JPH115807A - Production of vinyl chloride-based polymer - Google Patents
Production of vinyl chloride-based polymerInfo
- Publication number
- JPH115807A JPH115807A JP17762497A JP17762497A JPH115807A JP H115807 A JPH115807 A JP H115807A JP 17762497 A JP17762497 A JP 17762497A JP 17762497 A JP17762497 A JP 17762497A JP H115807 A JPH115807 A JP H115807A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- mol
- viscosity
- saponification degree
- polyvinyl alcohol
- 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
Links
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、成形体におけるフ
ィッシュアイの発生が少ない塩化ビニル系重合体の製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride polymer which does not generate fish eyes in a molded article.
【０００２】[0002]
【従来の技術】塩化ビニル系重合体は、その優れた物理
的および機械的性質により広範な分野に使用されている
が、最近、その軟質成形において、成形体の耐候性を向
上させるために、成形温度を低くすることが要求されて
いる。2. Description of the Related Art Vinyl chloride polymers have been used in a wide range of fields due to their excellent physical and mechanical properties. Recently, in their soft molding, in order to improve the weather resistance of molded articles, Lower molding temperatures are required.
【０００３】軟質用の塩化ビニル系重合体として、通常
懸濁重合法により得られた重合体が用いられるが、該重
合体中には、成形体におけるフィッシュアイの原因とな
る難溶融性の重合体粒子（以下、「難溶融性粒子」とい
う。）が含まれるため、該難溶融性粒子が溶融する温度
条件を用いることにより、成形体におけるフィッシュア
イの発生を抑制している。そのため、難溶融性粒子の含
有量の多い塩化ビニル系重合体を使用する場合には、成
形温度が高くなるため、その結果、成形体の耐候性が劣
るという問題が発生する。従って、軟質塩化ビニル系樹
脂用の材料として、低い温度での成形が可能な、難溶融
性粒子の含有量の少ない塩化ビニル系重合体が求められ
ている。[0003] As a vinyl chloride polymer for softness, a polymer obtained by a suspension polymerization method is usually used, and in the polymer, a hard-to-melt polymer which causes fish eyes in a molded product is contained. Since coalesced particles (hereinafter, referred to as “hardly meltable particles”) are included, the generation of fish eyes in the molded article is suppressed by using a temperature condition at which the hardly meltable particles are melted. Therefore, when a vinyl chloride-based polymer having a high content of hardly meltable particles is used, the molding temperature is increased, and as a result, there is a problem that the molded article has poor weather resistance. Therefore, as a material for a soft vinyl chloride resin, a vinyl chloride polymer which can be molded at a low temperature and has a low content of hardly meltable particles is required.
【０００４】フィッシュアイの発生が少ない塩化ビニル
系重合体の製造方法としては、ケン化度が６５〜７５モ
ル％の高部分ケン化ポリビニルアルコール、ケン化度が
３５〜４５モル％の低部分ケン化ポリビニルアルコール
およびメトキシ基含有率が２８〜３０％でヒドロキシ基
の含有量が７〜１２％のヒドロキシプロピルメチルセル
ロースの３種類の分散剤を併用する方法（特開昭６１−
１５２７０３号公報）が提案されているが、成形におい
て５分間以上の混練を必要とするなど、フィッシュアイ
の改良方法として、十分満足できるものではない。ま
た、高カサ比重の塩化ビニル系重合体の製造を目的に、
ケン化度が８５〜９５モル％であり、かつその４％水溶
液の２０℃における粘度が２５〜６５ｃｐｓである水溶
性部分ケン化ポリ酢酸ビニル、ケン化度が６５〜７５モ
ル％であり、かつその４％水溶液の２０℃における粘度
が５．０〜６．０ｃｐｓである水溶性部分ケン化ポリ酢
酸ビニルおよびケン化度が３５〜５０モル％であり、か
つその重合度が２００〜８００である油溶性部分ケン化
ポリ酢酸ビニルの３種類の分散剤を併用する方法（特公
平７−８０９２５号公報）が提案されているが、該方法
によれば、高カサ比重の重合体は得られるが、成形体に
おけるフィッシュアイの改良に対しては効果がないこと
がわかった。[0004] As a method for producing a vinyl chloride-based polymer with less generation of fish eyes, high partially saponified polyvinyl alcohol having a saponification degree of 65 to 75 mol%, and low partially saponified polyvinyl alcohol having a saponification degree of 35 to 45 mol%. Using three kinds of dispersants, i.e., polyvinyl alcohol and hydroxypropylmethylcellulose having a methoxy group content of 28 to 30% and a hydroxy group content of 7 to 12% (Japanese Patent Application Laid-Open (JP-A) No. 61-186).
No. 152703) has been proposed, but this method is not sufficiently satisfactory as a method for improving fish eyes, such as requiring kneading for 5 minutes or more in molding. Also, for the purpose of producing vinyl chloride polymer with high bulk specific gravity,
A water-soluble partially saponified polyvinyl acetate having a saponification degree of 85 to 95 mol% and a viscosity of the 4% aqueous solution at 20 ° C. of 25 to 65 cps, a saponification degree of 65 to 75 mol%, and A water-soluble partially saponified polyvinyl acetate having a 4% aqueous solution having a viscosity at 20 ° C. of 5.0 to 6.0 cps, a degree of saponification of 35 to 50 mol%, and a degree of polymerization of 200 to 800. Although a method (JP-B-7-80925) in which three dispersants of oil-soluble partially saponified polyvinyl acetate are used in combination has been proposed, a polymer having a high bulk specific gravity can be obtained. It was found that there was no effect on the improvement of fish eyes in the molded product.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、難溶融性粒
子の含有量が極めて少なく、成形体におけるフィッシュ
アイが少ない塩化ビニル系重合体の製造方法を提供する
ことを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a vinyl chloride polymer having a very low content of hardly meltable particles and having a small fish eye in a molded article.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討した結果、塩化ビニル系単量体
の水性媒体中の懸濁重合方法において、使用する分散剤
のケン化度およびその粘度の組合せが成形体におけるフ
ィッシュアイに大きな影響を与えるという知見を得、さ
らにフィッシュアイの発生に対して、その最適な組合せ
を見出し、本発明を完成するに至った。すなわち、本発
明は、塩化ビニル単量体または塩化ビニル単量体および
これと共重合可能な単量体からなる混合物を分散剤の存
在下に水性媒体中で懸濁重合させる塩化ビニル系重合体
の製造方法において、分散剤として（Ａ）ケン化度が８
５モル％以上であり、かつその４重量％水溶液の２０℃
における粘度が２〜２０ｃｐｓの部分ケン化ポリビニル
アルコール、（Ｂ）ケン化度が７０〜８５モル％であ
り、かつ４重量％水溶液の２０℃における粘度が２０〜
６０ｃｐｓの部分ケン化ポリビニルアルコールおよび
（Ｃ）ケン化度が２０〜６０モル％であり、かつ容量比
で１：１の水−メタノールの混合溶媒に４重量％となる
量溶解した溶液の２０℃における粘度が２〜７ｃｐｓの
部分ケン化ポリビニルアルコールの３種類を併用するこ
とを特徴とする、成形体におけるフィッシュアイの発生
が少ない塩化ビニル系重合体の製造方法である。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 the saponification of a dispersant used in a suspension polymerization method of a vinyl chloride monomer in an aqueous medium. The inventor has found that the combination of the degree and the viscosity has a great effect on the fish eye in the molded product. Further, the present inventors have found an optimum combination for the generation of fish eye, and have completed the present invention. That is, the present invention relates to a vinyl chloride polymer in which a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a copolymerizable monomer is suspension-polymerized in an aqueous medium in the presence of a dispersant. In the production method of (1), the dispersant (A) has a saponification degree of 8
At least 5 mol% and a 4% by weight aqueous solution at 20 ° C.
Partially saponified polyvinyl alcohol having a viscosity of 2 to 20 cps, (B) a degree of saponification of 70 to 85 mol%, and a 4 wt% aqueous solution having a viscosity at 20 ° C. of 20 to 20 cps.
20 ° C. of a partially saponified polyvinyl alcohol of 60 cps and a solution in which (C) a solution having a saponification degree of 20 to 60 mol% and a volume ratio of 4: 1 dissolved in a 1: 1 water-methanol mixed solvent. A method for producing a vinyl chloride-based polymer which is less likely to generate fish eyes in a molded product, characterized by using three kinds of partially saponified polyvinyl alcohols having a viscosity of 2 to 7 cps in Example 1.
【０００７】[0007]
【発明の実施の形態】本明細書中、ポリビニルアルコー
ルのケン化度および粘度は、ＪＩＳ Ｋ ６７２６（ポ
リビニルアルコール試験方法）に記載の方法で測定した
ものである。BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the degree of saponification and the viscosity of polyvinyl alcohol are measured by the method described in JIS K 6726 (Testing method for polyvinyl alcohol).
【０００８】本発明における塩化ビニル系重合体は、塩
化ビニル単量体または塩化ビニル単量体およびこれと共
重合可能な単量体からなる混合物（以下、「塩化ビニル
系単量体」という。）を水性媒体中で懸濁重合させて得
られたものであり、塩化ビニル単量体と共重合可能な単
量体としては、例えば、エチレン、プロピレン、酢酸ビ
ニル、アルキルビニルエーテル、アクリル酸もしくはメ
タクリル酸およびそのエステル類、マレイン酸もしくは
フマール酸およびそのエステル類等を挙げることがで
き、これらの単量体は、塩化ビニル単量体１００重量部
に対して２０重量部を越えない範囲で用いることが好ま
しい。[0008] The vinyl chloride polymer in the present invention is a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a monomer copolymerizable therewith (hereinafter, referred to as "vinyl chloride monomer"). ) Is obtained by suspension polymerization in an aqueous medium. Examples of monomers copolymerizable with a vinyl chloride monomer include ethylene, propylene, vinyl acetate, alkyl vinyl ether, acrylic acid and methacrylic acid. Acids and esters thereof, maleic acid or fumaric acid and esters thereof, and the like can be mentioned. These monomers should be used in an amount not exceeding 20 parts by weight based on 100 parts by weight of a vinyl chloride monomer. Is preferred.
【０００９】本発明の製造方法は、前記（Ａ）〜（Ｃ）
の３種類の分散剤を使用することに特徴がある。前記
（Ａ）の分散剤は、ケン化度が８５モル％以上であり、
かつその４重量％水溶液の２０℃における粘度が２〜２
０ｃｐｓの部分ケン化ポリビニルアルコールであるが、
フィッシュアイの面から、ケン化度８８〜９９モル％か
つ４重量％水溶液の２０℃における粘度が５〜７ｃｐｓ
のものがより好ましい。[0009] The production method of the present invention comprises the steps (A) to (C).
It is characterized by using three types of dispersants. The dispersant (A) has a degree of saponification of 85 mol% or more,
And the viscosity at 20 ° C. of the 4% by weight aqueous solution is 2 to 2
Although it is a partially saponified polyvinyl alcohol of 0 cps,
From the viewpoint of fish eye, the viscosity of the aqueous solution having a saponification degree of 88 to 99 mol% and 4 wt% at 20 ° C. is 5 to 7 cps
Are more preferred.
【００１０】前記（Ｂ）の分散剤は、ケン化度が７０〜
８５モル％であり、かつ４重量％水溶液の２０℃におけ
る粘度が２０〜６０ｃｐｓの部分ケン化ポリビニルアル
コールであるが、フィッシュアイの面から、ケン化度が
７５〜８３モル％、かつ４モル％水溶液の２０℃におけ
る粘度が３０〜４０ｃｐｓのものがより好ましい。The dispersant (B) has a saponification degree of 70 to 70.
It is a partially saponified polyvinyl alcohol having 85 mol% and a viscosity of 20 to 60 cps of a 4 wt% aqueous solution at 20 ° C. From the viewpoint of fish eyes, the degree of saponification is 75 to 83 mol% and 4 mol% More preferably, the viscosity of the aqueous solution at 20 ° C. is 30 to 40 cps.
【００１１】前記（Ｃ）の分散剤は、ケン化度が２０〜
６０モル％であり、かつ容量比で１：１の水−メタノー
ルの混合溶媒に４重量％となる量溶解した溶液の２０℃
における粘度が２〜７ｃｐｓであるが、フィッシュアイ
の面から、ケン化度が４０〜５５モル％であり、かつ容
量比で１：１の水−メタノールの混合溶媒に４重量％と
なる量溶解した溶液の２０℃における粘度が４〜６ｃｐ
ｓのものがより好ましい。The dispersant (C) has a saponification degree of 20 to
20 ° C. of a solution of 60 mol% and dissolved in an amount of 4% by weight in a mixed solvent of water and methanol at a volume ratio of 1: 1.
Is from 2 to 7 cps, but from the viewpoint of fish eyes, it has a saponification degree of 40 to 55 mol% and a volume ratio of 4 wt% in a 1: 1 water-methanol mixed solvent. The viscosity of the solution at 20 ° C. is 4 to 6 cp.
s is more preferred.
【００１２】上記３種類の分散剤の使用割合は、重量比
で（Ａ）／（Ｂ）＝５／１〜１／５であり、かつ、
（Ｃ）が（Ａ）〜（Ｃ）の合計量の１〜５０重量％の範
囲であることが好ましい。The use ratio of the above three types of dispersants is (A) / (B) = 5/1 to 1/5 by weight ratio, and
(C) is preferably in the range of 1 to 50% by weight of the total amount of (A) to (C).
【００１３】また、本発明の製造方法において、分散剤
として上記以外の分散剤を併用しても差し支えない。併
用できる分散剤としては、例えば、メチルセルロース、
ヒドロキシプロピルセルロースおよびメチルヒドロキシ
プロピルセルロース等の水溶性セルロースエーテル類、
アクリル酸共重合体、無水マレイン酸共重合体、ゼラチ
ンおよびデン粉等の様な保護コロイド性の薬剤、天然高
分子化合物、高級脂肪酸と多価アルコールとのエステル
類、ポリオキシエチレン誘導体等のノニオン界面活性
剤、高級脂肪酸の金属塩および高級アルコール硫酸エス
テルのアルカリ塩等のアニオン界面活性剤等が挙げられ
る。これらの（Ａ）〜（Ｃ）以外の分散剤の使用量は、
全分散剤量の５０重量％以下であることが好ましい。In the production method of the present invention, a dispersant other than those described above may be used in combination. As dispersants that can be used in combination, for example, methyl cellulose,
Water-soluble cellulose ethers such as hydroxypropylcellulose and methylhydroxypropylcellulose,
Nonionics such as acrylic acid copolymers, maleic anhydride copolymers, protective colloidal agents such as gelatin and starch powder, natural polymer compounds, esters of higher fatty acids and polyhydric alcohols, and polyoxyethylene derivatives Surfactants, anionic surfactants such as metal salts of higher fatty acids and alkali salts of higher alcohol sulfates, and the like. The amount of the dispersant other than (A) to (C) used is
It is preferable that the amount is 50% by weight or less of the total dispersant amount.
【００１４】本発明の製造方法において、全分散剤の使
用量は、塩化ビニル系単量体１００重量部当たり０．０
４〜０．３０重量部であることが好ましく、更に好まし
くは０．０５〜０．２５重量部である。分散剤の合計量
が０．０４重量部未満であると重合安定性が低下し易
く、一方、０．３０重量部を越えるとフィッシュアイの
発生が多くなり易い。In the production method of the present invention, the total amount of the dispersant used is 0.00.0 parts by weight per 100 parts by weight of the vinyl chloride monomer.
It is preferably from 4 to 0.30 parts by weight, more preferably from 0.05 to 0.25 parts by weight. If the total amount of the dispersants is less than 0.04 parts by weight, the polymerization stability tends to decrease, while if it exceeds 0.30 parts by weight, the occurrence of fish eyes tends to increase.
【００１５】本発明の製造方法において、重合触媒とし
て各種のラジカル重合触媒を用いることができる。例え
ば、ベンゾイルパーオキサイド、ラウロイルパーオキサ
イド、カプロイルパーオキサイド、ターシャリーブチル
パーオキシネオデカノエート、ジ（２−エトキシエチ
ル）パーオキシジカーボネート、ターシャリーヘキシル
パーオキシネオヘキサノエート、イソブチリルパーオキ
サイドおよびクミルパーオキシネオデカノエート等の有
機過酸化物、２，２’−アゾビスイソブチロニトリルお
よび２，２’−アゾビス−ジメチルバレロニトリル等の
アゾ化合物あるいはそれらを組み合わせて使用すること
も可能である。前記重合触媒の使用量は、塩化ビニル系
単量体１００重量部あたり０．０２〜０．２０重量部が
好ましく、より好ましくは０．０３〜０．１５重量部で
ある。In the production method of the present invention, various radical polymerization catalysts can be used as the polymerization catalyst. For example, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, tertiary butyl peroxy neodecanoate, di (2-ethoxyethyl) peroxy dicarbonate, tertiary hexyl peroxy neohexanoate, isobutyryl par Use of organic peroxides such as oxide and cumylperoxy neodecanoate, azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-dimethylvaleronitrile, or a combination thereof Is also possible. The amount of the polymerization catalyst to be used is preferably 0.02 to 0.20 parts by weight, more preferably 0.03 to 0.15 parts by weight, per 100 parts by weight of the vinyl chloride monomer.
【００１６】また、重合反応温度は３０〜９０℃の範囲
が好ましく、また、重合時間は２〜１５時間が適当であ
る。The polymerization temperature is preferably in the range of 30 to 90 ° C., and the polymerization time is suitably 2 to 15 hours.
【００１７】また、本発明の目的を損なわない範囲にお
いて、他の添加剤を任意に使用することができる。これ
らの添加剤として、例えば、アルコール類、脂肪酸塩
類、エステル類、緩衝剤、ハイドロタルサイトおよびゼ
オライト等の塩化水素補足剤等が挙げられる。これらの
添加剤の添加方法については、特に限定されない。Further, other additives can be optionally used as long as the object of the present invention is not impaired. Examples of these additives include alcohols, fatty acid salts, esters, buffering agents, and hydrogen chloride scavengers such as hydrotalcite and zeolite. The method of adding these additives is not particularly limited.
【００１８】[0018]
【実施例】以下、実施例によって本発明を更に具体的に
説明する。なお、重合体のフィッシュアイの測定は以下
の方法で測定した。 ・塩化ビニル系重合体１００重量部、トリメリット系可
塑剤５０重量部、２塩基性鉛５重量部、ステアリン酸鉛
１重量部を混合後、直径８インチ回転数１９／２１ｒｐ
ｍの２本ロールを１７０℃に加熱して、０．３ｍｍのロ
ール間隙でそれぞれ４分間混練し、シートを作成する。
しかる後、１０ｃｍ×１０ｃｍの面積に存在するフィッ
シュアイの数を数える。The present invention will be described more specifically with reference to the following examples. The fish eye of the polymer was measured by the following method.・ 100 parts by weight of vinyl chloride polymer, 50 parts by weight of trimellit plasticizer, 5 parts by weight of dibasic lead, and 1 part by weight of lead stearate are mixed, and the diameter is 8 inches.
The two rolls of m are heated to 170 ° C. and kneaded with a 0.3 mm roll gap for 4 minutes to form a sheet.
Thereafter, the number of fish eyes existing in the area of 10 cm × 10 cm is counted.
【００１９】実施例１ 内容積５リットルのオートクレーブに脱イオン水２７０
０ｇ、分散剤（Ａ）としてケン化度が９８モル％、かつ
４重量％水溶液の２０℃における粘度が５．６ｃｐｓの
ポリビニルアルコール０．８ｇ、分散剤（Ｂ）としてケ
ン化度８０モル％、かつ４重量％水溶液の２０℃におけ
る粘度が３４ｃｐｓのポリビニルアルコール０．８ｇ、
分散剤（Ｃ）としてケン化度５３モル％、かつ容量比で
１：１の水−メタノールの混合溶媒に４重量％となる量
溶解した溶液の２０℃における粘度が５ｃｐｓのポリビ
ニルアルコール０．４ｇ、クミルパーオキシネオデカノ
エート０．３ｇおよびジ（２−エトキシエチル）パーオ
キシイカーボネート１．０ｇを仕込み、オートクレーブ
内の空気を真空ポンプで除去した。その後、塩化ビニル
単量体１９００ｇを挿入し、攪拌下、５７℃の温度条件
で８時間重合を行った。Example 1 Deionized water 270 was added to an autoclave having an internal volume of 5 liters.
0.8 g of polyvinyl alcohol having a saponification degree of 98 mol% as a dispersant (A) and a viscosity of 5.6 cps at 20 ° C. of a 4% by weight aqueous solution, a saponification degree of 80 mol% as a dispersant (B), 0.8 g of polyvinyl alcohol having a viscosity of 34 cps at 20 ° C. of a 4% by weight aqueous solution;
0.4 g of polyvinyl alcohol having a viscosity of 5 cps at 20 ° C. as a dispersant (C) in which a solution having a saponification degree of 53 mol% and a volume ratio of 4 wt% dissolved in a 1: 1 water-methanol mixed solvent at 20 ° C. , 0.3 g of cumyl peroxy neodecanoate and 1.0 g of di (2-ethoxyethyl) peroxyicarbonate were charged, and the air in the autoclave was removed by a vacuum pump. Thereafter, 1900 g of a vinyl chloride monomer was inserted, and polymerization was carried out under stirring at a temperature of 57 ° C. for 8 hours.
【００２０】実施例２ 分散剤（Ａ）としてケン化度が８８モル％、かつ４重量
％水溶液の２０℃における粘度が４ｃｐｓのポリビニル
アルコール０．８ｇを使用した以外は、実施例１と同じ
条件で重合を行った。Example 2 The same conditions as in Example 1 except that 0.8 g of polyvinyl alcohol having a saponification degree of 88 mol% and a viscosity of 4 cps at 20 ° C. of 4 cps was used as the dispersant (A). The polymerization was carried out.
【００２１】実施例３ 分散剤（Ａ）としてケン化度が８８モル％、かつ４重量
％水溶液の２０℃における粘度が５ｃｐｓのポリビニル
アルコール０．８ｇを使用した以外は、実施例１と同じ
条件で重合を行った。Example 3 The same conditions as in Example 1 were used except that 0.8 g of polyvinyl alcohol having a saponification degree of 88 mol% and a viscosity at 20 ° C. of 5 cps was used as the dispersant (A). The polymerization was carried out.
【００２２】比較例１ 分散剤（Ａ）としてケン化度が９３モル％、かつ４重量
％水溶液の２０℃における粘度が３５ｃｐｓのポリビニ
ルアルコール１．０ｇ、分散剤（Ｂ）としてケン化度８
０モル％、かつ４重量％水溶液の２０℃における粘度が
６ｃｐｓのポリビニルアルコール０．５ｇ、分散剤
（Ｃ）としてケン化度５３モル％、かつ容量比で１：１
の水−メタノールの混合溶媒に４重量％となる量溶解し
た溶液の２０℃における粘度が５ｃｐｓのポリビニルア
ルコール０．２ｇを使用した以外は、実施例１と同じ条
件で重合を行った。Comparative Example 1 As a dispersant (A), 1.0 g of polyvinyl alcohol having a saponification degree of 93 mol% and a viscosity of 35 cps at 20 ° C. of a 4% by weight aqueous solution was used. As a dispersant (B), a saponification degree of 8 was used.
0.5 g of a 0 mol% and 4 wt% aqueous solution of polyvinyl alcohol having a viscosity of 6 cps at 20 ° C., a saponification degree of 53 mol% as a dispersant (C), and a volume ratio of 1: 1.
Polymerization was carried out under the same conditions as in Example 1 except that 0.2 g of polyvinyl alcohol having a viscosity at 20 ° C. of 5 cps was used in a solution prepared by dissolving an amount of 4 wt% in a mixed solvent of water and methanol.
【００２３】比較例２ 分散剤（Ａ）としてケン化度が７１モル％、かつ４重量
％水溶液の２０℃における粘度が６．２ｃｐｓのポリビ
ニルアルコール０．８ｇを使用した以外は、実施例１と
同じ条件で重合を行った。Comparative Example 2 The procedure of Example 1 was repeated except that 0.8 g of polyvinyl alcohol having a saponification degree of 71 mol% and a viscosity at 20 ° C. of 6.2 cps was used as a dispersant (A). Polymerization was performed under the same conditions.
【００２４】比較例３ 分散剤（Ａ）としてケン化度が８１モル％、かつ４重量
％水溶液の２０℃における粘度が５．８ｃｐｓのポリビ
ニルアルコール０．８ｇを使用した以外は、実施例１と
同じ条件で重合を行った。Comparative Example 3 The procedure of Example 1 was repeated except that 0.8 g of polyvinyl alcohol having a saponification degree of 81 mol% and a viscosity at 20 ° C. of 5.8 cps was used as a dispersant (A). Polymerization was performed under the same conditions.
【００２５】実施例１〜３および比較例１〜３の評価 上記実施例１〜３および比較例１〜３で得られた重合生
成物について、前記の方法により、フィッシュアイの個
数の測定を行った。その結果を表１に示す。Evaluation of Examples 1 to 3 and Comparative Examples 1 to 3 For the polymerization products obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the number of fish eyes was measured by the method described above. Was. Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明の製造方法によれば、成形体にお
けるフィッシュアイが極めて少ない塩化ビニル系重合体
を得ることができ、この重合体は、例えば、軟質塩化ビ
ニル樹脂用に極めて好適であり、工業的に利用価値が大
きい。According to the production method of the present invention, it is possible to obtain a vinyl chloride polymer having very few fish eyes in a molded product, and this polymer is extremely suitable for, for example, a soft vinyl chloride resin. Great industrial value.
Claims (1)
およびこれと共重合可能な単量体からなる混合物を分散
剤の存在下に水性媒体中で懸濁重合させる塩化ビニル系
重合体の製造方法において、分散剤として（Ａ）ケン化
度が８５モル％以上であり、かつその４重量％水溶液の
２０℃における粘度が２〜２０ｃｐｓの部分ケン化ポリ
ビニルアルコール、（Ｂ）ケン化度が７０〜８５モル％
であり、かつ４重量％水溶液の２０℃における粘度が２
０〜６０ｃｐｓの部分ケン化ポリビニルアルコールおよ
び（Ｃ）ケン化度が２０〜６０モル％であり、かつ容量
比で１：１の水−メタノールの混合溶媒に４重量％とな
る量溶解した溶液の２０℃における粘度が２〜７ｃｐｓ
の部分ケン化ポリビニルアルコールの３種類を併用する
ことを特徴とする、成形体におけるフィッシュアイの発
生が少ない塩化ビニル系重合体の製造方法。1. A vinyl chloride polymer obtained by subjecting a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a copolymerizable monomer to suspension polymerization in an aqueous medium in the presence of a dispersant. In the production method, (A) a partially saponified polyvinyl alcohol having a saponification degree of 85 mol% or more and a viscosity of 4 wt% aqueous solution at 20 ° C. of 2 to 20 cps as a dispersant; 70-85 mol%
And the viscosity at 20 ° C. of the 4% by weight aqueous solution is 2
A partially saponified polyvinyl alcohol having a saponification degree of 0 to 60 cps and (C) a solution having a saponification degree of 20 to 60 mol% and having a volume ratio of 1: 1 dissolved in a water-methanol mixed solvent in an amount of 4 wt%. Viscosity at 20 ° C is 2 to 7 cps
3. A method for producing a vinyl chloride-based polymer having less occurrence of fish eyes in a molded article, characterized by using three kinds of partially saponified polyvinyl alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17762497A JPH115807A (en) | 1997-06-18 | 1997-06-18 | Production of vinyl chloride-based polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17762497A JPH115807A (en) | 1997-06-18 | 1997-06-18 | Production of vinyl chloride-based polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH115807A true JPH115807A (en) | 1999-01-12 |
Family
ID=16034264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17762497A Pending JPH115807A (en) | 1997-06-18 | 1997-06-18 | Production of vinyl chloride-based polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH115807A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778394A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | The preparation method of cellular structure Corvic |
| WO2023191506A1 (en) * | 2022-03-31 | 2023-10-05 | 한화솔루션 주식회사 | Method for preparing chlorinated polyvinyl chloride resin composition |
-
1997
- 1997-06-18 JP JP17762497A patent/JPH115807A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778394A (en) * | 2016-08-27 | 2018-03-09 | 中国石油化工股份有限公司 | The preparation method of cellular structure Corvic |
| WO2023191506A1 (en) * | 2022-03-31 | 2023-10-05 | 한화솔루션 주식회사 | Method for preparing chlorinated polyvinyl chloride resin composition |
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