JPS6079009A - Production of saponified ethylene/vinyl acetate copolymer - Google Patents
Production of saponified ethylene/vinyl acetate copolymerInfo
- Publication number
- JPS6079009A JPS6079009A JP18631983A JP18631983A JPS6079009A JP S6079009 A JPS6079009 A JP S6079009A JP 18631983 A JP18631983 A JP 18631983A JP 18631983 A JP18631983 A JP 18631983A JP S6079009 A JPS6079009 A JP S6079009A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- acetate copolymer
- ethylene
- saponified
- weight
- 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.)
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Abstract
Description
【発明の詳細な説明】
本発明は、特定のエチレン−酢酸ビニル共重合体を特定
の加熱処理をすることによりメルトインデックスを低下
させ機械的物性、環境応力亀裂等の品質が優れたエチレ
ン−酢酸ビニル共重合体けん化物を製造する方法に関す
るものである。Detailed Description of the Invention The present invention provides an ethylene-acetic acid copolymer with excellent mechanical properties, environmental stress cracking, etc. by lowering the melt index by subjecting a specific ethylene-vinyl acetate copolymer to a specific heat treatment. The present invention relates to a method for producing a saponified vinyl copolymer.
一般に、エチレン−酢酸ビニル共重合体けん化物はその
原料樹脂であるエチレン−酢酸ビニル共重合体に比べ、
融点、硬度、拡張力、曲げ強度、曲げ剛性度が高く、さ
らに耐溶剤性、耐、摩耗性、耐気体透過性に優れている
。さらに金属をはじめ各種無機および有機基材との接着
性に優れており、粉体塗料等の被覆材、織物芯地用接着
剤あるいは各種積層接着剤等として広く用いられている
。In general, saponified ethylene-vinyl acetate copolymers have a lower
It has high melting point, hardness, expansion force, bending strength, and bending rigidity, and also has excellent solvent resistance, abrasion resistance, and gas permeation resistance. Furthermore, it has excellent adhesion to various inorganic and organic substrates including metals, and is widely used as coating materials for powder coatings, adhesives for textile interlining, and various lamination adhesives.
エチレン−酢酸ビニル共重合体は高圧重合、溶液重合、
サスペンション重合、エマルジョン重合等によるデジカ
ル共重合によって製造される。ところでエチレン−酢酸
ビニル共重合体けん化物を粉体塗料に使用する場合、粉
体塗料の金属への接着性を向上させるため、環境応力亀
裂の発生を抑制するため、表面硬度を上げるため、表面
光沢をよくするため等粉体塗料の品質を良好にするため
には、比較的酢酸ビニル含量が高いエチレン−酢酸ビニ
ル共重合体を原料にすることが好ましい。そこで酢酸ビ
ニル含量が高いエチレン−酢酸ビニル共重合体をラジカ
ノヒ共重合により製造しようとすると、酢酸ビニル単位
がフリーラジカル連鎖移動性が高いため、粉体塗料の物
性を満足するメルトインデックスの低いエチレン−酢酸
ビニル共重合体を容易に製造することができない。この
ため、粉体塗料用に物性を改良する目的でエチレン−酢
酸ビニル共重合体けん化物にポリイソシアネート化合物
を添加する方法(特開昭51−5858、特開昭5O−
116525)が提案されている。Ethylene-vinyl acetate copolymer can be produced by high-pressure polymerization, solution polymerization,
Manufactured by digital copolymerization such as suspension polymerization and emulsion polymerization. By the way, when saponified ethylene-vinyl acetate copolymer is used in powder coatings, it is necessary to improve the adhesion of the powder coating to metal, to suppress the occurrence of environmental stress cracks, and to increase surface hardness. In order to improve the quality of the powder coating, such as to improve gloss, it is preferable to use an ethylene-vinyl acetate copolymer with a relatively high vinyl acetate content as a raw material. Therefore, when attempting to produce an ethylene-vinyl acetate copolymer with a high vinyl acetate content by radical copolymerization, the vinyl acetate unit has a high free radical chain transfer property, so the ethylene-vinyl acetate copolymer has a low melt index that satisfies the physical properties of powder coatings. Vinyl acetate copolymers cannot be easily produced. For this reason, a method of adding a polyisocyanate compound to a saponified ethylene-vinyl acetate copolymer for the purpose of improving the physical properties for powder coatings (JP-A-51-5858, JP-A-5O-
116525) has been proposed.
しかしながら、これらの方法は食品衛生上の問題があっ
たり、加工安定性の問題があったり、環境応力亀裂等の
物性が十分でない。However, these methods have food hygiene problems, processing stability problems, and physical properties such as environmental stress cracking are not sufficient.
そこで、本発明者らは、これらの問題点を解決すべく鋭
意検討を行なった結果、比較的高い酢酸ビニル単位を有
するエチレン−酢酸ビニル共重合体けん化物を特定の加
熱処理をすることにより、メルトインデックスを低下さ
せ機械的物性、環境応力亀裂等の品質が優れたエチレン
−酢酸ビニル共重合体けん化物を製造する方法を見い出
し本発明に至った。Therefore, the present inventors conducted intensive studies to solve these problems, and found that by subjecting a saponified ethylene-vinyl acetate copolymer having a relatively high vinyl acetate unit to a specific heat treatment, The present inventors have discovered a method for producing a saponified ethylene-vinyl acetate copolymer that has a lower melt index and is superior in mechanical properties, environmental stress cracking, and other qualities, resulting in the present invention.
すなわち本発明は、酢酸ビニル単位を10〜60710
1%含有するエチレン−酢酸ビニル共重合体を50〜9
ci重量%けん化した後、アルカリ触媒の存在下に加熱
処理することからなるメルトインデックスの低下したエ
チレン−酢酸ビニル共重合体けん化物の製造法である。That is, the present invention has vinyl acetate units of 10 to 60,710
50 to 9 ethylene-vinyl acetate copolymer containing 1%
This is a method for producing a saponified ethylene-vinyl acetate copolymer having a reduced melt index, which comprises saponifying the saponified ethylene-vinyl acetate copolymer by weight% ci and then heat-treating it in the presence of an alkali catalyst.
エチレン−酢酸ビニル共重合体けん化物を加熱すること
によりメルトインデックスが低下するのは、ビニルアル
コール単位の水酸基と酢酸ビニル単位のアセトキシ基の
反応によって部分架橋反応が起るためと思われろ。以下
、本発明の詳細な説明する。The melt index is lowered by heating the saponified ethylene-vinyl acetate copolymer, probably because a partial crosslinking reaction occurs due to the reaction between the hydroxyl group of the vinyl alcohol unit and the acetoxy group of the vinyl acetate unit. The present invention will be explained in detail below.
本発明において用いられるエチレン−酢酸ビニル共重合
体は公知の高圧重合、溶液重合、サスペンション重合、
エマルション重合等のラジカル重合により製造される。The ethylene-vinyl acetate copolymer used in the present invention can be produced by known high-pressure polymerization, solution polymerization, suspension polymerization,
Manufactured by radical polymerization such as emulsion polymerization.
エチレン、酢酸ビニル以外にもプロピレン、ブテン−1
1スチレン等の不飽和炭化水素類をlO重量%程度以下
共重合させたものを用いることもできる。本発明におい
て用いられるエチレン−酢酸ビニル共重合体の酢酸ビニ
ル単位の含有量は10〜60重量%である。10重量%
より小さいと本発明のような特別な方法によらずとも、
充分メルトインデックスが小さいエチレン−酢酸ビニル
共重合体を製造でき、それより充分メルトインデックス
が小さいエチレン−酢酸ビニル共重合体けん化物を製造
できる。60重量%より大きいと、それから製造したエ
チレン−酢酸ビニルけん化物の耐水性が低下し粉体塗料
としての品質が低下するので好ましくない。In addition to ethylene and vinyl acetate, propylene and butene-1
It is also possible to use a material obtained by copolymerizing unsaturated hydrocarbons such as 1-styrene in an amount of about 10% by weight or less. The content of vinyl acetate units in the ethylene-vinyl acetate copolymer used in the present invention is 10 to 60% by weight. 10% by weight
If it is smaller, even without using a special method like the present invention,
An ethylene-vinyl acetate copolymer having a sufficiently small melt index can be produced, and a saponified ethylene-vinyl acetate copolymer having a sufficiently small melt index can be produced. If it is more than 60% by weight, the water resistance of the ethylene-vinyl acetate saponified product produced therefrom will decrease and the quality as a powder coating will deteriorate, which is not preferable.
エチレン−酢酸ビニル共重合体のけん化は公知の方法で
行ないうる。たとえばトルエンやキシレン等の炭化水素
類の良溶媒中あるいはこれにメタノール等のアルコール
類を加えた混合溶媒系における均一系、又はメタノール
やエタノール等のアルコール類と必要に応じて水を加え
た非溶媒中における不均一系において、ナトリウムやカ
リウムの水酸化物、アルコキシドなどのアルカリ金属化
合物をけん化反応触媒としてけん化させる。けん化率は
50〜99%が適している。けん化率が50重量%以下
になると硬度が低下して粉体塗料用等の品質が低下して
好ましくない。またげん化率が99重量%以上になると
本発明の方法を適用してもメルトインデックスがあまり
低下しなくなり好ましくない。Saponification of the ethylene-vinyl acetate copolymer can be carried out by known methods. For example, a homogeneous system in a good solvent of hydrocarbons such as toluene or xylene, or a mixed solvent system in which an alcohol such as methanol is added to this, or a non-solvent in which an alcohol such as methanol or ethanol and water is added as necessary. In the heterogeneous system inside, alkali metal compounds such as sodium and potassium hydroxides and alkoxides are used as saponification reaction catalysts for saponification. A saponification rate of 50 to 99% is suitable. If the saponification rate is less than 50% by weight, the hardness decreases and the quality for powder coatings etc. deteriorates, which is not preferable. Furthermore, if the saponification rate is 99% by weight or more, the melt index will not decrease much even if the method of the present invention is applied, which is not preferable.
加熱処理前のエチレン−酢酸ビニル共重合体のけん化物
はメルトインデックス20〜60のものが好ましい。The saponified ethylene-vinyl acetate copolymer before heat treatment preferably has a melt index of 20 to 60.
本発明で使用されるアルカリ触媒としてはリチウム、ナ
トリウム、カリウムの水酸化物、酸化物、アルコキシド
であり、エチレン−ビニルアルコール共重合体のアルコ
キシドも含まれる。The alkali catalysts used in the present invention include hydroxides, oxides, and alkoxides of lithium, sodium, and potassium, including alkoxides of ethylene-vinyl alcohol copolymers.
エチレン−酢酸ビニル共重合体をけん化するのに前述の
ごとく水酸化ナトリウム等のアルカリ金属化合物を使用
するが、これらの触媒は該エチレンー酢酸ビニルけん化
物中に残存しているので、この残存するアルカリ金属化
合物を本発明のアルカリ触媒として使用できる。本発明
のアルカリ触媒の使用量は、アルカリ金属換算でエチレ
ン−酢酸ビニルけん化物に対して100〜200 DI
?”が好ましい。触媒量が少ないと加熱処理時間を長く
要し、触媒量が多すぎると着色し易くなり好ましくない
。As mentioned above, alkali metal compounds such as sodium hydroxide are used to saponify the ethylene-vinyl acetate copolymer, but since these catalysts remain in the ethylene-vinyl acetate saponified product, this residual alkali Metal compounds can be used as alkaline catalysts in the present invention. The amount of the alkali catalyst used in the present invention is 100 to 200 DI in terms of alkali metal based on the saponified ethylene-vinyl acetate.
? " is preferable. If the amount of catalyst is small, the heat treatment time will be long, and if the amount of catalyst is too large, coloring will easily occur, which is not preferable.
本発明における加熱処理は、処理するエチレン−酢酸ビ
ニル共重合体けん化物中の揮発分を少なくしておく必要
がある。揮発分が存在すると架橋反応を阻害する。従っ
て、揮発分は1重量%以下にはしておくのが望ましい。In the heat treatment in the present invention, it is necessary to reduce the volatile content in the saponified ethylene-vinyl acetate copolymer to be treated. The presence of volatiles inhibits the crosslinking reaction. Therefore, it is desirable to keep the volatile content at 1% by weight or less.
加熱処理温度は、60°C〜250℃である。60℃未
満では、反応速度が遅くて加熱処理に長時間を要し25
0°Cを越えると、エチレン−酢酸ビニル共重合体けん
化物が着色するので好しくない。The heat treatment temperature is 60°C to 250°C. At temperatures below 60°C, the reaction rate is slow and the heat treatment takes a long time.
If the temperature exceeds 0°C, the saponified ethylene-vinyl acetate copolymer will be colored, which is not preferable.
加熱処理の方法としては、該エチレンー酢酸ビニル共重
合体けん化物を収納して昇温できるものであればどんな
方法でもよいが、アルカリ触媒が空気中の炭酸ガスを吸
収すると失活するので大気中は好ましくない。減圧の加
熱器、減圧の乾燥器、炭酸ガスを含まない不活性ガス雰
囲気での加熱器、乾燥器などが用いられる。又、溶融混
練するのも1つの方法であり押出機、パンバリミキサー
、ロールなどを用いることができる。加熱処理時間は、
エチレン−酢酸ビニル共重合体けん化物のけん化率、ア
ルカリ触媒量、加熱温度、加熱処理の方法、および処理
後のエチレン−酢酸ビニル共重合体けん化物の目標とす
るメルトインデックスによって変える。経時変化をチェ
ックしながら行うのも1つの方法である。これらの加熱
処理により、処理前のメルトインデックスの値の115
〜2/3 程度に低下させるのが好ましい。Any heat treatment method may be used as long as the saponified ethylene-vinyl acetate copolymer can be stored and heated, but since the alkaline catalyst is deactivated when it absorbs carbon dioxide gas in the air, is not desirable. A reduced pressure heater, a reduced pressure dryer, a heater in an inert gas atmosphere not containing carbon dioxide gas, a dryer, etc. are used. Melt kneading is also one method, and an extruder, Pan Bali mixer, roll, etc. can be used. The heat treatment time is
It varies depending on the saponification rate of the saponified ethylene-vinyl acetate copolymer, the amount of alkali catalyst, the heating temperature, the heat treatment method, and the target melt index of the saponified ethylene-vinyl acetate copolymer after treatment. One method is to check changes over time. Through these heat treatments, the melt index value before treatment was reduced to 115.
It is preferable to reduce it to about 2/3.
本発明の方法によるメルトインデックスを低下させたエ
チレン−酢酸ビニル共重合体けん化物は優れた機械的物
性、耐環境応力亀裂性を有しており、粉体塗料として良
好な品質をもっている。The saponified ethylene-vinyl acetate copolymer whose melt index is lowered by the method of the present invention has excellent mechanical properties and environmental stress cracking resistance, and has good quality as a powder coating.
なお本発明において示した各測定値はそれぞれ次の方法
によって測定したものである。In addition, each measurement value shown in this invention was measured by the following method, respectively.
(1) 酢酸ビニル含有量およびそのけん化率JI8に
−6780−1977に準拠してめた。(1) Vinyl acetate content and its saponification rate were measured in accordance with JI8-6780-1977.
(2) メルトインデックス(MI)
すA7酸のメタノール溶液により洗浄し、エチレン−酢
酸ビニル共重合体けん化物中のアルカリ成分を中和し、
乾燥したものをJI8に−6760−1971に準拠し
て2.16峠の荷重下190℃で測定した。測定値の単
位はfllO分である。(2) Melt index (MI) Washing with a methanol solution of A7 acid to neutralize the alkaline components in the saponified ethylene-vinyl acetate copolymer,
The dried material was measured at 190° C. under a load of 2.16 in accordance with JI8-6760-1971. The unit of measurement is fllO minutes.
(3) アルカリ成分含有量
エチレン−酢酸ビニル共重合体けん化物からアルカリ成
分を熱水で抽出し、指示薬にフェノールフタレンを使用
して塩酸で滴定してめた。(3) Alkaline component content The alkaline component was extracted from the saponified ethylene-vinyl acetate copolymer with hot water, and determined by titration with hydrochloric acid using phenolphthalene as an indicator.
IAs 中FL −1x、 21 m rt= +14
k m u Wk / V Q r! Tl 針& )
JI8に−6760に準拠して、厚さgm、ノ、チ深さ
0.5 N、イゲパールの10重量%水溶液を使用して
実施した。IAs Medium FL -1x, 21 m rt= +14
km u Wk / V Q r! Tl needle & )
The test was carried out in accordance with JI8-6760, using a 10% by weight aqueous solution of Igepearl with a thickness of gm and a depth of 0.5 N.
(5)引張試験
JI8に−6760に準拠して厚さ1m+のプレスシー
トについて実施した。(5) Tensile test A press sheet having a thickness of 1 m+ was tested in accordance with JI8-6760.
(6)揮発分(%)
乾燥条件105℃、5 Torr 、 3時間テ重量減
量を測定、減量を元試料の重量で除した値。(6) Volatile content (%) Weight loss was measured under drying conditions of 105°C, 5 Torr, and 3 hours, and the weight loss was divided by the weight of the original sample.
実施例1
高圧重合によるエチレン−酢酸ビニル共重合体(酢酸ビ
ニル単位含量48重量%、MI;60)をメタノール溶
媒中で水酸化ナトリウムを用いて不拘−牽でけん化を行
ない、エチレン−酢酸ビニル共重合体けん化物中の過剰
のアルカリ成分を除去するためのメタノール洗浄を行っ
た。アルカリ成分含有量(Na換算) 510F、けん
化率97.5重量%、メルトインデックス36のエチレ
ン−酢酸ビニル共重合体けん化物が得られた。乾燥及び
加熱処理を90℃、5.9Torrの条件でロータリー
ドライヤーで実施し、経時変化をメルトインデックス、
揮発分&E80R試験で確認した。その結果を第1表に
示す。又引張試験結果を第2表に示す。Example 1 An ethylene-vinyl acetate copolymer (vinyl acetate unit content: 48% by weight, MI: 60) obtained by high-pressure polymerization was saponified using sodium hydroxide in a methanol solvent without restraint. Methanol washing was performed to remove excess alkaline components in the saponified polymer. A saponified ethylene-vinyl acetate copolymer having an alkali component content (Na equivalent) of 510F, a saponification rate of 97.5% by weight, and a melt index of 36 was obtained. Drying and heat treatment were performed using a rotary dryer at 90°C and 5.9 Torr, and changes over time were measured by melt index,
Confirmed by volatile content & E80R test. The results are shown in Table 1. The tensile test results are also shown in Table 2.
第 1 表 比較例1 実施例1と同様にけん化を行ないメタノ−を中和した。Table 1 Comparative example 1 Saponification was performed in the same manner as in Example 1 to neutralize methanol.
乾燥及び加熱処理を90℃、50Torrの条件でロー
タリードライヤーで実施し、メルトインデックス、引張
試験、E8CR試験を実施した。その結果を第1表に示
す。Drying and heat treatment were performed using a rotary dryer at 90° C. and 50 Torr, and melt index, tensile test, and E8CR test were performed. The results are shown in Table 1.
比較例2
実施例1と同様にけん化、メタノール洗浄を行ない、ア
ルカリ成分含有量(Na換算)950F%けん化率99
.5重量%、メルトインデックス89のエチレン−酢酸
ビニル共重合体けん化物が得られた。乾燥及び加熱処理
を90℃、50 Torrの条件でロータリードライヤ
ーで実施し、実施例1と同様に物性測定をした結果を第
1表に示す。Comparative Example 2 Saponification and methanol washing were performed in the same manner as in Example 1, and the alkaline component content (Na equivalent) was 950F% saponification rate 99
.. A saponified ethylene-vinyl acetate copolymer containing 5% by weight and a melt index of 89 was obtained. Drying and heat treatment were performed using a rotary dryer at 90° C. and 50 Torr, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.
実施例2
高圧重合によるエチレン−酢酸ビニル共重合体(酢酸ビ
ニル単位含量48重量%、Mi;60)をメタノール溶
媒中で水酸化ナトリウムを用いて不均一系でけん化を行
ない、エチレン−酢酸ビニル共重合体けん化物中の過剰
のアル−カリ成分を除去するためにメタノール洗浄を行
なった。アルカリ成分含有量(Na換算) 820F、
けん化率97.0重量%、メルトインデックス88のエ
チレン−酢酸ビニル共重合体けん化物が得られた。Example 2 An ethylene-vinyl acetate copolymer (vinyl acetate unit content: 48% by weight, Mi: 60) produced by high-pressure polymerization was saponified in a heterogeneous system using sodium hydroxide in a methanol solvent to form an ethylene-vinyl acetate copolymer. Methanol washing was performed to remove excess alkali components in the saponified polymer. Alkaline component content (Na equivalent) 820F,
A saponified ethylene-vinyl acetate copolymer having a saponification rate of 97.0% by weight and a melt index of 88 was obtained.
ベント付aoiowz押出機で190℃、滞留時間8分
でメタノールを蒸発させながら押出し、造粒した。実施
例1と同様に物性測定をした結果を第1表に示す。The mixture was extruded and granulated using a vented Aoiowz extruder at 190° C. for a residence time of 8 minutes while evaporating methanol. The physical properties were measured in the same manner as in Example 1, and the results are shown in Table 1.
実施例8
高圧重合によるエチレン−酢酸ビニル共重合体(酢酸ビ
ニル単位含量48重量%、MI=60)をメタノール溶
媒中で水酸化ナトリウムを用いて不均一系でけん化を行
ない、エチレン−酢酸ビニル共重合体けん化物中の過剰
のアルカリ成分を除去するためメタノール洗浄を行なっ
た。アルカリ成分含有量(Na換算)290F、けん化
率79.5重量%、メルトインデックス40のエチレン
−酢酸ビニル共重合体けん化物が得られた。乾燥及び加
熱処理を90℃、50Torrの条件でロータリードラ
イヤーで実施し、メルトインデックス、引張試験、E8
(3R試験を実施した。その結果を第1表に示す。Example 8 An ethylene-vinyl acetate copolymer (vinyl acetate unit content: 48% by weight, MI=60) obtained by high-pressure polymerization was saponified in a heterogeneous system using sodium hydroxide in a methanol solvent to form an ethylene-vinyl acetate copolymer. Methanol washing was performed to remove excess alkali components in the saponified polymer. A saponified ethylene-vinyl acetate copolymer having an alkali component content (Na equivalent) of 290F, a saponification rate of 79.5% by weight, and a melt index of 40 was obtained. Drying and heat treatment were performed using a rotary dryer at 90°C and 50 Torr, and the melt index, tensile test, and E8
(A 3R test was conducted. The results are shown in Table 1.
実施例4
高圧重合によるエチレン−酢酸ビニル共重合体(酢酸ビ
ニル単位含量82重量%、MI=60)をメタノール溶
媒中で水酸化ナトリウムを用いて不均一けん化を行ない
、エチレン−酢酸ビニル共重合体けん化物中の過剰のア
ルカリ成分を除去するためメタノール洗浄を行なった。Example 4 An ethylene-vinyl acetate copolymer (vinyl acetate unit content: 82% by weight, MI=60) obtained by high-pressure polymerization was subjected to heterogeneous saponification using sodium hydroxide in a methanol solvent, and an ethylene-vinyl acetate copolymer was obtained. Methanol washing was performed to remove excess alkaline components in the saponified material.
アルカリ成分含有量(Na換算)250F、けん化率8
0重量%、メルトインデックス46のエチレン−酢酸ビ
ニル共重合体けん化物が得られた。乾燥及び加熱処理を
90℃、5Torrの条件でロータリードライヤーで実
施し、メルトインデックス、引張試験、ESC!R試験
を実施した。その結果を第1表に示す。Alkaline component content (Na equivalent) 250F, saponification rate 8
A saponified ethylene-vinyl acetate copolymer having a melt index of 0% by weight and a melt index of 46 was obtained. Drying and heat treatment were performed using a rotary dryer at 90°C and 5 Torr, and the melt index, tensile test, and ESC! An R test was conducted. The results are shown in Table 1.
Claims (3)
チレン−酢酸ビニル共重合体を50〜99重量%けん化
した後、アルカリ触媒の存在下に加熱処理することから
なるメルトインデックスの低下したエチレン−酢酸ビニ
ル共重合体けん化物の製造方法。(1) Ethylene-vinyl acetate copolymer containing 10-60% by weight of vinyl acetate units is saponified to 50-99% by weight, and then heat-treated in the presence of an alkali catalyst to produce ethylene-vinyl acetate with a reduced melt index. A method for producing a saponified vinyl acetate copolymer.
つその量がエチレン−酢酸ビニル共重合体けん化物当り
アルカリ金属換算でtoo−L2000Waである特許
請求の範囲第1項記載の製造方法。(2) The production method according to claim 1, wherein the alkali catalyst is an alkali or metal compound, and the amount thereof is too-L 2000 Wa in terms of alkali metal per saponified ethylene-vinyl acetate copolymer.
加熱処理前のエチレン−酢酸ビニル共重合体けん化物中
の揮発分が1重量%以下であス姑鯰轄ψ小箭開筐1頂記
載の製造方法。(3) The temperature of the heat treatment is 60 to 250°C, and the volatile content in the saponified ethylene-vinyl acetate copolymer before the heat treatment is 1% by weight or less. 1. The manufacturing method described above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18631983A JPS6079009A (en) | 1983-10-04 | 1983-10-04 | Production of saponified ethylene/vinyl acetate copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18631983A JPS6079009A (en) | 1983-10-04 | 1983-10-04 | Production of saponified ethylene/vinyl acetate copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6079009A true JPS6079009A (en) | 1985-05-04 |
JPS6339004B2 JPS6339004B2 (en) | 1988-08-03 |
Family
ID=16186248
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18631983A Granted JPS6079009A (en) | 1983-10-04 | 1983-10-04 | Production of saponified ethylene/vinyl acetate copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6079009A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021215264A1 (en) * | 2020-04-21 | 2021-10-28 | オイレス工業株式会社 | Polyamide resin composition and sliding member |
-
1983
- 1983-10-04 JP JP18631983A patent/JPS6079009A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021215264A1 (en) * | 2020-04-21 | 2021-10-28 | オイレス工業株式会社 | Polyamide resin composition and sliding member |
CN115605544A (en) * | 2020-04-21 | 2023-01-13 | 奥依列斯工业株式会社(Jp) | Polyamide resin composition and sliding member |
Also Published As
Publication number | Publication date |
---|---|
JPS6339004B2 (en) | 1988-08-03 |
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