JPH0370714A - Production of vinylidene chloride-vinyl chloride copolymer - Google Patents
Production of vinylidene chloride-vinyl chloride copolymerInfo
- Publication number
- JPH0370714A JPH0370714A JP20665389A JP20665389A JPH0370714A JP H0370714 A JPH0370714 A JP H0370714A JP 20665389 A JP20665389 A JP 20665389A JP 20665389 A JP20665389 A JP 20665389A JP H0370714 A JPH0370714 A JP H0370714A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- vinyl chloride
- copolymer
- vinylidene chloride
- chloride
- 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
- 229920001986 Vinylidene chloride-vinyl chloride copolymer Polymers 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010457 zeolite Substances 0.000 claims abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 16
- 239000005022 packaging material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000012760 heat stabilizer Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- -1 alkyl methacrylate Chemical compound 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は塩化ビニリデン−塩化ビニル共重合体の製造法
に関するものであり、更に詳しくは熱安定性に優れた共
重合体の製造法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a vinylidene chloride-vinyl chloride copolymer, and more specifically to a method for producing a copolymer with excellent thermal stability. It is.
〔従来の技術及び発明が解決しようとする課題〕塩化ビ
ニリデンー塩化ビニル共重合体から製造されるフィルム
、チューブ等の包装材は、その防湿性、防気性、透明性
等の優れた特徴を生かして食品の包装に使用されている
。これらの食品包装用材料に要求される特性としては、
強度はもちろんであるが、食品包装用であるため無臭無
毒であることが要求される。例えば、フィルム臭がある
ときは被包装物に匂いが移り商品として全く不適となっ
てしまう。[Prior art and problems to be solved by the invention] Packaging materials such as films and tubes manufactured from vinylidene chloride-vinyl chloride copolymers take advantage of their excellent characteristics such as moisture resistance, air resistance, and transparency. Used for food packaging. The characteristics required for these food packaging materials are:
In addition to being strong, it is also required to be odorless and non-toxic since it is used for food packaging. For example, if there is a film odor, the odor will be transferred to the packaged item, making it completely unsuitable as a product.
塩化ビニリデン−塩化ビニル系共重合体は、熱安定性に
乏しいため、重合時及び加工時においてポリマーの分解
臭である塩酸具がどうしても残ってしまう。従って、こ
れを防ぐためには、ポリマー中に分解物のトラップ剤（
熱安定化剤）が必要となる。Vinylidene chloride-vinyl chloride copolymers have poor thermal stability, so hydrochloric acid, which is the odor of polymer decomposition, inevitably remains during polymerization and processing. Therefore, in order to prevent this, a decomposition product trapping agent (
heat stabilizer) is required.
一般に、重合時に添加する熱安定化剤としては、エポキ
シ化植物油のような塩酸トラップ剤やフェノール系の酸
化防止剤等があげられる。しかし、これらの安定剤は重
合速度を低下させるものであリ、生産性に影響を与える
。また、これらは共重合体を着色せしめるため使用量が
制限されるものである。Generally, heat stabilizers added during polymerization include hydrochloric acid trapping agents such as epoxidized vegetable oil, phenolic antioxidants, and the like. However, these stabilizers reduce the polymerization rate and affect productivity. Further, since these colors the copolymer, the amount used is limited.
また、加工時にエポキシ化植物油を添加することも報告
されているが、同様に共重合体を着色させることは否め
ない。It has also been reported that epoxidized vegetable oil is added during processing, but it cannot be denied that it also colors the copolymer.
これらを改善する方法として、加工時にゼオライトを熱
安定化剤として添加することが特開昭５４−３４３５６
に報告されている。しかし、加工時に添加するとゼオラ
イトが均一に分散し難く、それゆえ、成型したシートに
ゼオライトが塊として残るという欠点があった。As a method to improve these problems, adding zeolite as a heat stabilizer during processing is proposed in JP-A No. 54-34356.
has been reported. However, when added during processing, it is difficult to disperse the zeolite uniformly, resulting in the disadvantage that the zeolite remains as a lump in the formed sheet.
（課題を解決するための手段）
本発明は、熱安定性に優れた塩化ビニリデン−塩化ビニ
ル共重合体の製造法を提供することを目的とするもので
ある。(Means for Solving the Problems) An object of the present invention is to provide a method for producing a vinylidene chloride-vinyl chloride copolymer having excellent thermal stability.
本発明者らは、前記目的を達成するために鋭意努力した
結果、重合反応系中にゼオライトを分散せしめ、塩化ビ
ニリデンと塩化ビニルの懸濁共重合を行うことによって
、得られた共重合体が、上記の目的を満たすことを見い
出し、本発明を完成するに至った。As a result of our earnest efforts to achieve the above object, the present inventors have discovered that by dispersing zeolite in a polymerization reaction system and carrying out suspension copolymerization of vinylidene chloride and vinyl chloride, the resulting copolymer is The present inventors have discovered that the above objects are met, and have completed the present invention.
即ち、本発明は、塩化ビニリデンと塩化ビニルの共重合
反応において、重合反応系中にゼオライトを全モノマー
に対して０．１〜１０重量％分散せしめることを特徴と
する塩化ビニリデン−塩化ビニル共重合体の製造方法に
関するものである。That is, the present invention provides a vinylidene chloride-vinyl chloride copolymer, which is characterized in that in the copolymerization reaction of vinylidene chloride and vinyl chloride, zeolite is dispersed in the polymerization reaction system in an amount of 0.1 to 10% by weight based on the total monomers. The present invention relates to a method for manufacturing a combination.
重合反応系中のゼオライト量が全モノマーに対して０．
１ｆｆｉｆｆｉ％未満であると、共重合体の熱安定性
が改善されない。また、１０重量％より多いと重合反応
の分散系を不安定にする等の問題点が生ずる。The amount of zeolite in the polymerization reaction system is 0.
If it is less than 1ffiffi%, the thermal stability of the copolymer will not be improved. Moreover, if the amount is more than 10% by weight, problems such as destabilizing the dispersion system of the polymerization reaction will occur.
本発明で用いられるゼオライトは、金属イオン含有アル
ミノ珪酸塩を意味する。Zeolite used in the present invention means a metal ion-containing aluminosilicate.
本発明で用いられるゼオライトの種類としては、Ａ型、
Ｘ型、Ｙ型、Ｌ型、チャバサイト、モルデナイト、エリ
オナイト、クリノブチライト等が挙げられる。特に、Ａ
型ゼオライトが好ましい。Types of zeolite used in the present invention include type A,
Examples include X-type, Y-type, L-type, chabasite, mordenite, erionite, clinobutyrite, and the like. In particular, A
Type zeolites are preferred.
金属イオンとしては、Ｉａ族、■ａ族、ＩＶａ族に属す
る金属が挙げられる。特に、Ｎａ、Ｃａ。Examples of the metal ion include metals belonging to Group Ia, Group IIa, and Group IVa. In particular, Na, Ca.
Ｍｇが好ましい。Mg is preferred.
ゼオライトの粒径としては、０．５〜１０ミクロンの範
囲が挙げられる。ゼオライトの分散性を向上させるため
には小さい程良く、５ミクロン以下のものが特に好まし
い。The particle size of the zeolite may range from 0.5 to 10 microns. In order to improve the dispersibility of zeolite, the smaller the better, and 5 microns or less is particularly preferable.
ゼオライトの添加時期としては、原料の仕込み時から重
合終了時までのいずれにおいて添加しても良いが、原料
の仕込み時に同時に添加するのが好ましい。Zeolite may be added at any time from the time of charging the raw materials to the end of polymerization, but it is preferably added at the same time as the time of charging the raw materials.
また、ゼオライトの全量を一括仕込みしても、分割仕込
みしても良い。Further, the entire amount of zeolite may be charged at once or dividedly.
本発明の方法による塩化ビニリデンと塩化ビニルとから
なる共重合体の製造は、懸濁重合により、３０〜７０℃
、好ましくは３５〜６５℃の温度で１５〜３０時間加熱
して行われる。The copolymer consisting of vinylidene chloride and vinyl chloride is produced by the method of the present invention by suspension polymerization at 30 to 70°C.
, preferably by heating at a temperature of 35 to 65°C for 15 to 30 hours.
本発明で使用される塩化ビニリデンと塩化ビニルの質量
比は１：１〜２０：１の範囲であり、特に２；１〜６：
１の範囲が好ましい。尚、必要ならば、１重量％以内の
他のモノマーを共重合させることも可能である。他のモ
ノマーとしては、アルキルアクリレート、アルキルメタ
アクリレート。The mass ratio of vinylidene chloride to vinyl chloride used in the present invention ranges from 1:1 to 20:1, in particular from 2:1 to 6:
A range of 1 is preferred. Incidentally, if necessary, it is also possible to copolymerize other monomers within 1% by weight. Other monomers include alkyl acrylate and alkyl methacrylate.
アクリロニリル、スチレン等が挙げられる。Examples include acrylonilyl and styrene.
本発明で使用される重合触媒としては、一般にビニルモ
ノマーの重合で用いられる過酸化物が使用可能であるが
、特に、パーオキシジカーボネート系、パーオキシエス
テル系触媒が好ましい。As the polymerization catalyst used in the present invention, peroxides generally used in the polymerization of vinyl monomers can be used, but peroxydicarbonate-based and peroxyester-based catalysts are particularly preferred.
本発明において、他の塩酸トラップ剤や酸化防止剤等の
熱安定化剤との併用も可能である。In the present invention, it is also possible to use in combination with other hydrochloric acid trapping agents and heat stabilizers such as antioxidants.
以下に本発明を実施例によって示すが、これらによって
本発明が限定されるものではない。The present invention will be illustrated below by examples, but the present invention is not limited by these examples.
また、該共重合体の熱安定性及び成型品におけるゼオラ
イトの分散状態は次の方法によって測定し、その結果を
第１表に示した。Further, the thermal stability of the copolymer and the dispersion state of zeolite in the molded product were measured by the following methods, and the results are shown in Table 1.
（１）熱安定性評価
ＪＩＳ Ｋ６７２３に従って、各樹脂の静的熱安定性
を測定した。(1) Thermal stability evaluation The static thermal stability of each resin was measured according to JIS K6723.
外形１５ｍｍ、長さ１５０ｍｍの硬質ガラス試験管に、
試料粉体２ｇを取り、試験管上部にグリセリンで湿らせ
たコンゴーレッド試験紙を固定した。これを１８０℃に
保った油浴に浸し、熱分解によって生じた塩化水素によ
り試験紙の下部が青色に変化するまでの時間を測定した
。測定は各試料につき３回ずつ行い、平均値を測定値と
した。In a hard glass test tube with an outer diameter of 15 mm and a length of 150 mm,
2 g of sample powder was taken and a Congo red test paper moistened with glycerin was fixed on the top of the test tube. This was immersed in an oil bath maintained at 180°C, and the time required for the lower part of the test paper to turn blue due to hydrogen chloride generated by thermal decomposition was measured. The measurement was performed three times for each sample, and the average value was taken as the measured value.
（２）ゼオライトの分散状態の評価
熱プレス機を用い、縦横１５ｃｍ、厚み３ｍｍのシート
を成型し、シート全体へのゼオライトの分散状態を目視
により行った。(2) Evaluation of the state of dispersion of zeolite A sheet of 15 cm in length and width and 3 mm in thickness was molded using a hot press machine, and the state of dispersion of zeolite throughout the sheet was visually observed.
０、 ３ｆｆｉｆ１％含んだ塩化ビニリデン２０ｋｇ、
塩化ビニル５ｋｇを重合鑵に加え、攪拌しながら４４℃
の温度で３０時間重合を行った。反応終了後、未反応単
量体を回収し、共重合体を分離した（収率８６％）。ま
た、この共重合体を成型したシートには、ゼオライトの
塊は観察されなかった。20kg of vinylidene chloride containing 0.3ffif1%,
Add 5 kg of vinyl chloride to the polymerization iron and heat to 44°C while stirring.
Polymerization was carried out at a temperature of 30 hours. After the reaction was completed, unreacted monomers were collected and the copolymer was separated (yield: 86%). Furthermore, no zeolite lumps were observed in the sheet formed from this copolymer.
実施例２
重合鑵に熱安定剤としてエポキシ化植物油０．３重量％
を加えた以外は前記実施例１と同様に行った。得られた
共重合体の収率は８３％であった。 また、この共重合
体を成型したシートにもゼオライトの塊は観察されなか
った。Example 2 0.3% by weight of epoxidized vegetable oil as a heat stabilizer in polymerized iron
The same procedure as in Example 1 was carried out except that . The yield of the obtained copolymer was 83%. Furthermore, no zeolite lumps were observed in the sheet formed from this copolymer.
実施例１
５０ｇ耐圧重合罐にメチルセルロース０．Ｏ５ｆｆ１ｍ
％、ゼオライト（東ソー沖製、商品名、「トヨビルダー
粉末Ｊ）１．２重量％を含むイオン交換水４０１を仕込
み空間を充分な窒素で置換後、ジイソプロピルパーオキ
シジカーボネート・を比較例１
重合中にゼオライトを加えずに前記実施例１と同様に行
った。Example 1 Methyl cellulose was added to a 50g pressure-resistant polymerization can. O5ff1m
%, ion-exchanged water 401 containing 1.2% by weight of zeolite (manufactured by Tosoh Oki Co., Ltd., trade name "Toyobuilder Powder J"), and after purging the space with sufficient nitrogen, diisopropyl peroxydicarbonate was polymerized in Comparative Example 1. The same procedure as in Example 1 was carried out without adding zeolite.
得られた共重合体の収率は８５％であったが、加熱する
とゼオライトを添加したものよりひどい塩酸具があった
。The yield of the obtained copolymer was 85%, but when heated, there was a hydrochloric acid content worse than that with zeolite added.
比較例２
コンパウンド時にゼオライトを１．２重量％加えた以外
は前記比較例１と同様に行った。Comparative Example 2 The same procedure as Comparative Example 1 was conducted except that 1.2% by weight of zeolite was added during compounding.
得られた共重合体を加熱しても、熱安定性の良好な重合
体であった。Even when the obtained copolymer was heated, it was a polymer with good thermal stability.
しかし、この共重合体を成型したシートには、ゼオライ
トの塊が斑点として観察された。However, on the sheet formed from this copolymer, zeolite lumps were observed as spots.
表１
〔発明の効果〕
本発明により、熱安定性に優れた塩化ビニ１ノデン一塩
化ビニル共重合体が製造でき、フィルム。Table 1 [Effects of the Invention] According to the present invention, a vinyl chloride-1-nodene-vinyl chloride copolymer with excellent thermal stability can be produced, and a film can be obtained.
チューブ等の包装材用途に有用である。Useful for packaging materials such as tubes.
Claims (1)
て、重合反応系中にゼオライトを全モノマーに対して０
．１〜１０重量％分散せしめることを特徴とする塩化ビ
ニリデン−塩化ビニル共重合体の製造方法。(1) In the copolymerization reaction of vinylidene chloride and vinyl chloride, zeolite is added to the polymerization reaction system in a proportion of 0% to the total monomers.
．． A method for producing a vinylidene chloride-vinyl chloride copolymer, which comprises dispersing 1 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20665389A JPH0370714A (en) | 1989-08-11 | 1989-08-11 | Production of vinylidene chloride-vinyl chloride copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20665389A JPH0370714A (en) | 1989-08-11 | 1989-08-11 | Production of vinylidene chloride-vinyl chloride copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0370714A true JPH0370714A (en) | 1991-03-26 |
Family
ID=16526914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20665389A Pending JPH0370714A (en) | 1989-08-11 | 1989-08-11 | Production of vinylidene chloride-vinyl chloride copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0370714A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998049210A1 (en) * | 1997-04-25 | 1998-11-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene chloride latex and process for the preparation thereof |
-
1989
- 1989-08-11 JP JP20665389A patent/JPH0370714A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998049210A1 (en) * | 1997-04-25 | 1998-11-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene chloride latex and process for the preparation thereof |
| US6172158B1 (en) | 1997-04-25 | 2001-01-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Vinylidene chloride-based latex and process for producing the same |
| KR100353186B1 (en) * | 1997-04-25 | 2002-09-16 | 아사히 가세이 가부시키가이샤 | Polyvinylidene chloride latex and process for the preparation thereof |
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