JPS62280205A - Removal of volatile matter from styrenic synthetic resin - Google Patents
Removal of volatile matter from styrenic synthetic resinInfo
- Publication number
- JPS62280205A JPS62280205A JP12128086A JP12128086A JPS62280205A JP S62280205 A JPS62280205 A JP S62280205A JP 12128086 A JP12128086 A JP 12128086A JP 12128086 A JP12128086 A JP 12128086A JP S62280205 A JPS62280205 A JP S62280205A
- Authority
- JP
- Japan
- Prior art keywords
- zone
- polymer
- pressure
- water
- vent
- 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
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 10
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- 238000001125 extrusion Methods 0.000 abstract description 12
- 238000002347 injection Methods 0.000 abstract description 12
- 239000007924 injection Substances 0.000 abstract description 12
- 230000006835 compression Effects 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- 238000013022 venting Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003925 fat Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
（産業上の利用分野〕
本発明はスチレン系合成樹脂から、その樹脂中に含有さ
れている揮発性物質を除去する方法に関するものでおる
。Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for removing volatile substances contained in a styrenic synthetic resin from the resin.
最近、スチレン系合成（か１脂は自動車部品、家庭電化
製品、玩具、食品容器等広範囲の用途で使用されている
。この原料別脂中に未反応単量体および溶媒などの揮発
性物質が残留すると、樹脂製品の機械的性質、耐熱性な
どの熱的性質または耐薬部前などの化学的性質を低下さ
せることがよく知られている。Recently, styrene-based synthetic fats have been used in a wide range of applications such as automobile parts, home appliances, toys, and food containers. Volatile substances such as unreacted monomers and solvents are contained in this raw material fat. It is well known that when they remain, they deteriorate the mechanical properties, thermal properties such as heat resistance, or chemical properties such as chemical resistance of resin products.
また樹脂成形時に、これらの揮発性物質か揮敗し成形加
工作業環境を悪化させる。Furthermore, during resin molding, these volatile substances evaporate and deteriorate the molding work environment.
これらの点からスチレン系合成樹脂中の揮発性物質を効
率的に除去し、残留揮発性物質含有量を低下ざぜること
が技術課題となっている。From these points of view, it has become a technical issue to efficiently remove volatile substances from styrenic synthetic resins and reduce the residual volatile substance content.
一方、スチレン系合成樹脂の揮発性物質除去方法として
、特公昭５２−３１２７１号公報に記載されているよう
にベント式押出機を用い、ベント部前に水またはスチー
ムを注入し、ベント部を減圧下に保持することが提案さ
れている。On the other hand, as a method for removing volatile substances from styrene-based synthetic resins, as described in Japanese Patent Publication No. 52-31271, a vented extruder is used, water or steam is injected in front of the vent part, and the vent part is depressurized. It is suggested to keep it below.
しかし、水注入の場合には押出機の押出能力を増大させ
ると、注入した水の発泡による丈−ジンクなとの押出・
吐出不安定性を生ずる。また水注入部でポリマの過冷へ
口を生じ、ポリマの溶融粘度が巽常上昇し、ポリマのベ
ントアップにより真空ベント部が閉塞し、生産を再三中
断することになり、生産効率を低下させる。However, in the case of water injection, if the extrusion capacity of the extruder is increased, the length-zinc extrusion and
Causes discharge instability. In addition, the water injection section creates an opening for supercooling of the polymer, the melt viscosity of the polymer increases rapidly, and the vacuum vent section is clogged due to polymer venting, resulting in repeated interruptions of production and lowering production efficiency. .
更に、水蒸気注入の場合には、押出機内での樹脂の発泡
が激しく、押出能力が低下するとともに、定常的な樹脂
の吐出か困難となり、ベントアップの頻度が激しく、生
産を再三中断し、生産効率を低下させることもある。Furthermore, in the case of steam injection, the resin foams violently in the extruder, reducing the extrusion capacity and making it difficult to discharge the resin regularly, resulting in frequent vent-ups and repeated interruptions of production. It may also reduce efficiency.
そこで本発明者らは、前記欠点を克服すべく鋭意研究し
たところ、スチレン系合成、樹脂から揮発性物質をベン
ト式押出機にて効率的に除去し、残留揮発性物質の含有
徂を著しく低下する方法を見出した。Therefore, the present inventors conducted intensive research to overcome the above drawbacks, and found that volatile substances were efficiently removed from styrene-based synthetic resins using a vented extruder, and the content of residual volatile substances was significantly reduced. I found a way to do it.
本発明は、スチレン系溶融ポリマから揮発性物質を除去
するに際し、ベント式押出はを使用し、ベント前のバレ
ル部に１２０°Ｃ以上の加圧加熱水を１ベント当り、押
出ポリマ通過量の０．５重ａ％以上注入し、ペン１〜部
圧力を３００＃Ｈｇ（絶対圧）以下に保持する方法であ
る。In the present invention, when removing volatile substances from molten styrenic polymer, vent-type extrusion is used, and pressurized heated water of 120°C or higher is poured into the barrel section before venting per vent to reduce the amount of extruded polymer passing through. This is a method in which 0.5% by weight or more is injected and the pen 1-part pressure is maintained at 300 #Hg (absolute pressure) or less.
本発明を適用し得るスチレン系合成樹脂は、汎用ポリス
チレン、耐衝撃性ポリスチレン、へＢＳ樹脂、スチレン
−アクリロニド１ノル共串合体、スチレン−ブタジェン
共重合体等か必り、これらの合成樹脂を製造する方法と
しては１鬼状重合、溶液重合、懸濁重合、乳化重合など
の製造法のいずれでもよい。Styrenic synthetic resins to which the present invention can be applied include general-purpose polystyrene, high-impact polystyrene, HeBS resin, styrene-acrylonide 1-nor copolymer, styrene-butadiene copolymer, etc., and these synthetic resins can be manufactured using As a method for doing this, any production method such as monopolymerization, solution polymerization, suspension polymerization, or emulsion polymerization may be used.
例えば、塊状重合設備からスチレン系合成）ｎ」脂を溶
融状態でベント式押出機に直接供給し、揮発性物質を除
去するプロセスにも適用できる。For example, the method can also be applied to a process in which styrenic synthetic (n) fat is directly fed in a molten state from bulk polymerization equipment to a vented extruder to remove volatile substances.
押出機内に注入する加圧ｈ０熱水は、１２０℃以上、好
ましくは１２０〜２５０°Ｃ１更に好ましくは１４５〜
１７０℃である。この温度が１２０℃以下ならば、サー
ジング、ベントアップが生じ好ましくない。また、加圧
り口熱水は重合体の品質劣化および押出機に使用されて
いる材種への悪影響を与える物質を含有していないこと
が好ましく、加圧加熱した純水が最も良い。The pressurized h0 hot water injected into the extruder has a temperature of 120°C or higher, preferably 120 to 250°C, more preferably 145 to 250°C.
The temperature is 170°C. If this temperature is below 120°C, surging and venting may occur, which is not preferable. Further, it is preferable that the pressurized hot water does not contain substances that cause quality deterioration of the polymer or adversely affect the material used in the extruder, and pure water heated under pressure is best.
また加圧加熱水は、水の水蒸気圧以上、通常３Ｃ）〜６
０ＫＩ／ｃｒｉ ・Ｇ、最大６５Ｋｇ／ｃｍ ・Ｇて使
用する。In addition, pressurized heated water has a water vapor pressure higher than that of water, usually 3C) to 6
Use at 0KI/cri ・G, maximum 65Kg/cm ・G.
注入する加圧加熱水の量は、１ベント当り押出ポリマ通
過ｄの０．５重量％以上、好ましくは２〜１０重母％、
更に好ましくは２〜５重宿％であり、押出機タイプ、ポ
１ツマ温度、（創脂の溶融粘度等を考慮し、最適の注水
量を選定することになる。The amount of pressurized heated water to be injected is 0.5% by weight or more of the extruded polymer passing d per vent, preferably 2 to 10% by weight,
More preferably, it is 2 to 5%, and the optimum amount of water to be poured should be selected in consideration of the extruder type, pot temperature, melt viscosity of the wound fat, etc.
０．５型組％以下ならば揮発性物質の除去を十分てきな
いため、水蒸気蒸溜か十分達成できない。If it is less than 0.5%, volatile substances cannot be removed sufficiently and steam distillation cannot be achieved satisfactorily.
また、この■か多過ぎるとベントアップが起り易いため
好ましくない。Also, if the amount of () is too large, vent-up is likely to occur, which is not preferable.
本発明にて使用される押出機は単軸または２軸で、ベン
ト部を１ケ所以上有し、加圧加熱水の注入ケ所は１ケ所
以上の復数ケ所であってもよい。The extruder used in the present invention may be a single-screw or twin-screw extruder, and may have one or more vents, and the pressurized and heated water may be injected at one or more locations.
加圧加熱水の注入装嵌としては、例えば定量容積式加圧
ポンプ（プランジャポンプ）にて純水を数十気圧にｊＯ
圧後、２重管式加熱器でそのシャケラ］・側をスチーム
にて１２０℃以上に加熱することによって）ヱ成できる
。For injection of pressurized heated water, for example, pure water is heated to several tens of atmospheres using a fixed displacement pressurization pump (plunger pump).
After pressurizing, it can be formed by heating its side with steam to 120° C. or higher using a double-pipe heater.
またベント部にお（プる真空度（は３００ｍｍ ｌ−Ｉ
ＣＩ（絶対圧）以下、好ましくは３０〜３００ｓＨＣ
ｌとする。多段ベント式押出機において（よ、１段ベン
ト部の真空度を２００醋ＨＱ（絶対圧）以下、２段ベン
ト部以降を１００ｍ日Ｑ（絶対圧）以下とするのが好ま
しい。In addition, the vacuum level (approximately 300 mm l-I) is
CI (absolute pressure) or less, preferably 30 to 300 sHC
Let it be l. In a multi-stage vent type extruder, it is preferable that the degree of vacuum in the first stage vent part be 200 HQ (absolute pressure) or less, and the degree of vacuum in the second stage vent part and thereafter be 100 m day Q (absolute pressure) or less.
本発明の作用を第１図のベン１〜式押出渫霞念図をもっ
て説明する。The operation of the present invention will be explained with reference to the diagram of Ben 1-type extrusion shown in FIG.
スチレン系！容融樹脂またはペレットを樹脂供給口１よ
り供給し、単軸または２＠ｌ＋の押出スクリュー７にて
加熱溶融圧縮する。Styrene type! Molten resin or pellets are supplied from the resin supply port 1 and heated and melted and compressed by a single or 2@1+ extrusion screw 7.
ポリマ供給圧縮部（Ａ部）に定ｆｆ１ｊＤ圧ポンプにて
、注入水を水注入バレル部４のポリマ圧力以上の圧力に
保持し、１２０℃以上に加熱した加圧１ノ０熱水をｈ０
圧加熱水注入口２より注入する。The injected water is maintained at a pressure higher than the polymer pressure in the water injection barrel section 4 using a constant ff1jD pressure pump in the polymer supply compression section (section A), and pressurized 1-0 hot water heated to 120°C or higher is heated to h0.
Inject from pressure-heated water inlet 2.
注入された加圧加熱水は、ベント部（Ｄ部）においてス
クリューの剪断混合作用で溶融ポリマと均一混合され、
ベント部圧力３００１７１７ＩＩＨＣＩ以下の圧力に保
持することｔこよって、ポリマ中の揮発性物質とともに
ベント孔３から除去される。揮発ＩＩ動物質水が除去さ
れたポリマはスクリュ計量部て圧縮定損され、ダイス部
６より吐出される。The injected pressurized heated water is uniformly mixed with the molten polymer in the vent section (D section) by the shear mixing action of the screw.
By maintaining the pressure at the vent part pressure 3001717IIHCI or lower, the volatile substances in the polymer are removed from the vent hole 3. The polymer from which the volatile II animal water has been removed is compressed at a screw metering section and discharged from the die section 6.
（実施例） 本発明を実施例、比較例てもって説明する。(Example) The present invention will be explained with reference to Examples and Comparative Examples.
２軸のベント式押出機を用い、ＡＢＳ （アクリロ二１
〜リルーブタジエンースチレン共重合）樹脂の揮発性物
質除去試験を行なった。Using a twin-screw vented extruder, ABS
A volatile substance removal test was conducted on the resin (~lylubutadiene-styrene copolymerization).
使用したベント式押出機は第１図に示されるとおりであ
り、軸径か６０ｍφ、Ｌ／Ｄ＝３２で、ベント部前のバ
レル部４に加熱加圧水の注入口を設けた（Ｄ部）。The vent type extruder used was as shown in FIG. 1, with a shaft diameter of 60 mφ, L/D=32, and an injection port for heated and pressurized water was provided in the barrel section 4 in front of the vent section (section D).
試験に供したＡＢＳ＠脂中には揮発性物質が３５０ｏｐ
ｐｍ存在し、樹脂供給孔１から押出機内に供給した。供
給された樹脂は、供給圧縮部（Ａ部）で溶融される。溶
融樹脂流れに対し、加圧加熱水注入口２より所定量の加
熱水をプランジャポンプにてポリマ中に注入する。Volatile substances in the ABS @ fat used in the test were 350 op.
pm was present and was supplied into the extruder from the resin supply hole 1. The supplied resin is melted in the supply compression section (A section). A predetermined amount of heated water is injected into the polymer from the pressurized heated water inlet 2 using a plunger pump against the flow of the molten resin.
注入された水はベント孔３にて３００ｍＨＣｌ以下の圧
力に（呆持され、揮発性物質とともに排気され、開開中
の揮発性物質が除去される。揮発性物質が除去された樹
脂は計曇部（Ｂ部）で加圧され、ヘッドダイ部（０部）
より押出しされる。The injected water is held at a pressure of 300 mHCl or less in the vent hole 3, and is exhausted together with volatile substances to remove volatile substances during development.The resin from which volatile substances have been removed is Pressure is applied at the part (B part), and the head die part (0 part)
more extruded.
試験結果を表１に示す。The test results are shown in Table 1.
実施例１〜５では注入水量０．５％以上、注入水温１２
０〜１５０℃１注入水圧力３５〜４３Ｋｇ／ ｃｔｒｔ
Ｇ、ベント真空度１ｏＯ〜３００＃Ｈｇ（絶対圧）で
樹脂中の揮発性物質含有量を０．１％以下に減少させる
ことができ、押出時のサージング、ベントアップもなく
押出量も２０３〜２０８に３／Ｈｒと運転状態は安定し
ていた。In Examples 1 to 5, the injection water amount was 0.5% or more, and the injection water temperature was 12
0~150℃ 1 injection water pressure 35~43Kg/ctrt
G. The volatile substance content in the resin can be reduced to 0.1% or less at a vent vacuum level of 1oO~300#Hg (absolute pressure), and there is no surging or vent up during extrusion, and the extrusion amount is 203~300#Hg (absolute pressure). The operating condition was stable at 3/Hr at 208.
これに対し比較例６．７．１０は注入水温がそれぞれ３
０℃１８０°Ｃと１２０℃以下て必るため、押出時にサ
ージングを生じ運転状態が不安定でおった。比較例８で
は注入水量か０．３％と低く、揮発性物質含有量を０．
１％以下にすることができなかった。比較例９にて加圧
加熱水のかわりに４に３／ｃｔＡＧの飽和水蒸気を注入
したところ、ベント部での発泡が激しく、ベントアップ
を生じ、生産継続が困難でめった。比較例］１において
は、ベント真空度が３５０ｍｍＨＣＪとなり、揮発性物
質含有量を０．１％以下にすることができなかった。On the other hand, in Comparative Examples 6, 7, and 10, the injection water temperature was 3.
Since the temperature was between 0°C and 180°C and below 120°C, surging occurred during extrusion and the operating conditions were unstable. In Comparative Example 8, the amount of water injected was as low as 0.3%, and the volatile substance content was 0.3%.
It was not possible to reduce the amount to 1% or less. In Comparative Example 9, when saturated steam of 3/ctAG was injected into 4 instead of pressurized and heated water, foaming at the vent part was severe and vent up occurred, making it difficult to continue production. In Comparative Example] 1, the degree of vent vacuum was 350 mmHCJ, and the volatile substance content could not be reduced to 0.1% or less.
本発明ではベント部前のバレル部に加圧り口熱水を注入
し、ベント部の圧力を低くすることにより、スチレン系
溶融ポリマから揮発性物質を効率良く０．１％以下にす
ることかできる。しかも、この揮発ｉ生物質の除去は、
押出時のサージング、ベントアップ等のトラブルもなく
、安定した運転状態で行なうことかできる。In the present invention, by injecting pressurized hot water into the barrel section in front of the vent section and lowering the pressure at the vent section, volatile substances can be efficiently reduced to 0.1% or less from the molten styrene polymer. can. Moreover, the removal of this volatile biological substance is
There are no problems such as surging or venting during extrusion, and the extrusion can be carried out under stable operating conditions.
第１図は本発明の実施態様を示すためのベント式押出典
慨形図である。
１は樹脂供給口、２は加圧加熱水注入口、３はベント孔
、４はバレル部、５は押出機ヘッド、６はダイス部、７
は単軸または２軸スクリユーを示す。 Ａ部は供給圧縮
部、Ｂ部は計曇部、０部はヘッドダイ部、Ｄ部は加圧加
熱水注入部／ベント部を示す。FIG. 1 is a schematic diagram of a vented pusher to illustrate an embodiment of the present invention. 1 is a resin supply port, 2 is a pressurized heated water inlet, 3 is a vent hole, 4 is a barrel part, 5 is an extruder head, 6 is a die part, 7
indicates a single or dual screw. Part A is a supply compression part, part B is a metering part, part 0 is a head die part, and part D is a pressurized and heated water injection part/vent part.
Claims (1)
、ベント式押出機を使用し、ベント部前のバレル部に１
２０℃以上の加圧加熱水を１ベント当り、押出ポリマ通
過量の０．５重量％以上注入し、ベント部圧力を３００
ｍｍＨｇ（絶対圧）以下に保持することを特徴とするス
チレン系合成樹脂より揮発性物質を除去する方法。When removing volatile substances from molten styrenic polymer, a vented extruder is used, and one
Pressurized heated water at 20°C or higher is injected into each vent in an amount of 0.5% by weight or more of the amount of extruded polymer passing through, and the pressure at the vent part is set to 300°C.
A method for removing volatile substances from a styrene-based synthetic resin, characterized by maintaining the pressure below mmHg (absolute pressure).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12128086A JPS62280205A (en) | 1986-05-28 | 1986-05-28 | Removal of volatile matter from styrenic synthetic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12128086A JPS62280205A (en) | 1986-05-28 | 1986-05-28 | Removal of volatile matter from styrenic synthetic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62280205A true JPS62280205A (en) | 1987-12-05 |
| JPH0374681B2 JPH0374681B2 (en) | 1991-11-27 |
Family
ID=14807345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12128086A Granted JPS62280205A (en) | 1986-05-28 | 1986-05-28 | Removal of volatile matter from styrenic synthetic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62280205A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0356504A (en) * | 1989-07-26 | 1991-03-12 | Idemitsu Petrochem Co Ltd | Method for removing residual volatile content of styrenic polymer |
| WO2002022723A1 (en) * | 2000-09-14 | 2002-03-21 | Jsp Corporation | Core material for vacuum heat insulation material and vacuum heat insulation material |
| WO2005021227A1 (en) * | 2003-08-28 | 2005-03-10 | Zeon Corporation | Apparatus for producing polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60231750A (en) * | 1984-05-02 | 1985-11-18 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
-
1986
- 1986-05-28 JP JP12128086A patent/JPS62280205A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60231750A (en) * | 1984-05-02 | 1985-11-18 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0356504A (en) * | 1989-07-26 | 1991-03-12 | Idemitsu Petrochem Co Ltd | Method for removing residual volatile content of styrenic polymer |
| WO2002022723A1 (en) * | 2000-09-14 | 2002-03-21 | Jsp Corporation | Core material for vacuum heat insulation material and vacuum heat insulation material |
| US7166348B2 (en) | 2000-09-14 | 2007-01-23 | Jsp Corporation | Core material for vacuum heat insulation material, and vacuum heat insulation material |
| JP4978979B2 (en) * | 2000-09-14 | 2012-07-18 | 株式会社ジェイエスピー | Vacuum insulation core material and vacuum insulation material |
| WO2005021227A1 (en) * | 2003-08-28 | 2005-03-10 | Zeon Corporation | Apparatus for producing polymer |
| JPWO2005021227A1 (en) * | 2003-08-28 | 2006-10-26 | 大見 忠弘 | Polymer production equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0374681B2 (en) | 1991-11-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |