JPH06344410A - Manufacture of polyvinyl alcohol resin molded product - Google Patents

Manufacture of polyvinyl alcohol resin molded product

Info

Publication number
JPH06344410A
JPH06344410A JP5134714A JP13471493A JPH06344410A JP H06344410 A JPH06344410 A JP H06344410A JP 5134714 A JP5134714 A JP 5134714A JP 13471493 A JP13471493 A JP 13471493A JP H06344410 A JPH06344410 A JP H06344410A
Authority
JP
Japan
Prior art keywords
resin
pva
polyvinyl alcohol
mesh
based resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP5134714A
Other languages
Japanese (ja)
Inventor
Takashi Gonda
貴司 権田
Yusuke Morita
雄介 森田
Masami Fukushima
正巳 福島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Polymer Co Ltd
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Polymer Co Ltd
Shin Etsu Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin Etsu Polymer Co Ltd, Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Polymer Co Ltd
Priority to JP5134714A priority Critical patent/JPH06344410A/en
Publication of JPH06344410A publication Critical patent/JPH06344410A/en
Pending legal-status Critical Current

Links

Landscapes

  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To carry out a specific quantity-extrusion by a single screw extruder without causing thermal decomposition by a method wherein a polyvinyl alcohol resin having specific physical chemical properties independently or a mixed composition wherein a specific quantity of polyhydric alcohol is added thereto is melt extrusion molded in an anhydrous state. CONSTITUTION:Polyvinyl alcohol resin(PVA) of at least 95wt.%, within a range of 3.5 mesh on cut, and 3.5 to 50 mesh in particle size distribution and 10 deg. to 40 deg. of repose angle, 5.0 to 98.0mol% of saponification degree, and 100 to 600 of polimerization degree is melt extrusion molded in an anhydrous state, or a composition wherein 0.01 to 30 pts.wt. of polyhydric alcohol is mixed in 100 pts.wt. of PVA resin of at least 95wt.% within a range of 3.5 mesh on cut and 3.5 to 50 mesh of particle size distribution and 10 deg. to 40 deg. of repose angle, 5.0 to 98.0mol% of saponification degree, and 100 to 2000 of polymerization degree, is melt extrusion molded in an anhydrous state.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、特定の粒度分布と安息
角を有するポリビニルアルコール系樹脂(以下PVA系
樹脂と略称する)をペッレト化することなく、単軸押出
機により定量的に未溶融物がなく熱分解による変色も引
き起こすことなしに実質的に無水の状態で溶融押出成形
することができるPVA系樹脂成形物の製造方法に関す
るものである。
FIELD OF THE INVENTION The present invention relates to a polyvinyl alcohol resin having a specific particle size distribution and angle of repose (hereinafter referred to as PVA resin), which is quantitatively unmelted by a single-screw extruder without pelletizing. The present invention relates to a method for producing a PVA-based resin molded product which can be melt-extruded in a substantially anhydrous state without causing discoloration due to thermal decomposition.

【0002】[0002]

【従来の技術】一般にPVA系樹脂組成物の溶融押出成
形は、ポリエチレン、ポリプロピレンおよびポリ塩化ビ
ニル等の熱可塑性樹脂とは異なり、融点より熱分解温度
の方が低いのでPVA系樹脂単独で行うのは非常に困難
であった。そこで、従来からPVA系樹脂の溶融押出成
形は、水を可塑剤とした成形法が行われていた。
2. Description of the Related Art In general, melt extrusion molding of a PVA resin composition is carried out with a PVA resin alone because its thermal decomposition temperature is lower than its melting point unlike thermoplastic resins such as polyethylene, polypropylene and polyvinyl chloride. Was very difficult. Therefore, conventionally, the melt extrusion molding of the PVA-based resin has been performed by a molding method using water as a plasticizer.

【0003】従来より一般的なPVA系樹脂の成形方法
である流延成形法および溶融押出成形法は、水を可塑剤
として使用するため、成形後の乾燥および熱処理等には
複雑な工程を必要とする。また、溶融押出成形法の場合
は樹脂のペレット化を必要とし、また成形物に内蔵され
た泡や未溶融物を防ぐため押出機および金型内の温度管
理を厳密にコントロールしなければならない。無水の状
態でPVA系樹脂の溶融押出成形を行う方法としては、
特公昭42-26930号、特公昭44-28588号、特公昭53-24975
号、特公昭56-49733号及び特開昭50-22049号が提案され
ているが、これらの方法で単軸押出機を用いた溶融押出
成形を行った場合、ホッパー内で樹脂がブリッジを形成
し易くなるため、単軸押出機内への樹脂の供給が円滑に
行われなくなる。そのため押出機から樹脂の定量押出が
困難になると共に溶融押出成形物中に未溶融物が生じ
る。
In the conventional casting methods of PVA-based resins, which are casting methods and melt extrusion methods, since water is used as a plasticizer, drying and heat treatment after molding require complicated steps. And Further, in the case of the melt extrusion molding method, resin pelletization is required, and the temperature control in the extruder and the mold must be strictly controlled in order to prevent bubbles and unmelted substances contained in the molded product. As a method of performing melt extrusion molding of a PVA-based resin in an anhydrous state,
Japanese Patent Publication No. 42-26930, Japanese Patent Publication No. 44-28588, Japanese Patent Publication No. 53-24975
Japanese Patent Publication No. 56-49733 and Japanese Patent Publication No. 50-22049 have been proposed, but when melt extrusion molding is performed using a single screw extruder by these methods, the resin forms a bridge in the hopper. As a result, the resin is not smoothly supplied into the single-screw extruder. Therefore, it becomes difficult to quantitatively extrude the resin from the extruder and an unmelted product is generated in the melt-extruded product.

【0004】[0004]

【本発明が解決しようとする課題】PVA系樹脂は、融
点より熱分解温度の方が低いために溶融押出成形物中に
熱分解物あるいは着色が生じるため、一般的な熱可塑性
樹脂で用いられている方法では溶融押出成形を行うこと
はできない。しかしながら、PVA系樹脂に多価アルコ
ールを添加した場合、流動開始温度を低下できることが
知られている[長野浩一、山根三郎、豊島賢太郎、ポバ
ール、高分子刊行会 221〜 224(1989)]。そこで、本
発明者らは、この点に着目し鋭意検討した結果、PVA
系樹脂の粒度分布と安息角を調整することによりペレッ
ト化することなく単軸押出機で未溶融物がなく熱分解に
よる変色も引き起こすことなしに実質的に無水の状態で
溶融押出成形が可能なことを見い出し、本発明に到達し
た。従って、本発明の目的は、PVA系樹脂をペッレト
化することなく、実質的に無水の状態で溶融押出成形で
きるPVA系樹脂成形物、とくには単軸押出機で未溶融
物がなく熱分解による変色も引き起こすことなく定量押
出が可能な成形物の製造方法を提供しようとするもので
ある。
Since the PVA resin has a lower thermal decomposition temperature than its melting point, a thermal decomposition product or coloration occurs in the melt extruded product, so that it is used as a general thermoplastic resin. Melt extrusion cannot be performed by the method described above. However, it is known that the flow initiation temperature can be lowered by adding a polyhydric alcohol to the PVA-based resin [Koichi Nagano, Saburo Yamane, Kentaro Toyoshima, Poval, Kobunshi Kobunkai 221-224 (1989)]. Therefore, as a result of diligent study focusing on this point, the present inventors have found that PVA
By adjusting the particle size distribution and angle of repose of the base resin, melt extrusion can be performed in a substantially anhydrous state without pelletizing without unmelting and without causing discoloration due to thermal decomposition without pelletizing. As a result, they have reached the present invention. Therefore, an object of the present invention is to melt-extrude a PVA-based resin in a substantially anhydrous state without pelletizing the PVA-based resin, and in particular, to obtain a PVA-based resin by a thermal decomposition without unmelted matter in a single screw extruder. An object of the present invention is to provide a method for producing a molded product which can be quantitatively extruded without causing discoloration.

【0005】[0005]

【課題を解決するための手段】本発明者らはかかる課題
を解決するためにPVA系樹脂の物性と押出成形条件と
の関連に着目し、検討を続けた結果、最適条件を確立す
ることに成功し、本発明を完成したもので、その要旨
は、(1)粒度分布が 3.5メッシュオンカット、 3.5〜
50メッシュの範囲で95重量%以上、安息角 10〜40度、
ケン化度 5.0〜98.0モル%、重合度 100〜 600の範囲内
であるポリビニルアルコール系樹脂、または(2)粒度
分布が 3.5メッシュオンカット、 3.5〜50メッシュの範
囲で95重量%以上、安息角 10〜40度、ケン化度 5.0〜
98.0モル%、重合度 100〜2000の範囲内であるポリビニ
ルアルコール系樹脂 100重量部に対して多価アルコール
を0.01〜30重量部配含してなる組成物を実質的に無水の
状態で溶融押出成形することを特徴とするポリビニルア
ルコール系樹脂成形物の製造方法にあり、特に組成物
(2)は、多価アルコールをポリビニルアルコール系樹
脂の温度を70〜 120℃に加熱して含浸させた後、室温ま
で冷却したものとする、というものである。
The inventors of the present invention focused on the relationship between the physical properties of PVA-based resins and the extrusion molding conditions in order to solve such problems, and as a result of continued investigations, the inventors established the optimum conditions. The present invention has been completed successfully, and its gist is (1) particle size distribution of 3.5 mesh on-cut, 3.5-
95% by weight or more in the range of 50 mesh, angle of repose 10-40 degrees,
Polyvinyl alcohol resin having a saponification degree of 5.0 to 98.0 mol% and a polymerization degree of 100 to 600, or (2) a particle size distribution of 3.5 mesh on-cut, 95 to 50% by weight or more in the range of 3.5 to 50 mesh, angle of repose. 10-40 degrees, saponification degree 5.0-
Melt extrusion of a composition containing 0.01 to 30 parts by weight of polyhydric alcohol to 100 parts by weight of polyvinyl alcohol resin having a polymerization degree of 98.0 mol% and a polymerization degree of 100 to 2000 in a substantially anhydrous state. A method for producing a polyvinyl alcohol-based resin molded article characterized by molding, in particular, the composition (2) is obtained by heating the temperature of the polyvinyl alcohol-based resin to 70 to 120 ° C. to impregnate the polyhydric alcohol with the polyhydric alcohol. It should be cooled to room temperature.

【0006】以下、本発明を詳細に説明する。本発明で
用いられるPVA系樹脂としては、ポリ酢酸ビニルをケ
ン化して得られるケン化度 5.0〜98.0モル%、重合度 1
00から2000の範囲内のものである。ケン化度が98.0モル
%を越えと、多価アルコールを含浸させても溶融押出成
形時に樹脂が熱分解を引き起こす。ケン化度5.0 モル%
未満ではPVAの特性が完全に失われてしまい使用でき
ない。重合度が 100未満のものは溶融押出成形後の成形
物の機械的強度が小さく、重合度が2000を越えるものは
多価アルコールを含浸させても樹脂の熱分解を引き起こ
すことなく溶融押出成形を行うことはできない。
The present invention will be described in detail below. The PVA-based resin used in the present invention has a saponification degree of 5.0 to 98.0 mol% and a polymerization degree of 1 obtained by saponifying polyvinyl acetate.
It is in the range of 00 to 2000. When the saponification degree exceeds 98.0 mol%, the resin causes thermal decomposition during melt extrusion molding even when impregnated with a polyhydric alcohol. Saponification degree 5.0 mol%
If it is less than the above range, the properties of PVA are completely lost and it cannot be used. If the degree of polymerization is less than 100, the mechanical strength of the molded product after melt extrusion molding is low, and if the degree of polymerization exceeds 2000, melt extrusion molding does not occur even if impregnated with polyhydric alcohol without causing thermal decomposition of the resin. I can't do it.

【0007】押出機に供給されるPVA系樹脂の形態と
しては、粒度分布が 3.5メッシュオンカット、 3.5〜50
メッシュの範囲が95重量%以上と粗く、かつ安息角が10
〜40度のものを使用するのが良い。樹脂の上記粒度分布
が95重量%未満と細かく、または安息角が40度を越える
場合は、押出機のホッパー内で樹脂がブリッジを形成し
易く、単軸押出機への樹脂の供給が円滑に行われなくな
り、樹脂の定量押出が困難となると共に溶融押出成形物
中に未溶融物が生じる。 3.5メッシュオンの粗粒もまた
押出機への供給が困難となり、未溶融物を生じ易い。P
VA系樹脂としては、上記の他、これらのポリビニルア
ルコールをリン酸化、硫酸化、エーテル化させたポリビ
ニルアルコール誘導体、さらに酢酸ビニルモノマーとア
リールアルコールあるいはアクリル酸、クロトン酸、マ
レイン酸、イタコン酸等の不飽和カルボン酸を共重合さ
せた共重合体をケン化することにより得られる変性ポリ
ビニルアルコールも使用可能である。
The PVA resin supplied to the extruder has a particle size distribution of 3.5 mesh on cut, 3.5 to 50.
The mesh range is 95% by weight or more, and the angle of repose is 10
It is better to use one that is ~ 40 degrees. When the above particle size distribution of the resin is as small as less than 95% by weight, or when the angle of repose exceeds 40 degrees, the resin easily forms a bridge in the hopper of the extruder and the resin is smoothly supplied to the single-screw extruder. Since it is not carried out, it becomes difficult to extrude the resin in a fixed amount, and an unmelted product is produced in the melt extruded product. It is difficult to supply coarse particles of 3.5 mesh on to the extruder, and unmelted material is easily generated. P
Examples of the VA-based resin include, in addition to the above, polyvinyl alcohol derivatives obtained by phosphorylating, sulfating, or etherifying these polyvinyl alcohols, vinyl acetate monomers and aryl alcohols, acrylic acid, crotonic acid, maleic acid, itaconic acid, and the like. A modified polyvinyl alcohol obtained by saponifying a copolymer obtained by copolymerizing an unsaturated carboxylic acid can also be used.

【0008】使用される多価アルコールとしては、エチ
レングリコール、ジエチレングリコール、プロピレング
リコール、ジプロピレングリコールあるいはグリセリン
等のポリビニルアルコールの可塑剤として一般的に知ら
れているものが例示される。多価アルコールの添加量
は、PVA系樹脂の重合度によって異なる。重合度 100
〜 600、ケン化度 5.0〜98モル%のPVA系樹脂で含水
率がPVA系樹脂製造上不可避の量以下の範囲内であれ
ば水分が可塑剤として働くために特に多価アルコールを
添加する必要はない。多価アルコールを添加する場合
は、PVA系樹脂 100重量部に対して0.01〜30重量部、
好ましくは、 1.0〜20重量部である。特に重合度が 600
を越える場合は、多価アルコールを添加しないと溶融押
出成形に適した流動性が得られない。多価アルコールの
添加量が30重量部を越える場合は成形物から多価アルコ
ールがブリーディングするので実用的でない。
Examples of the polyhydric alcohol used include those generally known as plasticizers for polyvinyl alcohol such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and glycerin. The amount of polyhydric alcohol added varies depending on the degree of polymerization of the PVA resin. Degree of polymerization 100
-600, saponification degree 5.0-98 mol% PVA-based resin, if the water content is within the range inevitable in the production of PVA-based resin, it is necessary to add a polyhydric alcohol because water acts as a plasticizer. There is no. When polyhydric alcohol is added, 0.01 to 30 parts by weight to 100 parts by weight of PVA resin,
It is preferably 1.0 to 20 parts by weight. Especially the degree of polymerization is 600
If it exceeds, the flowability suitable for melt extrusion molding cannot be obtained unless a polyhydric alcohol is added. If the amount of the polyhydric alcohol added exceeds 30 parts by weight, the polyhydric alcohol bleeds from the molded product, which is not practical.

【0009】さらに必要に応じて、ポリエチレン、ポロ
プロピレン等の熱可塑性樹脂、澱粉、カルボキシメチル
セルロース、ヒドロキエチルセルロース等のセルロース
誘導体、キサンタンガム、カラギナン、キチン、キトサ
ン等の多糖類、ステアリン酸、リン酸エステル、グリセ
リン脂肪酸エステル、ソルビタン酸脂肪酸エステル等の
滑剤、タルク、炭酸カルシウム等の充填剤、発泡剤、硫
酸マグネシウム、硫酸亜鉛または特公昭 35-1669号公報
等に記載されている硫酸銅、硫酸コバルト、酢酸第1す
ず蟻酸鉛及び臭化マンガン等の着色防止剤、有機または
無機の酸、酸化チタン、カーボンブラック等の各種顔料
または染料等の補強または着色物質等を添加することも
できる。
Further, if necessary, thermoplastic resins such as polyethylene and polypropylene, cellulose derivatives such as starch, carboxymethyl cellulose and hydroxyethyl cellulose, polysaccharides such as xanthan gum, carrageenan, chitin and chitosan, stearic acid, phosphate ester, Glycerin fatty acid ester, lubricant such as sorbitan acid fatty acid ester, talc, filler such as calcium carbonate, foaming agent, magnesium sulfate, zinc sulfate or copper sulfate, cobalt sulfate, acetic acid described in JP-B-35-1669 It is also possible to add a coloring inhibitor such as primary lead tin formate and manganese bromide, an organic or inorganic acid, various pigments such as titanium oxide and carbon black, or a reinforcing or coloring substance such as a dye.

【0010】次に成形物の製造方法について述べる。P
VA系樹脂に多価アルコールを含浸させる場合は、加熱
されたミキサー内で樹脂の温度を70〜 120℃、好ましく
は80〜 110℃の範囲内に設定して30分間から4時間かけ
て行うのが望ましい。樹脂の温度が70℃未満の場合は多
価アルコールの含浸を完全に行うことができず、また12
0℃を越える場合は樹脂が溶融凝集するので好ましくな
い。30分間未満の場合は多価アルコールの含浸が不十分
となり、実用上4時間以内で十分である。含浸後は押出
安定化のため含浸混合物を室温まで冷却する。多価アル
コールの含浸が不十分な場合は、樹脂のべとつきが激し
く樹脂同士の密着、あるいは押出機のホッパー内に樹脂
がこびり着きブリッジを形成して単軸押出機への樹脂の
供給が円滑に行われ難くなり、押出機からの定量押出が
困難となる。ここで含浸とは、PVA系樹脂粒子構造中
の隙間に多価アルコールを取り込ませた状態で、多価ア
ルコールが樹脂粒子表面の一部分でも覆っていない状態
を言う。
Next, a method for producing a molded product will be described. P
When the VA resin is impregnated with the polyhydric alcohol, the temperature of the resin is set within a range of 70 to 120 ° C., preferably 80 to 110 ° C. in a heated mixer, and it is carried out for 30 minutes to 4 hours. Is desirable. If the temperature of the resin is less than 70 ° C, the impregnation of polyhydric alcohol cannot be carried out completely.
If the temperature exceeds 0 ° C, the resin melts and aggregates, which is not preferable. If it is less than 30 minutes, the impregnation of the polyhydric alcohol will be insufficient, and 4 hours or less will be sufficient for practical use. After impregnation, the impregnation mixture is cooled to room temperature for extrusion stabilization. If the polyhydric alcohol is not sufficiently impregnated, the resin becomes extremely sticky and the resins stick to each other, or the resin sticks to the inside of the hopper of the extruder to form a bridge and the resin is smoothly supplied to the single-screw extruder. Therefore, it becomes difficult to perform quantitative extrusion from the extruder. Here, impregnation means a state in which the polyhydric alcohol is incorporated into the gaps in the PVA-based resin particle structure, and the polyhydric alcohol does not cover even a part of the resin particle surface.

【0011】この含浸に用いられるミキサーとしては、
混合時に樹脂の破壊或は剪断発熱による樹脂の溶融凝集
を防ぐ目的で剪断応力のかからないナウターミキサー、
リボンブレンダー或はこれと同種のものが適当である。
溶融押出成形を行う場合は、金型の温度を 120〜 200
℃、押出機のシリンダー温度は 120〜 200℃に設定して
行うことが望ましい。金型の温度が 120℃未満の場合は
樹脂の流動性が低下し、 200℃を越える場合は樹脂の熱
分解が起こる。押出機のシリンダー温度が 110℃未満の
場合には樹脂の溶融混練が十分に行われず、 200℃を越
える場合は樹脂の熱分解が起こるので好ましくない。
なお、本発明で実質的な無水状態とは、PVA系樹脂に
多価アルコールを配合後にこのPVA系樹脂組成物に水
を添加しないことを言う。以上のようにして得られたP
VA系樹脂組成物は、粒子状のままで、ペッレト化の必
要はなく、単軸押出機を用いて定量的に熱分解や変色を
引き起こすことなしに実質的に無水の状態で溶融押出成
形を行うことができる。また、多軸押出機を用いても単
軸押出機と同様に溶融押出成形を行うことができる。
As the mixer used for this impregnation,
A Nauta mixer that does not apply shear stress for the purpose of preventing the resin from melting or agglomerating due to shear heat generation during mixing.
A ribbon blender or the like is suitable.
When performing melt extrusion, set the mold temperature at 120 to 200.
℃, it is desirable to set the cylinder temperature of the extruder to 120 ~ 200 ℃. If the mold temperature is less than 120 ° C, the fluidity of the resin will decrease, and if it exceeds 200 ° C, thermal decomposition of the resin will occur. If the cylinder temperature of the extruder is lower than 110 ° C, the resin is not sufficiently melt-kneaded, and if it exceeds 200 ° C, the resin is thermally decomposed, which is not preferable.
In the present invention, the substantially anhydrous state means that water is not added to the PVA-based resin composition after blending the polyhydric alcohol with the PVA-based resin. P obtained as described above
The VA-based resin composition remains in the form of particles, does not need to be pelletized, and is melt-extruded in a substantially anhydrous state using a single-screw extruder without causing quantitative thermal decomposition or discoloration. It can be carried out. Further, even if a multi-screw extruder is used, melt extrusion molding can be performed in the same manner as a single-screw extruder.

【0012】次にPVA系樹脂成形物の製造方法の一例
として単軸押出機、金型としてT−ダイを用いたT−ダ
イ押出成形法によるシート、フィルム成形を説明する。
前述の多価アルコール含浸配合樹脂組成物粒子を冷却
後、単軸押出機のホッパーに投入し、シリンダーの温度
(C1 〜C4 )を 120〜 200℃とした押出機に連続的に
供給して溶融混練し、 120〜 200℃に加熱されたT−ダ
イ(D1 〜D3 )より吐出させ、第1ロールとの間で種
々の厚みのシート或はフィルムを成形させる。本発明に
なるPVA系樹脂成形物は、T−ダイ押出成形法に限ら
ず、インフレーション成形法、射出成形法あるいはブロ
ー成形法等の従来公知の成形法にも適用できる。
Next, as an example of a method for producing a PVA-based resin molded product, a single-screw extruder and a T-die extrusion molding method using a T-die as a mold will be described to form a sheet or film.
After cooling the above-mentioned polyhydric alcohol-impregnated resin composition particles, they are put into the hopper of a single-screw extruder and continuously supplied to the extruder at a cylinder temperature (C 1 to C 4 ) of 120 to 200 ° C. Then, the mixture is melt-kneaded and discharged from a T-die (D 1 to D 3 ) heated to 120 to 200 ° C. to form sheets or films of various thicknesses with the first roll. The PVA-based resin molded product according to the present invention can be applied not only to the T-die extrusion molding method but also to any conventionally known molding method such as an inflation molding method, an injection molding method or a blow molding method.

【0013】[0013]

【作用】[Action]

(1)本願発明の製造方法によれば、特定物性を持つP
VA系樹脂粒子を実質的に無水状態で押出成形機へ供給
することができ、PVA系樹脂のペッレト化が不要とな
る。 (2)押出機内へ円滑に供給することができるため、単
軸押出機でも定量押出が可能となり、また未溶融物の発
生も防止することができる。 (3)水を添加することなく溶融押出成形が可能なた
め、成形後の乾燥工程が不要となり、製造工程の簡素化
が図れる。
(1) According to the manufacturing method of the present invention, P having specific physical properties
The VA-based resin particles can be supplied to the extruder in a substantially anhydrous state, which eliminates the need for pelletizing the PVA-based resin. (2) Since it can be smoothly supplied into the extruder, it is possible to carry out quantitative extrusion even with a single-screw extruder, and it is possible to prevent the generation of unmelted matter. (3) Since melt extrusion molding can be performed without adding water, a drying step after molding is unnecessary, and the manufacturing process can be simplified.

【0014】[0014]

【実施例】以下、本発明の実施態様を実施例により具体
的に説明するが、本発明はこれらに限定されるものでは
ない。 (実施例1)表1に示す各PVA系樹脂をL/D=28、
圧縮比 2.5倍のフルフライトスクリューを使用したシリ
ンダー内径50mmφ汎用単軸押出機に供給して表2に示す
条件で溶融混練を行い、表1に示す条件で幅 600mmのT
−ダイ2より吐出し、PVA系樹脂のシートおよびフィ
ルムを得た。押出時の樹脂圧の変動は5kg/cm2未満で定
量的に供給され押出されていた。また得られたPVA系
樹脂のシートおよびフィルムには、熱分解物、変色およ
び未溶融物などは全く認められなかった。
EXAMPLES The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these. (Example 1) Each PVA-based resin shown in Table 1 had L / D = 28,
Cylinder inner diameter 50mm using a full-flight screw with a compression ratio of 2.5 times is fed to a general-purpose single-screw extruder and melt-kneaded under the conditions shown in Table 2, and under the conditions shown in Table 1
-It was discharged from the die 2 to obtain a sheet and a film of PVA type resin. The fluctuation of the resin pressure during extrusion was less than 5 kg / cm 2 , and the resin was quantitatively supplied and extruded. Further, in the obtained PVA-based resin sheet and film, thermal decomposition products, discoloration, unmelted products, etc. were not observed at all.

【0015】(比較例1)表1に示すPVA系樹脂を、
実施例1と同様のスクリュー、押出機、T−ダイを用い
て表1に示す条件により溶融押出を行った。試料番号1
〜3は溶融押出時の樹脂圧が著しく変動しており定量押
出は困難であった。また得られたPVA系樹脂のシート
およびフィルムには多数の未溶融物が認められた。試料
番号4は成形後の機械的強度が小さく成形物を得ること
ができなかった。試料番号5は押出機のシリンダー温度
が 215℃未満の場合は溶融押出成形を行うことができな
かった。一方、 215℃を越える場合は、得られたシート
中に多数の熱分解物および変色が認められた。
(Comparative Example 1) The PVA resin shown in Table 1 was
Using the same screw, extruder, and T-die as in Example 1, melt extrusion was performed under the conditions shown in Table 1. Sample number 1
In Nos. 3 to 3, the resin pressure during melt extrusion remarkably fluctuated, and quantitative extrusion was difficult. Further, a large number of unmelted substances were observed in the obtained PVA-based resin sheet and film. Sample No. 4 had a low mechanical strength after molding and could not be molded. Sample No. 5 could not be melt-extruded when the cylinder temperature of the extruder was lower than 215 ° C. On the other hand, when the temperature exceeds 215 ° C, many thermal decomposition products and discoloration were observed in the obtained sheet.

【0016】(実施例2)PVA系樹脂、多価アルコー
ルからなる表2に示す各試料をナウターミキサーに投入
した。投入後表2に示す条件下で攪拌した。攪拌後室温
まで冷却し、実質的に無水の状態で溶融押出成形が可能
なPVA系樹脂成形物を得た。得られたPVA系樹脂成
形物中には多価アルコールの未含浸物、樹脂同士の密着
あるいは溶融凝集物は全く認められなかった。ここで得
られた実質的に無水の状態で溶融可能なPVA系成形物
を実施例1と同様のスクリュー、押出機、T−ダイを用
いて表2に示す条件により溶融押出を行った。押出時の
樹脂圧の変動は5kg/cm2未満で定量的に供給され押出さ
れていた。また得られたPVA系樹脂のシートおよびフ
ィルムには、熱分解物、変色および未溶融物などは全く
認められなかった。
Example 2 Each sample shown in Table 2 consisting of a PVA resin and a polyhydric alcohol was put into a Nauta mixer. After charging, the mixture was stirred under the conditions shown in Table 2. After stirring, the mixture was cooled to room temperature to obtain a PVA-based resin molded product capable of melt extrusion molding in a substantially anhydrous state. In the obtained PVA-based resin molded product, no polyhydric alcohol unimpregnated product, adhesion of resins to each other, or melt agglomeration was not observed at all. The substantially anhydrous meltable PVA-based molded product obtained here was melt-extruded using the same screw, extruder and T-die as in Example 1 under the conditions shown in Table 2. The fluctuation of the resin pressure during extrusion was less than 5 kg / cm 2 , and the resin was quantitatively supplied and extruded. Further, in the obtained PVA-based resin sheet and film, thermal decomposition products, discoloration, unmelted products, etc. were not observed at all.

【0017】(比較例2)PVA系樹脂、多価アルコー
ルからなる表3に示す各試料をナウターミキサーに投入
した。投入後表3に示す条件下で攪拌した。試料番号
1、2は多価アルコールの未含浸物および樹脂同士の密
着が認められた。試料番号3、4は樹脂が溶融凝集して
しまった。ここで得られたPVA系成形物を実施例1と
同様のスクリュー、押出機、T−ダイを用いて表3に示
す条件により溶融押出を行った。試料番号1、2はホッ
パー内に樹脂がこびり着きつブリッジを形成するため、
樹脂圧が激しく変動し、得られたシート中には多数の未
溶融物が存在していた。試料番号3、4は溶融凝集物が
押出機内へ供給することが出来なかった。従って、成形
物を得ることが出来なかった。
(Comparative Example 2) Each sample shown in Table 3 consisting of a PVA resin and a polyhydric alcohol was put into a Nauta mixer. After the addition, the mixture was stirred under the conditions shown in Table 3. In Sample Nos. 1 and 2, unimpregnated products of polyhydric alcohol and adhesion of resins were observed. In Sample Nos. 3 and 4, the resin was melted and agglomerated. The PVA-based molded product obtained here was melt-extruded using the same screw, extruder, and T-die as in Example 1 under the conditions shown in Table 3. Sample Nos. 1 and 2 have resin sticking in the hopper and forming a tight bridge,
The resin pressure fluctuated drastically, and many unmelted materials were present in the obtained sheet. Sample Nos. 3 and 4 could not be melt-aggregated into the extruder. Therefore, a molded product could not be obtained.

【0018】試料番号5〜8は、溶融押出時の樹脂圧が
著しく変動しており、定量押出は困難であった。また、
得られたシートおよびフィルムには多数の未溶融物が認
められた。試料番号9は押出機のシリンダー温度が220
℃未満の場合は溶融押出成形を行うことが出来なかっ
た。一方、220 ℃を越える場合は、得られたシート中に
多数の熱分解物および変色が認められた。試料番号10
も同様に押出機のシリンダー温度が 215℃未満の場合は
溶融押出成形を行うことが出来ず、215 ℃を越える場合
は、得られたシート中に多数の熱分解物および変色が認
められた。試料番号11、12および13は、得られた
フィルムあるいはシート成形物中には多数の熱分解物お
よび変色が認められた。
In Sample Nos. 5 to 8, the resin pressure at the time of melt extrusion fluctuated remarkably, and quantitative extrusion was difficult. Also,
Many unmelted materials were found in the obtained sheets and films. Sample No. 9 has an extruder cylinder temperature of 220.
When the temperature was lower than ° C, melt extrusion could not be performed. On the other hand, when the temperature exceeds 220 ° C, many thermal decomposition products and discoloration were observed in the obtained sheet. Sample number 10
Similarly, when the cylinder temperature of the extruder was less than 215 ° C, melt extrusion molding could not be performed, and when it exceeded 215 ° C, many thermal decomposition products and discoloration were observed in the obtained sheet. In Sample Nos. 11, 12 and 13, many thermal decomposition products and discoloration were observed in the obtained film or sheet molded product.

【0019】[註]本発明の実施例および比較例にに使
用される単軸押出機のシリンダー及びT−ダイの温度測
定位置は次の通りである。 シリンダーC1 :原料供給口中心より31cmの位置。 C2 :圧縮部−C1 より25cmの位置。 C3 :圧縮部−C1 より50cmの位置。 C4 :計量部−C1 より75cmの位置。 金型 D1 :押出機側から見てT−ダイ左側1/3 、
2 より20cmの位置。 D2 :押出機側から見てT−ダイ中央1/3 、溶融樹脂流
入口より0cmの位置。 D3 :押出機側から見てT−ダイ右側1/3 、D2 より20
cmの位置。
[Note] The temperature measurement positions of the cylinder and the T-die of the single-screw extruder used in the examples and comparative examples of the present invention are as follows. Cylinder C 1 : 31 cm from the center of the raw material supply port. C 2: the position of the compression unit -C 1 25 cm. C 3: Position of 50cm from the compression unit -C 1. C 4: position of 75cm from the metering section -C 1. Mold D 1 : T-die left side 1/3 as seen from the extruder side,
20 cm from D 2 . D 2: as viewed from the extruder side T- die center 1/3 position of 0cm from molten resin inlet. D 3: extruder viewed from side T- die right 1/3, D 2 from 20
The position in cm.

【0020】[0020]

【表1】 [Table 1]

【0021】[0021]

【表2】 [Table 2]

【0022】[0022]

【表3】 [Table 3]

【0023】[0023]

【発明の効果】本発明によれば、従来のようにPVA系
樹脂に水を添加することなく、またペッレト化せずに実
質的に無水の状態で単軸押出機を用いて定量的に溶融押
出成形を行うことができ、泡、未溶融物、熱分解による
変色等のないPVA系樹脂成形物が得られる。従って、
従来の製造工程からペッレト化工程、乾燥工程および熱
処理工程等の複雑な工程を省略することができるので生
産性が向上し、しかも汎用の単軸押出機で溶融押出成形
が可能なためポリエチレン、ポリプロピレン、ポリ塩化
ビニル等の汎用熱可塑性樹脂用の製造ラインでも製造す
ることが可能である。また、ポリエチレン、ポリプロピ
レン等の熱可塑性樹脂との共押出あるいはポリマーブレ
ンド化も可能となり、工業上その利用価値は極めて高
い。
EFFECTS OF THE INVENTION According to the present invention, it is possible to quantitatively melt a PVA-based resin in a substantially anhydrous state without adding water to a PVA-based resin and in a substantially anhydrous state by using a single-screw extruder. Extrusion molding can be performed, and a PVA-based resin molded product having no bubbles, unmelted substances, discoloration due to thermal decomposition, etc. can be obtained. Therefore,
Since complex processes such as pelletizing process, drying process and heat treatment process can be omitted from the conventional manufacturing process, productivity is improved, and since melt extrusion molding is possible with a general-purpose single screw extruder, polyethylene, polypropylene It can also be manufactured on a manufacturing line for general-purpose thermoplastic resins such as polyvinyl chloride. In addition, coextrusion with a thermoplastic resin such as polyethylene or polypropylene or polymer blending is possible, and its industrial utility value is extremely high.

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】(1)粒度分布が 3.5メッシュオンカッ
ト、3.5 〜50メッシュの範囲で95重量%以上、安息角
10〜40度、ケン化度 5.0〜98.0モル%、重合度 100〜 6
00の範囲内であるポリビニルアルコール系樹脂、または
(2)粒度分布が3.5メッシュオンカット、 3.5〜50メ
ッシュの範囲で95重量%以上、安息角 10〜40度、ケン
化度 5.0〜98.0モル%、重合度 100〜2000の範囲内であ
るポリビニルアルコール系樹脂 100重量部に対して多価
アルコールを0.01〜30重量部配含してなる組成物を実質
的に無水の状態で溶融押出成形することを特徴とするポ
リビニルアルコール系樹脂成形物の製造方法。
(1) Particle size distribution is 3.5 mesh on-cut, 95% by weight or more in the range of 3.5 to 50 mesh, angle of repose
10-40 degrees, saponification degree 5.0-98.0 mol%, degree of polymerization 100-6
Polyvinyl alcohol resin within the range of 00, or (2) 3.5 mesh on cut, 95% by weight or more in the range of 3.5 to 50 mesh, angle of repose 10 to 40 degrees, saponification degree 5.0 to 98.0 mol% , A composition comprising 0.01 to 30 parts by weight of a polyhydric alcohol with respect to 100 parts by weight of a polyvinyl alcohol resin having a polymerization degree of 100 to 2000 is melt-extruded in a substantially anhydrous state. A method for producing a polyvinyl alcohol-based resin molded article, comprising:
【請求項2】組成物(2)は、多価アルコールをポリビ
ニルアルコール系樹脂の温度を70〜 120℃に加熱して含
浸させた後、室温まで冷却したものから成る請求項1に
記載のポリビニルアルコール系樹脂成形物の製造方法。
2. The polyvinyl composition according to claim 1, wherein the composition (2) comprises a polyvinyl alcohol resin heated to 70 to 120 ° C. for impregnation and then cooled to room temperature. Method for producing alcohol-based resin molded product.
【請求項3】溶融押出成形条件として金型の温度を 120
〜 200℃、押出機のシリンダー温度を 120〜 200℃に設
定して行う請求項1に記載のポリビニルアルコール系樹
脂成形物の製造方法。
3. A mold temperature of 120 as a melt extrusion molding condition.
The method for producing a polyvinyl alcohol-based resin molded product according to claim 1, wherein the method is carried out at a temperature of ˜200 ° C. and an extruder cylinder temperature of 120˜200 ° C. 3.
JP5134714A 1993-06-04 1993-06-04 Manufacture of polyvinyl alcohol resin molded product Pending JPH06344410A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5134714A JPH06344410A (en) 1993-06-04 1993-06-04 Manufacture of polyvinyl alcohol resin molded product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5134714A JPH06344410A (en) 1993-06-04 1993-06-04 Manufacture of polyvinyl alcohol resin molded product

Publications (1)

Publication Number Publication Date
JPH06344410A true JPH06344410A (en) 1994-12-20

Family

ID=15134884

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5134714A Pending JPH06344410A (en) 1993-06-04 1993-06-04 Manufacture of polyvinyl alcohol resin molded product

Country Status (1)

Country Link
JP (1) JPH06344410A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016515653A (en) * 2013-03-25 2016-05-30 ピーター モリス リサーチ アンド デベロップメント リミテッド Water-soluble polymer and polymer internal lubricant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016515653A (en) * 2013-03-25 2016-05-30 ピーター モリス リサーチ アンド デベロップメント リミテッド Water-soluble polymer and polymer internal lubricant

Similar Documents

Publication Publication Date Title
US4218350A (en) Shaped synthetic polymers containing a biodegradable substance
EP0611382A1 (en) Method of producing plasticised polyvinyl alcohol, and its use
JPH06248150A (en) Extrudable polyvinyl alcohol composition containing modified starch
JPH0649288B2 (en) Method for producing polyvinyl chloride material for extrusion molding
CN109504041A (en) Using the TPS/PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation
CN107936430A (en) High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof
IE62729B1 (en) Gelatine granules as well as methods and apparatus for their manufacture
CN109535674A (en) Using the PPC/PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation
US5948848A (en) Biodegradable plastic material and a method for its manufacture
CN109553934A (en) Using the PBS/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation
CN115011083A (en) Fully biodegradable composite material capable of being repeatedly processed and preparation method thereof
CN109401227A (en) Using the PLA/PBAT blending and modifying Biodegradable resin and preparation method thereof of chain extender preparation
JPH0192203A (en) Saponified ethylene-vinyl acetate copolymer having improved property
CN113817296A (en) Novel biodegradable material special for winding film and preparation method thereof
CN113912989A (en) Novel biodegradable tackifying master batch and preparation method thereof
US4058904A (en) Process for drying wet particles of hydrolyzed ethylene-vinyl acetate copolymer
CN117106289A (en) Thermoplastic composite laminated material and preparation method thereof
JPH06344410A (en) Manufacture of polyvinyl alcohol resin molded product
JP2520518B2 (en) Method for producing polyvinyl alcohol type molded article
CN112029224B (en) Environment-friendly plastic with controllable transparency and multicolor patterns and preparation method thereof
KR20180119479A (en) Multi-degradable polyolefin-based resin composition and manufacturing method of the composition
US7713451B2 (en) Process for manufacturing a water-resistant telecommunication cable
JPH04132748A (en) Production of bio-decomposable sheet
JPH01261440A (en) Colorant composition for thermoplastic resin
JP2001081197A (en) Drying of saponified ethylene-vinyl acetate copolymer