JP2002249538A - Curable composition - Google Patents
Curable compositionInfo
- Publication number
- JP2002249538A JP2002249538A JP2001046281A JP2001046281A JP2002249538A JP 2002249538 A JP2002249538 A JP 2002249538A JP 2001046281 A JP2001046281 A JP 2001046281A JP 2001046281 A JP2001046281 A JP 2001046281A JP 2002249538 A JP2002249538 A JP 2002249538A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silyl group
- crosslinkable silyl
- resin
- curable composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、大気中などの水分
により硬化してゴム状弾性体となる、作業性、接着性、
並びに耐熱性、耐水性などの耐久性に優れた硬化性組成
物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a workability, an adhesive property, a rubber-like elastic material which is cured by moisture in the air or the like.
And a curable composition having excellent durability such as heat resistance and water resistance.
【０００２】[0002]
【従来の技術】従来から、建築物用、土木用、自動車用
などの防水シーリング材、接着剤、塗料などに使用され
る湿気硬化型の樹脂成分として、一般に変成シリコーン
樹脂とよばれている主鎖ポリエーテルで分子内に架橋性
シリル基を含有する樹脂やポリウレタン樹脂などが、作
業性や接着性などに優れている点から、広く使用されて
いる。2. Description of the Related Art Conventionally, as a moisture-curable resin component used in waterproofing sealing materials, adhesives, paints and the like for buildings, civil engineering, automobiles, etc., a modified silicone resin is generally used. A resin having a crosslinkable silyl group in the molecule and a polyurethane resin, which is a chain polyether, is widely used because of its excellent workability and adhesiveness.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、近年、
建築物、土木、自動車などの分野においては長期に渡っ
て性能を維持する、いわゆる超長寿命化のニーズが高ま
り、これらに使用されるシーリング材、接着剤、塗料な
どに対しても、接着性及び耐熱性、耐水性、耐候性など
の耐久性のさらなる向上が求められている。変成シリコ
ーン樹脂を含有するシーリング材、接着剤、塗料などに
おいては、作業性は良いのであるが、耐候性がまだ不十
分で、耐水性や耐熱性などの耐久性に劣るという欠点を
有し、さらには変成シリコーン樹脂の合成には特殊な装
置を必要とし、製造が困難で高価であるという問題があ
る。一方、ポリウレタン樹脂においては、接着性や耐水
性に優れ、製造し易く、比較的安価であるという利点を
有するものの、耐候性が劣るという欠点を有する。ここ
において、イソシアネート基含有ポリウレタン樹脂に分
子内に活性水素と架橋性シリル基を含有する化合物を反
応させた架橋性シリル基含有ポリウレタン樹脂が知られ
ている（例えば、特公昭４６−３０７１１号公報参
照）。しかし、この樹脂は合成方法が容易であり、接着
性も優れているという特徴を有する反面、粘度が高く、
耐水性、耐熱性、耐候性などの耐久性に劣るという問題
を有している。また、ポリエーテルポリオールなどのポ
リオールにイソシアネート基と架橋性シリル基を含有す
る化合物を反応させた、架橋性シリル基とウレタン結合
を含有する樹脂も知られている（例えば、特開平０３−
４７８２５号公報参照）。しかし、この樹脂は粘度が低
いが、耐水性、耐熱性、耐候性などの耐久性に劣るとい
う問題を有している。However, in recent years,
In the fields of buildings, civil engineering, automobiles, etc., there is an increasing need for so-called ultra-long service life, which maintains performance over a long period of time, and has an adhesive property to sealing materials, adhesives, paints, etc. used for these. Further, further improvement in durability such as heat resistance, water resistance and weather resistance is required. Sealing materials containing modified silicone resin, adhesives, paints, etc., have good workability, but have insufficient weather resistance, and have the disadvantage of poor durability such as water resistance and heat resistance. Further, the synthesis of the modified silicone resin requires a special apparatus, and has a problem that it is difficult and expensive to manufacture. On the other hand, polyurethane resins have excellent adhesiveness and water resistance, are easy to manufacture, and have the advantage of being relatively inexpensive, but have the disadvantage of poor weather resistance. Here, a crosslinkable silyl group-containing polyurethane resin obtained by reacting an active hydrogen and a compound having a crosslinkable silyl group in a molecule with an isocyanate group-containing polyurethane resin is known (see, for example, Japanese Patent Publication No. 46-30711). ). However, this resin is easy to synthesize and has excellent adhesiveness, but has a high viscosity,
There is a problem that durability such as water resistance, heat resistance and weather resistance is poor. Further, a resin containing a crosslinkable silyl group and a urethane bond obtained by reacting a compound containing an isocyanate group and a crosslinkable silyl group with a polyol such as a polyether polyol is also known (see, for example, Japanese Patent Application Laid-Open No.
No. 47825). However, although this resin has a low viscosity, it has a problem that it is inferior in durability such as water resistance, heat resistance and weather resistance.
【０００４】本発明の目的は、上記従来公知技術の問題
点を解決して、製造し易く、かつ作業性の良い、大気中
などの水分により硬化して物性の優れたゴム状弾性体と
なる、接着性、耐候性、耐熱性並びに特に耐水性に優れ
た低粘度の一液湿気硬化型の硬化性組成物を提供するこ
とである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a rubber-like elastic body which is easy to manufacture, has good workability, and is hardened by moisture in the air or the like, and has excellent physical properties. Another object of the present invention is to provide a low-viscosity, one-part, moisture-curable curable composition having excellent adhesiveness, weather resistance, heat resistance and especially excellent water resistance.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明は、水酸基含有ポリオキシアルキレン系重合
体と架橋性シリル基含有イソシアネート化合物と有機モ
ノイソシアネートとを逐次或いは同時に反応させて得ら
れる架橋性シリル基含有樹脂を硬化成分として含有する
こと、を特徴とする硬化性組成物である。In order to achieve the above object, the present invention is achieved by reacting a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate sequentially or simultaneously. A curable composition comprising a crosslinkable silyl group-containing resin as a curing component.
【０００６】本発明は、水酸基含有ポリオキシアルキレ
ン系重合体と架橋性シリル基含有イソシアネート化合物
と有機モノイソシアネートとを逐次或いは同時に反応さ
せて得られる架橋性シリル基含有樹脂と、添加剤とを含
有すること、を特徴とする硬化性組成物である。The present invention comprises a crosslinkable silyl group-containing resin obtained by sequentially or simultaneously reacting a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate, and an additive. A curable composition.
【０００７】本発明は、前記添加剤が、酸化防止剤及び
／又は架橋触媒である、前記硬化性組成物である。[0007] The present invention is the curable composition, wherein the additive is an antioxidant and / or a crosslinking catalyst.
【０００８】本発明は、前記添加剤が、酸化防止剤、架
橋触媒、充填剤、カップリング剤、揺変剤、及び／又は
保存安定性改良剤である、前記硬化性組成物である。[0008] The present invention is the curable composition, wherein the additive is an antioxidant, a crosslinking catalyst, a filler, a coupling agent, a thixotropic agent, and / or a storage stability improving agent.
【０００９】[0009]
【発明の実施の形態】まず、本発明における架橋性シリ
ル基含有樹脂について説明する。本発明における架橋性
シリル基含有樹脂は、湿気（水分）と反応してシロキサ
ン結合を形成することにより架橋してゴム状硬化物とな
るシリル基を分子内に１個以上含有する樹脂であり、架
橋性シリル基含有樹脂を製造するための水酸基含有ポリ
オキシアルキレン系重合体は、アルキレンオキシドを開
環付加重合させた重合体や、開始剤にアルキレンオキシ
ドを開環付加重合させた重合体などである。開始剤とし
ては、エチレングリコール、ジエチレングリコール、プ
ロピレングリコール、ジプロピレングリコール、ネオペ
ンチルグリコール、１，４−ブタンジオール、１，６−
ヘキサンジオール、グリセリン、トリメチロールプロパ
ン、ペンタエリスリトール、シュークローズ等の低分子
アルコール類、ビスフェノールＡ等の多価フェノール
類、エチレンジアミン等の低分子ポリアミン類、ジエタ
ノールアミン等の低分子アミノアルコール類、又はこれ
らの２種以上の混合物などが挙げられる。アルキレンオ
キシドとしては、エチレンオキシド、プロピレンオキシ
ド、ブチレンオキシド、テトラヒドロフラン、又はこれ
らの２種以上の混合物などが挙げられる。すなわち、水
酸基含有ポリオキシアルキレン系重合体は、分子内に２
個以上の水酸基を含有するポリオキシアルキレン重合体
であって、具体的には、例えば、ポリオキシエチレング
リコール、ポリオキシプロピレングリコール、ポリテト
ラメチレンエーテルグリコール、ポリ（オキシエチレ
ン）−ポリ（オキシプロピレン）−グリコール、ポリ
（オキシエチレン）−ポリ（オキシブチレン）−グリコ
ールを挙げることができ、このうちポリオキシプロピレ
ングリコールが特に好ましい。また、水酸基含有ポリオ
キシアルキレン系重合体としては、上記に挙げた各種ポ
リオールと、トルエンジイソシアネート、ジフェニルメ
タンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイ
ソシアネート、イソホロンジイソシアネート等の従来公
知のポリイソシアネートとを、イソシアネート基に対し
水酸基過剰で反応させて、分子末端を水酸基とした重合
体も挙げられる。これらは単独或いは２種以上を混合し
て使用できる。本発明において、水酸基含有ポリオキシ
アルキレン系重合体は、硬化性組成物の低粘度化や硬化
物の高い伸びなどの点から、数平均分子量が５００〜４
０，０００、更に２，０００〜３０，０００、特に１
０，０００〜３０，０００のものが好ましく、また、１
分子当たり平均の水酸基の数は２〜８、特に２〜４が好
ましく、更に、総不飽和度が０．０７（ｍｅｑ／ｇ）以
下、特に０．０４（ｍｅｑ／ｇ）以下の分子量分布の狭
いものが好ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the crosslinkable silyl group-containing resin of the present invention will be described. The crosslinkable silyl group-containing resin in the present invention is a resin containing at least one silyl group in a molecule which forms a siloxane bond by reacting with moisture (moisture) to form a rubber-like cured product, Hydroxyl-containing polyoxyalkylene polymer for producing a crosslinkable silyl group-containing resin is a polymer obtained by ring-opening addition polymerization of an alkylene oxide or a polymer obtained by ring-opening addition polymerization of an alkylene oxide to an initiator. is there. Initiators include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-
Hexanediol, glycerin, trimethylolpropane, pentaerythritol, low molecular weight alcohols such as sucrose, polyhydric phenols such as bisphenol A, low molecular weight polyamines such as ethylenediamine, low molecular weight amino alcohols such as diethanolamine, or these. Examples thereof include a mixture of two or more kinds. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and a mixture of two or more thereof. That is, the hydroxyl group-containing polyoxyalkylene polymer has 2
A polyoxyalkylene polymer containing at least two hydroxyl groups, specifically, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, poly (oxyethylene) -poly (oxypropylene) -Glycol, poly (oxyethylene) -poly (oxybutylene) -glycol, of which polyoxypropylene glycol is particularly preferred. In addition, as the hydroxyl group-containing polyoxyalkylene polymer, the above-mentioned various polyols and a conventionally known polyisocyanate such as toluene diisocyanate, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, and isophorone diisocyanate are used for the isocyanate group. Polymers having a hydroxyl group at the molecular end by reacting with an excess of hydroxyl groups are also included. These can be used alone or in combination of two or more. In the present invention, the hydroxyl group-containing polyoxyalkylene polymer has a number average molecular weight of 500 to 4 from the viewpoint of lowering the viscosity of the curable composition and increasing the elongation of the cured product.
0,000, even 2,000-30,000, especially 1
It is preferably from 3,000 to 30,000.
The average number of hydroxyl groups per molecule is preferably from 2 to 8, particularly preferably from 2 to 4, and further, the total unsaturation is 0.07 (meq / g) or less, particularly 0.04 (meq / g) or less. A narrow one is preferred.
【００１０】本発明における架橋性シリル基含有樹脂を
製造するための架橋性シリル基含有イソシアネート化合
物は、分子内に１個以上のイソシアネート基と１個以上
の架橋性シリル基を少なくとも含有すればよく、架橋性
シリル基は、製造しやすく架橋しやすい次の一般式で示
されるものが好ましい。The crosslinkable silyl group-containing isocyanate compound for producing the crosslinkable silyl group-containing resin in the present invention may contain at least one or more isocyanate groups and one or more crosslinkable silyl groups in a molecule. The crosslinkable silyl group is preferably one represented by the following general formula, which is easy to produce and easily crosslinks.
【００１１】[0011]
【化１】 Embedded image
【００１２】（式中、Ｒは炭化水素基であり、炭素数１
〜２０のアルキル基、炭素数６〜２０のアリール基又は
炭素数７〜２０のアラルキル基が好ましく、メチル基が
最も好ましい。Ｘで示される反応性基はハロゲン原子、
水素原子、水酸基、アルコキシ基、アシルオキシ基、ケ
トキシメート基、アミド基、酸アミド基、メルカプト
基、アルケニルオキシ基及びアミノオキシ基より選ばれ
る基であり、Ｘが複数の場合には、Ｘは同じ基であって
も異なった基であってもよい。このうちＸはアルコキシ
基が好ましく、メトキシ基、エトキシ基又はイソプロポ
キシ基が更に好ましい。ａは０、１又は２の整数であ
り、０又は１が好ましい。）Wherein R is a hydrocarbon group and has 1 carbon atom
Preferred are an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and a methyl group is most preferred. The reactive group represented by X is a halogen atom,
A group selected from a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group and an aminooxy group, and when X is plural, X is the same group Or a different group. Among them, X is preferably an alkoxy group, more preferably a methoxy group, an ethoxy group or an isopropoxy group. a is an integer of 0, 1 or 2, and preferably 0 or 1. )
【００１３】架橋性シリル基含有イソシアネート化合物
としては、具体的には、３−イソシアネートプロピルト
リメトキシシラン、３−イソシアネートプロピルトリエ
トキシシラン、３−イソシアネートプロピルメチルジエ
トキシシラン、３−イソシアネートプロピルメチルジメ
トキシシラン、３−イソシアネートプロピルイソプロポ
キシシラン、イソシアネートトリメトキシシラン、ジイ
ソシアネートジメトキシシランなどが挙げられ、これら
は単独で或いは２種以上混合して使用できる。Examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane. And 3-isocyanatopropylisopropoxysilane, isocyanatetrimethoxysilane, diisocyanatedimethoxysilane, and the like. These can be used alone or in combination of two or more.
【００１４】本発明における架橋性シリル基含有樹脂を
製造するための有機モノイソシアネートは、分子内に１
個のイソシアネート基を少なくとも含有すればよいが、
架橋性シリル基は含有していない。すなわち、有機モノ
イソシアネートのイソシアネート基以外の有機基は湿気
（水分）硬化性の官能基を含有していない、好ましくは
疎水性の有機基である。具体的には、ｎ−ブチルモノイ
ソシアネート、ｎ−ヘキシルモノイソシアネート、ｎ−
テトラデシルモノイソシアネート、ｎ−ヘキサデシルモ
ノイソシアネート、オクタデシルモノイソシアネート、
ｎ−クロロエチルモノイソシアネートなどの脂肪族モノ
イソシアネート、クロロフェニルモノイソシアネート、
３，５−ジクロロフェニルモノイソシアネート、ｐ−フ
ルオロフェニルモノイソシアネート、２，４−ジフルオ
ロフェニルモノイソシアネート、ｏ−トリフルオロメチ
ルフェニルモノイソシアネート、ｐ−ニトロフェニルモ
ノイソシアネート、ｐ−イソプロピルフェニルモノイソ
シアネート、２，６−ジイソプロピルモノイソシアネー
ト、ｐ−トルエンスルホニルモノイソシアネート、ｐ−
ベンジルオキシフェニルモノイソシアネートなどの芳香
族モノイソシアネート、その他に２−メタクリロイルオ
キシエチルイソシアネートなどが挙げられる。このう
ち、脂肪族モノイソシアネートが耐水性向上のため好ま
しい。これらは単独でも或いは２種以上混合しても使用
できる。The organic monoisocyanate for producing the crosslinkable silyl group-containing resin according to the present invention has one molecule in the molecule.
At least one isocyanate group,
It does not contain a crosslinkable silyl group. That is, the organic group other than the isocyanate group of the organic monoisocyanate is a hydrophobic organic group that does not contain a moisture (moisture) curable functional group. Specifically, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-
Tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate,
aliphatic monoisocyanate such as n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate,
3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2,6 -Diisopropyl monoisocyanate, p-toluenesulfonyl monoisocyanate, p-
Examples thereof include aromatic monoisocyanates such as benzyloxyphenyl monoisocyanate, and 2-methacryloyloxyethyl isocyanate. Of these, aliphatic monoisocyanates are preferred for improving water resistance. These can be used alone or in combination of two or more.
【００１５】本発明における架橋性シリル基含有樹脂
は、水酸基含有ポリオキシアルキレン系重合体の水酸基
に対し架橋性シリル基含有イソシアネート化合物と有機
モノイソシアネートのそれぞれのイソシアネート基を、
逐次或いは同時に反応させて得ることができる。逐次に
反応させる場合、水酸基含有ポリオキシアルキレン系重
合体に、架橋性シリル基含有イソシアネート化合物と有
機モノイソシアネートとはいずれを先に反応させてもよ
いが、まず架橋性シリル基含有イソシアネート化合物を
反応させ、次いで有機モノイソシアネートを反応させる
のが好ましい。本発明の架橋性シリル基含有樹脂は、水
酸基含有ポリオキシアルキレン系重合体の水酸基に対し
架橋性シリル基含有イソシアネート化合物のイソシアネ
ート基を、一部水酸基を残す当量比で反応させて樹脂中
に架橋性シリル基を導入し、かつ残りの水酸基の一部或
いは全部に対し有機モノイソシアネートのイソシアネー
ト基を反応させ、水分硬化性を有しない疎水性の有機基
を導入した構造とすることにより、硬化後のモジュラス
や伸びなどのゴム弾性を自由に調節でき、かつ硬化後の
耐水性を著しく向上させた硬化性樹脂を得ることができ
たものである。なお、水酸基含有ポリオキシアルキレン
系重合体と架橋性シリル基含有イソシアネート化合物と
有機モノイソシアネートとは、イソシアネート基／水酸
基の当量比が０．１以上／１．０、更には０．５〜１．
５／１．０、特に０．７〜１．０／１．０の範囲で反応
させるのが好ましい。イソシアネート基／水酸基の当量
比が０．１／１．０を下まわると、架橋性シリル基含有
樹脂に架橋基が少なく水酸基が多く残るため硬化物の物
性が発現せず、かつ耐水性が向上しない。水酸基含有ポ
リオキシアルキレン系重合体と架橋性シリル基含有イソ
シアネート化合物と有機モノイソシアネートとを逐次反
応させる場合には、水酸基含有ポリオキシアルキレン系
重合体と架橋性シリル基含有イソシアネート化合物と
は、イソシアネート基／水酸基の当量比が０．０５〜
０．９／１．０、更には０．３〜０．９／１．０の範囲
で反応させ、次いで、この反応生成物と有機モノイソシ
アネートとは、架橋性シリル基含有イソシアネート化合
物との合計で、イソシアネート基／水酸基の当量比が
０．１以上／１．０、更には０．５〜１．５／１．０、
特に０．７〜１．０／１．０となる範囲で反応させるの
が好ましい。この反応の際には、ジブチル錫ジラウレー
ト、ジオクチル錫ジラウレート等の有機金属化合物、ト
リエチレンジアミン、トリエチルアミン、トリ−ｎ−ブ
チルアミン等の有機アミンやその塩等の公知のウレタン
化触媒を用いることができ、また、更に公知の有機溶媒
を用いることもできる。The crosslinkable silyl group-containing resin according to the present invention is obtained by adding the respective isocyanate groups of the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate to the hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer.
It can be obtained by reacting sequentially or simultaneously. When sequentially reacting, any of the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate may be reacted first with the hydroxyl group-containing polyoxyalkylene polymer, but first the crosslinkable silyl group-containing isocyanate compound is reacted. And then reacting with an organic monoisocyanate. The crosslinkable silyl group-containing resin of the present invention is obtained by reacting an isocyanate group of a crosslinkable silyl group-containing isocyanate compound with a hydroxyl group of a hydroxyl group-containing polyoxyalkylene polymer at an equivalent ratio that partially leaves a hydroxyl group, to form a crosslink in the resin. By introducing a hydrophobic silyl group and reacting an isocyanate group of an organic monoisocyanate with a part or all of the remaining hydroxyl groups to form a hydrophobic organic group having no moisture curability, It is possible to obtain a curable resin in which rubber elasticity such as modulus and elongation can be freely adjusted and water resistance after curing is remarkably improved. The hydroxyl group-containing polyoxyalkylene polymer, the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate have an isocyanate group / hydroxyl group equivalent ratio of 0.1 or more / 1.0, and more preferably 0.5 to 1.0.
The reaction is preferably performed in a range of 5 / 1.0, particularly 0.7 to 1.0 / 1.0. When the equivalent ratio of isocyanate group / hydroxyl group is less than 0.1 / 1.0, the crosslinkable silyl group-containing resin has a small number of crosslinkable groups and a large amount of hydroxyl groups, so that the physical properties of the cured product are not expressed and the water resistance is improved. do not do. When the hydroxyl group-containing polyoxyalkylene polymer, the crosslinkable silyl group-containing isocyanate compound and the organic monoisocyanate are successively reacted, the hydroxyl group-containing polyoxyalkylene polymer and the crosslinkable silyl group-containing isocyanate compound have an isocyanate group. / Equivalent ratio of hydroxyl group is 0.05 to
The reaction is carried out at a ratio of 0.9 / 1.0, more preferably 0.3 to 0.9 / 1.0, and then the reaction product and the organic monoisocyanate are combined with the crosslinkable silyl group-containing isocyanate compound. And the equivalent ratio of isocyanate group / hydroxyl group is 0.1 or more / 1.0, further 0.5 to 1.5 / 1.0,
In particular, the reaction is preferably performed in a range of 0.7 to 1.0 / 1.0. In this reaction, a known urethanization catalyst such as an organic metal compound such as dibutyltin dilaurate or dioctyltin dilaurate, an organic amine such as triethylenediamine, triethylamine, or tri-n-butylamine or a salt thereof can be used. Further, a known organic solvent can also be used.
【００１６】架橋性シリル基含有樹脂分子中に、その硬
化性や硬化後の物性等の点から、架橋性シリル基は平均
１〜５個含まれるのが好ましい。It is preferable that an average of 1 to 5 crosslinkable silyl groups is contained in the crosslinkable silyl group-containing resin molecule from the viewpoint of the curability and physical properties after curing.
【００１７】次に、本発明の硬化性組成物における添加
剤について説明する。本発明における添加剤としては、
酸化防止剤、紫外線吸収剤、架橋触媒、充填剤、カップ
リング剤、揺変剤、保存安定性改良剤（脱水剤）、着色
剤等が挙げられる。Next, additives in the curable composition of the present invention will be described. As the additive in the present invention,
Examples include antioxidants, ultraviolet absorbers, crosslinking catalysts, fillers, coupling agents, thixotropic agents, storage stability improvers (dehydrating agents), coloring agents, and the like.
【００１８】酸化防止剤、紫外線吸収剤は、硬化樹脂の
酸化や光劣化、熱劣化を防止して、耐候性だけでなく耐
熱性を更に向上させるために使用されるものである。酸
化防止剤としては具体的には、ヒンダードアミン系やヒ
ンダードフェノール系の酸化防止剤を挙げることができ
る。The antioxidant and the ultraviolet absorber are used for preventing oxidation, light deterioration and heat deterioration of the cured resin to further improve not only weather resistance but also heat resistance. Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants.
【００１９】ヒンダードアミン系酸化防止剤としては、
例えば、［デカン二酸ビス（２，２，６，６−テトラメ
チル−１（オクチルオキシ）−４−ピペリジル）エステ
ル、ビス（１，２，２，６，６−ペンタメチル−４−ピ
ペリジル）［［３，５−ビス（１，１−ジメチルエチ
ル）−４−ヒドロキシフェニル］メチル］ブチルマロネ
ート、メチル１，２，２，６，６−ペンタメチル−４−
ピペリジルセバケート、ビス（１，２，２，６，６−ペ
ンタメチル−４−ピペリジル）セバケート、１−［２−
〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキ
シフェニル）プロピオニルオキシ〕エチル］−４−〔３
−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフ
ェニル）プロピオニルオキシ〕−２，２，６，６−テト
ラメチルピペリジン、４−ベンゾイルオキシ−２，２，
６，６−テトラメチルピペリジンが挙げられる。また、
旭電化工業（株）製のアデカスタブシリーズの各化合物
も挙げられる。The hindered amine antioxidants include:
For example, [decane diacid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [ [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-
Piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2-
[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,
6,6-tetramethylpiperidine. Also,
Each compound of the ADK STAB series manufactured by Asahi Denka Kogyo Co., Ltd. is also included.
【００２０】ヒンダードフェノール系酸化防止剤として
は、例えば、ペンタエリストール−テトラキス［３−
（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェ
ニル）プロピオネート］、オクタデシル−３−（３，５
−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プ
ロピオネート］、Ｎ，Ｎ′−ヘキサン−１，６−ジイル
ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒド
ロキシフェニルプロピオアミド］、ベンゼンプロパン酸
３，５−ビス（１，１−ジメチルエチル）−４−ヒドロ
キシＣ７−Ｃ９側鎖アルキルエステル、２，４−ジメチ
ル−６−（１−メチルペンタデシル）フェノールが挙げ
られる。Examples of the hindered phenol-based antioxidant include, for example, pentaeristol-tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), benzene 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester of propanoic acid and 2,4-dimethyl-6- (1-methylpentadecyl) phenol.
【００２１】紫外線吸収剤としては、例えば、２−
（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェ
ニル）ベンゾトリアゾール等のベンゾトリアゾール系紫
外線吸収剤、２−（４，６−ジフェニル−１，３，５−
トリアジン−２−イル）−５−［（ヘキシル）オキシ］
−フェノール等のトリアジン系紫外線吸収剤、オクタベ
ンゾン等のベンゾフェノン系紫外線吸収剤、２，４−ジ
−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−
ブチル−４−ヒドロキシベンゾエート等のベンゾエート
系紫外線吸収剤が挙げられる。As the ultraviolet absorber, for example, 2-
Benzotriazole-based ultraviolet absorbers such as (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (4,6-diphenyl-1,3,5-
Triazin-2-yl) -5-[(hexyl) oxy]
A triazine-based ultraviolet absorber such as phenol; a benzophenone-based ultraviolet absorber such as octabenzone; 2,4-di-tert-butylphenyl-3,5-di-tert-
Benzoate ultraviolet absorbers such as butyl-4-hydroxybenzoate are exemplified.
【００２２】酸化防止剤、紫外線吸収剤はそれぞれ、架
橋性シリル基含有樹脂１００重量部に対して、０．１〜
１０重量部、特に０．５〜５重量部配合するのが好まし
い。The antioxidant and the ultraviolet absorber are each added in an amount of 0.1 to 100 parts by weight of the crosslinkable silyl group-containing resin.
It is preferred to add 10 parts by weight, especially 0.5 to 5 parts by weight.
【００２３】架橋触媒は、架橋性シリル基含有樹脂を架
橋（硬化）させるための触媒であり、具体的には、有機
金属化合物、アミン類等が挙げられるが、このうち架橋
速度にすぐれた有機錫化合物が好ましい。この有機錫化
合物は具体的には、スタナスオクトエート、ジブチル錫
ジオクトエート、ジブチル錫ジラウレート、ジブチル錫
ジアセテート、ジブチル錫ジアセチルアセトナート、ジ
ブチル錫オキサイド、ジブチル錫ビストリエトキシシリ
ケート、ジブチル錫ジステアレート、ジオクチル錫ジラ
ウレート、ジオクチル錫ジバーサテート等であるが、こ
のうち架橋速度が高く、毒性及び輝発性の比較的低い液
体である点から、ジブチル錫ジアセチルアセトナートが
最も好ましい。架橋触媒は、架橋速度、硬化物の物性な
どの点から、架橋性シリル基含有樹脂１００重量部に対
して、０．１〜１０重量部、特に０．３〜５重量部配合
するのが好ましい。The cross-linking catalyst is a catalyst for cross-linking (curing) the cross-linkable silyl group-containing resin, and specific examples thereof include organometallic compounds and amines. Tin compounds are preferred. The organic tin compound is specifically, stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin Examples thereof include dilaurate and dioctyltin diversate. Of these, dibutyltin diacetylacetonate is most preferable because it has a high crosslinking rate and is a liquid having relatively low toxicity and brightness. The crosslinking catalyst is preferably used in an amount of 0.1 to 10 parts by weight, particularly 0.3 to 5 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-containing resin, from the viewpoint of the crosslinking rate, the physical properties of the cured product, and the like. .
【００２４】充填剤、カップリング剤、揺変剤、保存安
定性改良剤（脱水剤）、着色剤等は、接着性向上、補
強、だれ防止等のために必要に応じて、本発明の硬化性
組成物に配合して使用することができる。Fillers, coupling agents, thixotropic agents, storage stability improvers (dehydrating agents), coloring agents, and the like may be used in the present invention to improve adhesion, strengthen, or prevent dripping. It can be used by blending it with a hydrophilic composition.
【００２５】充填剤としては、炭酸カルシウム、クレ
ー、タルク、スレート粉、マイカ、カオリン、ゼオライ
ト、珪藻土、脂肪酸処理炭酸カルシウム等が挙げられ、
粒径１〜１００μｍのものが好ましく、このうち脂肪酸
処理炭酸カルシウムが更に好ましい。Examples of the filler include calcium carbonate, clay, talc, slate powder, mica, kaolin, zeolite, diatomaceous earth, and fatty acid-treated calcium carbonate.
Particles having a particle size of 1 to 100 μm are preferred, and fatty acid-treated calcium carbonate is more preferred.
【００２６】カップリング剤としては、シラン系、アル
ミニウム系、ジルコアルミネート系などのものを挙げる
ことができ、このうちシラン系カップリング剤が接着性
に優れているので好ましい。シラン系カップリング剤と
しては、具体的には、Ｎ−（β−アミノエチル）−γ−
アミノプロピルメチルジメトキシシラン、Ｎ−（β−ア
ミノエチル）−γ−アミノプロピルトリメトキシシラ
ン、Ｎ−（β−アミノエチル）−γ−アミノプロピルメ
チルジメトキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、γ−グリシドキシプロピルメチルジエ
トキシシランなどのアルコキシシリル基を含有する分子
量５００以下、好ましくは４００以下の低分子化合物を
挙げることができる。Examples of the coupling agent include silane-based, aluminum-based, and zirco-aluminate-based coupling agents. Among them, silane-based coupling agents are preferable because of their excellent adhesiveness. As the silane coupling agent, specifically, N- (β-aminoethyl) -γ-
Aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, Examples thereof include low molecular weight compounds containing an alkoxysilyl group such as γ-glycidoxypropylmethyldiethoxysilane and having a molecular weight of 500 or less, preferably 400 or less.
【００２７】揺変剤としては、コロイダルシリカ、石綿
粉等の無機揺変剤、有機ベントナイト、変性ポリエステ
ルポリオール、脂肪酸アマイド等の有機揺変剤が挙げら
れる。Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, and organic thixotropic agents such as organic bentonite, modified polyester polyol and fatty acid amide.
【００２８】保存安定性改良剤としては、組成物中に存
在する水分と反応する、ビニルトリメトキシシランなど
の低分子の架橋性シリル基含有化合物、酸化カルシウム
などが挙げられる。Examples of the storage stability improver include low molecular weight crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, which react with water present in the composition, and calcium oxide.
【００２９】着色剤としては、酸化チタンや酸化鉄など
の無機系顔料、銅フタロシアニンなどの有機系顔料、カ
ーボンブラックなどが挙げられる。Examples of the coloring agent include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.
【００３０】充填剤、カップリング剤、揺変剤、保存安
定性改良剤、及び着色剤の合計の配合量は、架橋性シリ
ル基含有樹脂１００重量部に対して０〜５００重量部、
特に５０〜３００重量部の範囲が好ましい。The total amount of the filler, the coupling agent, the thixotropic agent, the storage stability improver, and the colorant is 0 to 500 parts by weight based on 100 parts by weight of the crosslinkable silyl group-containing resin.
Particularly, the range of 50 to 300 parts by weight is preferable.
【００３１】本発明の硬化性組成物において、前記各成
分はそれぞれ１種類又は２種以上を混合して使用するこ
とができる。In the curable composition of the present invention, each of the above components can be used alone or in combination of two or more.
【００３２】本発明の硬化性組成物において、必要に応
じて、酢酸エチルなどのエステル系溶剤、メチルエチル
ケトンなどのケトン系溶剤、ｎ−ヘキサンなどの脂肪族
系溶剤、シクロヘキサンなどの脂環族系溶剤、トルエン
やキシレンなどの芳香族系溶剤など従来公知の有機溶剤
で架橋性シリル基と反応しないものであればどのような
ものでも、単独あるいは２種以上を混合して使用するこ
とができる。その種類と使用量は硬化性組成物の用途に
応じて適宜決定すれば良い。In the curable composition of the present invention, if necessary, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, an aliphatic solvent such as n-hexane, or an alicyclic solvent such as cyclohexane. Any known organic solvent, such as an aromatic solvent such as toluene or xylene, which does not react with the crosslinkable silyl group, can be used alone or in combination of two or more. The type and amount used may be appropriately determined according to the use of the curable composition.
【００３３】[0033]
【実施例】以下、本発明について実施例等により更に詳
細に説明する。ここにおいて、硬化性組成物の例として
シーリング材組成物を示したが、これに限定されるもの
ではない。The present invention will be described below in more detail with reference to examples. Here, although the sealing material composition is shown as an example of the curable composition, the present invention is not limited to this.
【００３４】合成例１ 攪拌機、温度計、窒素シール管及び冷却器の付いた加温
反応容器に、ポリオキシプロピレングリコール（数平均
分子量１６，０００、総不飽度０．０２ｍｅｑ／ｇ、旭
硝子（株）製ＰＭＬ−４０１６）を８００ｇ（ＯＨ当
量：０．１）仕込み、攪拌しながら３−イソシアネート
プロピルトリエトキシシラン（信越化学工業（株）製Ｋ
ＢＥ−９００７、滴定による実測イソシアネート基含有
量１６．４重量％）１５．４ｇ（ＮＣＯ当量：０．０
６）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．６）とジブ
チル錫ジラウレート０．８２ｇを加えたのち、加温して
８０℃で１０分間攪拌を行い、滴定による実測イソシア
ネート基含有量０．００重量％、またＦＴＩＲによりイ
ソシアネート基のピークの消失を確認して冷却した。次
いでこの中に、オクタデシルモノイソシアネート１１．
８ｇ（ＮＣＯ当量：０．０４）（Ｒ値（ＮＣＯ当量／Ｏ
Ｈ当量）＝０．４）を加え、再度加温して８０℃で２０
分間攪拌を行い、ＦＴＩＲによりイソシアネート基のピ
ークの消失を確認し、常温まで冷却して反応を終了させ
た。得られたトリエトキシシリル基含有ポリオキシプロ
ピレン−ウレタン系樹脂は、常温で半透明の理論、滴定
による実測イソシアネート基含有量０．００重量％、粘
度１４，８００ｍＰａ・ｓ／２５℃の液体であった。こ
の樹脂をＮＵ−１と称する。Synthesis Example 1 Polyoxypropylene glycol (number-average molecular weight 16,000, total unsaturation 0.02 meq / g, Asahi Glass) was added to a heated reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and cooler. 800 g (OH equivalent: 0.1) of PML-4016) and 3-isocyanatopropyltriethoxysilane (K by Shin-Etsu Chemical Co., Ltd.) with stirring.
BE-9007, 15.4 g of isocyanate group content measured by titration (16.4% by weight) (NCO equivalent: 0.0
6) After adding (R value (NCO equivalent / OH equivalent) = 0.6) and 0.82 g of dibutyltin dilaurate, the mixture was heated and stirred at 80 ° C. for 10 minutes, and the measured isocyanate group content of 0 was determined by titration. 0.000% by weight, and the mixture was cooled after confirming disappearance of the peak of the isocyanate group by FTIR. Then, octadecyl monoisocyanate was added therein.
8 g (NCO equivalent: 0.04) (R value (NCO equivalent / O
H) = 0.4), and the mixture was heated again at 80 ° C. for 20 minutes.
The mixture was stirred for 1 minute, the disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature. The obtained triethoxysilyl group-containing polyoxypropylene-urethane resin is a liquid having a translucent theory at room temperature, an isocyanate group content of 0.00% by weight measured by titration, and a viscosity of 14,800 mPa · s / 25 ° C. Was. This resin is called NU-1.
【００３５】合成例２ 合成例１において、３−イソシアネートプロピルトリエ
トキシシラン（信越化学工業（株）製ＫＢＥ−９００
７）を２０．５ｇ（ＮＣＯ当量：０．０８）（Ｒ値（Ｎ
ＣＯ当量／ＯＨ当量）＝０．８）使用し、オクタデシル
モノイソシアネートを５．９ｇ（ＮＣＯ当量：０．０
２）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．２）使用し
た以外は同様にして、反応を行った。得られたトリエト
キシシリル基含有ポリオキシプロピレン−ウレタン系樹
脂は、常温で半透明の理論、滴定による実測イソシアネ
ート基含有量０．００重量％、粘度１６，０００ｍＰａ
・ｓ／２５℃の液体であった。この樹脂をＮＵ−２と称
する。Synthesis Example 2 In Synthesis Example 1, 3-isocyanatopropyltriethoxysilane (KBE-900 manufactured by Shin-Etsu Chemical Co., Ltd.)
7) (20.5 g (NCO equivalent: 0.08)) (R value (N
(CO equivalent / OH equivalent) = 0.8) and 5.9 g of octadecyl monoisocyanate (NCO equivalent: 0.0
2) The reaction was carried out in the same manner except that (R value (NCO equivalent / OH equivalent) = 0.2) was used. The obtained triethoxysilyl group-containing polyoxypropylene-urethane resin has a translucent theory at room temperature, a measured isocyanate group content by titration of 0.00% by weight, and a viscosity of 16,000 mPa.
-It was a liquid of s / 25 ° C. This resin is called NU-2.
【００３６】合成例３ 合成例１と同様の加温反応容器に、ポリオキシプロピレ
ングリコール（数平均分子量１６，０００、総不飽度
０．０２ｍｅｑ／ｇ、旭硝子（株）製ＰＭＬ−４０１
６）を８００ｇ（ＯＨ当量：０．１）仕込み、攪拌しな
がら３−イソシアネートプロピルトリエトキシシラン
（信越化学工業（株）製ＫＢＥ−９００７）１５．４ｇ
（ＮＣＯ当量：０．０６）（Ｒ値（ＮＣＯ当量／ＯＨ当
量）＝０．６）とジブチル錫ジラウレート０．８２ｇを
加えたのち、加温して８０℃で１０分間攪拌を行い、滴
定による実測イソシアネート基含有量０．００重量％、
またＦＴＩＲによりイソシアネート基のピークの消失を
確認し、常温まで冷却して反応を終了させた。得られた
トリエトキシシリル基含有ポリオキシプロピレン−ウレ
タン系樹脂は、常温で半透明の理論、滴定による実測イ
ソシアネート基含有量０．００重量％、粘度１４，００
０ｍＰａ・ｓ／２５℃の液体であった。この樹脂をＮＵ
−３と称する。Synthesis Example 3 A polyoxypropylene glycol (number average molecular weight: 16,000, total unsaturation: 0.02 meq / g, PML-401 manufactured by Asahi Glass Co., Ltd.) was placed in a heating reaction vessel similar to that of Synthesis Example 1.
6) 800 g (OH equivalent: 0.1) was charged and 15.4 g of 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.) while stirring.
(NCO equivalent: 0.06) (R value (NCO equivalent / OH equivalent) = 0.6) and 0.82 g of dibutyltin dilaurate were added, and the mixture was heated, stirred at 80 ° C. for 10 minutes, and titrated. Measured isocyanate group content 0.00% by weight,
The disappearance of the peak of the isocyanate group was confirmed by FTIR, and the reaction was terminated by cooling to room temperature. The obtained triethoxysilyl group-containing polyoxypropylene-urethane resin has a translucent theory at room temperature, isocyanate group content measured by titration of 0.00% by weight, and viscosity of 14,00.
The liquid was 0 mPa · s / 25 ° C. This resin is NU
-3.
【００３７】合成例４ 合成例３において、３−イソシアネートプロピルトリエ
トキシシラン（信越化学工業（株）製ＫＢＥ−９００
７）を２０．５ｇ（ＮＣＯ当量：０．０８）（Ｒ値（Ｎ
ＣＯ当量／ＯＨ当量）＝０．８）使用した以外は同様に
して、反応を行った。得られたトリエトキシシリル基含
有ポリオキシプロピレン−ウレタン系樹脂は、常温で半
透明の理論、滴定による実測イソシアネート基含有量
０．００重量％、粘度１５，８００ｍＰａ・ｓ／２５℃
の液体であった。この樹脂をＮＵ−４と称する。Synthesis Example 4 In Synthesis Example 3, 3-isocyanatopropyltriethoxysilane (KBE-900 manufactured by Shin-Etsu Chemical Co., Ltd.)
7) (20.5 g (NCO equivalent: 0.08)) (R value (N
The reaction was carried out in the same manner except that CO equivalent / OH equivalent) = 0.8) was used. The obtained triethoxysilyl group-containing polyoxypropylene-urethane resin has a translucent theory at room temperature, isocyanate group content measured by titration of 0.00% by weight, and viscosity of 15,800 mPa · s / 25 ° C.
Liquid. This resin is called NU-4.
【００３８】合成例５ 合成例３において、３−イソシアネートプロピルトリエ
トキシシラン（信越化学工業（株）製ＫＢＥ−９００
７）を２５．６ｇ（ＮＣＯ当量：０．１）（Ｒ値（ＮＣ
Ｏ当量／ＯＨ当量）＝１．０）使用した以外は同様にし
て、反応を行った。得られたトリエトキシシリル基含有
ポリオキシプロピレン−ウレタン系樹脂は、常温で半透
明の理論、滴定による実測イソシアネート基含有量０．
００重量％、粘度１８，０００ｍＰａ・ｓ／２５℃の液
体であった。この樹脂をＮＵ−５と称する。Synthesis Example 5 In Synthesis Example 3, 3-isocyanatopropyltriethoxysilane (KBE-900 manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
7) (25.6 g (NCO equivalent: 0.1)) (R value (NC
The reaction was carried out in the same manner except that (O equivalent / OH equivalent) = 1.0) was used. The obtained triethoxysilyl group-containing polyoxypropylene-urethane-based resin has a translucent theory at room temperature and a measured isocyanate group content of 0.1 by titration.
The liquid was 00% by weight and had a viscosity of 18,000 mPa · s / 25 ° C. This resin is called NU-5.
【００３９】実施例１ 加熱装置付き混練容器に、トリエトキシシリル基含有ポ
リオキシプロピレン−ウレタン系樹脂ＮＵ−１ ４００
ｇ、ヒンダードフェノール系酸化防止剤：ペンタエリス
トールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチ
ル−４−ヒドロキシフェニル）プロピオネート］（チバ
・スペシャリティ・ケミカルズ（株）製イルガノックス
１０１０）４ｇ、脂肪酸（表面）処理炭酸カルシウム
（丸尾カルシウム（株）製カルファイン２００Ｍ）３５
０ｇ、脂肪酸アマイド（花王（株）製脂肪酸アマイド
Ｓ）４．５ｇ、ビニルトリメトキシシラン（チッソ
（株）製サイラエースＳ２１０）６ｇを仕込み、内容物
が均一になるまで攪拌、混合した。その後１１０℃で１
時間滅圧脱水を行い、冷却後、ジブチル錫ジアセチルア
セトナート（日東化成（株）製ネオスタンＵ−２２０）
２ｇ及びＮ−（β−アミノエチル）−γ−アミノプロピ
ルメチルジメトキシシラン（チッソ（株）製サイラエー
スＳ３１０）２ｇを仕込み、攪拌、混合してシーリング
材組成物を調製した。EXAMPLE 1 A triethoxysilyl group-containing polyoxypropylene-urethane resin NU-1400 was placed in a kneading vessel equipped with a heating device.
g, hindered phenolic antioxidant: 4 g of pentaeristol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.) , Fatty acid (surface) treated calcium carbonate (Calfine 200M manufactured by Maruo Calcium Co., Ltd.) 35
0 g, 4.5 g of fatty acid amide (fatty acid amide S manufactured by Kao Corporation) and 6 g of vinyltrimethoxysilane (Sila Ace S210 manufactured by Chisso Corporation) were stirred and mixed until the contents became uniform. Then at 110 ° C 1
After decompression dehydration for a time, and after cooling, dibutyltin diacetylacetonate (Neostan U-220 manufactured by Nitto Kasei Co., Ltd.)
2 g and 2 g of N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane (Silaace S310 manufactured by Chisso Corporation) were charged, stirred and mixed to prepare a sealing material composition.
【００４０】実施例２、比較例１〜３ 実施例１において、トリエトキシシリル基含有ポリオキ
シプロピレン−ウレタン系樹脂ＮＵ−１の代わりにＮＵ
−２〜５それぞれを使用した以外は同様にして、シーリ
ング材組成物を調製した。Example 2, Comparative Examples 1 to 3 In Example 1, NU-1 was used in place of the triethoxysilyl group-containing polyoxypropylene-urethane resin NU-1.
A sealing material composition was prepared in the same manner except that each of -2 to 5 was used.
【００４１】〔性能試験〕前記実施例１、２と比較例１
〜３で調製したシーリング材組成物を用いて、以下の試
験を行った。 （１）押出し性 ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の
試験方法」の「４．１４試験用カートリッジによる押出
し試験」に準拠して測定した（測定温度２３℃）。 （２）スランプ ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の
試験方法」の「４．１スランプ試験」に準拠して、スラ
ンプ（縦）を測定した（測定温度２３℃）。 （３）引張接着性 ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の
試験方法」の「４．２１引張接着性試験」に準拠し、養
生後、養生後５０℃で７日間温水浸漬処理後それぞれの
試験体に付いて引張り試験した。なお、試験体は、スレ
ートをプライマー（ＯＰ２５３１、オート化学工業
（株）製）で処理しシーリング材組成物を打設、養生し
て作製した。モジュラスは、５０％引張応力（Ｍ５０）
の値が５Ｎ／ｃｍ2 以上で３０Ｎ／ｃｍ2 未満のものを
○、５Ｎ／ｃｍ2 未満又は３０Ｎ／ｃｍ2 以上のものを
×と評価した。伸びは、引張試験において、Ｅｍａｘが
４００％以上のものを○、４００％未満のものを×と評
価した。これらの結果とシーリング材組成物の組成をま
とめて表１に示す。なお、表１には、引張接着性保持率
として、養生後のＭ５０、Ｔｍａｘ、Ｅｍａｘに対する
５０℃温水浸漬７日後のそれらの値の比を併記した。[Performance Test] The above Examples 1 and 2 and Comparative Example 1
The following tests were performed using the sealing material compositions prepared in Nos. 1 to 3. (1) Extrudability: Measured in accordance with JIS A1439: 1997 "Testing method for building sealing materials""Extrusion test with 4.14 test cartridge" (measuring temperature 23 ° C). (2) Slump Slump (longitudinal) was measured (measuring temperature 23 ° C.) in accordance with “4.1 Slump test” of JIS A1439: 1997 “Testing method for building sealing material”. (3) Tensile adhesion According to "4.21 Tensile adhesion test" of JIS A1439: 1997 "Testing method of sealing materials for building", after curing, each test after immersion in hot water at 50 ° C for 7 days after curing. The body was subjected to a tensile test. The test body was prepared by treating the slate with a primer (OP2531, manufactured by Auto Chemical Industry Co., Ltd.), casting and curing the sealing material composition. Modulus is 50% tensile stress (M50)
Values were evaluated as × ones of less than 30N / cm 2 ○, less than 5N / cm 2 or 30 N / cm 2 or more at 5N / cm 2 or more. In the tensile test, elongation was evaluated as ○ when Emax was 400% or more, and evaluated as × when Emax was less than 400%. Table 1 summarizes these results and the composition of the sealing material composition. In Table 1, the ratio of the values of M50, Tmax and Emax after aging in hot water at 50 ° C. for 7 days is also shown as the tensile adhesiveness retention.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【発明の効果】以上説明した通り、本発明における架橋
性シリル基含有樹脂は粘度が低く、硬化後、モジュラス
と伸びが適当な範囲で且つ強度などが高いため、これを
含有する硬化性組成物は作業性に優れており、更に、硬
化後の接着性などが優れている。また、本発明の硬化性
組成物は、前記特性に加えて耐候性や耐熱性並びに特に
耐水性に優れているため、最近の建築物、土木、自動車
などの超長寿命化、高性能化に十分適応することができ
る。特に、本発明の硬化性組成物は、建築物外壁目地な
どの超長寿命化、高性能化シーリング材又は建築部材、
自動車部品などの接着剤に適している。As described above, the crosslinkable silyl group-containing resin according to the present invention has a low viscosity, and after curing, the modulus and elongation are in an appropriate range and the strength is high. Has excellent workability, and further has excellent adhesiveness after curing. In addition, the curable composition of the present invention is excellent in weather resistance, heat resistance, and especially water resistance in addition to the above-mentioned properties. Can be well adapted. In particular, the curable composition of the present invention has a very long life such as a building outer wall joint, a high performance sealing material or a building member,
Suitable for adhesives for automobile parts.
フロントページの続き Ｆターム(参考） 4J002 CK041 DA030 DE110 DE130 DE238 DJ008 DJ010 DJ020 DJ030 DJ038 DJ048 DJ058 EA01 EA02 EA03 EE03 EE039 EF099 EG047 EH03 EJ026 EP000 EU02 EU076 EU086 EU179 EU189 EX030 EX037 FD018 FD059 FD076 FD090 FD157 FD200 GJ00 GL00 4J034 DA01 DB03 DC50 DG03 DG04 DG06 DG08 DG09 HA01 HA04 HA07 HB16 HC03 HC16 KA01 QA03 Continued on the front page F-term (reference) 4J002 CK041 DA030 DE110 DE130 DE238 DJ008 DJ010 DJ020 DJ030 DJ038 DJ048 DJ058 EA01 EA02 EA03 EE03 EE039 EF099 EG047 EH03 EJ026 EP000 EU02 EU076 EU086 EU179 EU189 EX030 EX037 FD018 FD0100 FD018 FD0100 FD018 FD00G DC50 DG03 DG04 DG06 DG08 DG09 HA01 HA04 HA07 HB16 HC03 HC16 KA01 QA03
Claims (4)
体と架橋性シリル基含有イソシアネート化合物と有機モ
ノイソシアネートとを逐次或いは同時に反応させて得ら
れる架橋性シリル基含有樹脂を硬化成分として含有する
こと、を特徴とする硬化性組成物。Claims: 1. A curable resin containing a crosslinkable silyl group-containing resin obtained by sequentially or simultaneously reacting a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound, and an organic monoisocyanate. Characteristic curable composition.
体と架橋性シリル基含有イソシアネート化合物と有機モ
ノイソシアネートとを逐次或いは同時に反応させて得ら
れる架橋性シリル基含有樹脂と、添加剤とを含有するこ
と、を特徴とする硬化性組成物。2. A resin containing a crosslinkable silyl group-containing resin obtained by sequentially or simultaneously reacting a hydroxyl group-containing polyoxyalkylene polymer, a crosslinkable silyl group-containing isocyanate compound and an organic monoisocyanate, and an additive. A curable composition characterized by the following.
橋触媒である、請求項２に記載の硬化性組成物。3. The curable composition according to claim 2, wherein the additive is an antioxidant and / or a crosslinking catalyst.
充填剤、カップリング剤、揺変剤、及び／又は保存安定
性改良剤である、請求項２に記載の硬化性組成物。4. The method according to claim 1, wherein the additive is an antioxidant, a crosslinking catalyst,
The curable composition according to claim 2, which is a filler, a coupling agent, a thixotropic agent, and / or a storage stability improver.
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|---|---|---|---|
| JP2001046281A JP3449991B2 (en) | 2001-02-22 | 2001-02-22 | Curable composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001046281A JP3449991B2 (en) | 2001-02-22 | 2001-02-22 | Curable composition |
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| Publication Number | Publication Date |
|---|---|
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| JP3449991B2 JP3449991B2 (en) | 2003-09-22 |
Family
ID=18907936
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