JPH10195147A - Production of vinyl-chloride-grafted copolymer - Google Patents
Production of vinyl-chloride-grafted copolymerInfo
- Publication number
- JPH10195147A JPH10195147A JP1450097A JP1450097A JPH10195147A JP H10195147 A JPH10195147 A JP H10195147A JP 1450097 A JP1450097 A JP 1450097A JP 1450097 A JP1450097 A JP 1450097A JP H10195147 A JPH10195147 A JP H10195147A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- vinyl chloride
- polymerization
- vinyl
- ethylene
- 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
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化ビニル系グラ
フト共重合体の製造方法に関する。さらに詳しくは、本
発明は、フィルム、シートなどに成形したとき、フィッ
シュアイの発生の少ない塩化ビニル系グラフト共重合体
の製造方法に関する。[0001] The present invention relates to a method for producing a vinyl chloride-based graft copolymer. More specifically, the present invention relates to a method for producing a vinyl chloride-based graft copolymer which is less likely to generate fish eyes when formed into a film, a sheet, or the like.
【０００２】[0002]
【従来の技術】ポリ塩化ビニルは優れた機械的特性を有
しており、塩化ビニル樹脂として広く用いられている
が、ポリ塩化ビニルには熱可塑性が劣るという欠点があ
る。従来、ポリ塩化ビニルの熱可塑性を向上する目的
で、ポリ塩化ビニルに少量の可塑剤を添加し、あるいは
塩化ビニルにエチレン、プロピレン、酢酸ビニルなどを
共重合し、あるいはポリ塩化ビニルに軟質樹脂をブレン
ドする方法が知られている。これらの方法によって、塩
化ビニル樹脂組成物の成形加工性はある程度改良される
ものの、決して十分ではなく、可塑剤の揮発又は移行に
よる物性低下が問題となり、共重合系、ブレンド系はそ
の改良効果が十分でなく、一つの欠点を改良すると、塩
化ビニル樹脂の他の特性の低下を招くなどの問題があ
る。他方、エチレン−ビニルエステル共重合体に、ラジ
カル重合法により塩化ビニルをグラフト重合させること
により、塩化ビニル系グラフト共重合体を製造する方法
が知られている。この方法により得られた塩化ビニル系
グラフト共重合体は、ブレンド系では見られない優れた
耐衝撃性、加工性、内部可塑性、電気絶縁性を有し、包
装用シート、建材、電線被覆材などの幅広い分野で使用
されている。しかし、塩化ビニル系グラフト共重合体に
見られる問題点として、重合系の均一化が不十分なまま
重合し、あるいは、前の重合バッチの重合物粒子を残し
たまま重合することにより、部分的に塩化ビニル単量体
組成の高い重合物粒子を生成し、加工時に未溶融のまま
残って成形品表面にフィッシュアイを発生させる場合が
ある。特公平５−５４４８３号公報には、エチレン−ビ
ニルエステル共重合体に塩化ビニルをグラフト重合する
際に、ソルビタン高級脂肪酸エステル系又はポリビニル
アルコール系分散剤の存在下に重合を開始し、さらに重
合転化率が５〜４０％である間に水溶性分散剤を添加す
ることにより、製品表面にフィッシュアイの少ない塩化
ビニル系グラフト共重合体を得る方法が提案されてい
る。しかし、この方法は重合中の操作が煩雑である上
に、エチレン−ビニルエステル共重合体と単量体の組成
比により水溶性分散剤の添加時期、添加量の調整が必要
である。このため、エチレン−ビニルエステル共重合体
に、ラジカル重合法により塩化ビニル又は塩化ビニルと
他の単量体の混合物をグラフト重合し、フィッシュアイ
の少ない塩化ビニル系グラフト共重合体を容易に製造す
ることができる方法の開発が求められている。2. Description of the Related Art Polyvinyl chloride has excellent mechanical properties and is widely used as a vinyl chloride resin. However, polyvinyl chloride has a drawback of poor thermoplasticity. Conventionally, in order to improve the thermoplasticity of polyvinyl chloride, a small amount of a plasticizer is added to polyvinyl chloride, or ethylene, propylene, or vinyl acetate is copolymerized with polyvinyl chloride, or a soft resin is added to polyvinyl chloride. Methods for blending are known. By these methods, although the molding processability of the vinyl chloride resin composition is improved to some extent, it is not sufficient, and the physical properties decrease due to volatilization or migration of the plasticizer becomes a problem. If it is not sufficient and one of the disadvantages is improved, there is a problem that other characteristics of the vinyl chloride resin are deteriorated. On the other hand, there is known a method of producing a vinyl chloride graft copolymer by graft-polymerizing vinyl chloride to an ethylene-vinyl ester copolymer by a radical polymerization method. The vinyl chloride graft copolymer obtained by this method has excellent impact resistance, processability, internal plasticity, and electrical insulation properties not found in blends, and is used for packaging sheets, building materials, wire covering materials, etc. Is used in a wide range of fields. However, the problem encountered with vinyl chloride graft copolymers is that the polymerization is partially carried out with insufficient homogenization of the polymerization system or with the polymerization particles remaining from the previous polymerization batch. In some cases, polymer particles having a high vinyl chloride monomer composition are generated, remain unmelted during processing, and generate fish eyes on the surface of the molded product. Japanese Patent Publication No. 5-54383 discloses that when vinyl chloride is graft-polymerized to an ethylene-vinyl ester copolymer, polymerization is started in the presence of a sorbitan higher fatty acid ester-based or polyvinyl alcohol-based dispersant, and further subjected to polymerization conversion. A method has been proposed in which a water-soluble dispersant is added while the ratio is 5 to 40% to obtain a vinyl chloride-based graft copolymer having few fish eyes on the product surface. However, in this method, the operation during polymerization is complicated, and it is necessary to adjust the addition timing and amount of the water-soluble dispersant depending on the composition ratio of the ethylene-vinyl ester copolymer and the monomer. For this reason, vinyl chloride or a mixture of vinyl chloride and other monomers is graft-polymerized to the ethylene-vinyl ester copolymer by a radical polymerization method to easily produce a vinyl chloride-based graft copolymer having less fish eyes. There is a need to develop ways to do this.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、フィルム、
シートなどに成形したとき、フィッシュアイの発生の少
ない塩化ビニル系グラフト共重合体の製造方法を提供す
ることを目的としてなされたものである。SUMMARY OF THE INVENTION The present invention relates to a film,
An object of the present invention is to provide a method for producing a vinyl chloride-based graft copolymer which is less likely to generate fish eyes when molded into a sheet or the like.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を重ねた結果、エチレン−ビニ
ルエステル共重合体に、塩化ビニル又は塩化ビニルと他
の単量体の混合物をグラフト重合させる際に、エチレン
−ビニルエステル共重合体と単量体の合計量１００重量
部当たり０.１〜０.３重量部の分散安定剤を使用し、分
散安定剤の半量以上を昇温前に仕込み、半量未満を重合
転化率が０.５〜４重量％の間に仕込むことにより、塩
化ビニル系グラフト共重合体成形品中のフィッシュアイ
を効果的に減少し得ることを見いだし、この知見に基づ
いて本発明を完成するに至った。すなわち、本発明は、
（１）エチレン−ビニルエステル共重合体に、ラジカル
重合法により塩化ビニル又は塩化ビニル及びこれと共重
合し得るエチレン系不飽和単量体の混合物をグラフト重
合させる塩化ビニル系グラフト共重合体の製造方法にお
いて、エチレン−ビニルエステル共重合体と単量体の合
計量１００重量部当たり０.１〜０.３重量部の分散安定
剤を使用し、分散安定剤の５０〜８５重量％を昇温前に
仕込み、次いで昇温して重合反応を開始し、残余の分散
安定剤１５〜５０重量％を重合転化率が０.５〜４重量
％の間に仕込むことを特徴とする塩化ビニル系グラフト
共重合体の製造方法、（２）エチレン−ビニルエステル
共重合体の量が４０〜７０重量％であり、塩化ビニル又
は塩化ビニル及びこれと共重合し得るエチレン系不飽和
単量体の混合物の量が３０〜６０重量％である第(１)項
記載の塩化ビニル系グラフト共重合体の製造方法、及
び、（３）エチレン−ビニルエステル共重合体が、エチ
レン３５〜８５重量％及びビニルエステル１５〜６５重
量％からなる共重合体である第(１)項又は第(２)項記載
の塩化ビニル系グラフト共重合体の製造方法、を提供す
るものである。さらに、本発明の好ましい態様として、
（４）塩化ビニル及びこれと共重合し得るエチレン系不
飽和単量体の混合物中の塩化ビニルの量が５０重量％以
上である第(１)項、第(２)項又は第(３)項記載の塩化ビ
ニル系グラフト共重合体の製造方法、を挙げることがで
きる。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that ethylene-vinyl ester copolymers have vinyl chloride or vinyl chloride and other monomers. When the mixture is graft-polymerized, 0.1 to 0.3 parts by weight of the dispersion stabilizer is used per 100 parts by weight of the total amount of the ethylene-vinyl ester copolymer and the monomer, and half or more of the dispersion stabilizer is used. It has been found that fish eyes in a vinyl chloride graft copolymer molded article can be effectively reduced by charging before the temperature rise and charging less than half the amount while the polymerization conversion is 0.5 to 4% by weight. The present invention has been completed based on this finding. That is, the present invention
(1) Production of a vinyl chloride-based graft copolymer in which vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith is graft-polymerized to an ethylene-vinyl ester copolymer by a radical polymerization method. In the method, 0.1 to 0.3 parts by weight of the dispersion stabilizer is used per 100 parts by weight of the total amount of the ethylene-vinyl ester copolymer and the monomer, and 50 to 85% by weight of the dispersion stabilizer is heated. A vinyl chloride graft wherein the polymerization reaction is started by raising the temperature and then raising the temperature to start the polymerization reaction, and the remaining 15 to 50% by weight of the dispersion stabilizer is charged to a polymerization conversion of 0.5 to 4% by weight. A method for producing a copolymer, wherein (2) the amount of the ethylene-vinyl ester copolymer is 40 to 70% by weight, and vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith. amount (1) The method for producing a vinyl chloride-based graft copolymer according to (1), which is 30 to 60% by weight, and (3) 35 to 85% by weight of ethylene-vinyl ester copolymer and 15 to 50% of vinyl ester. It is intended to provide a method for producing a vinyl chloride-based graft copolymer according to the above (1) or (2), which is a copolymer comprising 65% by weight. Further, as a preferred embodiment of the present invention,
(4) Item (1), (2) or (3) wherein the amount of vinyl chloride in the mixture of vinyl chloride and the ethylenically unsaturated monomer copolymerizable therewith is 50% by weight or more. And a method for producing a vinyl chloride-based graft copolymer described in the section.
【０００５】[0005]
【発明の実施の形態】本発明方法においては、エチレン
−ビニルエステル共重合体に、ラジカル重合法により塩
化ビニル又は塩化ビニル及びこれと共重合し得るエチレ
ン系不飽和単量体の混合物をグラフト重合する。エチレ
ン−ビニルエステル共重合体は、エチレン３５〜８５重
量％及びビニルエステル１５〜６５重量％からなる共重
合体であることが好ましい。エチレン−ビニルエステル
共重合体のエチレン単位が３５重量％未満であると、十
分な衝撃強度を確保できないおそれがある。エチレン−
ビニルエステル共重合体のエチレン単位が８５重量％を
超えると、グラフト重合点が不足し、グラフト重合して
いないポリ塩化ビニル又は塩化ビニルと他のエチレン系
不飽和単量体の共重合体が多量に生成するおそれがあ
る。本発明方法において使用するエチレン−ビニルエス
テル共重合体に特に制限はなく、エチレン−酢酸ビニル
共重合体、エチレン−プロピオン酸ビニル共重合体など
を使用することができるが、これらの中でエチレン−酢
酸ビニル共重合体を特に好適に使用することができる。
本発明方法においては、エチレン−ビニルエステル共重
合体に塩化ビニルを単独でグラフト重合し、あるいは、
エチレン−ビニルエステル共重合体に塩化ビニル及び塩
化ビニルと共重合し得るエチレン系不飽和単量体の混合
物をグラフト重合する。塩化ビニルと共重合し得るエチ
レン系不飽和単量体としては、例えば、酢酸ビニル、プ
ロピオン酸ビニル、ラウリン酸ビニルなどの炭素数１〜
１８のモノカルボン酸のビニルエステル、(メタ)アクリ
ル酸メチル、(メタ)アクリル酸ブチルなどの炭素数１〜
１８のアルコールの(メタ)アクリル酸エステル、ブチル
ビニルエーテル、ラウリルビニルエーテルなどのアルキ
ルビニルエーテル、さらに塩化ビニリデンなどを挙げる
ことができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the method of the present invention, an ethylene-vinyl ester copolymer is graft-polymerized with vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith by a radical polymerization method. I do. The ethylene-vinyl ester copolymer is preferably a copolymer composed of 35 to 85% by weight of ethylene and 15 to 65% by weight of a vinyl ester. If the ethylene unit of the ethylene-vinyl ester copolymer is less than 35% by weight, it may not be possible to secure sufficient impact strength. Ethylene-
When the ethylene unit of the vinyl ester copolymer exceeds 85% by weight, the graft polymerization point becomes insufficient, and a large amount of ungrafted polyvinyl chloride or a copolymer of vinyl chloride and another ethylenically unsaturated monomer is used. May be generated. The ethylene-vinyl ester copolymer used in the method of the present invention is not particularly limited, and ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer and the like can be used. A vinyl acetate copolymer can be particularly preferably used.
In the method of the present invention, vinyl chloride alone is graft-polymerized to an ethylene-vinyl ester copolymer, or
A mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable with vinyl chloride is graft-polymerized to the ethylene-vinyl ester copolymer. Examples of the ethylenically unsaturated monomer that can be copolymerized with vinyl chloride include, for example, vinyl acetate, vinyl propionate, vinyl laurate, etc.
Vinyl esters of 18 monocarboxylic acids, (meth) methyl acrylate, 1 to 1 carbon atoms such as butyl (meth) acrylate
Alkyl 18 (meth) acrylic acid esters, alkyl vinyl ethers such as butyl vinyl ether and lauryl vinyl ether, and vinylidene chloride.
【０００６】本発明方法において、塩化ビニル及び塩化
ビニルと共重合し得るエチレン系不飽和単量体の混合物
をグラフト重合する場合は、単量体混合物中の塩化ビニ
ルの量が５０重量％以上であることが好ましく、７５重
量％以上であることがより好ましい。単量体混合物中の
塩化ビニルの量が５０重量％未満であると、得られる共
重合体が塩化ビニル系グラフト共重合体が本来有する優
れた特性を十分に備えなくなるおそれがある。本発明方
法においては、エチレン−ビニルエステル共重合体と塩
化ビニル又は塩化ビニル及びこれと共重合し得るエチレ
ン系不飽和単量体の混合物の比は、エチレン−ビニルエ
ステル共重合体が４０〜７０重量％であり、塩化ビニル
又は塩化ビニル及びこれと共重合し得るエチレン系不飽
和単量体の混合物が３０〜６０重量％であることが好ま
しい。エチレン−ビニルエステル共重合体の量が４０重
量％未満であると、十分な伸びや柔軟性が得難くなるお
それがある。エチレン−ビニルエステル共重合体の量が
７０重量％を超えると、抗張力が低下したり、粘着性が
増す傾向が出て、物性面、作業面に問題を生ずるおそれ
がある。本発明方法においては、エチレン−ビニルエス
テル共重合体に、ラジカル重合法により塩化ビニル又は
塩化ビニル及びこれと共重合し得るエチレン系不飽和単
量体の混合物をグラフト重合させる方法には特に制限は
なく、例えば、懸濁重合法、微細懸濁重合法などを用い
ることができる。懸濁重合法においては、先ず撹拌機を
備えた重合槽に水性媒体を仕込み、分散剤と、必要に応
じて少量の界面活性剤などを溶解し、エチレン−ビニル
エステル共重合体を仕込み、油溶性ラジカル重合開始剤
を添加して撹拌する。次いで、重合槽を脱気し、必要に
応じて窒素などの不活性気体で雰囲気を置換する。次い
で、塩化ビニル又は塩化ビニル及びこれと共重合し得る
エチレン系不飽和単量体の混合物を仕込み、撹拌しつつ
所定の重合温度まで昇温する。重合槽のジャケットの水
温の変化から、重合の開始を把握することができる。重
合を続けて、転化率が所定の値に達したとき、重合を停
止し、未反応の塩化ビニルを回収する。粉末状ないし粒
状の共重合体は、ろ過脱水し、乾燥して、塩化ビニル系
グラフト共重合体を得ることができる。懸濁重合で用い
る上記分散剤としては、ポリビニルアルコール；ゼラチ
ン；メチルセルロース、ヒドロキシプロピルオキシメチ
ルセルロースなどの水溶性セルロース誘導体などが例示
される。また、懸濁重合法において使用する上記油溶性
ラジカル重合開始剤としては、例えば、アセチルパーオ
キシド、３,５,５−トリメチルヘキサノイルパーオキシ
ド、ラウロイルパーオキシド、ベンゾイルパーオキシ
ド、ナフトイルパーオキシドなどのジアシルパーオキシ
ド；メチルエチルケトンパーオキシドなどのケトンパー
オキシド；クメンヒドロパーオキシド、ｐ−シメンヒド
ロパーオキシド、ｔ−ブチルヒドロパーオキシドなどの
ヒドロパーオキシド；ｔ−ブチルパーオキシピバレート
などのパーオキシエステル、ジイソプロピルパーオキシ
ジカーボネート、ジエチルヘキシルパーオキシジカーボ
ネートなどのパーオキシジカーボネート；アセチルシク
ロヘキシルスルフォニルパーオキシドなどのスルフォニ
ルパーオキシドなどの有機過酸化物；これらの有機過酸
化物とロンガリットなどの還元剤を組み合わせた酸化還
元型重合開始剤；２,２'−アゾビスイソブチロニトリ
ル、２,２'−アゾビス(２−メチルブチロニトリル)、
２,２'−アゾビス(２,４−ジメチルバレロニトリル)、
２,２'−アゾビス(４−メトキシ−２,４−ジメチルバレ
ロニトリル)などのアゾ化合物などを挙げることができ
る。使用する油溶性ラジカル重合開始剤は、単量体に対
して０.００１〜０.５重量％を用いることが好ましい。
これらの油溶性ラジカル重合開始剤は、１種を単独で用
いることができ、２種以上を組み合わせて用いることも
できる。In the method of the present invention, when graft-polymerizing a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable with vinyl chloride, the amount of vinyl chloride in the monomer mixture is not less than 50% by weight. Preferably, it is at least 75% by weight. If the amount of vinyl chloride in the monomer mixture is less than 50% by weight, the obtained copolymer may not sufficiently have the excellent properties inherent in the vinyl chloride graft copolymer. In the method of the present invention, the ratio of the ethylene-vinyl ester copolymer to vinyl chloride or a mixture of vinyl chloride and the ethylenically unsaturated monomer copolymerizable therewith is such that the ethylene-vinyl ester copolymer is 40 to 70. %, And preferably 30 to 60% by weight of vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith. If the amount of the ethylene-vinyl ester copolymer is less than 40% by weight, it may be difficult to obtain sufficient elongation and flexibility. When the amount of the ethylene-vinyl ester copolymer exceeds 70% by weight, the tensile strength tends to decrease and the tackiness tends to increase, which may cause problems in physical properties and workability. In the method of the present invention, there is no particular limitation on the method of graft-polymerizing vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith with an ethylene-vinyl ester copolymer by a radical polymerization method. For example, a suspension polymerization method, a fine suspension polymerization method, or the like can be used. In the suspension polymerization method, first, an aqueous medium is charged into a polymerization tank equipped with a stirrer, a dispersing agent and, if necessary, a small amount of a surfactant are dissolved, and an ethylene-vinyl ester copolymer is charged, and the oil is charged. A soluble radical polymerization initiator is added and stirred. Next, the polymerization tank is degassed, and the atmosphere is replaced with an inert gas such as nitrogen as necessary. Next, vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith is charged, and the temperature is raised to a predetermined polymerization temperature while stirring. From the change in the water temperature of the jacket of the polymerization tank, the start of polymerization can be grasped. The polymerization is continued, and when the conversion reaches a predetermined value, the polymerization is stopped and unreacted vinyl chloride is recovered. The powdery or granular copolymer is filtered, dehydrated, and dried to obtain a vinyl chloride-based graft copolymer. Examples of the dispersant used in suspension polymerization include polyvinyl alcohol; gelatin; and water-soluble cellulose derivatives such as methylcellulose and hydroxypropyloxymethylcellulose. Examples of the oil-soluble radical polymerization initiator used in the suspension polymerization method include acetyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and naphthoyl peroxide. Diacyl peroxides; ketone peroxides such as methyl ethyl ketone peroxide; hydroperoxides such as cumene hydroperoxide, p-cymene hydroperoxide and t-butyl hydroperoxide; peroxyesters such as t-butyl peroxypivalate Peroxydicarbonates such as diisopropyl peroxydicarbonate and diethylhexyl peroxydicarbonate; organic peroxides such as sulfonyl peroxide such as acetylcyclohexylsulfonyl peroxide. Oxidation-reduction polymerization initiator obtained by combining these organic peroxides with a reducing agent such as Rongalit; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) ,
2,2′-azobis (2,4-dimethylvaleronitrile),
An azo compound such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be used. The oil-soluble radical polymerization initiator used is preferably used in an amount of 0.001 to 0.5% by weight based on the monomer.
One of these oil-soluble radical polymerization initiators can be used alone, or two or more can be used in combination.
【０００７】微細懸濁重合法においては、先ず水性媒体
中に、単量体、エチレン−ビニルエステル共重合体、油
溶性ラジカル重合開始剤、界面活性剤、必要に応じて高
級脂肪酸などの重合助剤、その他の添加剤を加えてプレ
ミックスし、ホモジナイザにより均質化処理して油滴の
粒径調節を行う。使用する界面活性剤としては、例え
ば、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホ
ン酸ナトリウムなどのアニオン性界面活性剤、ポリオキ
シエチレンノニルフェニルエーテル、エチレンオキシド
−プロピレンオキシドブロック共重合体などのノニオン
性界面活性剤などを挙げることができる。油溶性ラジカ
ル重合開始剤としては、前記懸濁重合法において用いら
れるものと同様のものが例示される。ホモジナイザとし
ては、例えば、コロイドミル、振動撹拌機などを用いる
ことができる。均質化処理した液を重合装置に送り、緩
やかに撹拌しつつ重合温度に昇温して、所定の転化率に
達するまで重合を行う。本発明方法においては、重合温
度は使用する単量体、重合開始剤などに応じて適宜選択
することができるが、通常は３０〜８０℃とすることが
好ましい。重合温度が３０℃未満であると、反応が遅
く、重合が進まなかったり、あるいは重合に長時間を要
するおそれがある。重合温度が８０℃を超えると、重合
反応の制御が困難になるおそれがある。In the fine suspension polymerization method, first, a monomer, an ethylene-vinyl ester copolymer, an oil-soluble radical polymerization initiator, a surfactant, and, if necessary, a The mixture is premixed with an additive and other additives, and homogenized by a homogenizer to adjust the particle size of the oil droplets. Examples of the surfactant used include, for example, anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and nonionic surfactants such as polyoxyethylene nonylphenyl ether and ethylene oxide-propylene oxide block copolymer. Can be mentioned. Examples of the oil-soluble radical polymerization initiator are the same as those used in the suspension polymerization method. As the homogenizer, for example, a colloid mill, a vibration stirrer, or the like can be used. The homogenized liquid is sent to a polymerization apparatus, and the temperature is raised to the polymerization temperature while gently stirring, and polymerization is performed until a predetermined conversion is reached. In the method of the present invention, the polymerization temperature can be appropriately selected according to the monomer used, the polymerization initiator and the like, but is usually preferably 30 to 80 ° C. If the polymerization temperature is lower than 30 ° C., the reaction may be slow and the polymerization may not proceed, or the polymerization may take a long time. When the polymerization temperature exceeds 80 ° C., it may be difficult to control the polymerization reaction.
【０００８】本発明方法においては、エチレン−ビニル
エステル共重合体と塩化ビニル又は塩化ビニル及びこれ
と共重合し得るエチレン系不飽和単量体の混合物の合計
量１００重量部当たり０.１〜０.３重量部の分散安定剤
を使用し、より好ましくは０.１５〜０.２０重量部の分
散安定剤を使用する。使用する分散安定剤の量が、エチ
レン−ビニルエステル共重合体と単量体の合計量１００
重量部当たり０.１重量部未満であると、重合時におけ
る水系媒体中の粒子の分散安定性を保持することが困難
になるおそれがある。使用する分散安定剤の量が、エチ
レン場合ビニルエステル共重合体と単量体の合計量１０
０重量部当たり０.３重量部を超えると、重合系が完全
に均一化しにくく、フィッシュアイを多く発生する塩化
ビニル系グラフト共重合体となるおそれがある。本発明
方法においては、使用する分散安定剤の５０〜８５重量
％を昇温前に仕込み、次いで昇温して重合反応を開始
し、残余の分散安定剤１５〜５０重量％を重合転化率が
０.５〜４重量％の間に仕込む。さらに、使用する分散
安定剤の６０〜７０重量％を昇温前に仕込み、残余の分
散安定剤３０〜４０重量％を重合転化率が０.５〜４重
量％の間に仕込むことがより好ましい。昇温する前の分
散安定剤の仕込み量が５０重量％未満であると、昇温ま
での液滴の分散安定性を保持することが難しく、重合と
ともに液滴の合一現象が激しくなって粗粒が多くなり、
あるいは、重合系が固結するにいたるおそれがある。昇
温する前の分散安定剤の仕込み量が８５重量％を超える
と、分散安定性は向上するが、重合系が完全に均一化し
にくく、結果として部分的に塩化ビニル単量体組成の高
い重合物粒子を生成し、フィッシュアイを多く発生する
塩化ビニル系グラフト共重合体となるおそれがある。残
余の分散安定剤１５〜５０重量％を重合転化率が０.５
重量％に達する前に仕込むと、フィッシュアイを多く発
生する塩化ビニル系グラフト共重合体となるおそれがあ
る。残余の分散安定剤１５〜５０重量％を重合転化率が
４重量％を超えた後に仕込むと、粗粒の多い塩化ビニル
系グラフト共重合体となるおそれがある。本発明方法に
おいては、重合媒体となる水、エチレン−ビニルエステ
ル共重合体、単量体、重合開始剤、分散剤、界面活性剤
などのほかに、さらに必要に応じて、pH調整剤、連鎖移
動剤、酸化防止剤などの改良剤を添加してグラフト重合
を行うことができる。In the method of the present invention, 0.1 to 0 parts by weight per 100 parts by weight of the total amount of the ethylene-vinyl ester copolymer and vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith. 0.3 parts by weight of a dispersion stabilizer is used, more preferably 0.15 to 0.20 parts by weight of a dispersion stabilizer. The amount of the dispersion stabilizer used is 100% of the total amount of the ethylene-vinyl ester copolymer and the monomer.
If the amount is less than 0.1 part by weight per part by weight, it may be difficult to maintain the dispersion stability of the particles in the aqueous medium during polymerization. When the amount of the dispersion stabilizer used is ethylene, the total amount of the vinyl ester copolymer and the monomer is 10
If the amount exceeds 0.3 parts by weight per 0 parts by weight, the polymerization system is difficult to completely homogenize, and a vinyl chloride-based graft copolymer which generates many fish eyes may be obtained. In the method of the present invention, 50 to 85% by weight of the dispersion stabilizer to be used is charged before the temperature is raised, and then the temperature is raised to start the polymerization reaction. Charge between 0.5-4% by weight. More preferably, 60 to 70% by weight of the dispersion stabilizer to be used is charged before the temperature is raised, and the remaining 30 to 40% by weight of the dispersion stabilizer is charged during the polymerization conversion of 0.5 to 4% by weight. . If the charged amount of the dispersion stabilizer before the temperature rise is less than 50% by weight, it is difficult to maintain the dispersion stability of the droplets until the temperature rises, and the coalescence phenomenon of the droplets becomes severe along with the polymerization, and the The grains increase,
Alternatively, the polymerization system may be solidified. If the amount of the dispersion stabilizer before the temperature rise exceeds 85% by weight, the dispersion stability is improved, but the polymerization system is difficult to completely homogenize, and as a result, the polymerization of the vinyl chloride monomer composition is partially high. There is a possibility that a vinyl chloride-based graft copolymer that generates product particles and generates many fish eyes will be obtained. The remaining 15 to 50% by weight of the dispersion stabilizer is used in a polymerization conversion of 0.5.
If it is charged before reaching the weight%, there is a possibility that a vinyl chloride-based graft copolymer which generates a lot of fish eyes may be obtained. If the remaining 15 to 50% by weight of the dispersion stabilizer is charged after the polymerization conversion exceeds 4% by weight, a vinyl chloride graft copolymer having many coarse particles may be obtained. In the method of the present invention, in addition to water serving as a polymerization medium, an ethylene-vinyl ester copolymer, a monomer, a polymerization initiator, a dispersant, and a surfactant, a pH adjuster, a chain Graft polymerization can be carried out by adding a modifier such as a transfer agent and an antioxidant.
【０００９】[0009]
【実施例】以下に、実施例を挙げて本発明をさらに詳細
に説明するが、本発明はこれらの実施例によりなんら限
定されるものではない。 実施例１ 撹拌機付きの容量１００リットルのオートクレーブに、
イオン交換水３５.０kg、２,２'−アゾビスイソブチロ
ニトリル９.３ｇ、エチレン−酢酸ビニル共重合体［三
井ポリケミカル(株)、エバフレックスＥＶ４０Ｙ、エチ
レン５９重量％、酢酸ビニル４１重量％］１６.０kgを
仕込んだのち、撹拌しながらオートクレーブ内を真空脱
気した。その後、ヒドロキシプロピルセルロース［信越
化学工業(株)、メトローズ６５ＳＨ−５０］の１.０重
量％水溶液３.６kgをオートクレーブ内に吸引させて仕
込み、３０分間撹拌した。次いで、オートクレーブに塩
化ビニル１８.０kgを仕込み、９０分間で６０℃に昇温
した。オートクレーブ内の温度が６０℃に達してから１
５分経過後、重合転化率測定のため、スラリーの一部を
サンプリングしたのち、２段目のヒドロキシプロピルセ
ルロースの１.０重量％水溶液２.４kgを加圧して仕込ん
だ。オートクレーブ内の温度を６０℃に保持したまま重
合を継続し、重合開始から５時間５０分後にオートクレ
ーブ内圧力が４.２kg／cm2Ｇに低下したとき、重合を終
了し、未反応の塩化ビニルを回収した。ろ過脱水し、乾
燥して、白色粉末状の塩化ビニル系グラフト共重合体３
０.５kgを得た。サンプリングスラリーを用いて、２段
目のヒドロキシプロピルセルロース１.０重量％水溶液
２.４kgを加圧して仕込んだときの重合転化率を調べた
ところ、１.２重量％であった。得られた塩化ビニル系
グラフト共重合体１００ｇに、ジブチル錫マレエート３
ｇ、ステアリン酸０.５ｇ及びカーボンブラック２０ｇ
を添加し、１５０℃で５分間ロール練りを行って、厚さ
１５０μｍのシートを作製した。シート裏面より光をあ
て、拡大鏡を用いて１０cm四方内のフィッシュアイを数
え、直径０.３mmより大きいフィッシュアイをフィッシ
ュアイ(大)とし、直径０.１〜０.３mmのフィッシュアイ
をフィッシュアイ(小)として評価した。フィッシュアイ
(大)は０個、フィッシュアイ(小)は８個であった。 実施例２ ヒドロキシプロピルセルロース水溶液の仕込み量を、昇
温前に４.５kg、昇温完了１５分後に１.５kgとした以外
は、実施例１と同様にして重合を行い、白色粉末状の塩
化ビニル系グラフト共重合体３０.６kgを得た。２段目
のヒドロキシプロピルセルロース水溶液を仕込んだとき
の重合転化率は１.２重量％であった。実施例１と同様
にしてシートを作製し、フィッシュアイを評価した。フ
ィッシュアイ(大)は０個、フィッシュアイ(小)は１２個
であった。 実施例３ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に４.８kg、昇温完了１５分後に１.２kgと
した以外は、実施例１と同様にして重合を行い、白色粉
末状の塩化ビニル系グラフト共重合体３０.９kgを得
た。２段目のヒドロキシプロピルセルロース水溶液を仕
込んだときの重合転化率は１.３重量％であった。実施
例１と同様にしてシートを作製し、フィッシュアイを評
価した。フィッシュアイ(大)は１個、フィッシュアイ
(小)は２０個であった。 実施例４ 塩化ビニル１８.０kgの代わりに塩化ビニル１６.０kgと
酢酸ビニル２.０kgを仕込んだ以外は、実施例１と同様
にして重合を行い、白色粉末状の塩化ビニル系グラフト
共重合体３０.０kgを得た。２段目のヒドロキシプロピ
ルセルロース水溶液を仕込んだときの重合転化率は１.
１重量％であった。実施例１と同様にしてシートを作製
し、フィッシュアイを評価した。フィッシュアイ(大)は
１個、フィッシュアイ(小)は６個であった。 比較例１ ヒドロキシプロピルセルロース１重量％水溶液６.０kg
を昇温前に仕込み、昇温完了後にはヒドロキシプロピル
セルロース水溶液の仕込みを行わないこと以外は実施例
１と同様にして重合を行い、白色粉末状の塩化ビニル系
グラフト共重合体３０.５kgを得た。実施例１と同様に
してシートを作製し、フィッシュアイを評価した。フィ
ッシュアイ(大)は５個、フィッシュアイ(小)は４３個で
あった。 比較例２ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に５.４kg、昇温完了１５分後に０.６kgと
した以外は、実施例１と同様にして重合を行い、白色粉
末状の塩化ビニル系グラフト共重合体３０.９kgを得
た。２段目のヒドロキシプロピルセルロース水溶液を仕
込んだときの重合転化率は１.１重量％であった。実施
例１と同様にしてシートを作製し、フィッシュアイを評
価した。フィッシュアイ(大)は４個、フィッシュアイ
(小)は２９個であった。 比較例３ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に２.４kg、昇温完了１５分後に３.６kgと
した以外は、実施例１と同様にして重合を行い、粗粒を
多く含んだ白色粉末状の塩化ビニル系グラフト共重合体
３１.０kgを得た。２段目のヒドロキシプロピルセルロ
ース水溶液を仕込んだときの重合転化率は１.２重量％
であった。実施例１と同様にしてシートを作製し、フィ
ッシュアイを評価した。フィッシュアイ(大)は０個、フ
ィッシュアイ(小)は３個であった。 比較例４ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に１.２kg、昇温完了１５分後に４.８kgと
した以外は、実施例１と同様にして重合を行った。２段
目のヒドロキシプロピルセルロース水溶液を仕込んだと
きの重合転化率は１.３重量％であった。６０℃への昇
温が完了したのち２時間後にオートクレーブ内が固結
し、撹拌が不可能になったので重合を中止した。 比較例５ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に１.０kg、昇温完了１５分後に０.７kgと
した以外は、実施例１と同様にして重合を行った。２段
目のヒドロキシプロピルセルロース水溶液を仕込んだと
きの重合転化率は１.１重量％であった。６０℃への昇
温が完了したのち１.５時間後にオートクレーブ内が固
結し、撹拌が不可能になったので重合を中止した。 比較例６ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に８.０kg、昇温完了１５分後に４.０kgと
した以外は、実施例１と同様にして重合を行い、白色粉
末状の塩化ビニル系グラフト共重合体３０.６kgを得
た。２段目のヒドロキシプロピルセルロース水溶液を仕
込んだときの重合転化率は１.１重量％であった。実施
例１と同様にしてシートを作製し、フィッシュアイを評
価した。フィッシュアイ(大)は５個、フィッシュアイ
(小)は３５個であった。 比較例７ ヒドロキシプロピルセルロース１重量％水溶液の仕込み
量を、昇温前に３.６kg、昇温完了１２０分後に２.４kg
とした以外は、実施例１と同様にして重合を行い、粗粒
を多く含んだ白色粉末状の塩化ビニル系グラフト共重合
体３０.７kgを得た。昇温完了１２０分後のサンプリン
グスラリーを用いて、重合転化率を調べたところ、１３
重量％であった。実施例１と同様にしてシートを作製
し、フィッシュアイを評価した。フィッシュアイ(大)は
０個、フィッシュアイ(小)は１１個であった。実施例１
〜４及び比較例１〜７の結果を、第１表に示す。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Example 1 In a 100-liter autoclave with a stirrer,
35.0 kg of ion-exchanged water, 9.3 g of 2,2'-azobisisobutyronitrile, an ethylene-vinyl acetate copolymer [Mitsui Polychemical Co., Ltd., Evaflex EV40Y, 59% by weight of ethylene, 41% by weight of vinyl acetate %], And the inside of the autoclave was evacuated to vacuum while stirring. Thereafter, 3.6 kg of a 1.0% by weight aqueous solution of hydroxypropylcellulose [Shin-Etsu Chemical Co., Ltd., Metroose 65SH-50] was charged into the autoclave by suction, and stirred for 30 minutes. Next, 18.0 kg of vinyl chloride was charged into the autoclave, and the temperature was raised to 60 ° C. in 90 minutes. 1 after the temperature in the autoclave reaches 60 ° C
After a lapse of 5 minutes, a part of the slurry was sampled to measure the polymerization conversion rate, and then 2.4 kg of a 1.0% by weight aqueous solution of hydroxypropylcellulose in the second stage was charged under pressure. The polymerization was continued while maintaining the temperature in the autoclave at 60 ° C. When the pressure in the autoclave dropped to 4.2 kg / cm 2 G after 5 hours and 50 minutes from the start of the polymerization, the polymerization was terminated and unreacted vinyl chloride was added. Was recovered. After filtration, dehydration and drying, white powdery vinyl chloride graft copolymer 3
0.5 kg was obtained. When 2.4 kg of a 1.0% by weight aqueous solution of hydroxypropylcellulose in the second stage was charged and charged using the sampling slurry, the polymerization conversion was 1.2% by weight. To 100 g of the obtained vinyl chloride graft copolymer, dibutyltin maleate 3 was added.
g, 0.5 g of stearic acid and 20 g of carbon black
Was roll-kneaded at 150 ° C. for 5 minutes to prepare a 150 μm thick sheet. Light from the back of the sheet, count the fish eyes within 10cm square using a magnifying glass, and use the fish eyes larger than 0.3mm in diameter as the fish eyes (large), and the fish eyes with diameters of 0.1 to 0.3mm It was evaluated as an eye (small). Fish eye
The number of (large) was 0 and the number of fish eyes (small) was 8. Example 2 Polymerization was carried out in the same manner as in Example 1 except that the charged amount of the aqueous solution of hydroxypropylcellulose was 4.5 kg before heating and 1.5 kg after 15 minutes from the completion of heating, and the white powdered chloride was obtained. 30.6 kg of a vinyl graft copolymer was obtained. The polymerization conversion when the second-stage aqueous solution of hydroxypropylcellulose was charged was 1.2% by weight. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. There were 0 fish eyes (large) and 12 fish eyes (small). Example 3 Polymerization was carried out in the same manner as in Example 1 except that the charged amount of a 1% by weight aqueous solution of hydroxypropylcellulose was changed to 4.8 kg before heating and to 1.2 kg after 15 minutes from completion of heating, to obtain a white powder. 30.9 kg of a vinyl chloride graft copolymer in the form of a solid were obtained. The polymerization conversion when the second stage aqueous hydroxypropylcellulose solution was charged was 1.3% by weight. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. 1 fisheye (large), fisheye
(Small) was 20 pieces. Example 4 Polymerization was carried out in the same manner as in Example 1 except that 16.0 kg of vinyl chloride and 2.0 kg of vinyl acetate were charged instead of 18.0 kg of vinyl chloride, and a vinyl chloride graft copolymer in the form of a white powder was obtained. 30.0 kg were obtained. The polymerization conversion rate when the second stage hydroxypropylcellulose aqueous solution was charged was 1.
It was 1% by weight. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. There was one fisheye (large) and six fisheye (small). Comparative Example 1 6.0 kg of a 1% by weight aqueous solution of hydroxypropylcellulose
Was polymerized in the same manner as in Example 1 except that the aqueous solution of hydroxypropylcellulose was not charged after the completion of the temperature increase, and 30.5 kg of a white powdery vinyl chloride graft copolymer was obtained. Obtained. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. There were 5 fish eyes (large) and 43 fish eyes (small). Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that the charged amount of the 1% by weight aqueous solution of hydroxypropylcellulose was changed to 5.4 kg before heating and to 0.6 kg after 15 minutes from completion of the heating. 30.9 kg of a vinyl chloride graft copolymer in the form of a solid were obtained. The polymerization conversion when the second stage aqueous hydroxypropylcellulose solution was charged was 1.1% by weight. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. 4 fisheye (large), fisheye
(Small) was 29 pieces. Comparative Example 3 Polymerization was carried out in the same manner as in Example 1 except that the charged amount of a 1% by weight aqueous solution of hydroxypropylcellulose was changed to 2.4 kg before heating and to 3.6 kg after 15 minutes from completion of heating. 31.0 kg of a white powdery vinyl chloride graft copolymer containing a large amount of The polymerization conversion rate when the second-stage aqueous solution of hydroxypropylcellulose was charged was 1.2% by weight.
Met. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. There were 0 fisheye (large) and 3 fisheye (small). Comparative Example 4 Polymerization was carried out in the same manner as in Example 1 except that the amount of the 1% by weight aqueous solution of hydroxypropylcellulose was changed to 1.2 kg before the heating and 4.8 kg after 15 minutes from the completion of the heating. The polymerization conversion when the second stage aqueous hydroxypropylcellulose solution was charged was 1.3% by weight. Two hours after the temperature was raised to 60 ° C, the inside of the autoclave solidified and stirring became impossible, so the polymerization was stopped. Comparative Example 5 Polymerization was carried out in the same manner as in Example 1 except that the amount of a 1% by weight aqueous solution of hydroxypropylcellulose was changed to 1.0 kg before heating and 0.7 kg 15 minutes after completion of heating. The polymerization conversion when the second stage aqueous hydroxypropylcellulose solution was charged was 1.1% by weight. 1.5 hours after the completion of the temperature rise to 60 ° C, the inside of the autoclave solidified and stirring became impossible, so the polymerization was stopped. Comparative Example 6 Polymerization was carried out in the same manner as in Example 1, except that the charged amount of a 1% by weight aqueous solution of hydroxypropylcellulose was changed to 8.0 kg before heating and to 4.0 kg after 15 minutes from completion of heating, and a white powder was obtained. 30.6 kg of a vinyl chloride graft copolymer in the form of a solid were obtained. The polymerization conversion when the second stage aqueous hydroxypropylcellulose solution was charged was 1.1% by weight. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. 5 fisheye (large), fisheye
(Small) was 35 pieces. Comparative Example 7 The charged amount of a 1% by weight aqueous solution of hydroxypropyl cellulose was 3.6 kg before heating, and 2.4 kg 120 minutes after completion of heating.
Polymerization was carried out in the same manner as in Example 1 except that the above procedure was repeated to obtain 30.7 kg of a white powdery vinyl chloride graft copolymer containing many coarse particles. Using the sampling slurry 120 minutes after the completion of the temperature rise, the polymerization conversion rate was examined.
% By weight. A sheet was prepared in the same manner as in Example 1, and fish eyes were evaluated. There were 0 fish eyes (large) and 11 fish eyes (small). Example 1
Tables 1 to 4 show the results of Comparative Examples 1 to 7.
【００１０】[0010]
【表１】 [Table 1]
【００１１】エチレン−酢酸ビニル共重合体と単量体の
合計量１００重量部当たり０.１８重量部のヒドロキシ
プロピルセルロースを使用し、昇温前にその６０〜８０
重量％を仕込み、重合温度まで昇温した後にその２０〜
４０重量％を仕込んだ実施例１〜４においては、白色粉
末状のグラフト共重合体が得られ、グラフト共重合体か
ら作製したシートのフィッシュアイは少ない。これに対
して、同じ量のヒドロキシプロピルセルロースを使用し
ても、昇温前にその９０重量％又は全量を仕込んだ比較
例１〜２においては、得られたグラフト共重合体から作
製したシートのフィッシュアイが多い。また、同じ量の
ヒドロキシプロピルセルロースを使用しても、昇温前の
仕込み量が４０重量％と少ない比較例３においては、共
重合体粒子中に粗粒が多く、昇温前の仕込み量が２０重
量％とさらに少ない比較例４においては、固結を生じて
重合を完結することができなかった。使用するヒドロキ
シプロピルセルロースの量が少なすぎる比較例５におい
ても、固結を生じて重合を完結することができず、一
方、使用するヒドロキシプロピルセルロースの量が多す
ぎる比較例６においては、白色粉末状のグラフト共重合
体が得られたが、グラフト共重合体から作製したシート
のフィッシュアイが多い。使用するヒドロキシプロピル
セルロースの昇温前仕込み量が６０重量％であっても、
重合転化率が１３重量％に達してから残りの４０重量％
を仕込んだ比較例７のグラフト共重合体は、共重合体粒
子中に粗粒の多いものとなった。0.18 parts by weight of hydroxypropylcellulose is used per 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer and the monomer.
% By weight, and the temperature is raised to the polymerization temperature.
In Examples 1 to 4 in which 40% by weight was charged, a white powdery graft copolymer was obtained, and the sheet produced from the graft copolymer had few fish eyes. On the other hand, even if the same amount of hydroxypropylcellulose was used, in Comparative Examples 1 and 2 in which 90% by weight or the whole amount was charged before the temperature was raised, the sheet produced from the obtained graft copolymer was used. There are many fish eyes. Further, even when the same amount of hydroxypropylcellulose was used, in Comparative Example 3 in which the charged amount before the temperature rise was as low as 40% by weight, there were many coarse particles in the copolymer particles, and the charged amount before the temperature rise was low. In Comparative Example 4 as much as 20% by weight, consolidation occurred and the polymerization could not be completed. In Comparative Example 5 in which the amount of hydroxypropylcellulose used was too small, solidification occurred and the polymerization could not be completed. On the other hand, in Comparative Example 6 in which the amount of hydroxypropylcellulose used was too large, white powder was used. A graft copolymer was obtained, but the sheet produced from the graft copolymer had many fish eyes. Even if the amount of hydroxypropylcellulose used before heating is 60% by weight,
After the polymerization conversion reaches 13% by weight, the remaining 40% by weight
In the graft copolymer of Comparative Example 7 charged with, there were many coarse particles in the copolymer particles.
【００１２】[0012]
【発明の効果】本発明方法によれば、重合に際して適当
量の分散安定剤を使用し、昇温前と、重合温度まで昇温
した後の２回に分割して仕込むという簡単かつ容易な操
作により、フィルム、シートなどに成形したとき、フィ
ッシュアイの発生の少ない塩化ビニル系グラフト共重合
体を製造することができる。According to the method of the present invention, an appropriate amount of a dispersion stabilizer is used at the time of polymerization, and a simple and easy operation is performed in which the mixture is charged twice before the temperature is raised and after the temperature is raised to the polymerization temperature. Thereby, when molded into a film, a sheet, or the like, a vinyl chloride-based graft copolymer with less generation of fish eyes can be produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ (Ｃ０８Ｆ 263/02 214:06） ──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. 6 Identification code FI (C08F 263/02 214: 06)
Claims (3)
ジカル重合法により塩化ビニル又は塩化ビニル及びこれ
と共重合し得るエチレン系不飽和単量体の混合物をグラ
フト重合させる塩化ビニル系グラフト共重合体の製造方
法において、エチレン−ビニルエステル共重合体と単量
体の合計量１００重量部当たり０.１〜０.３重量部の分
散安定剤を使用し、分散安定剤の５０〜８５重量％を昇
温前に仕込み、次いで昇温して重合反応を開始し、残余
の分散安定剤１５〜５０重量％を重合転化率が０.５〜
４重量％の間に仕込むことを特徴とする塩化ビニル系グ
ラフト共重合体の製造方法。1. A vinyl chloride-based graft copolymer obtained by graft-polymerizing an ethylene-vinyl ester copolymer with vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith by a radical polymerization method. Wherein 0.1 to 0.3 parts by weight of the dispersion stabilizer is used per 100 parts by weight of the total amount of the ethylene-vinyl ester copolymer and the monomer, and 50 to 85% by weight of the dispersion stabilizer is used. The polymerization reaction was started by raising the temperature before the temperature was raised, and then raising the temperature to start the polymerization reaction.
A method for producing a vinyl chloride-based graft copolymer, which is charged between 4% by weight.
４０〜７０重量％であり、塩化ビニル又は塩化ビニル及
びこれと共重合し得るエチレン系不飽和単量体の混合物
の量が３０〜６０重量％である請求項１記載の塩化ビニ
ル系グラフト共重合体の製造方法。2. The amount of the ethylene-vinyl ester copolymer is 40 to 70% by weight, and the amount of vinyl chloride or a mixture of vinyl chloride and an ethylenically unsaturated monomer copolymerizable therewith is 30 to 60%. 2. The method for producing a vinyl chloride-based graft copolymer according to claim 1, wherein the amount of the graft copolymer is 1% by weight.
チレン３５〜８５重量％及びビニルエステル１５〜６５
重量％からなる共重合体である請求項１又は請求項２記
載の塩化ビニル系グラフト共重合体の製造方法。3. An ethylene-vinyl ester copolymer comprising 35 to 85% by weight of ethylene and 15 to 65% of vinyl ester.
The method for producing a vinyl chloride-based graft copolymer according to claim 1 or 2, wherein the copolymer is a copolymer comprising 1% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1450097A JP3559412B2 (en) | 1997-01-10 | 1997-01-10 | Method for producing vinyl chloride-based graft copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1450097A JP3559412B2 (en) | 1997-01-10 | 1997-01-10 | Method for producing vinyl chloride-based graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10195147A true JPH10195147A (en) | 1998-07-28 |
| JP3559412B2 JP3559412B2 (en) | 2004-09-02 |
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ID=11862791
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| Application Number | Title | Priority Date | Filing Date |
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| JP1450097A Expired - Fee Related JP3559412B2 (en) | 1997-01-10 | 1997-01-10 | Method for producing vinyl chloride-based graft copolymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101182068B1 (en) | 2006-09-11 | 2012-09-11 | 주식회사 엘지화학 | Method for preparing graft copolymer resin of vinyl chloride |
| CN103694779A (en) * | 2013-12-14 | 2014-04-02 | 衢州市中通化工有限公司 | Mixed wax for printing oil and preparation method for mixed wax |
-
1997
- 1997-01-10 JP JP1450097A patent/JP3559412B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101182068B1 (en) | 2006-09-11 | 2012-09-11 | 주식회사 엘지화학 | Method for preparing graft copolymer resin of vinyl chloride |
| CN103694779A (en) * | 2013-12-14 | 2014-04-02 | 衢州市中通化工有限公司 | Mixed wax for printing oil and preparation method for mixed wax |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3559412B2 (en) | 2004-09-02 |
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