JPH07268051A - Thermally curable urethane composition - Google Patents
Thermally curable urethane compositionInfo
- Publication number
- JPH07268051A JPH07268051A JP6062496A JP6249694A JPH07268051A JP H07268051 A JPH07268051 A JP H07268051A JP 6062496 A JP6062496 A JP 6062496A JP 6249694 A JP6249694 A JP 6249694A JP H07268051 A JPH07268051 A JP H07268051A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curable urethane
- urethane composition
- heat
- solid amine
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は加熱硬化性ウレタン組成
物、更に詳しくは、アミン分散型の加熱硬化性ウレタン
組成物に２官能以上のエポキシ樹脂を配合したことから
成り、接着剤、シーリング材、コーティング材として有
用で、該エポキシ樹脂の配合により、弾性かつ強靭な物
性を付与せしめ圧縮永久歪み等を改善した、特に陶管用
ジョイント材料の品質規格に適合しうる一液型無溶剤の
加熱硬化性ウレタン組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-curable urethane composition, more specifically, an amine-dispersed heat-curable urethane composition containing a bifunctional or higher functional epoxy resin. It is useful as a coating material, and by mixing the epoxy resin, it imparts elastic and tough physical properties to improve the compression set, etc., and is a one-component solventless heat-curing type that can meet the quality standards of joint materials for ceramic pipes. -Related urethane composition.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】従来よ
り、いわゆるイソシアネート成分にポリアミン化合物を
分散せしめたアミン分散型の加熱硬化性組成物として、
たとえば、ポリオール成分に過剰量のポリイソシアネー
ト化合物を反応させて得られる末端活性イソシアネート
基含有ウレタンプレポリマーに、固形アミンと流動パラ
フィンの分散液を４０℃以下で混合して成る、接着剤や
シーリング材に適用しうる、加熱硬化性ウレタン組成物
が知られている（特開平５−３２９４８号公報参照）。
この公知組成物は、固形アミンの融点＋２０℃（たとえ
ば８０℃）の温度で硬化を起すことから、低温硬化性に
優れるが、硬化物性として特に圧縮永久歪みに欠け、産
業上における実用レベル（たとえば陶管用ジョイント材
料の品質規格ＪＩＳ−Ｒ−１２０１）に達していなかっ
た。2. Description of the Related Art Conventionally, as a heat-curable composition of amine dispersion type in which a polyamine compound is dispersed in a so-called isocyanate component,
For example, an adhesive or sealing material prepared by mixing a dispersion liquid of solid amine and liquid paraffin at 40 ° C. or lower with a urethane prepolymer containing an end-active isocyanate group obtained by reacting a polyol component with an excess amount of a polyisocyanate compound. There is known a heat-curable urethane composition applicable to (see JP-A-5-32948).
This known composition is excellent in low-temperature curability because it cures at a temperature of the melting point of solid amine + 20 ° C. (for example, 80 ° C.), but it lacks particularly compression set as a cured physical property and is industrially practical (for example, It did not reach the quality standard of the joint material for pottery tubes, JIS-R-1201).
【０００３】[0003]
【課題を解決するための手段】そこで、本発明者らは、
かかる圧縮永久歪みを改善すべき鋭意研究を進めたとこ
ろ、上記アミン分散型の公知組成物をベース成分とし、
これに２官能以上のエポキシ樹脂を配合すれば、イソシ
アネート成分と固形アミンの反応に加えて、該エポキシ
樹脂と固形アミンの反応が起こり、この三次元化反応に
基づき網状構造を採ることから、弾性かつ強靭な物性を
発現させることができ、しかもイソシアネート成分とし
て末端活性イソシアネート基含有ウレタンプレポリマー
に代えてまたは併用してポリイソシアネート化合物その
ものを使用しうることを見出し、本発明を完成させるに
至った。Therefore, the present inventors have
As a result of intensive research to improve such compression set, the known composition of the amine dispersion type was used as a base component,
If a bifunctional or higher functional epoxy resin is blended with this, in addition to the reaction between the isocyanate component and the solid amine, the reaction between the epoxy resin and the solid amine occurs, and a network structure is formed based on this three-dimensional reaction, which results in elasticity. It was found that the polyisocyanate compound itself can be used as an isocyanate component instead of or in combination with the urethane prepolymer containing an end-active isocyanate group, and has completed the present invention. .
【０００４】すなわち、本発明は、（Ａ）ポリイソシア
ネート化合物と、ポリオール成分に過剰量のポリイソシ
アネート化合物を反応させて得られる末端活性イソシア
ネート基含有ウレタンプレポリマーのそれぞれ単独また
はそれらの混合物；および（Ｂ）固形アミンと流動パラ
フィンの分散液から成るベース成分に、２官能以上のエ
ポキシ樹脂を配合したことを特徴とする加熱硬化性ウレ
タン組成物を提供するものである。That is, the present invention relates to (A) a polyisocyanate compound and a urethane prepolymer having a terminal active isocyanate group obtained by reacting an excess amount of a polyisocyanate compound with a polyol component, respectively, or a mixture thereof; and ( B) A heat-curable urethane composition comprising a base component composed of a dispersion liquid of solid amine and liquid paraffin, and a bifunctional or higher functional epoxy resin blended therein.
【０００５】本発明における上記ポリイソシアネート化
合物としては、芳香族、脂肪族または脂環族に属する任
意のものが使用されてよく、たとえばトリレンジイソシ
アネート（ＴＤＩ）、４，４′−ジフェニルメタンジイ
ソシアネート、３，３′−ジメチル−４，４′−ビフェ
ニレンジイソシアネート、１，４−フェニレンジイソシ
アネート、キシリレンジイソシアネート、テトラメチル
キシリレンジイソシアネート、ナフチレンジイソシアネ
ート、ジシクロヘキシルメタン−４，４′−ジイソシア
ネート、粗製ＴＤＩ、ポリメチレン・ポリフェニルイソ
シアネート、イソホロンジイソシアネート、ヘキサメチ
レンジイソシアネート、水素化キシリレンジイソシアネ
ート、これらのイソシアヌレート化物、カルボジイミド
化物、ビューレット化物等が挙げられ、これらの１種ま
たは２種以上の混合物を使用に供してよい。特に芳香族
ポリイソシアネート化合物が好ましい。As the above-mentioned polyisocyanate compound in the present invention, any one belonging to aromatic, aliphatic or alicyclic may be used, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate, 3 , 3'-Dimethyl-4,4'-biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, polymethylene Polyphenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, their isocyanurates, carbodiimides, bures Products and the like, may be subjected to one kind of them or a mixture of two or more in use. Aromatic polyisocyanate compounds are particularly preferable.
【０００６】本発明における上記末端活性イソシアネー
ト基（ＮＣＯ）含有ウレタンプレポリマー（以下、末端
ＮＣＯプレポリマーと称す）は、通常のポリオール成分
に過剰量のポリイソシアネート化合物をたとえばＯＨ／
ＮＣＯの当量比が１／１.２〜３.５となるように反応さ
せることにより製造することができる。反応は、要すれ
ば適当な反応溶媒（たとえば酢酸エチル、トルエン、キ
シレン）および反応触媒（たとえばジブチル錫ジラウレ
ート等の有機錫系触媒、オクチル酸ビスマス等のビスマ
ス系触媒、１，４−ジアザ〔２.２.２〕ビシクロオクタ
ン等の三級アミン系触媒）の存在下、通常常温乃至６０
〜９０℃で１〜７時間の条件で行うことができる。得ら
れる末端ＮＣＯ含有プレポリマーは通常、末端ＮＣＯ含
有量０.５〜５％（重量％、以下同様）、粘度５０００
〜５０００００cps/２０℃に設定されておればよい。The above-mentioned urethane prepolymer containing a terminal active isocyanate group (NCO) in the present invention (hereinafter referred to as a terminal NCO prepolymer) contains an excessive amount of polyisocyanate compound in an ordinary polyol component, for example, OH /.
It can be produced by reacting so that the equivalent ratio of NCO is 1 / 1.2-3.5. The reaction is carried out if necessary with a suitable reaction solvent (eg ethyl acetate, toluene, xylene) and a reaction catalyst (eg dibutyltin dilaurate or other organotin catalyst, bismuth octylate or other bismuth catalyst, 1,4-diaza [2] [2.2.2] In the presence of a tertiary amine-based catalyst such as bicyclooctane, usually at room temperature to 60.
It can be carried out under the conditions of ~ 90 ° C for 1 to 7 hours. The terminal NCO-containing prepolymer obtained usually has a terminal NCO content of 0.5 to 5% (% by weight, hereinafter the same) and a viscosity of 5000.
It suffices if it is set to -500000 cps / 20 ° C.
【０００７】なお、上記ポリオール成分としては、たと
えばエチレングリコール、プロピレングリコール、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、ソルビトール、ショ糖などの多価アルコールにプロ
ピレンオキサイドまたはプロピレンオキサイドとエチレ
ンオキサイドなどのアルキレンオキサイドとを付加重合
したポリエーテルポリオール類；エチレングリコール、
プロピレングリコールおよびこれらのオリゴグリコール
類；ブチレングリコール、ヘキシレングリコール、ポリ
テトラメチレンエーテルグリコール類；ポリカプロラク
トンポリオール類；ポリエチレンアジペートのようなポ
リエステルポリオール類；ポリブタジエンポリオール
類；ヒマシ油のようなヒドロキシル基を有する高級脂肪
酸エステル類；ポリエーテルポリオール類またはポリエ
ステルポリオール類にビニルモノマーをグラフト化した
ポリマーポリオール類等が挙げられる。Examples of the polyol component include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and sucrose, and propylene oxide or propylene oxide and alkylene oxide such as ethylene oxide. Addition-polymerized polyether polyols; ethylene glycol,
Propylene glycol and these oligoglycols; butylene glycol, hexylene glycol, polytetramethylene ether glycols; polycaprolactone polyols; polyester polyols such as polyethylene adipate; polybutadiene polyols; having hydroxyl groups such as castor oil Higher fatty acid esters; polymer polyols obtained by grafting vinyl monomers onto polyether polyols or polyester polyols, and the like.
【０００８】本発明においてイソシアネート成分である
成分（Ａ）として、上述のポリイソシアネート化合物そ
のもの単独、もしくは末端ＮＣＯ含有プレポリマー単独
またはこれらを併用混合して使用する。In the present invention, as the component (A) which is an isocyanate component, the above-mentioned polyisocyanate compound itself, the prepolymer containing terminal NCO or a mixture thereof is used.
【０００９】本発明における上記固形アミンとしては、
通常融点５０℃以上の芳香族、脂肪族または脂環族に属
する任意のものが使用されてよく、たとえば４，４′−
ジアミノジフェニルメタン、２，４′−ジアミノジフェ
ニルメタン、３，３′−ジアミノジフェニルメタン、
３，４′−ジアミノジフェニルメタン、２，２′−ジア
ミノビフェニル、２，４′−ジアミノビフェニル、３，
３′−ジアミノビフェニル、２，４−ジアミノフェノー
ル、２，５−ジアミノフェノール、ｏ−フェニレンジア
ミン、ｍ−フェニレンジアミン、２，３−トリレンジア
ミン、２，４−トリレンジアミン、２，５−トリレンジ
アミン、２，６−トリレンジアミン、３，４−トリレン
ジアミン等の芳香族、１，１２−ドデカンジアミン、
１，１０−デカンジアミン、１，８−オクタンジアミ
ン、１，１４−テトラデカンジアミン、１，１６−ヘキ
サデカンジアミン等の脂肪族が挙げられ、これらの１種
または２種以上の混合物を使用に供してよい。かかる固
形アミンは、たとえば５〜３０μの平均粒径で使用する
ことが好ましい。The above-mentioned solid amine in the present invention includes
Any of aromatic, aliphatic or alicyclic compounds having a melting point of 50 ° C. or higher may be used, for example, 4,4′-
Diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,
3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5- Aromatic such as tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, 1,12-dodecanediamine,
Aliphatic compounds such as 1,10-decanediamine, 1,8-octanediamine, 1,14-tetradecanediamine, and 1,16-hexadecanediamine may be mentioned, and one or a mixture of two or more thereof may be used. Good. Such solid amine is preferably used with an average particle size of, for example, 5 to 30 μ.
【００１０】かかる固形アミンと流動パラフィンを通
常、１／５〜１／１の重量比で混合して分散液とし、本
発明における成分（Ｂ）として使用する。使用量は通
常、イソシアネート成分（Ａ）のＮＣＯと固形アミンの
アミノ基（ＮＨ2）の当量比（ＮＣＯ／ＮＨ2）が１／
０.７〜１.５、好ましくは１／０.９〜１.３となるよう
に選定すればよい。ＮＨ2の比率が０.７未満では、所望
の硬化物性が得られなく、また１.５を越えると、硬化
物が着色化する傾向にある。The solid amine and liquid paraffin are usually mixed in a weight ratio of 1/5 to 1/1 to form a dispersion, which is used as the component (B) in the present invention. The amount used is usually such that the equivalent ratio (NCO / NH 2 ) of NCO of the isocyanate component (A) and amino group (NH 2 ) of the solid amine is 1 /.
It may be selected so as to be 0.7 to 1.5, preferably 1 / 0.9 to 1.3. When the ratio of NH 2 is less than 0.7, desired cured physical properties cannot be obtained, and when it exceeds 1.5, the cured product tends to be colored.
【００１１】本発明における上記エポキシ樹脂として
は、ビスフェノールＡ型、Ｆ型、ＡＤ型、フェノール
型、クレゾール型、環状脂肪族系、グリシジルエステル
系、グリシジルアミン系等が挙げられ、特に液状のもの
が好ましい。該エポキシ樹脂の配合量は通常、系全量中
３％（重量％、以下同様）以上に設定すれば、エポキシ
樹脂の物性効果が発揮される。なお、硬化物性としてＪ
ＩＳ−Ｒ−１２０１の品質規格に合格するためには２０
％以下とする。２０％を越えると、ウレタン硬化物の弾
性が損なわれる傾向となる。しかし、エポキシ樹脂の硬
化物性が望まれる場合には、エポキシ樹脂を多くするこ
ともできる。特に、エポキシ樹脂の中に成分（Ｂ）であ
る固形アミンと流動パラフィンの分散液を配合して一液
型低温硬化型エポキシ樹脂組成物とすることもできる。
この場合、エポキシ基に対してアミノ基がほぼ当量割合
となるように配合する。Examples of the epoxy resin in the present invention include bisphenol A type, F type, AD type, phenol type, cresol type, cycloaliphatic type, glycidyl ester type, glycidyl amine type and the like, and particularly liquid type preferable. When the compounding amount of the epoxy resin is set to 3% (% by weight, the same applies hereinafter) or more in the total amount of the system, the effect of physical properties of the epoxy resin is exhibited. In addition, as a cured physical property, J
20 to pass the IS-R-1201 quality standard
% Or less. If it exceeds 20%, the elasticity of the urethane cured product tends to be impaired. However, when the cured physical properties of the epoxy resin are desired, the amount of the epoxy resin can be increased. In particular, the one-component low temperature curing type epoxy resin composition can be prepared by blending a dispersion liquid of solid amine as the component (B) and liquid paraffin in the epoxy resin.
In this case, the amino group is blended so as to have an approximately equivalent ratio to the epoxy group.
【００１２】本発明に係る加熱硬化性ウレタン組成物
は、上述のイソシアネート成分（Ａ）および固形アミン
の分散液（Ｂ）から成るベース成分に、上記エポキシ樹
脂を配合した無溶剤の系で構成される。かかる組成物構
成において、固形アミンは加熱溶融によって、イソシア
ネート成分（Ａ）との反応、また一方ではエポキシ樹脂
との反応を開始する。従って、固形アミンの融点未満の
条件下では、ベース成分にエポキシ樹脂を添加しても、
反応は起らず、系全体の流動性が保持される。これに対
し、固形アミンの融点以上の温度に熱を与えると、二つ
の反応が同時に進行して三次元化（架橋密度の増加）に
よる網状構造をもたらし、初期目的の弾性かつ強靭な物
性（特に圧縮永久歪みに対して有効）を具備した硬化物
が形成されることになる。The heat-curable urethane composition according to the present invention is composed of a solvent-free system in which the above-mentioned epoxy resin is blended with a base component consisting of the above-mentioned isocyanate component (A) and solid amine dispersion (B). It In such a composition constitution, the solid amine starts to react with the isocyanate component (A) and also with the epoxy resin by heating and melting. Therefore, under the conditions below the melting point of the solid amine, even if the epoxy resin is added to the base component,
No reaction occurs and the fluidity of the entire system is maintained. On the other hand, when heat is applied to a temperature higher than the melting point of the solid amine, two reactions simultaneously proceed, resulting in a network structure due to three-dimensionalization (increased crosslink density), and the elastic and tough physical properties of the initial purpose (especially A cured product having an effective compression set) is formed.
【００１３】さらに系の貯蔵安定化あるいは物性調整等
を目的とし、必要に応じて可塑剤および／または充填剤
を適量添加されてよい。上記可塑剤としては、フタル酸
誘導体（たとえばジブチルフタレート、ジオクチルフタ
レート、ジシクロヘキシルフタレート、ジイソオクチル
フタレート、ジイソデシルフタレート、ジベンジルフタ
レート、ブチルベンジルフタレート）、イソフタル酸誘
導体、テトラヒドロフタル酸誘導体、アジピン酸誘導体
（たとえばアジピン酸エステル）、アゼライン酸誘導
体、セバシン酸誘導体、マレイン酸誘導体、フマル酸誘
導体、トリメリット酸誘導体、ピロメリット酸誘導体、
オレイン酸誘導体、ステアリン酸誘導体、パラフィン誘
導体（たとえばクロロパラフィン）、その他トリオクチ
ルホスフェート、エポキシ系可塑剤、トルエン−スルホ
アミド、ヒマシ油等が挙げられる。添加量は通常、系全
量中１０〜３０％の範囲で選定すればよい。For the purpose of stabilizing the storage of the system or adjusting the physical properties, a plasticizer and / or a filler may be added in an appropriate amount, if necessary. Examples of the plasticizer include phthalic acid derivatives (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dibenzyl phthalate, butyl benzyl phthalate), isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives ( Adipic acid ester), azelaic acid derivative, sebacic acid derivative, maleic acid derivative, fumaric acid derivative, trimellitic acid derivative, pyromellitic acid derivative,
Examples thereof include an oleic acid derivative, a stearic acid derivative, a paraffin derivative (for example, chloroparaffin), trioctyl phosphate, an epoxy plasticizer, toluene-sulfoamide, castor oil and the like. The addition amount is usually selected in the range of 10 to 30% in the total amount of the system.
【００１４】上記充填剤としては、たとえば重質炭酸カ
ルシウム、脂肪酸で表面処理した炭酸カルシウム、カー
ボンブラック、無水ケイ酸、クレー、タルク、マイカ、
繊維質材料、金属粉等が挙げられ、特に貯蔵安定化の上
でクレーの使用が有利である。添加量は通常、系全量中
５〜２０％の範囲で選定すればよい。さらにまた、他の
添加剤としてウレタン触媒、揺変剤、紫外線吸収剤、老
化防止剤、染顔料、密着剤、脱水剤等を適量添加されて
もよい。なお、上記ウレタン触媒としては、ＤＢＵ
〔１，８−ジアザビシクロ（５.４.０）ウンデセン−
７〕、ＤＢＵフェノール塩、ＤＢＵオクチル酸塩、ＤＢ
Ｕギ酸塩などのＤＢＵ系；モノアミン（トリエチルアミ
ン等）、ジアミン（Ｎ,Ｎ,Ｎ′,Ｎ′−テトラメチルエ
チレンジアミン等）、トリアミン（テトラメチルグアニ
ジン等）、環状アミン（トリエチレンジアミン等）、ア
ルコールアミン（ジメチルアミノメタノール等）、エー
テルアミン〔ビス（２−ジメチルアミノエチル）エーテ
ル等〕などのアミン系；Ｓn系（ジブチル錫ジラウレー
ト、オクチル酸錫等）、Ｐb系（オクチル酸鉛等）、Ｚn
系（オクチル酸亜鉛等）などの有機カルボン酸金属塩；
２−メチルイミダゾール、１，２−ジメチルイミダゾー
ルなどのイミダゾール系が挙げられる。Examples of the filler include heavy calcium carbonate, calcium carbonate surface-treated with fatty acid, carbon black, silicic acid anhydride, clay, talc, mica,
Examples include fibrous materials and metal powders, and the use of clay is particularly advantageous for stabilizing storage. The addition amount may be usually selected in the range of 5 to 20% in the total amount of the system. Furthermore, as other additives, a urethane catalyst, a thixotropic agent, an ultraviolet absorber, an antiaging agent, a dye / pigment, an adhesive agent, a dehydrating agent and the like may be added in appropriate amounts. As the urethane catalyst, DBU
[1,8-diazabicyclo (5.4.0) undecene-
7], DBU phenol salt, DBU octylate, DB
U formates such as DBU; monoamines (triethylamine, etc.), diamines (N, N, N ', N'-tetramethylethylenediamine, etc.), triamines (tetramethylguanidine, etc.), cyclic amines (triethylenediamine, etc.), alcohol amines (Dimethylaminomethanol, etc.), ether amines [bis (2-dimethylaminoethyl) ether, etc.], amines; Sn (dibutyltin dilaurate, tin octylate, etc.), Pb (lead octylate, etc.), Zn
Organic carboxylic acid metal salts such as a system (zinc octylate, etc.);
Examples thereof include imidazole compounds such as 2-methylimidazole and 1,2-dimethylimidazole.
【００１５】[0015]
【実施例】次に実施例および比較例を挙げて、本発明を
より具体的に説明する。なお、例文中、「部」とは「重
量部」を意味する。 実施例１〜４および比較例１ （１）末端ＮＣＯ含有プレポリマーの製造 水酸基価２９.０mgＫＯＨ/gのポリオキシプロピレンジ
オール１００ｇおよび水酸基価５１.８mgＫＯＨ/gの水
添１，４−ブタジエン系ポリオール１７６ｇに、４，
４′−ジフェニルメタンジイソシアネート１７０ｇを加
え（ＯＨ／ＮＣＯ＝１／２.０）、８０℃で１０時間反
応させ、末端ＮＣＯ含有量２.１２％、粘度２００００c
ps/２０℃の末端ＮＣＯ含有プレポリマーを得る。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the example sentence, "part" means "part by weight". Examples 1 to 4 and Comparative Example 1 (1) Production of Prepolymer Containing Terminal NCO: 100 g of polyoxypropylene diol having a hydroxyl value of 29.0 mg KOH / g and hydrogenated 1,4-butadiene-based polyol having a hydroxyl value of 51.8 mg KOH / g. 176g, 4,
170 g of 4'-diphenylmethane diisocyanate was added (OH / NCO = 1 / 2.0) and reacted at 80 ° C. for 10 hours to give a terminal NCO content of 2.12% and a viscosity of 20000 c.
A terminal NCO containing prepolymer with ps / 20 ° C. is obtained.
【００１６】（２）固形アミン分散液の調製 １，１２−ドデカンジアミン／流動パラフィン（重量比
＝２５／７５）をハイスピードミキサーにて十分に混合
し、微粒子状ジアミンが分散したスラリー化液を得る。(2) Preparation of solid amine dispersion liquid 1,12-dodecanediamine / liquid paraffin (weight ratio = 25/75) was sufficiently mixed with a high speed mixer to prepare a slurry liquid in which fine particle diamine was dispersed. obtain.
【００１７】（３）加熱硬化性ウレタン組成物の調製 上記（１）の末端ＮＣＯ含有プレポリマーと、上記
（２）のジアミン分散スラリー化液を重量比８３.２／
１６.８の割合（すなわち、ＮＣＯ／ＮＨ2＝１／１.
０）で混合してベース成分とし、これに下記表１に示す
割合（部数）で、エポキシ樹脂〔油化シェル(株)製のエ
ピコート８０７、エピコート６０４〕、可塑剤〔ジオク
チルフタレート（ＤＯＰ）〕、充填剤（炭酸カルシウ
ム、クレー）、上記（１）の末端ＮＣＯ含有プレポリマ
ーを配合して、加熱硬化性ウレタン組成物を調製する。(3) Preparation of heat-curable urethane composition The weight ratio of the terminal NCO-containing prepolymer of (1) above and the diamine-dispersed slurry solution of (2) above is 83.2 /
A ratio of 16.8 (ie NCO / NH 2 = 1/1.
0) were mixed to form a base component, and epoxy resin [Epicoat 807 and Epicoat 604 manufactured by Yuka Shell Co., Ltd.] and a plasticizer [dioctyl phthalate (DOP)] were added in the proportions (parts) shown in Table 1 below. A filler (calcium carbonate, clay) and the terminal NCO-containing prepolymer of (1) above are blended to prepare a heat-curable urethane composition.
【００１８】性能試験 （１）１００℃硬化性と物性測定 各組成物を剥離紙上に乾燥膜厚２.０mmにて塗布し、１
００℃で１０分間加熱硬化を行った後、形成する硬化膜
の３号ダンベル物性と硬度（ショアーＡ）と圧縮永久歪
み（ＪＩＳ Ｋ６３０１）を測定し、結果を表１に示
す。 （２）貯蔵安定性 各組成物を４０℃で密閉貯蔵し、７日経過後の上昇した
粘度を測定し（但し、貯蔵直前の粘度を１００とす
る）、結果を表１に示す。 Performance Test (1) Curability at 100 ° C. and Measurement of Physical Properties Each composition was coated on a release paper at a dry film thickness of 2.0 mm and
After heat-curing at 00 ° C. for 10 minutes, physical properties, hardness (Shore A) and compression set (JIS K6301) of the cured film to be formed were measured, and the results are shown in Table 1. (2) Storage stability Each composition was sealed and stored at 40 ° C., and the increased viscosity after 7 days was measured (however, the viscosity immediately before storage is 100), and the results are shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】本発明組成物によれば、良好な貯蔵安定
性および低温硬化性を保持しつつ、かつたとえば１００
℃×１０分の加熱硬化により、圧縮永久歪みの少ない強
靭な硬化膜を形成でき、特に陶管用ジョイント材料の品
質規格ＪＩＳ−Ｒ−１２０１に適合しうる。また用途展
開として、浄化槽用シーリング材、滑り止め材等に適
用、さらに一液型低温熱硬化型エポキシ樹脂組成物への
利用が可能であり、一方、硬化反応時に有害ガスの発生
が起らない（無溶剤系）ため、安全衛生面でも有利とな
る。EFFECTS OF THE INVENTION According to the composition of the present invention, while maintaining good storage stability and low temperature curing property, for example, 100
By heat-curing at ℃ × 10 minutes, a tough cured film with less compression set can be formed, and in particular, it can meet the quality standard JIS-R-1201 of the joint material for ceramic pipes. In addition, it can be applied to septic tank sealing materials, anti-slip materials, etc., and can also be used for one-component low-temperature thermosetting epoxy resin compositions, while no harmful gas is generated during the curing reaction. Since it is solvent-free, it is also advantageous in terms of safety and hygiene.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 175/04 ＪＦＡ ＪＦＦ (72)発明者 後藤 錠志 大阪府高槻市明田町７番１号 サンスター 技研株式会社内Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical display location C09J 175/04 JFA JFF (72) Inventor Lockoshi Goto 7-1 Akita-cho, Takatsuki-shi, Osaka Sunstar Giken Co. In the company
Claims (3)
リオール成分に過剰量のポリイソシアネート化合物を反
応させて得られる末端活性イソシアネート基含有ウレタ
ンプレポリマーのそれぞれ単独またはそれらの混合物；
および（Ｂ）固形アミンと流動パラフィンの分散液；か
ら成るベース成分に、２官能以上のエポキシ樹脂を配合
したことを特徴とする加熱硬化性ウレタン組成物。1. A polyisocyanate compound (A) and a urethane prepolymer containing a terminal active isocyanate group obtained by reacting a polyol component with an excess amount of a polyisocyanate compound, respectively, or a mixture thereof.
And (B) a dispersion liquid of solid amine and liquid paraffin; and a bifunctional or higher functional epoxy resin mixed with a base component.
請求項１に記載の加熱硬化性ウレタン組成物。2. The heat-curable urethane composition according to claim 1, further comprising a plasticizer and / or a filler.
請求項２に記載の加熱硬化性ウレタン組成物。3. The heat-curable urethane composition according to claim 2, wherein at least clay is used as a filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06249694A JP3364314B2 (en) | 1994-03-31 | 1994-03-31 | Heat-curable urethane composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06249694A JP3364314B2 (en) | 1994-03-31 | 1994-03-31 | Heat-curable urethane composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07268051A true JPH07268051A (en) | 1995-10-17 |
| JP3364314B2 JP3364314B2 (en) | 2003-01-08 |
Family
ID=13201838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06249694A Expired - Fee Related JP3364314B2 (en) | 1994-03-31 | 1994-03-31 | Heat-curable urethane composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3364314B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0769338A1 (en) * | 1995-10-18 | 1997-04-23 | Borden Chemical, Inc. | Urethane foundry binders resistant to water-based coatings |
| US5872297A (en) * | 1995-08-24 | 1999-02-16 | S. C. Johnson Commercial Markets, Inc. | Ethylenically-unsaturated 1,3-diketoamide functional compounds |
| JP2002020686A (en) * | 2000-07-13 | 2002-01-23 | Asahi Glass Co Ltd | Two-component polyurethane coated film waterproof material |
| JP2004210977A (en) * | 2003-01-06 | 2004-07-29 | Yokohama Rubber Co Ltd:The | Curable resin composition |
| JP2005054040A (en) * | 2003-08-04 | 2005-03-03 | Okura Ind Co Ltd | Flame-retardant thermoplastic polyurethane composition and molded form |
| JP2007505200A (en) * | 2003-05-19 | 2007-03-08 | スリーエム イノベイティブ プロパティズ カンパニー | Epoxy adhesive and bonding substrate |
| JP2007262260A (en) * | 2006-03-29 | 2007-10-11 | Nok Corp | Adhesive composition |
| WO2009090947A1 (en) * | 2008-01-15 | 2009-07-23 | Sunstar Giken Kabushiki Kaisha | Pressure-sensitive adhesive composition |
| JP4639506B2 (en) * | 2001-03-30 | 2011-02-23 | 横浜ゴム株式会社 | Thermosetting one-component urethane composition |
| JP2016526063A (en) * | 2013-05-13 | 2016-09-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Isocyanate-epoxide hybrid resin |
| JP2018044090A (en) * | 2016-09-15 | 2018-03-22 | 日清紡ホールディングス株式会社 | Resin composition and thermally conductive soft sheet using the same, and heat radiation structure |
| WO2022102467A1 (en) * | 2020-11-16 | 2022-05-19 | 東レ株式会社 | Thermosetting epoxy resin composition, molded article of same, fiber-reinforced composite material, molding material for fiber-reinforced composite materials, and method for producing fiber-reinforced composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5556172A (en) * | 1978-10-20 | 1980-04-24 | Oosakafu | Adhesive composition |
| JPH03220222A (en) * | 1989-10-04 | 1991-09-27 | Takeda Chem Ind Ltd | High-hardness resin composition, molding thereof, and production of molding |
| JPH03296525A (en) * | 1990-04-16 | 1991-12-27 | Fuji Kasei Kogyo Kk | Thermally curable one-component epoxide composition |
| JPH0532948A (en) * | 1991-07-26 | 1993-02-09 | Asahi Glass Co Ltd | Adhesive composition, its production and curing method |
| JPH0543864A (en) * | 1991-08-12 | 1993-02-23 | Nitta Gelatin Inc | Urethane adhesive composition |
-
1994
- 1994-03-31 JP JP06249694A patent/JP3364314B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5556172A (en) * | 1978-10-20 | 1980-04-24 | Oosakafu | Adhesive composition |
| JPH03220222A (en) * | 1989-10-04 | 1991-09-27 | Takeda Chem Ind Ltd | High-hardness resin composition, molding thereof, and production of molding |
| JPH03296525A (en) * | 1990-04-16 | 1991-12-27 | Fuji Kasei Kogyo Kk | Thermally curable one-component epoxide composition |
| JPH0532948A (en) * | 1991-07-26 | 1993-02-09 | Asahi Glass Co Ltd | Adhesive composition, its production and curing method |
| JPH0543864A (en) * | 1991-08-12 | 1993-02-23 | Nitta Gelatin Inc | Urethane adhesive composition |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872297A (en) * | 1995-08-24 | 1999-02-16 | S. C. Johnson Commercial Markets, Inc. | Ethylenically-unsaturated 1,3-diketoamide functional compounds |
| US5733952A (en) * | 1995-10-18 | 1998-03-31 | Borden Chemical, Inc. | Foundry binder of phenolic resole resin, polyisocyanate and epoxy resin |
| US5981622A (en) * | 1995-10-18 | 1999-11-09 | Borden Chemical, Inc. | Foundry binder of polyurethane, phenolic resin, polyisocyanate and epoxy resin |
| EP0769338A1 (en) * | 1995-10-18 | 1997-04-23 | Borden Chemical, Inc. | Urethane foundry binders resistant to water-based coatings |
| JP4581195B2 (en) * | 2000-07-13 | 2010-11-17 | 旭硝子株式会社 | Two-component polyurethane waterproof membrane |
| JP2002020686A (en) * | 2000-07-13 | 2002-01-23 | Asahi Glass Co Ltd | Two-component polyurethane coated film waterproof material |
| JP4639506B2 (en) * | 2001-03-30 | 2011-02-23 | 横浜ゴム株式会社 | Thermosetting one-component urethane composition |
| JP2004210977A (en) * | 2003-01-06 | 2004-07-29 | Yokohama Rubber Co Ltd:The | Curable resin composition |
| JP2007505200A (en) * | 2003-05-19 | 2007-03-08 | スリーエム イノベイティブ プロパティズ カンパニー | Epoxy adhesive and bonding substrate |
| JP2005054040A (en) * | 2003-08-04 | 2005-03-03 | Okura Ind Co Ltd | Flame-retardant thermoplastic polyurethane composition and molded form |
| JP2007262260A (en) * | 2006-03-29 | 2007-10-11 | Nok Corp | Adhesive composition |
| WO2009090947A1 (en) * | 2008-01-15 | 2009-07-23 | Sunstar Giken Kabushiki Kaisha | Pressure-sensitive adhesive composition |
| JP2009167272A (en) * | 2008-01-15 | 2009-07-30 | Sunstar Engineering Inc | Adhesive composition |
| JP2016526063A (en) * | 2013-05-13 | 2016-09-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Isocyanate-epoxide hybrid resin |
| JP2019070139A (en) * | 2013-05-13 | 2019-05-09 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Isocyanate-epoxide hybrid resin |
| JP2018044090A (en) * | 2016-09-15 | 2018-03-22 | 日清紡ホールディングス株式会社 | Resin composition and thermally conductive soft sheet using the same, and heat radiation structure |
| WO2018051740A1 (en) * | 2016-09-15 | 2018-03-22 | 日清紡ホールディングス株式会社 | Resin composition, heat-conductive flexible sheet using same, and heat dissipation structure |
| US11225548B2 (en) | 2016-09-15 | 2022-01-18 | Nisshinbo Holdings Inc. | Resin composition, heat-conductive flexible sheet using same, and heat dissipation structure |
| WO2022102467A1 (en) * | 2020-11-16 | 2022-05-19 | 東レ株式会社 | Thermosetting epoxy resin composition, molded article of same, fiber-reinforced composite material, molding material for fiber-reinforced composite materials, and method for producing fiber-reinforced composite material |
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