminal hydroxyl group to an allyl group, and unreacted chloride. Allyl was removed by vacuum devolatilization. Thereafter, the same purification operation as in Synthesis Example 1 was performed. Thus, polyoxypropylene (Q-6) having a carbon-carbon unsaturated bond at only one end was obtained. The polymer (Q-6) was found to have 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 platinum divinyldisiloxane complex (3-wt% 2-propanol solution in terms of platinum) was added, and 9.5 g of dimethoxymethylsilane was slowly added dropwise with stirring. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby a reactive silicon group-containing polyoxypropylene having a dimethoxymethylsilyl group only at one end (C— 1) was obtained. The polymer (C-1) was found to have an average of 0.8 dimethoxymethylsilyl groups only at one end.

(Examples 1 to 4 and Comparative Examples 1 to 9)
Polymers and plasticizers listed in Tables 1 and 2 [Sansosizer E-PS (manufactured by Nippon Nippon Chemical Co., Ltd .: di-2-ethylhexyl epoxyhexahydrophthalate), DINP (manufactured by J Plus Co., Ltd .: diisononyl phthalate) ], And further, 120 parts by weight of white glaze CCR (manufactured by Shiraishi Calcium Co., Ltd .: precipitated calcium carbonate), 20 parts by weight of Whiteon SB (manufactured by Shiraishi Kogyo Co., Ltd .: heavy calcium carbonate), Dispalon # 308 (Enomoto Chemical Co., Ltd. Manufactured: hydrogenated castor oil) 3 parts by weight, Tinuvin 326 (manufactured by BASF: 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol) 1 part by weight, Sanol LS770 (Ciba Specialty) Chemicals: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate) 1 part by weight, Aronix M309 ( Subsynthetic product: 1,1,1-trimethylolpropane triacrylic acid ester) 3 parts by weight, phenoxytrimethylsilane in amounts shown in Tables 1 and 2, and tris ((trimethylsiloxy) methyl) propane in Table 1 Based on the amounts shown in Table 2, 3.0 parts by weight of neostan U-28, 0.5 parts by weight of laurylamine, 6.4 parts by weight of DINP, 15 parts by weight of Whiten SB, and ASP170 (manufactured by BASF: Kaolin) 5 Using 4 parts by weight of DINP as a curing agent and 5 parts by weight of Taipei R820 (manufactured by Ishihara Sangyo Co., Ltd .: titanium oxide) as a color, mixed degassing was performed.

(Durability evaluation)
After mixing the obtained main agent, curing agent, and color, an H-shaped specimen having a joint width of 12 mm was prepared, and after curing at 23 ° C. for 7 days + 50 ° C. for 7 days, the fatigue resistance test of JIS A1439: 2016 (CR90 The test was carried out according to). That is, the specimen obtained by curing was fixed to a compression deformation ratio of 30% using a compression fixing spacer, and allowed to stand at 90 ° C. for 24 hours. For 24 hours. Thereafter, the specimen was placed in a repeated fatigue tester, the joint width was fixed at 12 mm at 23 ° C., and the joint was enlarged and reduced by ± 30% 6,000 times. The durability was determined according to the following criteria.

(Durability determination)
6: No cracks at four sealant interfaces 5: Cracks at four sealant interfaces are 1 mm or less in depth and 2 cm or less 4: Cracks at four sealant interfaces are 1 mm or less in depth and 2 to 10 cm in length
3: Cracks at four sealant interfaces are 1 mm or less in depth and 10 to 20 cm in length
2: Cracks at 4 locations of the sealant interface are 1 mm or more in depth and 10 cm or less in length 1: Cracks at 4 locations of the sealant interface are 1 mm or more in depth and 10 to 20 cm in length

According to Table 1 and Table 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, Comparative Example 1, 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, durability evaluation was performed. It turns out that it is low.
Furthermore, the comparative example 5 which does not contain a polymer (A), the comparative example 6 which does not contain a polymer (B), the polymer (A), and the comparative example 7 which does not contain a polymer (C) also have low durability evaluation. .
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 linear A-1 that is the polymer (A). However, it turns out that 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 linear A-1. I understand.

Claims (10)

  Reactive silicon group-containing polyoxyalkylene polymer (A) having two ends and having two or more reactive silicon groups, and three ends, per end A reactive silicon group-containing polyoxyalkylene polymer (B) having a number of reactive silicon groups of 0.3 to 1.0 and two terminals, and only one of them has a reactive silicon group Reactive silicon group-containing polyoxyalkylene containing no terminal, having a number of reactive silicon groups per molecule of 0.3 to 1.0 and having two or more reactive silicon groups A curable composition comprising a polymer (C) and a plasticizer (D) having an epoxy group. The terminal having two or more reactive silicon groups of the reactive silicon group-containing polyoxyalkylene polymer (A) has the general formula (1):

(In the formula, R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the two bonds that R ¹ and R ³ each have are each within the linking group. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is 1 to 10 carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms. And R ⁵ is independently a 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 is independently a hydroxyl group or a hydrolyzable group, and a is 1, 2, or 3.)
The curable composition of Claim 1 represented by these.   The terminal having two or more reactive silicon groups of the reactive silicon group-containing polyoxyalkylene polymer (A) is 0.1 to 2.0 on average 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) has the general formula (2):
-Si (R ⁶ ) _3-b (Y) _b (2)
(Wherein R ⁶ is each 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) Y is each independently a hydroxyl group or a hydrolyzable group, and b is 1, 2 or 3.)
The curable composition according to any one of claims 1 to 3, wherein   The plasticizer (D) having the epoxy group is bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate, according to any one of claims 1 to 4. Curable composition.   The reactive silicon group-containing polyoxyalkylene is 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, comprising 5 to 150 parts by weight of a polymer (C) and 2 to 100 parts by weight of a plasticizer (D) having the 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 reactive silicon group-containing polyoxyalkylene polymer. The curable composition according to any one of claims 1 to 6, which is 70/30 to 30/70 as (A) / reactive silicon group-containing polyoxyalkylene polymer (B).   Hardened | cured material obtained by hardening the curable composition of any one of Claims 1-7.   The building sealing material which consists of a curable composition of any one of Claims 1-7.   A sealing material for direct glazing, a sealing material for an SSG method, or a sealing material for a working joint of a building, comprising the curable composition according to any one of claims 1 to 7.