JP2006225501A - Vinyl chloride-based resin composition and its molded product - Google Patents
Vinyl chloride-based resin composition and its molded product Download PDFInfo
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Abstract
Description
本発明は、塩化ビニル系樹脂組成物およびその成形体に係り、特に重量平均分子量（以下、分子量と略す場合がある）が低い塩化ビニル系樹脂が有する良好な成形加工性と、分子量の高い塩化ビニル系樹脂の有する良好な機械強度を併せ持つ塩化ビニル系樹脂を用いることにより、優れた成形加工性と機械強度の両特性を有する塩化ビニル系樹脂組成物およびその成形体に関する。 The present invention relates to a vinyl chloride resin composition and a molded article thereof, and in particular, good moldability possessed by a vinyl chloride resin having a low weight average molecular weight (hereinafter sometimes abbreviated as a molecular weight) and a high molecular weight chloride. The present invention relates to a vinyl chloride resin composition having both excellent molding processability and mechanical strength by using a vinyl chloride resin having a good mechanical strength of a vinyl resin, and a molded article thereof.
塩化ビニル樹脂単独又は塩化ビニル系樹脂組成物を用いてなる押出成形品は、パイプ、平板（プレート）、シート等の分野で広く用いられている。このような分野では、生産性の向上（金型等の解体清掃のサイクル延長）のために溶融粘度の低い樹脂が望まれているが、溶融粘度は一般的に分子量が小さい方が低いのに対し、成形品の強度は、逆に分子量が大きい方が強いため、両特性の兼ね合いにより使用する塩化ビニル樹脂の分子量を決めていた。
そこで、分子量の大きさを変えずに溶融粘度を下げる手段として、樹脂中の低分子量成分を増大させる試みがなされている。例えば、塩化ビニルの重合途中で重合温度を変化させる方法が検討されている。しかし、この方法では、重合を安定して進める必要性から、急速に温度を変えることができないので、十分な量の低分子量成分を持つ塩化ビニル系樹脂を作製することが出来ない。
Extrusion products using a vinyl chloride resin alone or a vinyl chloride resin composition are widely used in the fields of pipes, flat plates (plates), sheets and the like. In such a field, a resin having a low melt viscosity is desired for improving productivity (extending the cycle of dismantling and cleaning of molds, etc.), but the melt viscosity is generally lower when the molecular weight is lower. On the other hand, since the strength of the molded product is stronger when the molecular weight is larger, the molecular weight of the vinyl chloride resin to be used is determined based on the balance of both characteristics.
Thus, attempts have been made to increase the low molecular weight component in the resin as a means for lowering the melt viscosity without changing the molecular weight. For example, a method of changing the polymerization temperature during the polymerization of vinyl chloride has been studied. However, in this method, since the temperature cannot be changed rapidly because of the necessity of proceeding the polymerization stably, a vinyl chloride resin having a sufficient amount of low molecular weight components cannot be produced.
そこで、上記課題を解決する方法として、例えば特許文献１に示された方法が提案されている。これは、通常の方法で重合した塩化ビニル系樹脂を種樹脂として、懸濁重合により再重合を行う二段階重合法により塩化ビニル系樹脂を作成する方法であり、ゲル化時間が早く、押出成形の生産性の高い塩化ビニル系重合体の製造方法を提供している。
しかしながら、この方法では、再重合を行う際に塩化ビニル系樹脂のモルフォロジー変化が生じ、ポロシティー（空隙率）が小さくなり、例えば可塑剤を用いるような軟質（透明）配合では可塑剤吸収にムラが生じ、得られた配合物を成形する際にブツやフィッシュアイが発生し外観不良や物性低下の原因となる恐れがある。
Therefore, as a method for solving the above problem, for example, a method disclosed in Patent Document 1 has been proposed. This is a method of creating a vinyl chloride resin by a two-stage polymerization method in which repolymerization is performed by suspension polymerization using a vinyl chloride resin polymerized by a normal method as a seed resin. A method for producing a highly productive vinyl chloride polymer is provided.
However, in this method, the morphological change of the vinyl chloride resin occurs during repolymerization, and the porosity (porosity) becomes small. For example, in a soft (transparent) formulation using a plasticizer, uneven absorption of the plasticizer is caused. When the resulting blend is molded, bumps and fish eyes are generated, which may cause poor appearance and reduced physical properties.
本発明者らは、このような現状に鑑み、鋭意検討を重ねた結果、特定の範囲の平均分子量を有し、重量平均分子量（ＭＷ）と数平均分子量（ＭＮ）の比ＭＷ／ＭＮが特定の範囲にあり、さらには上記のような分子量分布を、連鎖移動剤の使用と温度制御により操作したものを用いることにより上記課題を解消できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the present situation, the present inventors have an average molecular weight in a specific range, and a ratio MW / MN of a weight average molecular weight (MW) and a number average molecular weight (MN) is specified. In addition, the inventors have found that the above problem can be solved by using a molecular weight distribution as described above that has been manipulated by the use of a chain transfer agent and temperature control, and the present invention has been completed.
本発明の要旨は、
塩化ビニル系樹脂の重合度分布を、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、ポリスチレン換算法による重量平均分子量（ＭＷ）が１．２×１０５〜２．２×１０５であり、かつＭＷと数平均分子量（ＭＮ）の比ＭＷ／ＭＮが２．０５〜２．２０である塩化ビニル系樹脂を用いることを特徴とする塩化ビニル系樹脂組成物およびその成形体にある。
また、連鎖移動剤の使用と温度制御により重合度分布がブロードな塩化ビニル系樹脂を用いることを特徴とする塩化ビニル系樹脂組成物およびその成形体にある。
The gist of the present invention is as follows.
The polymerization degree distribution of the vinyl chloride resin is measured by gel permeation chromatography (GPC), the weight average molecular weight (MW) according to the polystyrene conversion method is 1.2 × 10 5 to 2.2 × 10 5 , and A vinyl chloride resin composition characterized by using a vinyl chloride resin having a ratio of MW / number average molecular weight (MN) MW / MN of 2.05 to 2.20, and a molded article thereof.
Further, the present invention provides a vinyl chloride resin composition and a molded article thereof, characterized by using a vinyl chloride resin having a broad polymerization degree distribution by use of a chain transfer agent and temperature control.
本発明により得られた塩化ビニル系樹脂組成物および成形体は、低分子量の塩化ビニル系樹脂が有する成形加工性と、高分子量の塩化ビニル系樹脂が有する機械強度を併せ持っており、本発明で使用する塩化ビニル系樹脂を用いることにより良好な成形加工性と機械強度を有する塩化ビニル系樹脂組成物およびその成形体を得ることができる。 The vinyl chloride resin composition and the molded body obtained by the present invention have both the moldability of the low molecular weight vinyl chloride resin and the mechanical strength of the high molecular weight vinyl chloride resin. By using the vinyl chloride resin to be used, it is possible to obtain a vinyl chloride resin composition having good moldability and mechanical strength and a molded body thereof.
以下、本発明を詳しく説明するが、本発明の範囲が以下に説明する実施形態に限定されるものではない。
本発明における塩化ビニル樹脂とは、塩化ビニル単独重合体のほか、塩化ビニルと共重合可能な単量体との共重合体（以下、塩化ビニル共重合体とする）、この塩化ビニル共重合体以外の重合体に塩化ビニルをグラフト共重合させたグラフト共重合体などが挙げられ、これらの共重合体は、共重合体中の塩化ビニル以外の構成単位含有量が多くなると機械的特性が低下するので、塩化ビニルを６０重量％以上含有するのが好ましく、より好ましいのは８０重量％以上である。上記の塩化ビニルと共重合可能な単量体としては、分子中に反応性二重結合を有するものであればよく、例えば、エチレン、プロピレン、ブチレンなどのα−オレフィン類；酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類；ブチルビニルエーテル、セチルビニルエーテルなどのビニルエーテル類；アクリル酸、メタクリル酸などの不飽和カルボン酸類；アクリル酸メチル、メタクリル酸エチル、メタクリル酸フェニルなどのアクリル酸またはメタクリル酸のエステル類；スチレン、α−メチルスチレンなどの芳香族ビニル類；塩化ビニリデン、フッ化ビニルなどのハロゲン化ビニル類；Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミドなどのＮ−置換マレイミド類；などが挙げられ、これらは１種単独または２種以上の組み合わせで用いられる。また、上記塩化ビニル共重合体以外の重合体としては、塩化ビニルをグラフト共重合できるものであればよく、例えば、エチレン・酢酸ビニル共重合体、エチレン・酢酸ビニル・一酸化炭素共重合体、エチレン・エチルアクリレート共重合体、エチレン・エチルアクリレート・一酸化炭素共重合体、エチレン・メチルメタクリレート共重合体、エチレン・プロピレン共重合体、アクリロニトリル・ブタジエン共重合体、ポリウレタン、塩素化ポリエチレン、塩素化ポリプロピレンなどが挙げられ、これらは１種単独または２種以上の組み合わせで用いられる。
Hereinafter, the present invention will be described in detail, but the scope of the present invention is not limited to the embodiments described below.
The vinyl chloride resin in the present invention is a vinyl chloride homopolymer, a copolymer with a monomer copolymerizable with vinyl chloride (hereinafter referred to as vinyl chloride copolymer), and this vinyl chloride copolymer. Examples include graft copolymers obtained by graft copolymerization of vinyl chloride with other polymers, and these copolymers have lower mechanical properties when the content of constituent units other than vinyl chloride in the copolymer increases. Therefore, it is preferable to contain 60% by weight or more of vinyl chloride, and more preferably 80% by weight or more. As the monomer copolymerizable with vinyl chloride, any monomer having a reactive double bond in the molecule may be used. For example, α-olefins such as ethylene, propylene, butylene; vinyl acetate, propionic acid Vinyl esters such as vinyl; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate, and phenyl methacrylate Aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Is a single type or a combination of two or more types Used in combination. The polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate / carbon monoxide copolymer, Ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene / propylene copolymer, acrylonitrile / butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated Examples thereof include polypropylene, and these are used alone or in combination of two or more.
分散剤としては、一般の部分ケン化ポリ酢酸ビニル、水溶性部分ケン化ポリ酢酸ビニル、セルロース誘導体、ゼラチン、ノニオン界面活性剤、アニオン界面活性剤等、通常、塩化ビニルの懸濁重合に用いられる分散剤を使用できる。
重合開始剤としては、一般に塩化ビニルの懸濁重合に用いられる油溶性重合開始剤、例えば過酸化ベンゾイル、ラウロイルペルオキシド、ｔ−ブチルペルオキシピバレート、ジオクチルペルオキシジカーボネート、ジイソプロピルペルオキシジカーボネート、ｔ−ブチルペルオキシネオデカノエート、α−クミルペルオキシネオデカノエート等の有機過酸化物、アゾビス（ジメチルパレロニトリル）等のアゾ化合物等が使用される。これら重合開始剤の使用量は一般に、塩化ビニル系単量体に対し、０．０１〜０．５０重量％の範囲である。
As the dispersant, general partially saponified polyvinyl acetate, water-soluble partially saponified polyvinyl acetate, cellulose derivative, gelatin, nonionic surfactant, anionic surfactant, etc. are usually used for suspension polymerization of vinyl chloride. A dispersant can be used.
As the polymerization initiator, an oil-soluble polymerization initiator generally used for suspension polymerization of vinyl chloride, such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, dioctyl peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl. Organic peroxides such as peroxyneodecanoate and α-cumylperoxyneodecanoate, azo compounds such as azobis (dimethylpareronitrile), and the like are used. These polymerization initiators are generally used in an amount of 0.01 to 0.50% by weight based on the vinyl chloride monomer.
本発明のブロードな重合度分布を示す塩化ビニル系樹脂を得るには、一般に知られている重合助剤、例えばトリクロルエチレン、ドデシルメルカプタン、２−メルカプトエタノール、プロピオンアルデヒド等の公知の連鎖移動剤を使用できるが、好適には２−メルカプトエタノールが使用される。
さらに酸化防止剤等を任意に使用することができる。
塩化ビニル単量体単独、又は塩化ビニル単量体を主体とする共重合可能な単量体の混合物は、重合開始前に一括で仕込んでもよいし、或は塩化ビニル系単量体の一部を重合開始前に仕込み、残部を重合開始後に、連続的又は断続的に仕込むこともできる。
重合温度は用いる重合開始剤の種類、重合方法、目標とする重合度（分子量）によっても異なるが、一般に０〜９０℃、特に４０〜７０℃の範囲が好適である。
また、反応に際しては通常の定温重合法を採っても良いし、また連続昇温重合法を採っても良い。
生成した塩化ビニル系重合体スラリーの脱水・乾燥等の操作は、従来から行われている、遠心脱水−流動乾燥等の手段が採用され、容易に含水率０．１％以下の塩化ビニル系重合体を得ることができる。
In order to obtain a vinyl chloride resin having a broad polymerization degree distribution according to the present invention, a known chain transfer agent such as a generally known polymerization aid such as trichloroethylene, dodecyl mercaptan, 2-mercaptoethanol, or propionaldehyde is used. Although it can be used, 2-mercaptoethanol is preferably used.
Furthermore, antioxidants etc. can be used arbitrarily.
The vinyl chloride monomer alone or a mixture of copolymerizable monomers mainly composed of the vinyl chloride monomer may be charged all at once before starting the polymerization, or a part of the vinyl chloride monomer. Can be charged before the start of polymerization, and the remainder can be charged continuously or intermittently after the start of polymerization.
The polymerization temperature varies depending on the type of polymerization initiator to be used, the polymerization method, and the target degree of polymerization (molecular weight), but is generally in the range of 0 to 90 ° C, particularly 40 to 70 ° C.
In the reaction, a normal constant temperature polymerization method may be employed, or a continuous temperature elevation polymerization method may be employed.
The operations such as dehydration and drying of the generated vinyl chloride polymer slurry employ conventional means such as centrifugal dehydration and fluidized drying, and can easily handle a vinyl chloride heavy polymer having a water content of 0.1% or less. Coalescence can be obtained.
本発明における塩化ビニル系樹脂は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した、ポリスチレン換算法による重量平均分子量（ＭＷ）が１．２×１０５〜２．２×１０５であり、かつ重量平均分子量（ＭＷ）と数平均分子量（ＭＮ）の比ＭＷ／ＭＮが２．０５〜２．２０の範囲であることを必要としている。分子量が１．２×１０５未満のものでは、引張強度や伸びなどの機械物性が十分でなく、また分子量が２．２×１０５を超えるものでは、溶融粘度が高くなり、加工時にせん断発熱して分解し易く、連続生産性に劣る。
また、ＭＷ／ＭＮが２．０５未満のものでは、重合度分布の広がりが十分（ブロード）ではなく、通常の塩化ビニル系樹脂と大差なくなり引張強度や伸びなどの機械物性が十分発現されず、ＭＷ／ＭＮが２．２０を超えるものでは、溶融までの時間差が生じ、物性のムラやブツの原因となる。より好ましいＭＷ／ＭＮは２．０８〜２．１５である。ちなみに通常の分子量分布を操作していない市販の塩化ビニル系樹脂のＭＷ／ＭＮは、２．００±０．０２程度であるので、この指標により分子量分布の広がりを判断できるものである。
The vinyl chloride resin in the present invention has a weight average molecular weight (MW) measured by gel permeation chromatography (GPC) by a polystyrene conversion method of 1.2 × 10 5 to 2.2 × 10 5 and has a weight. The ratio MW / MN of the average molecular weight (MW) to the number average molecular weight (MN) needs to be in the range of 2.05 to 2.20. When the molecular weight is less than 1.2 × 10 5 , mechanical properties such as tensile strength and elongation are not sufficient, and when the molecular weight exceeds 2.2 × 10 5 , the melt viscosity becomes high and shear heat is generated during processing. It is easy to decompose and inferior in continuous productivity.
In addition, when the MW / MN is less than 2.05, the spread of the polymerization degree distribution is not sufficiently broad (broad), the mechanical properties such as tensile strength and elongation are not sufficiently exhibited without being largely different from ordinary vinyl chloride resins, When the MW / MN exceeds 2.20, a time difference until melting occurs, which causes unevenness of physical properties and irregularities. A more preferable MW / MN is 2.08 to 2.15. Incidentally, since the MW / MN of a commercially available vinyl chloride resin that does not manipulate the normal molecular weight distribution is about 2.00 ± 0.02, the spread of the molecular weight distribution can be determined from this index.
本発明における組成物に用いられる添加剤は、通常塩化ビニル系樹脂組成物に用いられるものであれば特に限定されず、可塑剤、安定剤、加工助剤、衝撃改良剤、滑剤、防曇剤、紫外線吸収剤、帯電防止剤、酸化防止剤、充填剤、着色剤等を目的に応じて、上記の特性を損なわない範囲で添加して良い。
本発明における成形体とは、上記した組成物を通常の混合機などで混合した後、単軸、又は二軸押出成形機を用いた押出成形や、カレンダー成形等の通常の塩化ビニル系樹脂成形体を得る方法を用いてプレート、パイプ、シート（フィルム）状等の所望の形状に成形してなるものであるが、特に透明性やブツ、フィッシュアイ等の外観について要求品質の厳しい軟質透明シートとして好適に用いることができる。
The additive used in the composition in the present invention is not particularly limited as long as it is usually used in a vinyl chloride resin composition, and is a plasticizer, a stabilizer, a processing aid, an impact modifier, a lubricant, an antifogging agent. In addition, an ultraviolet absorber, an antistatic agent, an antioxidant, a filler, a colorant, and the like may be added in a range that does not impair the above characteristics.
The molded body in the present invention is a mixture of the above-described composition with a normal mixer, etc., and then normal vinyl chloride resin molding such as extrusion using a single screw or twin screw extruder or calendar molding. A soft transparent sheet that is formed into a desired shape such as a plate, pipe, or sheet (film) using a method for obtaining a body, but has particularly strict quality requirements for the appearance of transparency, butts, fish eyes, etc. Can be suitably used.
以下、本発明の効果を実施例に基づいて詳細に説明するが、本発明は以下の実施例に限定されるものではない。
下記に示す組成比率で各添加剤をミキサーに投入し、１３０℃、５分間撹拌し、６０℃まで冷却した後取り出して、塩化ビニル系樹脂組成物を得た。
Hereinafter, although the effect of the present invention is explained in detail based on an example, the present invention is not limited to the following examples.
Each additive was added to the mixer at the composition ratio shown below, stirred at 130 ° C. for 5 minutes, cooled to 60 ° C., and then taken out to obtain a vinyl chloride resin composition.
イ）ポリ塩化ビニル系樹脂：１００重量部（重量平均分子量、ＭＷ／ＭＮ値は表１に記載）
重合度分布操作は、連鎖移動剤（２−メルカプトエタノール）を使用して制御したものは「連鎖移動剤」、従来の二段階重合によるものは「二段重合」と記載した。
ロ）Ｃａ／Ｚｎ系安定剤：０．５重量部（旭電化工業社製 「アデカスタブ５９３」）
ハ）エポキシ化大豆油：１０重量部（旭電化工業社製 「Ｏ−１３０Ｐ」）
ハ）ＤＩＮＡ（可塑剤）：２０重量部（田岡化学社製 「ＤＩＮＡ」）
得られた組成物をφ４０ｍｍの単軸押出機（Ｌ／Ｄ＝２０）にて樹脂温度２００℃で押出成形し、厚さ１０μｍ、幅３００ｍｍのシートを作成し、以下の評価を行った。
（１） 分子量測定
B) Polyvinyl chloride resin: 100 parts by weight (weight average molecular weight, MW / MN values are listed in Table 1)
The polymerization degree distribution operation was described as “chain transfer agent” when it was controlled using a chain transfer agent (2-mercaptoethanol), and “two-stage polymerization” when it was a conventional two-stage polymerization.
B) Ca / Zn-based stabilizer: 0.5 part by weight ("Adeka Stub 593" manufactured by Asahi Denka Kogyo Co., Ltd.)
C) Epoxidized soybean oil: 10 parts by weight ("O-130P" manufactured by Asahi Denka Kogyo Co., Ltd.)
C) DINA (plasticizer): 20 parts by weight (“DINA” manufactured by Taoka Chemical Co., Ltd.)
The obtained composition was extrusion-molded at a resin temperature of 200 ° C. using a φ40 mm single screw extruder (L / D = 20) to prepare a sheet having a thickness of 10 μm and a width of 300 mm, and the following evaluation was performed.
(1) Molecular weight measurement
東ソー（株）製のゲルパーミエーションクロマトグラフィー「ＨＬＣ−８１２０ＧＰＣ」に、昭和電工（株）社製のクロマトカラム「ＫＦ−８０７Ｌ」を装着し、溶媒はテトラヒドロフラン（ＴＨＦ）とし、溶媒４ｍｌに対して塩化ビニル系樹脂試料を１０ｍｇ溶解し、得られた溶液につき、溶媒流速１．０ｍｌ／分、溶媒温度４０℃で測定を行い、ポリスチレン換算で、塩化ビニル系樹脂の重量平均分子量を算出した。用いた標準ポリスチレンの重量平均分子量は、２００万、６７万、１１万、２万、４千である。 A gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation is equipped with a chromatographic column “KF-807L” manufactured by Showa Denko KK, the solvent is tetrahydrofuran (THF), and the solvent is 4 ml. 10 mg of a vinyl chloride resin sample was dissolved, and the obtained solution was measured at a solvent flow rate of 1.0 ml / min and a solvent temperature of 40 ° C., and the weight average molecular weight of the vinyl chloride resin was calculated in terms of polystyrene. The weight average molecular weight of the standard polystyrene used is 2 million, 670,000, 110,000, 20,000, and 4,000.
ここで、分子量Ｍｉの高分子がＮｉ個存在する場合、数平均分子量（ＭＮ）、重量平均分子量（ＭＷ）を以下の式を用いて計算で求め、ＭＷ／ＭＮを算出した。
数平均分子量（ＭＮ）＝ΣＭｉＮｉ／ΣＮｉ
重量平均分子量（ＭＷ）＝ΣＭｉ２Ｎｉ／ΣＭｉＮｉ
（２） 溶融粘度（Ｐａ／ｓ）測定
Here, when there were Ni polymers having a molecular weight Mi, the number average molecular weight (MN) and the weight average molecular weight (MW) were determined by calculation using the following formulas to calculate MW / MN.
Number average molecular weight (MN) = ΣMiNi / ΣNi
Weight average molecular weight (MW) = ΣMi 2 Ni / ΣMiNi
(2) Melt viscosity (Pa / s) measurement
上記で得られたシートを約５ｍｍ角に裁断し、高化式フローテスター（島津製作所社製）にて温度２００℃における溶融粘度の剪断速度依存性を測定し、得られた粘度カーブから剪断速度１００（１／ｓｅｃ）における溶融粘度を読みとった。
表中の○は溶融粘度が、７．０×１０２（Ｐａ・ｓ）以下のもの
△は溶融粘度が、７．１×１０２〜９．０×１０２（Ｐａ・ｓ）のもの
×は溶融粘度が、９．１×１０２（Ｐａ・ｓ）以上のもの
（３） 外観
The sheet obtained above is cut into about 5 mm square, the shear rate dependence of melt viscosity at a temperature of 200 ° C. is measured with a Koka flow tester (manufactured by Shimadzu Corporation), and the shear rate is determined from the obtained viscosity curve. The melt viscosity at 100 (1 / sec) was read.
◯ in the table is a melt viscosity of 7.0 × 10 2 (Pa · s) or less Δ is a melt viscosity of 7.1 × 10 2 to 9.0 × 10 2 (Pa · s) × Has a melt viscosity of 9.1 × 10 2 (Pa · s) or more (3) Appearance
上記で得られたシートを観察し、以下の基準で目視判定を行った。
○……薄黄色で透明性が良好
△……黄色味が強いが透明性は維持
×……赤く着色し、透明性も悪い
（４）機械強度
上記で得られたシートを１０ｍｍ（Ｐ方向；シートの流れ方向）×１００ｍｍ（Ｖ方向；シートの流れの垂直方向）の短冊状に切り出し、２３℃、１時間放置後に１分間当たり２００ｍｍの速度でＶ方向に引張試験を行い、破断時の伸び率（％）を測定した。
○……２５１％以上
△……２３０〜２５０％
×……２３０％未満
○ …… Light yellow and good transparency Δ …… Strong yellowness but maintaining transparency × …… Colored red and poor transparency (4) Mechanical strength 10 mm (P direction; Sheet flow direction) x 100 mm (V direction; vertical direction of sheet flow) cut into strips, left to stand at 23 ° C for 1 hour, subjected to tensile test in the V direction at a speed of 200 mm per minute, and elongation at break The rate (%) was measured.
○ …… 251% or more △ …… 230-250%
× …… less than 230%
表１から本発明の重合度分布を示す実施例１乃至５はいずれの評価項目が優れていることが分かる。これに対して、ＭＷが低すぎる比較例１では機械強度に劣り、高すぎる比較例２では溶融粘度が高く、焼けが発生している。ＭＷ／ＭＮが大きすぎる比較例３ではブツが多く、機械強度に劣り、比較例４では機械強度が劣る。
二段重合にて調製したＰＶＣを用いた比較例５は溶融粘度が高く焼けが発生し、また未溶融ブツの発生で機械強度に劣ることがわかる。
From Table 1, it can be seen that Examples 1 to 5 showing the polymerization degree distribution of the present invention are excellent in any evaluation items. On the other hand, Comparative Example 1 in which MW is too low has poor mechanical strength, and Comparative Example 2 in which MW is too high has high melt viscosity and burns. In Comparative Example 3 in which MW / MN is too large, there are many irregularities and inferior in mechanical strength. In Comparative Example 4, mechanical strength is inferior.
It can be seen that Comparative Example 5 using PVC prepared by two-stage polymerization has high melt viscosity and burns, and is inferior in mechanical strength due to generation of unmelted spots.
Claims (2)
A vinyl chloride resin composition having a broad polymerization degree distribution by use of a chain transfer agent and temperature control, and a molded article thereof.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015511248A (en) * | 2012-01-13 | 2015-04-16 | ゲオルク フィッシャー デカ ゲゼルシャフト ミット ベシュレンクテル ハフツングＧｅｏｒｇ Ｆｉｓｃｈｅｒ ＤＥＫＡ ＧｍｂＨ | Polyvinyl chloride compositions, tubes, ducts or containers, use of PVC compositions, and uses of tubes, ducts or containers |
| JP2015209465A (en) * | 2014-04-25 | 2015-11-24 | リケンテクノス株式会社 | Vinyl chloride-based resin composition |
| JP2016147952A (en) * | 2015-02-12 | 2016-08-18 | リケンテクノス株式会社 | Vinyl chloride-based resin composition |
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| KR102075567B1 (en) | 2016-09-23 | 2020-02-10 | 주식회사 엘지화학 | Method of preparing vinyl chloride polymer |
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