JPH01210413A - Preparation of polyurethane resin - Google Patents
Preparation of polyurethane resinInfo
- Publication number
- JPH01210413A JPH01210413A JP63032635A JP3263588A JPH01210413A JP H01210413 A JPH01210413 A JP H01210413A JP 63032635 A JP63032635 A JP 63032635A JP 3263588 A JP3263588 A JP 3263588A JP H01210413 A JPH01210413 A JP H01210413A
- Authority
- JP
- Japan
- Prior art keywords
- diisocyanate
- extruder
- polyurethane resin
- reacting
- diol
- 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.)
- Pending
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 22
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 26
- 150000002009 diols Chemical class 0.000 claims abstract description 25
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 19
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- -1 diphehylmethane 4 Chemical class 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000004606 Fillers/Extenders Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229920001610 polycaprolactone Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011344 liquid material Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PAALZGOZEUHCET-UHFFFAOYSA-N 1,4-dioxecane-5,10-dione Chemical compound O=C1CCCCC(=O)OCCO1 PAALZGOZEUHCET-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は改良されたポリウレタン樹脂の製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an improved method for producing polyurethane resins.
（従来の技術）
一般にポリウレタン樹脂は多官能活性水素化合物と、ジ
インシアネートとの重付加反応によって得られるポリマ
ーであり、ゴムとグラスチックとの両特性を兼備してい
るためチューブ材、電線被榎材、シートの他数多くの製
品に使用されている。(Prior art) Generally, polyurethane resin is a polymer obtained by a polyaddition reaction between a polyfunctional active hydrogen compound and diincyanate, and because it has both rubber and glass properties, it can be used as a material for tubes and wires. It is used in many other products such as lumber and sheets.
従来のこのｆ リフレタン樹脂の製造方法としては、ま
す長鎖ポリオールと、ジイソシアネートとを反応せしめ
て！レポリマーを生成シ、コノブレポリマーと鎖延長剤
、架橋剤としての低分子量ポリマーとを反応せしめてう
る方法と、長鎖ポリオール、ジインシアネート及び低分
子量ジオールとを同時に反応せしめてうる方法とがある
。The conventional method for producing Refletane resin is to react a long-chain polyol with a diisocyanate! There are two methods for producing a repolymer: one method involves reacting a conobrepolymer with a low molecular weight polymer as a chain extender and a crosslinking agent, and the other method involves simultaneously reacting a long chain polyol, diincyanate and a low molecular weight diol. .
これらの方法は何れも上記の長鎖ポリオールと、ジイソ
シアネートと低分子量ジオールとを所定量混合した後、
加熱板上に注出し反応後、常温にて固化せしめ、得られ
た塊状物を押出成形によってペレット化してポリウレタ
ン樹脂ペレットをうるものである。In both of these methods, after mixing a predetermined amount of the above-mentioned long-chain polyol, diisocyanate, and low molecular weight diol,
After pouring onto a heating plate and reacting, the mixture is solidified at room temperature, and the resulting lump is pelletized by extrusion molding to obtain polyurethane resin pellets.
この樹脂ペレットをシート、チューブ又は電線被覆等の
所望の形状に加工する場合には、再度押出機或は射出成
形機に投入し押出成形を行っているものである。When processing the resin pellets into a desired shape such as a sheet, tube, or wire coating, the resin pellets are again fed into an extruder or injection molding machine and extrusion molded.
従ってポリウレタン樹脂を電線の被覆等に加工するに際
し極めて複雑な工数を必要としているため著しく生産性
、が劣るものであう九。Therefore, processing polyurethane resin into wire coatings, etc. requires extremely complicated man-hours, resulting in extremely low productivity.
本発明者等は簡単な工程にして生産性を向上させるポリ
ウレタン樹脂の製造方法を先に提案した（特願昭６２−
２４６６４０号）。この方法は長鎖−ジオール、ジイソ
シアネート及び低分子量ジオールを押出機内に直接同時
に投入し、核押出機の内部においてウレタン樹脂を連続
的に合成するものであるが、この反応において長鎖ポリ
オールとジイソシアネートとの反応性及び低分子量ジオ
ールとジイソシアネートとの反応性の間において時間的
にずれを生ずるため、合成されたウレタン樹脂中に局部
的に必然的に未反応の長鎖ポリオールが残存し混在し特
性を左右する硬度にバラツキを生ずるものであった。The present inventors previously proposed a method for producing polyurethane resin that improves productivity through a simple process (Japanese Patent Application No. 1983-
No. 246640). In this method, long-chain diols, diisocyanates, and low-molecular-weight diols are directly simultaneously introduced into an extruder, and urethane resin is continuously synthesized inside the core extruder. Because there is a time lag between the reactivity of the diol and the reactivity of the low molecular weight diol and the diisocyanate, unreacted long-chain polyols inevitably remain locally in the synthesized urethane resin and are mixed together, which may affect the properties. This caused variations in hardness.
（発明が解決しようとする課題）
本発明はかかる現状に鑑み鋭意研究を行つた結果、生産
性を向上し且つ常時硬度にバラツキを生じないポリウレ
タン樹脂の製造方法を開発したものである。(Problems to be Solved by the Invention) As a result of intensive research in view of the current situation, the present invention has developed a method for producing polyurethane resin that improves productivity and does not always cause variations in hardness.
（１１題を解決する丸めの手段）
本発明は押出機内部にて長鎖ポリオール、ジイソシアネ
ート及び低分子量ジオールとを合成反応せしめて高分子
化のポリウレタン樹脂を製造する方法において、予め該
長鎖ポリオールとジイソシアネートとを反応せしめて液
状物となし、この液状物と液状の低分子量ジオールとを
別個に押出機に投入して反応せしめることを特徴とする
ものである。(Rounding Means for Solving Problem 11) The present invention is a method for producing a polymerized polyurethane resin by subjecting a long chain polyol, diisocyanate, and a low molecular weight diol to a synthetic reaction inside an extruder. This method is characterized by reacting the diisocyanate and the diisocyanate to form a liquid product, and then separately charging the liquid product and the liquid low molecular weight diol into an extruder to cause the reaction to occur.
本発明方法において長鎖−ジオールとしては例えば、Ｉ
す（エチレンアジペート）、ポリ（１，４−ブチルアジ
ペート）、ポリ（１，６−ヘキサンジオ−ル）、ポリ−
Ｃ−カブロラクトン等のポリエステルジオール又は４リ
オキシテトラメチレングリコール、ポリグロビレングリ
コール等のポリエーテルジオールなどである。In the method of the present invention, long-chain diols include, for example, I
(ethylene adipate), poly(1,4-butyl adipate), poly(1,6-hexanediol), poly-
These include polyester diols such as C-cabrolactone, and polyether diols such as 4-lyoxytetramethylene glycol and polyglobylene glycol.
又ジイソシアネートとしては例えば４．４′−ジフェニ
ルメタンジイソシアネート、 ４．４’−ジシクロヘキ
シルメタンジイソシアネート、インホロンジイソシアネ
ートなどである。Examples of diisocyanates include 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and inphorone diisocyanate.
又低分子量ジオールとしては例えばエチレングリコール
、１．４−ブチレングリコール、１．６−ヘキサンジオ
ールなどである。Examples of low molecular weight diols include ethylene glycol, 1,4-butylene glycol, and 1,6-hexanediol.
而して本発明方法は長鎖ポリオールとジイソシアネート
の所定量を予め均一に混合し、これを所望温度に放置し
て液状物としたものと液体の低分子量ジオールとを別々
に押出機内に投入するものである。その理由はジイソシ
アネートと長鎖ポリオールとの反応性より、ジイソシア
ネートと低分子量ジオールとの反応性の方が速い九め、
上記の３成分を同時に押出機に投入するか、或は押出機
内に長鎖ポリオールとジインシアネートとを先に投入し
、低分子量ジオールのみを押出機の途中から投入して合
成を行ったとしてもジイソシアネートと低分子量ジオー
ルとの反応物が多量に出来、未反応の長鎖ポリオールが
樹脂中に局部的に存在して、合成反応が不安定となり得
られるポリウレタン樹脂の特性を大きく左右する硬度に
バラツキを生ずるためであル、前記の如き方法にて合成
を行うことにより長鎖ポリオールとジイソシアネートと
の反応後に低分子量ジオールとジイソシアネートとの反
応が確実に進行するため未反応の長鎖ｌジオールが得ら
れるポリウレタン樹脂中に局在化することなく、均一な
特性を有するポリウレタン樹脂をうろことが出来るもの
である。なおこの場合長鎖ポリオールとジイソシアネー
トとの液状物は３０°〜１８０’Ｃの範囲内にて反応さ
せることが好ましい、その理由は３０℃未満の場合には
液状物が固化して取扱いが困難となり、又１８０℃を超
える場合にはメンテナンスの問題を生ずると共にイソシ
アネート基の副反応がおこり得られるポリウレタン樹脂
の特性にバラツキを生ずるおそれがある。Accordingly, in the method of the present invention, predetermined amounts of long-chain polyol and diisocyanate are uniformly mixed in advance, and this is left to stand at a desired temperature to form a liquid, and the liquid low-molecular-weight diol is separately charged into an extruder. It is something. The reason for this is that the reactivity between diisocyanates and low molecular weight diols is faster than the reactivity between diisocyanates and long chain polyols.
Even if synthesis is carried out by charging the above three components into the extruder at the same time, or by charging the long chain polyol and diincyanate into the extruder first and only the low molecular weight diol from the middle of the extruder. A large amount of reaction product between diisocyanate and low molecular weight diol is formed, and unreacted long-chain polyol is locally present in the resin, making the synthesis reaction unstable and resulting in variations in hardness that greatly affect the properties of the resulting polyurethane resin. However, by performing the synthesis using the method described above, the reaction between the low molecular weight diol and the diisocyanate proceeds reliably after the reaction between the long chain polyol and the diisocyanate, so that an unreacted long chain diol can be obtained. It is possible to distribute the polyurethane resin having uniform properties without localization in the polyurethane resin. In this case, it is preferable to react the liquid material of the long-chain polyol and diisocyanate within the range of 30° to 180'C, because if the temperature is less than 30°C, the liquid material will solidify and be difficult to handle. If the temperature exceeds 180° C., maintenance problems may occur and side reactions of isocyanate groups may occur, leading to variations in the properties of the resulting polyurethane resin.
更に好ましくは長鎖ポリオールとジイソシアネートとを
混合して得た液状物を上記温度範囲内において５分〜３
時間放置しておくものである。その理由は５分未満の場
合には長鎖ポリオールとジイソシアネートとの反応が不
十分であシ、未反応の長鎖ポリオールが多量に残存し、
これがウレタン樹脂中に局在化する。又３時間を超えた
場合にはイソシアネート基の副反応がおこシ好ましくな
い。More preferably, a liquid obtained by mixing a long-chain polyol and a diisocyanate is heated within the above temperature range for 5 to 3 minutes.
It should be left alone for some time. The reason for this is that if the reaction time is less than 5 minutes, the reaction between the long chain polyol and diisocyanate is insufficient, and a large amount of unreacted long chain polyol remains.
This is localized in the urethane resin. Moreover, if it exceeds 3 hours, side reactions of isocyanate groups occur, which is not preferable.
又本発明方法において長鎖ポリオールとジイソシアネー
トとの混合液状物と低分子量ジオールとを押出機へ供給
するための供給装置としてはイヤポンｆｆ使用すること
が好ましい。これは上記の３成分を所定量の割合にて搬
送するにおいて、安定した混合比にて押出機に投入しう
るため、得られるポリウレタン樹脂は安定した構造を有
するポリウレタン樹脂となすことが出来る。Further, in the method of the present invention, it is preferable to use an earpon ff as a feeding device for feeding the liquid mixture of long-chain polyol and diisocyanate and the low molecular weight diol to the extruder. This allows the above-mentioned three components to be conveyed at a predetermined ratio and fed into the extruder at a stable mixing ratio, so the resulting polyurethane resin can have a stable structure.
この押出機としては、二軸押出機特に異方向回転の二軸
押出機が好ましく、これは押出機内に投入した前記の３
成分を搬送する際の渭シを防止しうるからである。又反
応の際に生ずる副生成物を系外圧取り除くことが可能な
ベント孔を有するものが好ましい。As this extruder, a twin-screw extruder, particularly a twin-screw extruder rotating in different directions, is preferable, and this
This is because it is possible to prevent sagging when transporting the components. Also, it is preferable to have a vent hole through which by-products produced during the reaction can be removed from the system.
又押出機の先端に取付けるダイスとしてはペレット化用
のストランドダイスに限らず種々の成形用ダイスを取付
けて所望の形状に成形するものであればよい。Furthermore, the die attached to the tip of the extruder is not limited to a strand die for pelletizing, but may be any other die that can be attached to various molding dies to form a desired shape.
又本発明方法において前記３成分と共に助剤例えば難燃
剤、発泡剤、酸化防止剤、防ばい剤、着色剤等を添加し
てもよく、その場合には長鎖ポリオール及び低分子量ジ
オール中のアルコール基とジイソシアネートのインシア
ネート基との反応に影響を及ぼさないものについては押
出機内に直接投入することが出来るが、アルコール基と
ノイソシアネート基との反応に影響を及ぼすものについ
ては本発明方法によりえたポリウレタン樹脂をＲレット
化し、これと共に押出機に投入するものである。In addition, in the method of the present invention, auxiliary agents such as flame retardants, blowing agents, antioxidants, fungicides, colorants, etc. may be added together with the above three components, in which case the alcohol in the long chain polyol and low molecular weight diol Those that do not affect the reaction between the alcohol group and the inocyanate group of the diisocyanate can be directly charged into the extruder, but those that affect the reaction between the alcohol group and the inocyanate group of the diisocyanate can be charged by the method of the present invention. The polyurethane resin is made into R-let and fed into the extruder together with this.
（実施例）
比較例（１）
脱水状態とした水酸基数５６の鎖状カプロラクトン１０
０重量部、１．４ブタンジオ一ル２７重１部、４．４′
−ジフェニルメタンジイソシアネート９２重量部との混
合物を９０℃にて約２分間攪拌後、加熱成形板上（１１
５°〜１２０℃）に注出し、約１０時間放置して室温で
冷却した。得られた板状の硬化物を粉砕機にて塊状物と
なし、押出機を使用してペレット化した。このペレット
を射出成形機により厚さ２■の４リクレタン樹脂シート
をえた。(Example) Comparative example (1) Chain caprolactone 10 having 56 hydroxyl groups in a dehydrated state
0 parts by weight, 1.4 butanediol 27 parts by weight, 4.4'
- After stirring the mixture with 92 parts by weight of diphenylmethane diisocyanate at 90°C for about 2 minutes, it was placed on a hot molding plate (11 parts by weight).
The mixture was poured out at a temperature of 5° to 120°C), left to stand for about 10 hours, and then cooled to room temperature. The obtained plate-shaped cured product was pulverized into lumps using a pulverizer, and pelletized using an extruder. The pellets were molded into a 4-recretan resin sheet having a thickness of 2 cm using an injection molding machine.
比較例（２）
比較例（１）による混和物を９０℃にて２分間加熱した
液状物を押出機のホッパーに流し込み、これを押出して
ペレット化を行りｆｔ。このペレットを使用し射出成形
機により厚さ２ｍのぼりウレタン樹脂シートをえ九。Comparative Example (2) A liquid mixture obtained by heating the mixture according to Comparative Example (1) at 90° C. for 2 minutes was poured into the hopper of an extruder, and the mixture was extruded and pelletized. Using these pellets, we made a 2m thick urethane resin sheet using an injection molding machine.
比較例（３）
鎖状カプロラクトンと４．４′−ソフェニルメタンジイ
ソシアネートとを比較例（１）と同様の比率にて混合し
、二軸押出機（Ｌ／Ｄ＝３０ 、Ｄ＝４０φ、１ペント
型）のホッパーへ投入すると共に、液状にした１、４−
ブタンジオールを比較例（１）と同様の比率になるよう
に押出機のホッパー側から７ピツチ目の位置に注入しポ
ンダによシ圧入し、これを押出してポリウレタン樹脂を
えた。このときの吐出状態及びストランドをつぶさに観
察した。なおこのときの押出機の条件は次に示す通りで
ある。Comparative Example (3) Chain caprolactone and 4,4'-sophenylmethane diisocyanate were mixed at the same ratio as in Comparative Example (1), and mixed using a twin screw extruder (L/D=30, D=40φ, 1 At the same time, the liquefied 1,4-
Butanediol was injected into the seventh pitch from the hopper side of the extruder at the same ratio as in Comparative Example (1) and press-fitted into the ponder, and this was extruded to obtain a polyurethane resin. At this time, the discharge state and the strand were carefully observed. The conditions of the extruder at this time are as shown below.
実施例（１）
図面に示す如く水酸基数５６の鎖状カプロラクトンと４
．４′−ジフェニルメタンイソシアネートとを比較例（
１）と同様の比率にて配合した混合物１を９０℃、３分
間放置し、これと比較例（１）と同量の液体とした１、
４ブタンジオール２とを二軸押出機３のホッノ母４へ別
々に投入し押出してえたペレットについて吐出状態及び
ストランド状況をつぶさに観察した。このペレットを射
出成形機を使用して厚さ２■のポリウレタン樹脂シート
をえた。Example (1) As shown in the drawing, linear caprolactone having 56 hydroxyl groups and 4
．． Comparative example with 4'-diphenylmethane isocyanate (
Mixture 1 mixed in the same ratio as 1) was left at 90°C for 3 minutes, and the same amount of liquid as in Comparative Example (1) was prepared.
4-butanediol 2 and 4-butanediol 2 were separately introduced into the hot spring 4 of the twin-screw extruder 3, and the extruded pellets were carefully observed for the discharge state and strand state. A polyurethane resin sheet having a thickness of 2 cm was obtained from the pellets using an injection molding machine.
なおｓ、、ｓ’は液状物輸送用ギャポンダ、６はダイス
、７ 、７’はスクリュー、８はベント孔である。Note that s, s' are gapponders for transporting liquid materials, 6 is a die, 7 and 7' are screws, and 8 is a vent hole.
実施例（２）
上記実施例（１）における混合物の放置時間を９０℃、
５分間行った以外はすべて実施例（１）と同様にして厚
さ２＋ｗ＋のポリ９レタン樹脂シートをえた。Example (2) The standing time of the mixture in Example (1) above was 90°C.
A poly9 urethane resin sheet having a thickness of 2+w+ was obtained in the same manner as in Example (1) except that the test was carried out for 5 minutes.
実施例（３） 実施例（１）における混合物の放置時間を９０℃。Example (3) The mixture was left to stand at 90°C in Example (1).
１８０分間行った以外はすべて実施例（１）と同様にし
て厚さ２暉のポリウレタン樹脂シートをえた。A polyurethane resin sheet having a thickness of 2 times was obtained in the same manner as in Example (1) except that the test was carried out for 180 minutes.
実施例（４） 実施例（１）における混合物の放置時間を９０℃。Example (4) The mixture was left to stand at 90°C in Example (1).
３６０分間行った以外はすべて実施例（１）と同様にし
て厚さ２電の、ｊＰ ＩＪウレタン樹脂シートをえ念。A jP IJ urethane resin sheet with a thickness of 2 densities was prepared in the same manner as in Example (1) except that the treatment was carried out for 360 minutes.
斯くして得たポリウレタン樹脂シートについてその物性
を評価した。また同様の操作評価を５０回行い硬度のバ
ラツ午を測定した。その結果は第１表に示す通りである
。The physical properties of the polyurethane resin sheet thus obtained were evaluated. Further, the same operational evaluation was performed 50 times to measure the variation in hardness. The results are shown in Table 1.
（発明の効果）
以上記述した如く
■ 比較例において、比較例（１）は特性が安定してい
るが工程が繁雑であシ、（２） （３）では押出合成に
より工程は簡単であるが特性にばらつきがあり不安定で
あった。(Effects of the invention) As described above, ■ Comparative examples (1) have stable properties but have complicated processes, and (2) and (3) have simple processes due to extrusion synthesis, but Characteristics varied and were unstable.
■ 実施例においては（１）〜（４）は押出合成により
工程が簡単であり、特性もばらつきが小さく安定してお
り特に（２） （３）では比較例（１）と同等のものが
得られた。■ In Examples (1) to (4), the process is simple due to extrusion synthesis, and the characteristics are stable with little variation, and in particular, (2) and (3) have the same properties as Comparative Example (1). It was done.
以上本発明の実施例（υ〜（４ンによれば工程が極めて
簡単でありながら特性の安定した４リウレタン樹脂を製
造することが出来、工業上有用なものである。According to the embodiments (υ~(4) of the present invention described above, it is possible to produce a 4-urethane resin with stable characteristics through an extremely simple process, and it is industrially useful.
♀！ハ８は本発明ポリウレタン樹脂の製造方法の１例を
示す概略説明図である。♀! FIG. 8 is a schematic explanatory diagram showing one example of the method for producing the polyurethane resin of the present invention.
Claims (1)
低分子量ジオールとを反応せしめて高分子量化ポリウレ
タン樹脂を製造する方法において、予め長鎖ポリオール
とジイソシアネートと混合し反応せしめて液状物となし
、この液状物と低分子量ジオールとを別個に押出機に投
入して押出機内で両者を反応せしめることを特徴とする
ポリウレタン樹脂の製造方法In a method for producing a high molecular weight polyurethane resin by reacting a long chain polyol with a diisocyanate and a low molecular weight diol inside an extruder, the long chain polyol and diisocyanate are mixed in advance and reacted to form a liquid product, and this liquid product is and a low molecular weight diol are separately introduced into an extruder and the two are reacted in the extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63032635A JPH01210413A (en) | 1988-02-17 | 1988-02-17 | Preparation of polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63032635A JPH01210413A (en) | 1988-02-17 | 1988-02-17 | Preparation of polyurethane resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01210413A true JPH01210413A (en) | 1989-08-24 |
Family
ID=12364316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63032635A Pending JPH01210413A (en) | 1988-02-17 | 1988-02-17 | Preparation of polyurethane resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01210413A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132718A (en) * | 1990-09-26 | 1992-05-07 | Nippon Polyurethane Ind Co Ltd | Thermoplastic polyurethane resin |
| JPH11292946A (en) * | 1998-04-07 | 1999-10-26 | Nippon Mektron Ltd | Production of granulated material of thermoplastic polyurethane |
| US7695588B2 (en) * | 2001-10-31 | 2010-04-13 | Mitsubishi Heavy Industries, Ltd. | Matrix resin composition for fiber-reinforced plastics and process for production of fiber-reinforced plastics |
-
1988
- 1988-02-17 JP JP63032635A patent/JPH01210413A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04132718A (en) * | 1990-09-26 | 1992-05-07 | Nippon Polyurethane Ind Co Ltd | Thermoplastic polyurethane resin |
| JPH11292946A (en) * | 1998-04-07 | 1999-10-26 | Nippon Mektron Ltd | Production of granulated material of thermoplastic polyurethane |
| US7695588B2 (en) * | 2001-10-31 | 2010-04-13 | Mitsubishi Heavy Industries, Ltd. | Matrix resin composition for fiber-reinforced plastics and process for production of fiber-reinforced plastics |
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