JP2007031725A - Method for manufacturing saponification product of ethylene-vinyl acetate copolymer - Google Patents
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本発明は、重合缶内にスケール付着の少ないエチレン−酢酸ビニル共重合体の重合法および着色が少なく、かつフィッシュアイの少ないフィルムを得ることが可能な該共重合体のケン化物の製造法に関する。 The present invention relates to a method for polymerizing an ethylene-vinyl acetate copolymer with little scale adhesion in a polymerization can and a method for producing a saponified product of the copolymer capable of obtaining a film with little coloring and less fish eyes. .
エチレン−酢酸ビニル共重合体ケン化物はガスバリアー性、機械的強度等の諸性質に優れていることから、フィルム、シート、容器、繊維等の各種用途に多用されている。該ケン化物はエチレンと酢酸ビニルを共重合し、次いでケン化することによって製造されるが、エチレン−酢酸ビニル共重合体の重合は、通常、ジャケット及び還流コンデンサーのついた高圧の重合缶を用いて、メタノール等のアルコール溶媒中に、原料であるエチレン及び酢酸ビニルを導入して行われる。 Saponified ethylene-vinyl acetate copolymer is widely used in various applications such as films, sheets, containers, and fibers because of its excellent properties such as gas barrier properties and mechanical strength. The saponified product is produced by copolymerizing ethylene and vinyl acetate, and then saponifying, and the polymerization of the ethylene-vinyl acetate copolymer is usually performed using a high-pressure polymerization can equipped with a jacket and a reflux condenser. Thus, ethylene and vinyl acetate as raw materials are introduced into an alcohol solvent such as methanol.
しかしながら、上記の方法でエチレン−酢酸ビニル共重合体の重合を行った場合、重合缶内部にスケールが付着し易く、該スケールが剥離して重合体中に混入すると、該重合体のケン化物をフィルムにした時、フィッシュアイが多発し、品質の低下を招くという問題が発生し、それ故スケール付着のない重合法が望まれているのである。 However, when the ethylene-vinyl acetate copolymer is polymerized by the above method, the scale easily adheres to the inside of the polymerization can, and when the scale is peeled off and mixed in the polymer, the saponified polymer is removed. When it is made into a film, there is a problem that fish eyes frequently occur and the quality is deteriorated. Therefore, a polymerization method without scale adhesion is desired.
本発明者は上記の問題を解決するため鋭意研究を重ねた結果、クロトンアルデヒドの共存下、溶媒中でエチレンと酢酸ビニルを共重合させると、重合缶内部のスケール付着が少なく良好なエチレン−酢酸ビニル共重合体が得られ、又、該共重合体より得られたケン化物は着色が少なく、該ケン化物をフィルムにした時、フィッシュアイが少ないことを見出し本発明を完成するに到った。 As a result of intensive studies to solve the above problems, the present inventor has found that when ethylene and vinyl acetate are copolymerized in a solvent in the presence of crotonaldehyde, there is little scale adhesion inside the polymerization can and good ethylene-acetic acid. A vinyl copolymer was obtained, and the saponified product obtained from the copolymer was less colored, and when the saponified product was made into a film, it was found that there were few fish eyes and the present invention was completed. .
本発明では、クロトンアルデヒドを共存下エチレンと酢酸ビニルを溶媒中で共重合させるので、重合缶内部のスケール付着が少なく、かかるエチレン−酢酸ビニル共重合体から製造されるエチレン−酢酸ビニル共重合体ケン化物は着色がなく、またかかるケン化物から得られたフィルムはフィッシュアイが少ない。 In the present invention, since ethylene and vinyl acetate are copolymerized in a solvent in the presence of crotonaldehyde, there is little adhesion of scale inside the polymerization can, and an ethylene-vinyl acetate copolymer produced from such an ethylene-vinyl acetate copolymer is produced. The saponified product is not colored, and the film obtained from the saponified product has less fish eyes.
以下に本発明を詳細に説明する。なお、以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、これらの内容に特定するものではない。エチレンと酢酸ビニルの共重合は溶媒中での重合、すなわち溶液重合法が実施される。エチレンと酢酸ビニルの溶液重合法は、溶媒中で触媒の存在下に行われ、連続式、回分式のいずれであっても良く、重合法に応じて適宜条件が設定される。溶媒としては炭素数４以下のアルコール又は炭素数４以下のアルコールを主とする混合溶媒が用いられ、該アルコールとしては、メタノール、エタノール、プロパノール等が挙げられるが、好ましくはメタノールが用いられ、溶媒量としては酢酸ビニル１００重量部に対して、１〜６０重量部が好ましい。 The present invention is described in detail below. In addition, description of the component requirements described below is an example (representative example) of the embodiment of this invention, and is not specified to these content. Copolymerization of ethylene and vinyl acetate is carried out in a solvent, that is, a solution polymerization method. The solution polymerization method of ethylene and vinyl acetate is performed in the presence of a catalyst in a solvent, and may be either a continuous type or a batch type, and conditions are appropriately set according to the polymerization method. As the solvent, an alcohol having 4 or less carbon atoms or a mixed solvent mainly containing an alcohol having 4 or less carbon atoms is used, and examples of the alcohol include methanol, ethanol, propanol, etc., preferably methanol is used, The amount is preferably 1 to 60 parts by weight with respect to 100 parts by weight of vinyl acetate.
触媒としては、ラジカル開始剤であれば特に制限なく用いられるが、好ましくは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−（２，４，４−トリメチルバレロニトリル）、２，２′−アゾビスイソブチロニトリル、２，２′−アゾビス−（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２′−アゾビス−（２−メチルイソブチラート）などのアゾ化合物、ｔ−ブチルパーオキシネオデカノエート、ｔ−ブチルパーピバレート、ｔ−ブチルパーオキシ−２−エチルヘキノエートなどのアルキルパーエステル類、ビス−（４−ｔ−ブチルシクロヘキシル）パーオキシ−ジ−カーボネート、ジ−シクロヘキシルパーオキシ−ジ−カーボネート、ビス（２−エチルヘキシル）ジ−ｓｅｃ−ブチルパーオキシ−ジ−カーボネート、ジ−イソプロピルパーオキシ−ジ−カーボネートなどのパーオキシ−ジ−カーボネート類、アセチルパーオキシド、ベンゾイルパーオキシド、ラウロイルパーオキシド、ジ−ラウロイルパーオキシド、ジ−デカノイルパーオキシド、ジ−オクタノイルパーオキシド、ジ−プロピルパーオキシドなどのパーオキシド類などがある。 The catalyst is not particularly limited as long as it is a radical initiator, but preferably 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (2,4,4- Trimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2-methyliso) Azo compounds such as butyrate), alkyl peresters such as t-butylperoxyneodecanoate, t-butylperpivalate, t-butylperoxy-2-ethylhexanoate, bis- (4-t -Butylcyclohexyl) peroxy-dicarbonate, di-cyclohexylperoxy-dicarbonate, bis (2-ethylhexyl) di-sec-butylper Peroxy-di-carbonates such as x-di-carbonate, di-isopropyl peroxy-di-carbonate, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, di-lauroyl peroxide, di-decanoyl peroxide, di -Peroxides such as octanoyl peroxide and di-propyl peroxide.
触媒の使用量は、回分式の場合、酢酸ビニル１００重量部に対して、０．００２〜０．１重量部が好ましく、０．００２重量部未満では、触媒効率が悪く重合時間が長くなったり、重合が進まない場合があり、０．１重量部を越えると、重合の制御が困難となったり、重合終了後も触媒が残存して後重合を起こすことがあり好ましくない。連続式の場合、酢酸ビニル１００重量部に対して、０．００２〜０．０６重量部が好ましく、０．００２重量部未満では、触媒効率が悪く重合時間が長くなったり、重合が進まない場合があり、０．０６重量部を越えると、重合の制御が困難となったり、重合終了後も触媒が残存して後重合を起こすことがあり好ましくない。 In the case of a batch system, the amount of catalyst used is preferably 0.002 to 0.1 parts by weight with respect to 100 parts by weight of vinyl acetate, and if it is less than 0.002 parts by weight, the catalyst efficiency is poor and the polymerization time is prolonged. In some cases, the polymerization does not proceed. If the amount exceeds 0.1 parts by weight, it is difficult to control the polymerization, or the catalyst may remain after the polymerization is completed, which is not preferable. In the case of continuous type, 0.002 to 0.06 parts by weight is preferable with respect to 100 parts by weight of vinyl acetate, and if it is less than 0.002 parts by weight, the catalyst efficiency is poor and the polymerization time is prolonged or the polymerization does not proceed. If the amount exceeds 0.06 parts by weight, it is difficult to control the polymerization, or the catalyst may remain after the completion of the polymerization and cause post-polymerization.
本発明では、エチレン−酢酸ビニル共重合体を重合するに当たり、クロトンアルデヒドを共存させることを最大の特徴とするのもので、クロトンアルデヒドの量は０．０００１〜０．５ｐｐｍが好ましく、更には０．０００２〜０．００５ｐｐｍである。０．０００１ｐｐｍ未満では重合の制御が困難となったり重合缶内部にスケールの付着し易い傾向があり好ましくなく、０．５ｐｐｍを越えると重合が抑制されて重合率が低くなったり、又重合時間が長く必要となり、更に重合缶内部にスケールの付着が見られる場合があり好ましくない。 In the present invention, the greatest feature is the presence of crotonaldehyde in the polymerization of the ethylene-vinyl acetate copolymer. The amount of crotonaldehyde is preferably 0.0001 to 0.5 ppm, and more preferably 0. .0002-0.005 ppm. If it is less than 0.0001 ppm, it is difficult to control the polymerization or the scale tends to adhere to the inside of the polymerization can, which is not preferable. If it exceeds 0.5 ppm, the polymerization is suppressed and the polymerization rate is lowered, or the polymerization time is decreased. It is necessary for a long time, and further, scale adhesion may be observed inside the polymerization can, which is not preferable.
重合を行うに当たっては、酢酸ビニルとクロトンアルデヒドを別々に、あるいはクロトンアルデヒド含有量を予めコントロールした酢酸ビニルをアルコール溶媒に溶解し、触媒を添加し、更にエチレンを高圧下に仕込む方法、酢酸ビニルをアルコール溶媒に溶解し、触媒及びクロトンアルデヒドを添加し、更にエチレンを高圧下に仕込む方法等が実施される。 In carrying out the polymerization, vinyl acetate and crotonaldehyde are separately added, or vinyl acetate whose crotonaldehyde content is controlled in advance is dissolved in an alcohol solvent, a catalyst is added, and ethylene is further charged under high pressure. A method of dissolving in an alcohol solvent, adding a catalyst and crotonaldehyde, and charging ethylene under high pressure is performed.
重合温度として好ましくは４０〜８０℃、更には５５〜７０℃である。該重合温度が４０℃未満では重合に長時間を要し、重合時間を短縮しようとすると触媒が多量に必要となり、８０℃を越えると重合制御が困難となり好ましくない。重合時間は、回分式の場合、好ましくは４〜１０時間、更には６〜９時間である。該重合時間が４時間未満では重合温度を高くしたり、触媒量を多く設定しなければならず、重合制御が困難となり、１０時間を越えると生産性の面で問題があり好ましくない。連続式の場合、重合缶内での平均滞留時間は２〜８時間が好ましく、更には２〜６時間である。該滞留時間が２時間未満では重合温度を高くしたり、触媒量を多く設定しなければならず、重合制御が困難となり、８時間を越えると生産性の面で問題があり好ましくない。 The polymerization temperature is preferably 40 to 80 ° C, more preferably 55 to 70 ° C. If the polymerization temperature is less than 40 ° C., it takes a long time for the polymerization. If the polymerization time is to be shortened, a large amount of catalyst is required, and if it exceeds 80 ° C., it is difficult to control the polymerization. In the case of a batch system, the polymerization time is preferably 4 to 10 hours, and more preferably 6 to 9 hours. If the polymerization time is less than 4 hours, the polymerization temperature must be increased or the amount of catalyst must be set large, and polymerization control becomes difficult, and if it exceeds 10 hours, there is a problem in terms of productivity, which is not preferred. In the case of the continuous type, the average residence time in the polymerization can is preferably 2 to 8 hours, more preferably 2 to 6 hours. If the residence time is less than 2 hours, the polymerization temperature must be increased or the amount of catalyst must be set large, and the polymerization control becomes difficult, and if it exceeds 8 hours, there is a problem in productivity and this is not preferred.
重合率（酢酸ビニル）は生産性の面から重合制御が可能な範囲で出来るだけ高く設定され、回分式の場合、好ましくは２０〜９０％に設定される。該重合率が２０％未満では工業的に生産性が悪く、未重合の酢酸ビニルが多量に残存するという問題があり、９０％を越えると重合制御が困難となり好ましくない。連続式の場合、重合率は、好ましくは２０〜６０％に設定される。該重合率が２０％未満では工業的に生産性が悪く、未重合の酢酸ビニルが多量に残存するという問題があり、６０％を越えると重合制御が困難となり好ましくない。 The polymerization rate (vinyl acetate) is set as high as possible in the range in which polymerization can be controlled from the viewpoint of productivity, and in the case of a batch system, it is preferably set to 20 to 90%. If the polymerization rate is less than 20%, the industrial productivity is poor and there is a problem that a large amount of unpolymerized vinyl acetate remains, and if it exceeds 90%, polymerization control becomes difficult, which is not preferable. In the case of the continuous type, the polymerization rate is preferably set to 20 to 60%. If the polymerization rate is less than 20%, the industrial productivity is poor, and there is a problem that a large amount of unpolymerized vinyl acetate remains. If it exceeds 60%, polymerization control becomes difficult, which is not preferable.
また、エチレン−酢酸ビニル共重合体中のエチレン含有量は、重合缶内のエチレン圧等によりコントロールすることができ、かかる含有量としては１５〜６０モル％が好ましく、更には２５〜５５モル％である。該エチレン含有量が１５モル％未満では、エチレン−酢酸ビニル共重合体をケン化して得られたケン化物を溶融成形する場合、溶融成形性が低下すると共に、溶融成形物の高湿時のガスバリヤー性が大きく低下し、６０モル％を越えると、該ケン化物の溶融成形した場合、成形物の機械的強度及びガスバリアー性が充分でなく好ましくない。 Further, the ethylene content in the ethylene-vinyl acetate copolymer can be controlled by the ethylene pressure in the polymerization can, and the content is preferably 15 to 60 mol%, more preferably 25 to 55 mol%. It is. When the ethylene content is less than 15 mol%, when melt-molding a saponified product obtained by saponifying an ethylene-vinyl acetate copolymer, the melt moldability deteriorates and the gas at high humidity of the melt-molded product is reduced. When the barrier property is greatly reduced and exceeds 60 mol%, the melt strength of the saponified product is not preferable because the mechanical strength and gas barrier property of the molded product are not sufficient.
この時のエチレン圧としては１５〜７５ｋｇ／ｃｍ2に設定される。 The ethylene pressure at this time is set to 15 to 75 kg / cm 2 .
又本発明において、エチレン−酢酸ビニル共重合体の重合法はエチレン、酢酸ビニル以外に、これらと共重合可能なエチレン性不飽和単量体を共重合成分として含有しても差し支えない。該単量体としては、例えばプロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸等の不飽和酸類あるいはその塩あるいはモノ又はジアルキルエステル等、アクリロニトリル、メタアクリロニトリル等のニトリル類、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸あるいはその塩、アルキルビニルエーテル類、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、塩化ビニリデン、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテルなどのポリオキシアルキレン（メタ）アリルエーテル、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリルアミド、ポリオキシプロピレン（メタ）アクリルアミド等のポリオキシアルキレン（メタ）アクリルアミド、ポリオキシエチレン（１−（メタ）アクリルアミド−１，１−ジメチルプロピル）エステル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン等が挙げられる。 In the present invention, the ethylene-vinyl acetate copolymer polymerization method may contain, as a copolymerization component, an ethylenically unsaturated monomer copolymerizable with ethylene and vinyl acetate. Examples of the monomer include olefins such as propylene, isobutylene, α-octene, α-dodecene, α-octadecene, and unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, and itaconic acid. Acids or salts thereof or mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, or salts thereof, Alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (Meth) allyl ether, polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyalkylene (meth) acrylate such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate , Polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamide such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether , Polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, etc. It is below.
かくして本発明の重合法でエチレン−酢酸ビニル共重合体が得られるわけであるが、かかるエチレン−酢酸ビニル共重合体は、接着剤、粘着剤、塗料、繊維・織物の加工剤、紙・皮革の加工剤、各種材料のバインダー、セメント・モルタルの混和液等に利用される。 Thus, an ethylene-vinyl acetate copolymer can be obtained by the polymerization method of the present invention. Such an ethylene-vinyl acetate copolymer can be used for adhesives, pressure-sensitive adhesives, paints, textile / textile processing agents, paper / leather. It is used in various processing agents, binders for various materials, and admixtures of cement and mortar.
上記の重合法で得られたエチレン−酢酸ビニル共重合体は更にケン化され、エチレン−酢酸ビニル共重合体ケン化物として用途拡大が可能であるが、かかる方法で得られたエチレン−酢酸ビニル共重合体ケン化物は着色がなく、またフィルムにした時フィッシュアイが少ないという顕著な効果が得られる。 The ethylene-vinyl acetate copolymer obtained by the above polymerization method can be further saponified to expand the use as an ethylene-vinyl acetate copolymer saponified product. However, the ethylene-vinyl acetate copolymer obtained by such a method can be used. The polymer saponified product is not colored and has a remarkable effect that the fish eye is less when formed into a film.
かかるケン化反応は、通常、アルカリ触媒の共存下に実施される。ケン化に当たっては、上記エチレン−酢酸ビニル共重合体を、アルコール（通常メタノールが用いられる）又はアルコール含有媒体中に通常２０〜６０重量％程度の濃度になる如く溶解し、アルカリ触媒（通常水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物が用いられる）を添加して４０〜１４０℃の温度で反応せしめる。 Such a saponification reaction is usually carried out in the presence of an alkali catalyst. In the saponification, the above ethylene-vinyl acetate copolymer is dissolved in an alcohol (usually methanol is used) or an alcohol-containing medium to a concentration of usually about 20 to 60% by weight, and an alkali catalyst (usually hydroxylated) is used. An alkali metal hydroxide such as sodium or potassium hydroxide is used) and the reaction is carried out at a temperature of 40 to 140 ° C.
かかるケン化により得られるエチレン−酢酸ビニル共重合体ケン化物の酢酸ビニル成分のケン化度は８０〜１００モル％とすることが好ましく、更にはケン化度９０〜１００モル％、特に９５〜１００モル％とするのが有利である。ケン化度が８０モル％未満の場合、該エチレン−酢酸ビニル共重合体ケン化物を溶融成形する場合の熱安定性が悪くなると共に、得られた成形物も機械的強度やガスバリアー性が大きく低下して好ましくない。 The saponification degree of the vinyl acetate component of the saponified ethylene-vinyl acetate copolymer obtained by such saponification is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, particularly 95 to 100 mol%. The mol% is advantageous. When the saponification degree is less than 80 mol%, the thermal stability when melt-molding the ethylene-vinyl acetate copolymer saponified product is deteriorated, and the obtained molded product also has high mechanical strength and gas barrier properties. Decreasing and not preferable.
次に上記で得られたエチレン−酢酸ビニル共重合体ケン化物のアルコール溶液はそのままでもよいが、好ましくは、水を加えるだけか、水を加えて、更に該ケン化物溶液を適宜濃度調整して、アルコール／水溶液としてストランド製造用の溶液とする。 Next, the alcohol solution of the ethylene-vinyl acetate copolymer saponified product obtained above may be used as it is, but preferably only water is added or water is added, and the concentration of the saponified solution is adjusted appropriately. A solution for producing a strand is used as an alcohol / water solution.
次いで、エチレン−酢酸ビニル共重合体ケン化物のアルコール／水溶液は、水又は水／アルコール（混合）溶液等の凝固液中にストランド状に押し出して析出させるのである。 Next, the alcohol / water solution of the saponified ethylene-vinyl acetate copolymer is extruded into a coagulating liquid such as water or a water / alcohol (mixed) solution and precipitated.
析出させたストランドは次に切断されてペレット状となり、次いで水洗される。水洗したペレットは酸及び／又はそれらの塩類等の薬剤の水溶液で浸漬させる等の方法で化学処理を行なうことが好ましく、かかる薬剤としては、ギ酸、酢酸、アジピン酸、リン酸、ホウ酸あるいはそれらの塩類等が挙げられ、より好ましくは酢酸が用いられる。 The precipitated strand is then cut into pellets and then washed with water. The pellets washed with water are preferably subjected to chemical treatment by a method such as immersion in an aqueous solution of a chemical such as acid and / or their salts. Examples of such chemicals include formic acid, acetic acid, adipic acid, phosphoric acid, boric acid, or the like. And, more preferably, acetic acid is used.
上記で得られたペレットは溶融成形されて所望する成形物に成形されるのであるが、溶融成形に際しての温度条件としては１６０〜２６０℃程度とするのが望ましい。成形に際しては必要に応じガラス繊維、炭素繊維などの補強材、フィラー、着色剤、ハイドロタルサイトなどの安定剤、発泡剤、乾燥剤などの公知の添加剤を適当量配合することもある。又、エチレン−酢酸ビニル共重合体ケン化物には改質用の熱可塑性樹脂を適当量配合することもできる。 The pellets obtained as described above are melt-molded and formed into a desired molded product. The temperature condition during melt-molding is preferably about 160 to 260 ° C. In molding, an appropriate amount of a known additive such as a reinforcing material such as glass fiber or carbon fiber, a filler, a colorant, a stabilizer such as hydrotalcite, a foaming agent or a drying agent may be blended as necessary. Further, an appropriate amount of a thermoplastic resin for modification can be blended in the saponified ethylene-vinyl acetate copolymer.
溶融成形法としては射出成形法、圧縮成形法、押出成形法など任意の成形法が採用できる。このうち押出成形法としてはＴ−ダイ法、中空成形法、パイプ押出法、線条押出法、異形ダイ押出法、インフレーション法などが挙げられるが、エチレン−酢酸ビニル共重合体ケン化物単独の成形物（フィルム、シート、テープ、ボトル、パイプ、フィラメント、異型断面押出物など）のみならず、エチレン−酢酸ビニル共重合体ケン化物層と他の熱可塑性樹脂層との共押出成形も可能である。 As the melt molding method, any molding method such as an injection molding method, a compression molding method, and an extrusion molding method can be employed. Among these, the extrusion molding method includes a T-die method, a hollow molding method, a pipe extrusion method, a linear extrusion method, a deformed die extrusion method, an inflation method, etc., but molding of an ethylene-vinyl acetate copolymer saponified product alone. Coextrusion of not only products (films, sheets, tapes, bottles, pipes, filaments, profile cross-section extrudates, etc.) but also saponified ethylene-vinyl acetate copolymer layers and other thermoplastic resin layers is possible. .
以下、実施例を挙げて本発明を具体的に説明する。本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。尚、実施例中、「部」、「％」とあるのは、特に断りのない限り重量基準である。 Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, “parts” and “%” are based on weight unless otherwise specified.
実施例１
内容量１０ｌで内部に冷却コイルをもつ撹拌機付き重合缶を用いて以下の条件でエチレン−酢酸ビニル共重合体を連続重合した。
酢酸ビニル供給量 １２９０ｇ／ｈｒ
メタノール供給量 ２００ｇ／ｈｒ
ベンゾイルパーオキサイド供給量 ２５０ｍｇ／ｈｒ
クロトンアルデヒド供給量 ０．００２ｐｐｍ共存（全系に対して）
重合温度 ６７℃
エチレン圧 ４０ｋｇ／ｃｍ2
平均滞留時間 ４ｈｒ
この時得られたエチレン−酢酸ビニル共重合体のエチレン含有量は３２モル％で、酢酸ビニルの重合率は３８％であった。１０日間の連続運転後の重合缶内の内部にはスケールの付着は全く見られなかった。
Example 1
An ethylene-vinyl acetate copolymer was continuously polymerized under the following conditions using a polymerization can with a stirrer having an internal volume of 10 l and a cooling coil inside.
Vinyl acetate supply 1290 g / hr
Methanol supply rate 200g / hr
Benzoyl peroxide supply amount 250mg / hr
Crotonaldehyde supply amount 0.002ppm coexistence (for all systems)
Polymerization temperature 67 ° C
Ethylene pressure 40kg / cm 2
Average residence time 4 hr
The ethylene content of the ethylene-vinyl acetate copolymer obtained at this time was 32 mol%, and the polymerization rate of vinyl acetate was 38%. No scale adherence was observed inside the polymerization can after continuous operation for 10 days.
上記エチレン−酢酸ビニル共重合体を５０％含むメタノール溶液１００部に、該共重合体中の酢酸ビニル基に対して０．０１７当量の水酸化ナトリウムを含有するメタノール溶液１５０部を供給し、１２０〜１３０℃、圧力４ｋｇ／ｃｍ2Ｇで、３０分間ケン化反応を行った。得られたエチレン−酢酸ビニル共重合体ケン化物（ケン化度９９．８モル％）のメタノール溶液の樹脂分濃度は３０％であった。次に含水率６２．５％のメタノール水溶液６０部を、該エチレン−酢酸ビニル共重合体ケン化物のメタノール溶液に共沸下で供給し、１００〜１１０℃、圧力３ｋｇ／ｃｍ2Ｇで、エチレン−酢酸ビニル共重合体ケン化物のメタノール／水溶液中の樹脂分濃度が４０％になるまでメタノールを留出させ、完全透明なメタノール／水均一溶液を得た。 To 100 parts of a methanol solution containing 50% of the ethylene-vinyl acetate copolymer, 150 parts of a methanol solution containing 0.017 equivalents of sodium hydroxide with respect to the vinyl acetate group in the copolymer is supplied. The saponification reaction was carried out at ˜130 ° C. and a pressure of 4 kg / cm 2 G for 30 minutes. The resin concentration of the methanol solution of the obtained ethylene-vinyl acetate copolymer saponified product (saponification degree: 99.8 mol%) was 30%. Next, 60 parts of an aqueous methanol solution having a water content of 62.5% was supplied azeotropically to the methanol solution of the ethylene-vinyl acetate copolymer saponified product, and the ethylene solution was 100-110 ° C. under a pressure of 3 kg / cm 2 G. -Methanol was distilled off until the resin concentration in the methanol / water solution of the saponified vinyl acetate copolymer reached 40% to obtain a completely transparent homogeneous methanol / water solution.
続いて得られたエチレン−酢酸ビニル共重合体ケン化物のメタノール／水溶液を、水／メタノール溶液（重量比９５／５）よりなる５℃に維持された凝固液槽に、内径０．４ｃｍ、長さ６．０ｃｍの円筒形状のノズルより、１０ｋｇ／時の速度でストランド状に押し出し、凝固液槽の端部に付設された引き取りローラーにより、凝固液中の滞留時間が３分となる様に生成ストランドを凝固液から引き出した。ここで該ノズル口は４個あり、ストランド数は４本で実施した。該ストランドをカッターで切断し、多孔性のペレットを得た。得られたペレットは形状が均一であり、変形物は全くなかった。該ペレットを温度３０℃の水槽中で１時間水洗し、これを４回繰り返して、酢酸ナトリウムを除去後、更に温度３０℃の酢酸水溶液中で１時間洗浄を行った後、乾燥して、エチレン−酢酸ビニル共重合体ケン化物（平均直径３．２ｍｍ、平均長さ３．５ｍｍの円筒形状の半透明ペレット）を得た。 Subsequently, the methanol / water solution of the saponified ethylene-vinyl acetate copolymer obtained was placed in a coagulating liquid tank made of water / methanol solution (weight ratio 95/5) and maintained at 5 ° C. A cylindrical nozzle with a length of 6.0 cm is extruded into a strand at a rate of 10 kg / hr, and generated by a take-off roller attached to the end of the coagulation liquid tank so that the residence time in the coagulation liquid is 3 minutes. The strand was drawn from the coagulation liquid. Here, there were four nozzle ports and the number of strands was four. The strand was cut with a cutter to obtain porous pellets. The obtained pellets were uniform in shape and had no deformation. The pellet was washed with water in a water bath at a temperature of 30 ° C. for 1 hour, and this was repeated 4 times. After removing sodium acetate, the pellet was further washed in an acetic acid aqueous solution at a temperature of 30 ° C., dried, and then dried. -A saponified vinyl acetate copolymer (cylindrical translucent pellets having an average diameter of 3.2 mm and an average length of 3.5 mm) was obtained.
得られたエチレン−酢酸ビニル共重合体ケン化物を以下の様に評価した。
（１）ペレットの色相
○・・・着色なし
△・・・目視でやや黄色に着色
×・・・目視で黄色に着色
次に上記で得られたケン化物を以下の条件で製膜し、得られたフィルムのフィッシュアイを以下の様に評価した。
（製膜条件）
押出機 ：４０ｍｍ径押出機
スクリュー ：Ｌ／Ｄ＝２８、圧縮比３．２
ダ イ ：コートハンガータイプダイ
押出温度 ：シリンダー先端部 ２３０℃
ダ イ ２１０℃
スクリュー回転数：４０ｒｐｍ
フィルム厚み ：３０μ
The obtained saponified ethylene-vinyl acetate copolymer was evaluated as follows.
(1) Hue of pellet ○ ・ ・ ・ No coloring △ ・ ・ ・ Colored slightly yellow visually × ・ ・ ・ Colored yellow by visual observation Next, the saponified product obtained above was formed into a film under the following conditions. The fish eyes of the obtained films were evaluated as follows.
(Film forming conditions)
Extruder: 40 mm diameter extruder Screw: L / D = 28, compression ratio 3.2
Die: Coat hanger type die Extrusion temperature: Cylinder tip 230 ° C
Die 210 ℃
Screw rotation speed: 40rpm
Film thickness: 30μ
（フィッシュアイの測定条件）フィルム１００ｃｍ2当たりのフィッシュアイの数を測定した。
○・・・５個以下
△・・・６〜９個以下
×・・・１０以上
結果を表１に示した。
(Fish Eye Measurement Conditions) The number of fish eyes per 100 cm 2 of film was measured.
... 5 or less. .DELTA.... 6 to 9 or less.
実施例２
実施例１でクロトンアルデヒドを０．００１ｐｐｍ共存させた以外は同様に実施し、実施例１と同様に評価した。この時得られたエチレン−酢酸ビニル共重合体のエチレン含有量は３２モル％で、酢酸ビニルの重合率は３６％であった。１０日間の連続運転後の重合缶内部にはスケールの付着は見られなかった。得られたエチレン−酢酸ビニル共重合体を、実施例１と同様にしてケン化物として、実施例１と同様に評価した。
Example 2
The same operation as in Example 1 was carried out except that 0.001 ppm of crotonaldehyde was allowed to coexist, and evaluation was performed in the same manner as in Example 1. The ethylene content of the ethylene-vinyl acetate copolymer obtained at this time was 32 mol%, and the polymerization rate of vinyl acetate was 36%. No scale adhesion was observed inside the polymerization can after 10 days of continuous operation. The obtained ethylene-vinyl acetate copolymer was evaluated in the same manner as in Example 1 as a saponified product in the same manner as in Example 1.
比較例１
実施例１において、クロトンアルデヒドを共存させなかった以外は同様に実施して、実施例１と同様に評価した。この時得られたエチレン−酢酸ビニル共重合体のエチレン含量は３２モル％で、酢酸ビニルの重合率は４０％であった。１０日間の連続運転後の重合缶内部にはスケールの付着が見られた。得られたエチレン−酢酸ビニル共重合体を、実施例１と同様にしてケン化物として、実施例１と同様に評価した。
Comparative Example 1
In Example 1, it carried out similarly except not having crotonaldehyde coexisted, and evaluated similarly to Example 1. The ethylene content of the ethylene-vinyl acetate copolymer obtained at this time was 32 mol%, and the polymerization rate of vinyl acetate was 40%. Scale adhesion was observed inside the polymerization can after 10 days of continuous operation. The obtained ethylene-vinyl acetate copolymer was evaluated in the same manner as in Example 1 as a saponified product in the same manner as in Example 1.
比較例２
実施例１において、クロトンアルデヒドを５ｐｐｍ共存させた以外は同様に実施して、実施例１と同様に評価した。この時得られたエチレン−酢酸ビニル共重合体のエチレン含有量は３２モル％で、酢酸ビニルの重合率は３２％であった。１０日間の連続運転後の重合缶内部にはスケールの付着が少し見られた。得られたエチレン−酢酸ビニル共重合体を、実施例１と同様にしてケン化物として、実施例１と同様に評価した。実施例１、２、比較例１、２で得られたエチレン−酢酸ビニル共重合体ケン化物の評価を表１に示した。
Comparative Example 2
In Example 1, it carried out similarly except coexisting 5 ppm of crotonaldehyde, and evaluated similarly to Example 1. The ethylene content of the ethylene-vinyl acetate copolymer obtained at this time was 32 mol%, and the polymerization rate of vinyl acetate was 32%. A small amount of scale was observed inside the polymerization can after 10 days of continuous operation. The obtained ethylene-vinyl acetate copolymer was evaluated in the same manner as in Example 1 as a saponified product in the same manner as in Example 1. Table 1 shows the evaluation of the saponified ethylene-vinyl acetate copolymers obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
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