JPS63223011A - Production of vinyl chloride based resin with hardly any whitening by transparent blending - Google Patents
Production of vinyl chloride based resin with hardly any whitening by transparent blendingInfo
- Publication number
- JPS63223011A JPS63223011A JP5728887A JP5728887A JPS63223011A JP S63223011 A JPS63223011 A JP S63223011A JP 5728887 A JP5728887 A JP 5728887A JP 5728887 A JP5728887 A JP 5728887A JP S63223011 A JPS63223011 A JP S63223011A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- degree
- partially saponified
- whitening
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 title claims abstract description 18
- 230000002087 whitening effect Effects 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000002156 mixing Methods 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000007127 saponification reaction Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 239000000375 suspending agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 238000009472 formulation Methods 0.000 claims 1
- 239000000725 suspension Substances 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 polyoxyethylene glycerin Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 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
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- FVAIEHAPKZFAGH-UHFFFAOYSA-N 6,6-dimethylheptanoyl 6,6-dimethylheptaneperoxoate Chemical compound CC(CCCCC(=O)OOC(CCCCC(C)(C)C)=O)(C)C FVAIEHAPKZFAGH-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 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
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、塩化ビニル系樹脂の製造方法、とくにはシー
ト、フィルムなどの成形材料として有用な、透明成形品
における白化の少ない塩化ビニル系樹脂の製造方法に関
するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a vinyl chloride resin, and in particular to a method for producing a vinyl chloride resin, which is useful as a molding material for sheets, films, etc., and which exhibits less whitening in transparent molded products. The present invention relates to a manufacturing method.
（従来の技術とその問題点）
従来、塩化ビニル系樹脂からの透明成形品が、ガラス様
の透明性が必要とされる各種容器類、工業板、化粧板、
フィルム、シートなどとして幅広く使用されている。(Conventional technology and its problems) Conventionally, transparent molded products made from vinyl chloride resin have been used for various containers, industrial boards, decorative boards, etc. that require glass-like transparency.
Widely used as films, sheets, etc.
しかし、これらの透明成形品には、これを水。However, these transparent molded products require water.
アルコール、アルコール水溶液などの商品の包装に使用
した場合、あるいは高温多湿の雰囲気下に長時間放置し
た場合などに１表面が白化して不透明となり、成形品の
価値を著しく損ねるという問題があり、その有効な対策
が望まれていた。When used to package products such as alcohol and alcohol aqueous solutions, or when left in a hot and humid atmosphere for a long time, the surface becomes white and opaque, significantly reducing the value of the molded product. Effective countermeasures were desired.
（問題点を解決するための手段）
本発明はこの問題を解決すべく鋭意研究の結果達成され
たもので、塩化ビニル単量体、または塩化ビニルを主体
とするビニル系単量体の混合物を。(Means for solving the problem) The present invention was achieved as a result of intensive research to solve this problem, and it uses vinyl chloride monomer or a mixture of vinyl monomers mainly composed of vinyl chloride. .
懸濁剤としてのけん化度６５〜８０モル％、平均重合度
６００〜１０００の部分けん化ポリビニルアルコールの
存在下、水性媒体中で懸濁重合する際に、あるいはこれ
によって得られた重合体中に、けん化度２０〜５５モル
％、平均重合度１５０〜６００の部分けん化ポリビニル
アルコールを生成重合体に対し０．０１〜５重量％の割
合で添加することを要旨とするものである。During suspension polymerization in an aqueous medium in the presence of a partially saponified polyvinyl alcohol having a degree of saponification of 65 to 80 mol% and an average degree of polymerization of 600 to 1000 as a suspending agent, or in the polymer obtained thereby, The gist is to add partially saponified polyvinyl alcohol having a degree of saponification of 20 to 55 mol % and an average degree of polymerization of 150 to 600 in a proportion of 0.01 to 5% by weight based on the resulting polymer.
これを説明すると、本発明が適用される重合体原料は、
塩化ビニル単量体のほか、塩化ビニルを主体とするこれ
と共重合可能なビニル系単量体の混合物（塩化ビニルが
５０重量％以上）であって、この塩化ビニルと共重合さ
れるコモノマーとしては、酢酸ビニル、プロピオン酸ビ
ニルなどのビニルエステル；アクリル酸メチル、アクリ
ル酸エチルなどのアクリル酸エステルもしくはメタアク
リル酸エステル；エチレン、プロピレンなどのオレフィ
ン；無水マレイン酸；アクリロニトリル：スチレン；塩
化ビニリデン；その他塩化ビニルと共重合可能な単量体
などが挙げられる。To explain this, the polymer raw materials to which the present invention is applied are:
In addition to vinyl chloride monomers, a mixture of vinyl monomers mainly consisting of vinyl chloride and copolymerizable with vinyl chloride (50% by weight or more of vinyl chloride), as a comonomer copolymerized with vinyl chloride. are vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters or methacrylic esters such as methyl acrylate and ethyl acrylate; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile: styrene; vinylidene chloride; others Examples include monomers copolymerizable with vinyl chloride.
これらの単量体を用いた本発明による水性媒体中での懸
濁重合は、懸濁剤としてのけん化度６５〜８０モル％１
重合度６００〜１０００の部分けん化ポリビニルアルコ
ールの存在下で行われるが。Suspension polymerization in an aqueous medium according to the invention using these monomers is carried out with a degree of saponification of 65 to 80 mol% 1 as a suspending agent.
It is carried out in the presence of partially saponified polyvinyl alcohol having a degree of polymerization of 600 to 1000.
これには塩化ビニルの水性媒体中での重合の際に通常使
用されている他の懸濁剤、例えばメチルセルロース、ヒ
ドロキシエチルセルロース、ヒドロキシプロピルセルロ
ース、ヒドロキシプロピルメチルセルロースなどの水溶
性セルロースエーテル；アクリル酸重合体；ゼラチンな
どの水溶性ポリマー；ソルビタンモノラウレート、ソル
ビタントリオレート、グリセリントリステアレート、エ
チレンオキシドプロピレンオキシドブロックコボリマー
などの油溶性乳化剤；ポリオキシエチレンソルビタンモ
ノラウレート、ポリオキシエチレングリセリンオレート
、ラウリン酸ナトリウムなどの水溶性乳化剤などを、一
種または二種以上の組み合わせで使用しても差し支えな
い。This includes other suspending agents commonly used during the polymerization of vinyl chloride in aqueous media, such as water-soluble cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose; acrylic acid polymers. ; Water-soluble polymers such as gelatin; Oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan triolate, glycerin tristearate, ethylene oxide propylene oxide block copolymer; polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, lauric acid Water-soluble emulsifiers such as sodium may be used alone or in combination of two or more.
本発明による透明成形品の白化防止効果はこの重合系に
、けん化度２０〜５５モル％、平均重合度１５０〜６０
０の部分けん化ポリビニルアルコールを、生成重合体に
対して０．０１〜５重量％添加することにより達成され
る。The whitening prevention effect of the transparent molded product according to the present invention is due to the saponification degree of 20 to 55 mol% and the average polymerization degree of 150 to 60%.
This is achieved by adding 0.01 to 5% by weight of partially saponified polyvinyl alcohol to the resulting polymer.
これが０．０１％未満では成形品の白化を防止すること
が出来ないし、また５％を超えると量の増加の割合には
白化防止の効果が向上せず経済的でなくなる。If it is less than 0.01%, whitening of the molded product cannot be prevented, and if it exceeds 5%, the whitening prevention effect will not improve as the amount increases, making it uneconomical.
この添加の方法は粉体状のまま、あるいは液体に溶解す
るなど特に制限は無く、その時期も重合開始前、重合中
５重合終了後のスラリー中、脱水後のケーキ中、あるい
は乾燥後の、さらには成形直前の重合体中などのいずれ
でも差し支えない。There are no particular restrictions on the method of addition, such as adding it as a powder or dissolving it in a liquid, and the time of addition may be before the start of polymerization, during polymerization, in the slurry after completion of polymerization, in the cake after dehydration, or after drying. Furthermore, it may be in the polymer immediately before molding.
この重合に際しての他の条件、重合器への水性媒体、塩
化ビニル単量体、場合によっては他のコモノマー、懸濁
剤、重合開始剤などの仕込み方法は従来と同様にして行
えばよく、これらの仕込み割合、重合温度などの重合条
件もまた同様でよい。The other conditions for this polymerization and the method of charging the aqueous medium, vinyl chloride monomer, and in some cases other comonomers, suspending agents, and polymerization initiators to the polymerization vessel can be carried out in the same manner as conventional methods. The polymerization conditions such as the charging ratio and polymerization temperature may also be the same.
さらに、この重合に使用される重合開始剤も従来塩化ビ
ニル系の重合に使用されているものでよく、これには例
えばジイソプロピルパーオキシジカーボネート、ジー２
−二チルヘキシルバーオキシジカーボネート、ジェトキ
シエチルパーオキシジカーボネート、などのパーカーボ
ネート化合物；ｔ−ブチルパーオキシネオデカネート、
ｔ−ブチルパーオキシピバレート、ｔ−ヘキシルパーオ
キシピバレート、α−クミルパーオキシネオデカネート
などのパーエステル化合物；アセチルシクロヘキシルス
ルホニルパーオキシド、２，４．４−トリメチルペンチ
ル−２−パーオキシフェノキシアセテート、３，５．５
−トリメチルヘキサノイルパーオキサイドなどの過酸化
物；アゾビス−２゜４−ジメチルバレロニトリル、アゾ
ビス（４−メトキシ−２，４−ジメチルバレロニトリル
）などのアゾ化合物；さらには過硫酸カリウム、過硫酸
アンモニウム、過酸化水素などがあり、これらは一種ま
たは二種以上の組み合わせで使用することができる。Furthermore, the polymerization initiator used in this polymerization may be one that has conventionally been used in vinyl chloride polymerization, such as diisopropyl peroxydicarbonate, di-2
- percarbonate compounds such as nitylhexyl oxydicarbonate, jetoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate,
Perester compounds such as t-butylperoxypivalate, t-hexylperoxypivalate, α-cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4.4-trimethylpentyl-2-peroxyphenoxy Acetate, 3,5.5
- peroxides such as trimethylhexanoyl peroxide; azo compounds such as azobis-2゜4-dimethylvaleronitrile and azobis(4-methoxy-2,4-dimethylvaleronitrile); and potassium persulfate, ammonium persulfate, Examples include hydrogen peroxide, and these can be used alone or in combination of two or more.
さらに必要に応じて、塩化ビニル系の重合に適宜使用さ
れる重合調整剤、連鎖移動剤、ｐＨ調整剤、ゲル化改良
剤、帯電防止剤、スケール防止剤などを添加することも
任意である。Further, if necessary, polymerization regulators, chain transfer agents, pH regulators, gelling improvers, antistatic agents, scale inhibitors, etc., which are appropriately used in vinyl chloride polymerization, may be added.
（実施例）
以下５本発明の具体的態様を実施例および比較例により
説明するが１本発明はこれに限定されるものではない。(Examples) Hereinafter, five specific embodiments of the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
（塩化ビニル樹脂の製造）
実施例 １゜
内容積２０００Ｑの攪拌器およびジャケット付きのステ
ンレス製オートクレーブに、脱イオン水を９００ｋｇ、
平均重合度７７０．けん化度７２゜４モル％の部分けん
化ポリビニルアルコールを３００ｇ、平均重合度３００
、けん化度４８．２モル％の部分けん化ポリビニルアル
コールを６０ｇ、アゾビス−２，４−ジメチルバレロニ
トリルを１８０ｇそれぞれ仕込み、器内を５０＋＋ｗ＊
Ｈｇになるまで脱気した後、塩化ビニル単量体を６００
ｋｇ仕込んだ。器内を攪拌しながらジャケットに熱水を
通して６３．５℃まで昇温し、その温度を保ちながら重
合を続けた６重合器内の圧力がｓ、ｏ）ｃｇ／ｃｄＧに
低下したところで未反応単量体を回収した１重合体を含
むスラリーを器外に取り出し、脱水乾燥して本発明によ
る塩化ビニル樹脂を得た。(Manufacture of vinyl chloride resin) Example 1 900 kg of deionized water was placed in a stainless steel autoclave with an internal volume of 2000 Q and a stirrer and a jacket.
Average degree of polymerization: 770. 300 g of partially saponified polyvinyl alcohol with a saponification degree of 72° and 4 mol%, an average degree of polymerization of 300
, 60g of partially saponified polyvinyl alcohol with a saponification degree of 48.2 mol% and 180g of azobis-2,4-dimethylvaleronitrile were charged, and the inside of the vessel was 50++w*.
After degassing to Hg, the vinyl chloride monomer was
I prepared kg. While stirring the vessel, hot water was passed through the jacket to raise the temperature to 63.5°C, and polymerization was continued while maintaining that temperature.6 When the pressure inside the polymerization vessel decreased to s, o) cg/cdG, unreacted monomers were removed. The slurry containing the monopolymer from which the monomer was recovered was taken out of the vessel and dehydrated and dried to obtain a vinyl chloride resin according to the present invention.
実施例 ２゜
前例において、平均重合度３００、けん化度４８．２モ
ル％の部分けん化ポリビニルアルコールの６０ｇを重合
開始前に投入する代りに、これの１２０ｇを重合終了後
のスラリー中に添加して脱水乾燥したほかは、前例と同
様にして塩化ビニル樹脂を得た。Example 2 In the previous example, instead of adding 60 g of partially saponified polyvinyl alcohol with an average degree of polymerization of 300 and a degree of saponification of 48.2 mol% before the start of polymerization, 120 g of this was added to the slurry after the completion of polymerization. A vinyl chloride resin was obtained in the same manner as in the previous example except for dehydration and drying.
実施例 ３゜
実施例１における平均重合度３００、けん化度４８．２
モル％の部分けん化ポリビニルアルコールの代りに、平
均重合度５００．けん化度３６゜８モル％の部分けん化
ポリビニルアルコールを使用したほかは、実施例１と同
様にして塩化ビニル樹脂を得た。Example 3゜ Average degree of polymerization in Example 1: 300, saponification degree: 48.2
Instead of mol % partially saponified polyvinyl alcohol, an average degree of polymerization of 500. A vinyl chloride resin was obtained in the same manner as in Example 1, except that partially saponified polyvinyl alcohol with a saponification degree of 36.8 mol % was used.
実施例 ４゜
実施例１における平均重合度７７０．けん化度７２．４
モル％の部分けん化ポリビニルアルコールの３００ｇの
代りに、平均重合度７９０、けん化度７３．０モル％の
部分けん化ポリビニルアルコールの３６０ｇと、メトキ
シ置換基２９％、ヒドロキシプロポキシ置換基１０％の
ヒドロキシプロピルメチルセルロース３ｇとを使用した
ほがは、実施例１と同様にして塩化ビニル樹脂を得た。Example 4゜Average degree of polymerization in Example 1: 770. Saponification degree 72.4
Instead of 300 g of partially saponified polyvinyl alcohol with an average degree of polymerization of 790 and a saponification degree of 73.0 mol%, and hydroxypropyl methyl cellulose with 29% of methoxy substituents and 10% of hydroxypropoxy substituents. A vinyl chloride resin was obtained in the same manner as in Example 1 using 3 g.
比較例 １゜
実施例１における平均重合度７７０、けん化度７２．４
モル％の部分けん化ポリビニルアルコールの３００ｇと
、平均重合度３００、けん化度４８．２モル％の部分け
ん化ポリビニルアルコールの６０ｇの使用に代えて、平
均重合度２６４０、けん化度８１．０モル％の部分けん
化ポリビニルアルコールの２７０ｇを使用したほかは、
実施例１と同様にして塩化ビニル樹脂を得た。Comparative example 1゜ Average degree of polymerization in Example 1: 770, saponification degree: 72.4
Instead of using 300 g of partially saponified polyvinyl alcohol with an average degree of polymerization of 300 and a degree of saponification of 48.2 mol %, a portion with an average degree of polymerization of 2640 and a degree of saponification of 81.0 mol % was used. Besides using 270g of saponified polyvinyl alcohol,
A vinyl chloride resin was obtained in the same manner as in Example 1.
比較例 ２゜
実施例１における平均重合度７７ｏ、けん化度７２．４
モル％の部分けん化ポリビニルアルコールの３００ｇと
、平均重合度３００、けん化度４８．２モル％の部分け
ん化ポリビニルアルコールの６０ｇの使用に代えて、メ
トキシ置換基２０％、ヒドロキシプロポキシ置換基８％
のヒドロキシプロピルメチルセルロース３００ｇを使用
したほかは、実施例１と同様にして塩化ビニル樹脂を得
た。Comparative example 2゜Average polymerization degree in Example 1: 77o, saponification degree: 72.4
Instead of using 300 g of partially saponified polyvinyl alcohol with mol % and 60 g of partially saponified polyvinyl alcohol with an average degree of polymerization of 300 and a saponification degree of 48.2 mol %, methoxy substituents 20% and hydroxypropoxy substituents 8%
A vinyl chloride resin was obtained in the same manner as in Example 1, except that 300 g of hydroxypropyl methyl cellulose was used.
（樹脂の白化による変質試験）
上記の実施例１〜４および比較例１〜２で得られた各塩
化ビニル樹脂について、
塩化ビニル樹脂 １００重量部ＤＯＰ
（３ｎジブチル錫メルカプタ
イド
ＴＶＳ−１３６０Ｃ日東化成社製）３，５７Ｆ加工助剤
Ｐ−７００（三菱レーヨン社製） ０．５＃Ｐ−５５
１（） ０．５＃
ステアリルアルコール ０．５〃ブチルステ
アレート ０，５〃の配合を行い、テスト
ロールで１７０℃で３分間混棟し、厚さ０．５＋ｍのシ
ートを作成し、これをさらに１８０℃で６分間プレスし
て透明な試験片を得た。これを８０℃に保った温水中に
３０分間浸した後水中から引き上げ、２４時間経過後デ
ジタル濁度計ＮＤＨ−２０Ｄ（日本重色工業社製）を用
いてヘイズおよび全透過率を測定した。(Deterioration test due to resin whitening) For each vinyl chloride resin obtained in Examples 1 to 4 and Comparative Examples 1 to 2 above, 100 parts by weight of vinyl chloride resin DOP
(3n dibutyltin mercaptide TVS-1360C manufactured by Nitto Kasei Co., Ltd.) 3,57F processing aid P-700 (manufactured by Mitsubishi Rayon Co., Ltd.) 0.5#P-55
1 () 0.5# Stearyl alcohol 0.5〃Butyl stearate 0.5〃 were mixed together for 3 minutes at 170℃ using a test roll to create a sheet with a thickness of 0.5+m, and this was Further, it was pressed at 180° C. for 6 minutes to obtain a transparent test piece. This was immersed in warm water kept at 80° C. for 30 minutes, then taken out of the water, and after 24 hours, the haze and total transmittance were measured using a digital turbidity meter NDH-20D (manufactured by Nihon Heavy Industries Co., Ltd.).
この結果を次の表に示した。The results are shown in the table below.
（発明の効果）
本発明によれば、塩化ビニル系樹脂からの透明成形品の
、水、アルコール、アルコール水溶液との接触、あるい
は高温多湿の雰囲気下での長時間の放置による表面の白
化を防止し品質を向上することができる。(Effects of the Invention) According to the present invention, whitening of the surface of a transparent molded product made of vinyl chloride resin due to contact with water, alcohol, or aqueous alcohol solution, or when left in a hot and humid atmosphere for a long time can be prevented. and improve quality.
Claims (1)
ビニル系単量体の混合物を、懸濁剤としてのけん化度６
５〜８０モル％、平均重合度６００〜１０００の部分け
ん化ポリビニルアルコールの存在下、水性媒体中で懸濁
重合する際に、あるいはこれによって得られた重合体中
に、けん化度２０〜５５モル％、平均重合度１５０〜６
００の部分けん化ポリビニルアルコールを生成重合体に
対して０．０１〜５重量％添加することを特徴とする透
明配合で白化の少ない塩化ビニル系樹脂の製造方法。1. Vinyl chloride monomer or a mixture of vinyl monomers mainly composed of vinyl chloride is used as a suspending agent with a saponification degree of 6.
During suspension polymerization in an aqueous medium in the presence of partially saponified polyvinyl alcohol with an average degree of polymerization of 5 to 80 mol% and an average degree of polymerization of 600 to 1000, or in the resulting polymer, a saponification degree of 20 to 55 mol% is added. , average degree of polymerization 150-6
A method for producing a vinyl chloride resin with a transparent formulation and less whitening, characterized by adding 0.01 to 5% by weight of partially saponified polyvinyl alcohol No. 00 to the produced polymer.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5728887A JPS63223011A (en) | 1987-03-12 | 1987-03-12 | Production of vinyl chloride based resin with hardly any whitening by transparent blending |
| ES8800712A ES2006108A6 (en) | 1987-03-12 | 1988-03-10 | Polyvinyl chloride resin composition |
| PT86940A PT86940B (en) | 1987-03-12 | 1988-03-10 | PROCESS FOR THE PREPARATION OF AN IMPROVED COMPOSITION OF POLYVINYL CHLORIDE RESIN |
| US07/406,967 US4972012A (en) | 1987-03-12 | 1989-09-13 | Polyvinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5728887A JPS63223011A (en) | 1987-03-12 | 1987-03-12 | Production of vinyl chloride based resin with hardly any whitening by transparent blending |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63223011A true JPS63223011A (en) | 1988-09-16 |
Family
ID=13051361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5728887A Pending JPS63223011A (en) | 1987-03-12 | 1987-03-12 | Production of vinyl chloride based resin with hardly any whitening by transparent blending |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63223011A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03170505A (en) * | 1983-08-23 | 1991-07-24 | Shin Etsu Chem Co Ltd | Method for suspension polymerizing vinyl chloride monomer |
| JP2010533761A (en) * | 2007-07-19 | 2010-10-28 | 株式会社クラレ | Polyvinyl alcohol as a co-stabilizer for PVC |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53136089A (en) * | 1977-05-02 | 1978-11-28 | Nippon Synthetic Chem Ind Co Ltd:The | Suspension polymerization of vinyl chloride |
-
1987
- 1987-03-12 JP JP5728887A patent/JPS63223011A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53136089A (en) * | 1977-05-02 | 1978-11-28 | Nippon Synthetic Chem Ind Co Ltd:The | Suspension polymerization of vinyl chloride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03170505A (en) * | 1983-08-23 | 1991-07-24 | Shin Etsu Chem Co Ltd | Method for suspension polymerizing vinyl chloride monomer |
| JP2010533761A (en) * | 2007-07-19 | 2010-10-28 | 株式会社クラレ | Polyvinyl alcohol as a co-stabilizer for PVC |
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