JPH0539428A - Room temperature-curable composition - Google Patents
Room temperature-curable compositionInfo
- Publication number
- JPH0539428A JPH0539428A JP21927191A JP21927191A JPH0539428A JP H0539428 A JPH0539428 A JP H0539428A JP 21927191 A JP21927191 A JP 21927191A JP 21927191 A JP21927191 A JP 21927191A JP H0539428 A JPH0539428 A JP H0539428A
- Authority
- JP
- Japan
- Prior art keywords
- group
- room temperature
- curable composition
- weight
- hydrolyzable silicon
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、加水分解性珪素基含有
重合体を含む室温硬化性組成物に関する。FIELD OF THE INVENTION The present invention relates to a room temperature curable composition containing a hydrolyzable silicon group-containing polymer.
【０００２】[0002]
【従来の技術】４大気水分中に暴露するとゴム状物質へ
と硬化しうる珪素官能基含有有機重合体の配合物はシー
リング材等の用途に使用されている。2. Description of the Related Art 4 A compound of an organic polymer containing a silicon functional group, which can be cured into a rubber-like substance when exposed to atmospheric moisture, is used for a sealing material or the like.
【０００３】一方ビスマス化合物は、ウレタンの触媒と
して有効であることは既に知られており、例えば特開昭
６１−２３５４２０号公報に記載されている。しかしこ
れまで、加水分解性珪素基含有重合体の硬化触媒として
用いられた例は知られていない。On the other hand, it is already known that a bismuth compound is effective as a catalyst for urethane, and it is described in, for example, JP-A-61-235420. However, to date, no examples have been known which have been used as curing catalysts for hydrolyzable silicon group-containing polymers.
【０００４】[0004]
【発明が解決しようとする課題】従来加水分解性珪素基
含有重合体を室温で硬化させる触媒としては、錫、鉛の
有機金属触媒を使用することが一般的である。しかしこ
れらの触媒はウレタン製造に適した触媒であり、加水分
解性珪素基含有重合体の硬化触媒として使用した場合得
られる硬化物の伸びが十分でなく、新たな硬化触媒の開
発が望まれている。Conventionally, organometallic catalysts of tin and lead are generally used as a catalyst for curing a hydrolyzable silicon group-containing polymer at room temperature. However, these catalysts are suitable for urethane production, and when used as a curing catalyst for a hydrolyzable silicon group-containing polymer, the resulting cured product does not have sufficient elongation, and the development of a new curing catalyst is desired. There is.
【０００５】[0005]
【課題を解決するための手段】本発明は、前述の問題点
を解決すべくなされたものであり、重合体１分子あたり
少なくとも１つの加水分解性珪素基を含有する加水分解
性珪素基含有重合体（Ａ）、および（Ａ）１００重量部
に対しビスマス化合物（Ｂ）を１０重量部以下含有する
室温硬化性組成物を提供する。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and contains a hydrolyzable silicon group-containing polymer containing at least one hydrolyzable silicon group per polymer molecule. A room temperature curable composition containing 10 parts by weight or less of a bismuth compound (B) based on 100 parts by weight of a combination (A) and (A).
【０００６】本発明はまた、重合体１分子あたり少なく
とも１つの加水分解性珪素基を含有する加水分解性珪素
基含有重合体（Ａ）、（Ａ）１００重量部に対しビスマ
ス化合物（Ｂ）を１０重量部以下および（Ａ）１００重
量部に対し酸性物質または塩基性物質（Ｃ）を１０重量
部以下含有する室温硬化性組成物を提供する。In the present invention, the bismuth compound (B) is added to 100 parts by weight of the hydrolyzable silicon group-containing polymer (A) containing at least one hydrolyzable silicon group per molecule of the polymer (A). Provided is a room temperature curable composition containing 10 parts by weight or less and 10 parts by weight or less of an acidic substance or a basic substance (C) with respect to 100 parts by weight of (A).
【０００７】今回、検討の結果、加水分解性珪素基含有
重合体の室温における硬化触媒としてビスマス化合物が
非常に有効であることが新たに判明した。ビスマス化合
物を硬化触媒として使用した硬化性組成物は伸びが改良
され、また、安全性の問題も少ない。As a result of the investigation, it was newly found that a bismuth compound is very effective as a curing catalyst for the hydrolyzable silicon group-containing polymer at room temperature. A curable composition using a bismuth compound as a curing catalyst has improved elongation and less safety problems.
【０００８】本発明で使用するビスマス化合物としては
特開昭６１−２３５４２０号公報に記載されているよう
なビスマス塩と炭素数２〜２０個好ましくは８〜１２個
有する有機カルボン酸との反応物があげられる。具体的
にはビスマス−トリス（ネオデカノエート）、ビスマス
−トリス（２−エチルヘキソエート）等がある。The bismuth compound used in the present invention is a reaction product of a bismuth salt as described in JP-A-61-235420 and an organic carboxylic acid having 2 to 20 carbon atoms, preferably 8 to 12 carbon atoms. Can be given. Specific examples include bismuth-tris (neodecanoate) and bismuth-tris (2-ethylhexoate).
【０００９】ビスマス化合物の使用量は１０重量部以
下、好ましくは０．０１〜５重量部、特に０．０１〜３
重量部が好ましい。The amount of the bismuth compound used is 10 parts by weight or less, preferably 0.01 to 5 parts by weight, particularly 0.01 to 3 parts by weight.
Parts by weight are preferred.
【００１０】本発明ではビスマス化合物は単独で用いて
もよいが、酸性物質または塩基性物質と併用することも
できる。酸性物質または塩基性物質との併用は硬化促進
効果がある。酸性物質または塩基性物質を使用する場
合、その使用量は加水分解性珪素基含有重合体に対し１
０重量部以下、特に０．００１〜５重量部が適当であ
る。最も好ましくは０．０１〜３重量部である。In the present invention, the bismuth compound may be used alone, but may be used in combination with an acidic substance or a basic substance. The combined use with an acidic substance or a basic substance has a curing acceleration effect. When an acidic substance or basic substance is used, the amount used is 1 with respect to the hydrolyzable silicon group-containing polymer.
An amount of 0 parts by weight or less, particularly 0.001 to 5 parts by weight is suitable. Most preferably, it is 0.01 to 3 parts by weight.
【００１１】酸性物質としては有機酸または無機酸が使
用できるが特に有機カルボン酸化合物が好ましい。例え
ば酢酸、プロピオン酸、カプロン酸、カプリル酸、ステ
アリン酸、クエン酸、クロル酢酸、アクリル酸、メタク
リル酸、ｍ−ニトロ安息香酸または、ｐ−ニトロ安息香
酸など通常炭素数１〜２０の有機カルボン酸が使用でき
る。また、無機酸としてはクレイやケイ酸アルミニウム
等の固体酸が使用できる。As the acidic substance, an organic acid or an inorganic acid can be used, but an organic carboxylic acid compound is particularly preferable. For example, acetic acid, propionic acid, caproic acid, caprylic acid, stearic acid, citric acid, chloroacetic acid, acrylic acid, methacrylic acid, m-nitrobenzoic acid or p-nitrobenzoic acid, usually an organic carboxylic acid having 1 to 20 carbon atoms. Can be used. As the inorganic acid, solid acids such as clay and aluminum silicate can be used.
【００１２】塩基性物質としては特に有機アミン化合物
が好ましく、例えばジエチレントリアミン、トリエチレ
ンテトラミン、テトラエチレンペンタミン、ブチルアミ
ン、ヘキシルアミン、オクチルアミン、デシルアミン、
ラウリルアミン、ヘキサメチレンジアミン、トリエタノ
ールアミン、ジブチルアミン、ジエタノールアミン、
Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−ブタンジ
アミン、ベンジルアミン、ジメチルエチレンジアミン、
ジメチルアミノエタノール、Ｎ，Ｎ，Ｎ’，Ｎ’−テト
ラメチルエチレンジアミン、トリエチルアミン、Ｎ，Ｎ
−ジメチルアニリン、ジメチルベンジルアニリン等が使
用できる。As the basic substance, an organic amine compound is particularly preferable, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, butylamine, hexylamine, octylamine, decylamine,
Laurylamine, hexamethylenediamine, triethanolamine, dibutylamine, diethanolamine,
N, N, N ', N'-tetramethyl-1,3-butanediamine, benzylamine, dimethylethylenediamine,
Dimethylaminoethanol, N, N, N ', N'-tetramethylethylenediamine, triethylamine, N, N
-Dimethylaniline, dimethylbenzylaniline and the like can be used.
【００１３】本発明の加水分解性珪素基含有重合体とし
ては、１分子中１個以上の加水分解性珪素基を有し主鎖
が本質的にポリエーテルやポリエステルからなる様々な
重合体が使用できる。具体的には下記の文献に記載され
ている化合物が挙げられる。As the hydrolyzable silicon group-containing polymer of the present invention, various polymers having one or more hydrolyzable silicon groups in one molecule and whose main chain is essentially composed of polyether or polyester are used. it can. Specific examples include compounds described in the following documents.
【００１４】例えば、特公昭４６−１２５１４号公報、
特開平３−４７８２５号公報、特開平３−７２５２７号
公報にはポリオキシアルキレン化合物の末端に下記に述
べるような方法で加水分解性珪素基を導入した加水分解
性珪素基含有重合体が記載されている。[0014] For example, Japanese Patent Publication No. 46-12514,
JP-A-3-47825 and JP-A-3-72527 describe a hydrolyzable silicon group-containing polymer in which a hydrolyzable silicon group is introduced at the end of a polyoxyalkylene compound by the method described below. ing.
【００１５】特公昭４５−３６３１９号公報は特定の結
合基によって結合した加水分解性珪素基を末端に有する
ポリグリコールやポリエステル系の重合体が記載されて
いる。Japanese Examined Patent Publication (Kokoku) No. 45-36319 describes a polyglycol or polyester polymer having a hydrolyzable silicon group bonded at the end by a specific bonding group.
【００１６】特開平３−７９６２７号公報にはアルキレ
ンオキシド等のモノエポキシドとアリルグリシジルエー
テル等の不飽和機含有モノエポキシドとの共重合体に加
水分解性珪素基を導入したものが記載されている。Japanese Unexamined Patent Publication (Kokai) No. 3-79627 describes a copolymer of a monoepoxide such as alkylene oxide and a monoepoxide containing an unsaturated machine such as allyl glycidyl ether into which a hydrolyzable silicon group is introduced. ..
【００１７】更に、水酸基末端ポリブタジエンにプロピ
レンオキシドなどのアルキレンオキシドを付加して得ら
れる重合体に加水分解性珪素基を導入したものなどの主
鎖が液状ゴムおよび／または水添液状ゴムの残基を有し
かつポリエーテル鎖を有する重合体鎖で分子量３００〜
３００００の加水分解性珪素基含有重合体（本出願人の
出願にかかわる特願平２−１１０５８８号明細書参照）
を使用できる。Further, the main chain of a polymer obtained by adding an alkylene oxide such as propylene oxide to a hydroxyl group-terminated polybutadiene to which a hydrolyzable silicon group is introduced is a residue of a liquid rubber and / or a hydrogenated liquid rubber. And a polymer chain having a polyether chain having a molecular weight of 300 to
30,000 hydrolyzable silicon group-containing polymers (see Japanese Patent Application No. 2-110588 related to the applicant's application)
Can be used.
【００１８】加水分解性珪素基含有重合体の主鎖は本質
的にポリオキシアルキレン鎖からなるか、側鎖にポリオ
キシアルキレン鎖を有するものが好ましい。加水分解性
珪素基含有重合体はこのようなポリオキシアルキレン鎖
を有しかつ官能基を有する化合物に加水分解性珪素基を
導入して製造される。It is preferable that the main chain of the hydrolyzable silicon group-containing polymer consists essentially of a polyoxyalkylene chain or has a polyoxyalkylene chain in its side chain. The hydrolyzable silicon group-containing polymer is produced by introducing a hydrolyzable silicon group into a compound having such a polyoxyalkylene chain and having a functional group.
【００１９】ポリオキシアルキレン鎖を有する化合物の
ポリオキシアルキレン鎖は、アルカリ金属触媒、複合金
属シアン化物錯体触媒、金属ポルフィリンなど触媒の存
在下少なくとも１個の水酸基を有するポリヒドロキシ化
合物などのイニシエータにアルキレンオキシドなどのモ
ノエポキシドなどを反応させて製造される。ポリオキシ
アルキレン鎖を有する化合物の官能基数は２以上が好ま
しく、特に、２または３が好ましい。The polyoxyalkylene chain of the compound having a polyoxyalkylene chain is an alkylene in the initiator such as a polyhydroxy compound having at least one hydroxyl group in the presence of a catalyst such as an alkali metal catalyst, a complex metal cyanide complex catalyst, and a metal porphyrin. It is produced by reacting a monoepoxide such as oxide. The number of functional groups of the compound having a polyoxyalkylene chain is preferably 2 or more, and particularly preferably 2 or 3.
【００２０】特に好ましい化合物はポリオキシプロピレ
ン鎖を有し、２個または３個の水酸基を有する化合物で
ある。具体的にはポリオキシプロピレンジオール、ポリ
オキシプロピレントリオール、液状ゴムおよび／または
水添液状ゴムのプロピレンオキシド付加体等である。A particularly preferred compound is a compound having a polyoxypropylene chain and having two or three hydroxyl groups. Specific examples thereof include polyoxypropylene diol, polyoxypropylene triol, propylene oxide adduct of liquid rubber and / or hydrogenated liquid rubber, and the like.
【００２１】また、下記（１）の方法に用いる場合、ア
リル末端ポリオキシプロピレンモノオールなどのオレフ
ィン末端のポリオキシアルキレン化合物も使用できる。When used in the method (1) below, an olefin-terminated polyoxyalkylene compound such as an allyl-terminated polyoxypropylene monool can also be used.
【００２２】上記ポリオキシアルキレン鎖を有する化合
物に導入される加水分解性珪素基としては、一般式
（ａ）で表されるシリル基がよい。 −ＳｉＸa Ｒ3-a ・・・（ａ）The hydrolyzable silicon group introduced into the compound having a polyoxyalkylene chain is preferably a silyl group represented by the general formula (a). -SiX a R 3-a (a)
【００２３】式中Ｒは１価の炭化水素基あるいはハロゲ
ン化炭化水素基であり、炭素数８以下、好ましくは６以
下のアルキル基やフルオロアルキル基である。特に好ま
しくは、メチル基やエチル基などの低級アルキル基であ
る。In the formula, R is a monovalent hydrocarbon group or a halogenated hydrocarbon group, and is an alkyl group or fluoroalkyl group having 8 or less carbon atoms, preferably 6 or less carbon atoms. Particularly preferred is a lower alkyl group such as a methyl group or an ethyl group.
【００２４】Ｘは加水分解性基であり、たとえばハロゲ
ン原子、アルコキシ基、アシルオキシ基、アミド基、ア
ミノ基、アミノオキシ基、ケトキシメート基などがあ
る。これらのうち炭素原子を有する加水分解性基の炭素
数は６以下が好ましく、特に４以下が好ましい。好まし
い加水分解性基は炭素数４以下の低級アルコキシ基、特
にメトキシ基やエトキシ基である。X is a hydrolyzable group, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amido group, an amino group, an aminooxy group and a ketoximate group. Of these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. A preferred hydrolyzable group is a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group or an ethoxy group.
【００２５】ａは１、２または３であり、特に２または
３であることが好ましい。It is preferable that a is 1, 2 or 3, and particularly 2 or 3.
【００２６】一般式（ａ）で示されるシリル基は全末端
基中で平均して５０％以上、好ましくは７０％以上含有
することが好ましい。The silyl group represented by the general formula (a) is contained in an average of 50% or more, preferably 70% or more in all the terminal groups.
【００２７】一般式（ａ）で示されるシリル基のポリオ
キシアルキレン鎖を有する化合物への導入の方法は特に
は限定されないが、例えば以下の方法で導入することが
できる。The method of introducing the silyl group represented by the general formula (a) into the compound having a polyoxyalkylene chain is not particularly limited, but it can be introduced, for example, by the following method.
【００２８】（１）ポリオキシアルキレン鎖を有する化
合物の末端にオレフィン基を導入したものと、一般式
（ｂ）で表されるヒドロシリル化合物を反応させる方
法。(1) A method of reacting a compound having a polyoxyalkylene chain with an olefin group introduced at the terminal and a hydrosilyl compound represented by the general formula (b).
【００２９】ＨＳｉＸa Ｒ3-a ・・・（ｂ） （式中Ｒ、Ｘ、ａは前記に同じ）HSiX a R 3-a (b) (wherein R, X and a are the same as above)
【００３０】ここでオレフィン基を導入する方法として
は、不飽和基および官能基を有する化合物をポリオキシ
アルキレンを有する化合物の末端水酸基に反応させて、
エーテル結合、エステル結合、ウレタン結合、カーボネ
ート結合などにより結合させる方法、あるいはアルキレ
ンオキシドを重合する際に、アリルグリシジルエーテル
などのオレフィン基含有エポキシ化合物を添加して共重
合させることにより側鎖にオレフィン基を導入する方法
などが挙げられる。As a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a compound having polyoxyalkylene,
A method of bonding by an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like, or when polymerizing an alkylene oxide, an olefin group-containing epoxy compound such as allyl glycidyl ether is added and copolymerized to form an olefin group in a side chain. And the like.
【００３１】（２）ポリオキシアルキレンを有する化合
物の末端に一般式（ｃ）で表される化合物を反応させる
方法。(2) A method of reacting a compound represented by the general formula (c) with a terminal of a compound having polyoxyalkylene.
【００３２】 Ｒ3-a −ＳｉＸa −Ｒ1 ＮＣＯ・・・（ｃ） （式中Ｒ、Ｘ、ａは前記に同じ。Ｒ1 は炭素数１〜１７
の２価炭化水素基。）R 3-a -SiX a -R 1 NCO ... (c) (In the formula, R, X and a are the same as above. R 1 is a carbon number of 1 to 17)
A divalent hydrocarbon group. )
【００３３】（３）ポリオキシアルキレンを有する化合
物の末端にトリレンジイソシアネートなどのポリイソシ
アネート化合物を反応させてイソシアネート基末端とし
た後、該イソシアネート基に一般式（ｄ）で表される珪
素化合物のＷ基を反応させる方法。(3) After a polyisocyanate compound such as tolylene diisocyanate is reacted with the terminal of the compound having polyoxyalkylene to form an isocyanate group terminal, the isocyanate group is converted into a silicon compound represented by the general formula (d). A method of reacting a W group.
【００３４】Ｒ3-a −ＳｉＸa −Ｒ1 Ｗ・・・（ｄ） （式中Ｒ、Ｒ1 、Ｘ、ａは前記に同じ。Ｗは水酸基、カ
ルボキシル基、メルカプト基およびアミノ基（１級また
は２級）から選ばれた活性水素含有基。）R 3-a -SiX a -R 1 W (d) (wherein R, R 1 , X and a are the same as above. W is a hydroxyl group, a carboxyl group, a mercapto group and an amino group (1 Group containing active hydrogen selected from primary or secondary).
【００３５】（４）ポリオキシアルキレンを有する化合
物の末端にオレフィン基を導入し、そのオレフィン基
と、Ｗがメルカプト基である一般式（ｄ）で表される珪
素化合物のメルカプト基を反応させる方法。(4) A method of introducing an olefin group into the terminal of a compound having polyoxyalkylene and reacting the olefin group with the mercapto group of the silicon compound represented by the general formula (d) in which W is a mercapto group. ..
【００３６】本発明における加水分解性珪素基含有重合
体は水分と接触すると架橋反応により３次元化して硬化
する。When the hydrolyzable silicon group-containing polymer of the present invention is brought into contact with water, the polymer is three-dimensionally cured by a crosslinking reaction.
【００３７】本発明における加水分解性珪素基含有重合
体の分子量は２０００〜５００００、特に６０００〜５
００００が好ましく、特に、１６０００〜３００００が
好ましい。The molecular weight of the hydrolyzable silicon group-containing polymer in the present invention is 2000 to 50000, particularly 6000 to 5
0000 is preferable, and 16000 to 30,000 is particularly preferable.
【００３８】本発明の組成物は更に種々の充填剤、添加
剤等を含むことができる。充填剤としては炭酸カルシウ
ム、カオリン、タルク、酸化チタン、ケイ酸アルミニウ
ムあるいはカーボンブラック等一般的なものが挙げられ
るが、硬化を速めるためにはカオリン、ケイ酸アルミニ
ウム等の酸性系充填剤が特に好ましい。The composition of the present invention may further contain various fillers, additives and the like. Examples of the filler include common ones such as calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate or carbon black, but in order to accelerate the curing, acidic fillers such as kaolin and aluminum silicate are particularly preferable. ..
【００３９】また、その使用量は加水分解性珪素基含有
重合体１００重量部に対して０〜３００重量部の範囲が
好ましい。The amount used is preferably in the range of 0 to 300 parts by weight with respect to 100 parts by weight of the hydrolyzable silicon group-containing polymer.
【００４０】可塑剤としてはＤＯＰ（ジオクチルフタレ
ート）、ＢＢＰ（ブチルベンジルフタレート）、塩素化
パラフィン、エポキシ化大豆油その他の通常のものが加
水分解性珪素基含有重合体１００重量部に対して０〜２
００重量部の範囲で使用できる。As the plasticizer, DOP (dioctyl phthalate), BBP (butyl benzyl phthalate), chlorinated paraffin, epoxidized soybean oil and other usual ones are used in an amount of 0 to 100 parts by weight of the hydrolyzable silicon group-containing polymer. Two
It can be used in the range of 00 parts by weight.
【００４１】タレ防止剤は水添ヒマシ油、無水ケイ酸ま
たは有機ベントナイト等が適当である。老化防止剤は紫
外線吸収剤、ラジカル連鎖禁止剤、または過酸化物分解
剤等に分類される各種のものを単独もしくは併用して用
いることができる。As the anti-sagging agent, hydrogenated castor oil, silicic acid anhydride, organic bentonite and the like are suitable. As the antiaging agent, various kinds classified into ultraviolet absorbers, radical chain inhibitors, peroxide decomposers and the like can be used alone or in combination.
【００４２】本発明の室温硬化性組成物は例えば建築用
シーリング材として用いる場合、１成分型あるいは２成
分型どちらの型にも応用できる。１成分型にする場合
は、該組成物を無水状態でニーダー等で調整し、水分を
遮断できる容器に詰めて製造する。また、２成分型の場
合には、硬化を促進する成分とそれ以外の成分を２つに
分離して製造する。The room-temperature curable composition of the present invention can be applied to either a one-component type or a two-component type when used as a building sealing material, for example. In the case of a one-component type, the composition is prepared in an anhydrous state by a kneader or the like and packed in a container capable of blocking moisture. In the case of a two-component type, a component that promotes curing and a component other than that are separated into two parts for production.
【００４３】[0043]
【実施例】以下に具体的に製造例、実施例および比較例
を挙げて、本発明を説明するが本発明はこれらに限定さ
れるものではない。EXAMPLES The present invention will be described below with reference to specific production examples, examples and comparative examples, but the present invention is not limited thereto.
【００４４】［製造例］ （重合体Ａ）特開平３−７２５２７号公報に記載の方法
で、ジプロピレングリコールにプロピレンオキシドを付
加させた分子量１７０００の線状のポリオキシプロピレ
ンポリオールの末端に−ＳｉＣＨ3 ( ＯＣＨ3 )2基を導
入した有機重合体。[Production Example] (Polymer A) A linear polyoxypropylene polyol having a molecular weight of 17,000 obtained by adding propylene oxide to dipropylene glycol by the method described in JP-A-3-72527 has -SiCH at the end. An organic polymer having a 3 (OCH 3 ) 2 group introduced.
【００４５】（重合体Ｂ）特開平３−７２５２７号公報
に記載の方法で、グリセリンにプロピレンオキシドを付
加させた分子量２２０００の線状のポリオキシプロピレ
ンポリオールの末端に−ＳｉＣＨ3 ( ＯＣＨ3 )2基を導
入した有機重合体。(Polymer B) According to the method described in JP-A-3-72527, a linear polyoxypropylene polyol having a molecular weight of 22000 obtained by adding propylene oxide to glycerin has -SiCH 3 (OCH 3 ) 2 at the end. A group-introduced organic polymer.
【００４６】（重合体Ｃ）特開平３−４７８２５号公報
に記載の方法で、ジプロピレングリコールにプロピレン
オキシドを付加させた分子量１００００の線状のポリオ
キシプロピレンポリオールに−ＳｉＣＨ3 ( ＯＣＨ3)2
基を導入した有機重合体。(Polymer C) A linear polyoxypropylene polyol having a molecular weight of 10,000 and obtained by adding propylene oxide to dipropylene glycol by the method described in JP-A-3-47825 has --SiCH 3 (OCH 3 ) 2
A group-introduced organic polymer.
【００４７】（重合体Ｄ）特開平２−１１０５８８号公
報に記載の方法で、水添ポリイソプレン系ポリオール
（出光石油化学製エポール；分子量２４００、官能基数
２．２）にプロピレンオキシドを付加させた分子量１０
０００の変成オキシプロピレン化合物の末端に−ＳｉＣ
Ｈ3 ( ＯＣＨ3 )2基を導入した有機重合体。(Polymer D) Propylene oxide was added to hydrogenated polyisoprene-based polyol (Epol manufactured by Idemitsu Petrochemical; molecular weight 2400, number of functional groups 2.2) by the method described in JP-A-2-110588. Molecular weight 10
-SiC at the end of 000 modified oxypropylene compounds
An organic polymer having H 3 (OCH 3 ) 2 groups introduced.
【００４８】以下に上記重合体Ａ〜Ｄを使用して調製し
た硬化性組成物の例を示す。なお、例１〜７は実施例、
例８は比較例を示す。Examples of curable compositions prepared by using the above polymers A to D are shown below. Examples 1 to 7 are examples,
Example 8 shows a comparative example.
【００４９】［例１］表１に示す重合体各１００重量部
に対し炭酸カルシウム１４０重量部、ＤＯＰ３０重量
部、酸化チタン２０重量部、水添ヒマシ油６重量部、老
化防止剤１重量部を実質的に水分の存在しない系で混練
した後、表１に示す硬化触媒を１重量部添加して均一に
混練し硬化性組成物を得た。[Example 1] 140 parts by weight of calcium carbonate, 30 parts by weight of DOP, 20 parts by weight of titanium oxide, 6 parts by weight of hydrogenated castor oil, and 1 part by weight of antioxidant were added to 100 parts by weight of each polymer shown in Table 1. After kneading in a system substantially free of water, 1 part by weight of the curing catalyst shown in Table 1 was added and uniformly kneaded to obtain a curable composition.
【００５０】［例２〜８］表１に示す酸性物質または塩
基性物質０．３重量部を硬化触媒とともに添加すること
以外は例１と同様の操作を行って硬化性組成物を得た。Examples 2 to 8 A curable composition was obtained in the same manner as in Example 1 except that 0.3 part by weight of the acidic substance or basic substance shown in Table 1 was added together with the curing catalyst.
【００５１】例１〜８で得た組成物を用い、ＪＩＳ−５
７５８に則してＨ型試験片を作製し２３℃、６０％湿度
雰囲気下で１４日間養生すると、何れの場合も内部まで
完全に硬化したゴム状弾性体が得られた。Using the compositions obtained in Examples 1 to 8, JIS-5
When an H-shaped test piece was prepared according to 758 and aged at 23 ° C. in a 60% humidity atmosphere for 14 days, a rubber-like elastic body whose inside was completely cured was obtained in each case.
【００５２】これらについて、５０ｍｍ／ｍｉｎの速度
で引っ張り試験を行った結果を表１に示す。Table 1 shows the results of tensile tests conducted on these materials at a speed of 50 mm / min.
【００５３】さらにこれらの硬化物を５０℃、３０％圧
縮の状態で２４時間セットし、続いてセットを解除して
復元率を測定した結果を併せて表１に示す。Further, these cured products were set at 50 ° C. and 30% compression for 24 hours, then released from the set and the recovery rate was measured.
【００５４】なお例１〜８で用いた硬化触媒、酸性物質
及び塩基性物質は次のとおり。 （硬化触媒） 触媒化合物Ｅ：ビスマス−トリス（エチルヘキサノエー
ト） 触媒化合物Ｆ：ビスマス−トリス（ネオデカノエート） 触媒化合物Ｇ：オクチル酸スズThe curing catalyst, acidic substance and basic substance used in Examples 1 to 8 are as follows. (Curing catalyst) Catalyst compound E: Bismuth-tris (ethylhexanoate) Catalyst compound F: Bismuth-tris (neodecanoate) Catalyst compound G: Tin octylate
【００５５】（酸性物質または塩基性物質） 酸性物質：カプリル酸 塩基性物質：ラウリルアミン(Acidic substance or basic substance) Acidic substance: caprylic acid Basic substance: laurylamine
【００５６】[0056]
【表１】 [Table 1]
【００５７】[0057]
【発明の効果】本発明により優れた物性を有する硬化性
組成物が得られる。特に従来触媒としてスズ化合物を使
用するものに比較して伸びが改良される。According to the present invention, a curable composition having excellent physical properties can be obtained. In particular, the elongation is improved as compared with a conventional catalyst using a tin compound.
Claims (8)
分解性珪素基を含有する加水分解性珪素基含有重合体
（Ａ）、および（Ａ）１００重量部に対しビスマス化合
物（Ｂ）を１０重量部以下含有する室温硬化性組成物。1. A hydrolyzable silicon group-containing polymer (A) containing at least one hydrolyzable silicon group per polymer molecule, and 10 parts by weight of a bismuth compound (B) per 100 parts by weight of (A). Room temperature curable composition containing not more than 1 part.
分解性珪素基を含有する加水分解性珪素基含有重合体
（Ａ）、（Ａ）１００重量部に対しビスマス化合物
（Ｂ）を１０重量部以下および（Ａ）１００重量部に対
し酸性物質または塩基性物質（Ｃ）を１０重量部以下含
有する室温硬化性組成物。2. A hydrolyzable silicon group-containing polymer (A) containing at least one hydrolyzable silicon group per molecule of the polymer (A), and 10 parts by weight of the bismuth compound (B) per 100 parts by weight of the polymer (A). A room temperature curable composition containing 10 parts by weight or less of the acidic substance or basic substance (C) per 100 parts by weight of the following or (A).
珪素官能基である、請求項１または請求項２の室温硬化
性組成物。 −ＳｉＸa Ｒ3-a （式中、Ｒは１価の炭化水素基あるいはハロゲン化炭化
水素基、Ｘは加水分解性基、ａは１、２または３の整
数）3. The room temperature curable composition according to claim 1, wherein the hydrolyzable silicon group is a silicon functional group represented by the following general formula. —SiX a R 3-a (wherein R is a monovalent hydrocarbon group or a halogenated hydrocarbon group, X is a hydrolyzable group, and a is an integer of 1, 2 or 3)
００〜５００００である、請求項１または請求項２の室
温硬化性組成物。4. The hydrolyzable silicon group-containing polymer has a molecular weight of 20.
The room temperature curable composition according to claim 1 or claim 2, which is from 00 to 50,000.
酸塩である、請求項１または請求項２の室温硬化性組成
物。5. The room temperature curable composition according to claim 1, wherein the bismuth compound is an organic carboxylic acid salt of bismuth.
−トリス（２−エチルヘキソエート）、またはビスマス
−トリス（ネオデカノエート）である請求項５の室温硬
化性組成物。6. The room temperature curable composition according to claim 5, wherein the organic carboxylic acid salt of bismuth is bismuth-tris (2-ethylhexoate) or bismuth-tris (neodecanoate).
項２の室温硬化性組成物。7. The room temperature curable composition according to claim 2, wherein the acidic substance is an organic carboxylic acid.
２の室温硬化性組成物。8. The room temperature curable composition according to claim 2, wherein the basic substance is an organic amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3219271A JP2993778B2 (en) | 1991-08-06 | 1991-08-06 | Room temperature curable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3219271A JP2993778B2 (en) | 1991-08-06 | 1991-08-06 | Room temperature curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0539428A true JPH0539428A (en) | 1993-02-19 |
| JP2993778B2 JP2993778B2 (en) | 1999-12-27 |
Family
ID=16732912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3219271A Expired - Lifetime JP2993778B2 (en) | 1991-08-06 | 1991-08-06 | Room temperature curable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2993778B2 (en) |
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| WO2004031299A1 (en) * | 2002-10-02 | 2004-04-15 | Kaneka Corporation | One-part curable composition |
| WO2005019345A1 (en) * | 2003-08-25 | 2005-03-03 | Kaneka Corporation | Curing composition with improved heat resistance |
| JP2005320447A (en) * | 2004-05-10 | 2005-11-17 | Sanyo Chem Ind Ltd | Curable composition |
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1991
- 1991-08-06 JP JP3219271A patent/JP2993778B2/en not_active Expired - Lifetime
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