JPH04173818A - Wear resistance modifier for non-rigid vinyl resin - Google Patents
Wear resistance modifier for non-rigid vinyl resinInfo
- Publication number
- JPH04173818A JPH04173818A JP30068590A JP30068590A JPH04173818A JP H04173818 A JPH04173818 A JP H04173818A JP 30068590 A JP30068590 A JP 30068590A JP 30068590 A JP30068590 A JP 30068590A JP H04173818 A JPH04173818 A JP H04173818A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- graft copolymer
- macromonomer
- vinyl chloride
- parts
- 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 14
- 239000003607 modifier Substances 0.000 title claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 12
- 239000011347 resin Substances 0.000 title claims description 37
- 229920005989 resin Polymers 0.000 title claims description 37
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 31
- 239000000463 material Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 238000005299 abrasion Methods 0.000 description 18
- -1 polyethylene Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 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
- 238000010992 reflux Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
〔産業上の利用分野〕
本発明は、軟質塩化ビニル樹脂用の耐摩耗性改質剤に関
するものである。本発明の改質剤か添加された軟質塩化
ビニル樹脂組成物は、高度の耐摩耗性を有しており、シ
ート、レザー、ホース、電線被覆材および日用雑貨品な
どに好適に使用される。Detailed Description of the Invention (a) Object of the Invention [Field of Industrial Application] The present invention relates to an abrasion resistance modifier for soft vinyl chloride resin. The soft vinyl chloride resin composition to which the modifier of the present invention has been added has a high degree of abrasion resistance, and is suitable for use in seats, leather, hoses, wire covering materials, and daily miscellaneous goods. .
塩化ビニル樹脂は、ナイロン、ポリエステルまたはポリ
エチレンなどと同様に、汎用プラスチックとして各種の
用途に用いられており、硬質塩化ビニル樹脂と軟質塩化
ビニル樹脂とに大きく分類される。Vinyl chloride resin, like nylon, polyester, polyethylene, etc., is used as a general-purpose plastic for various purposes, and is broadly classified into hard vinyl chloride resin and soft vinyl chloride resin.
軟質塩化ビニル樹脂は、ポリ塩化ビニルに例えはＤＯＰ
（ジオクチルテレフタレート）なとの低分子量の可塑
剤、または脂肪族ポリエステルなとの高分子可塑剤が配
合された樹脂であり、その主な用途としては、各種シー
ト材料、ホース、電線被覆材などがある。Soft vinyl chloride resin is likened to polyvinyl chloride, DOP.
It is a resin containing a low molecular weight plasticizer such as (dioctyl terephthalate) or a polymeric plasticizer such as aliphatic polyester. Its main uses include various sheet materials, hoses, and wire coating materials. be.
最近、軟質塩化ビニル樹脂の上記用途、特に電線被覆材
の分野において、従来より、−層重摩耗性に優れる軟質
塩化ビニル樹脂に対する要求か高まっている。軟質塩化
ビニル樹脂に関して、耐摩耗性を改良する方法としては
、ポリウレタンなとの耐摩耗性に優れる樹脂を配合する
方法が知られているか、十分な耐摩耗性を得るには高耐
摩耗性樹脂を多量に使用する必要かあるため、その結果
望ましい他の物性か失われるという問題かあった。Recently, in the above-mentioned applications of soft vinyl chloride resins, particularly in the field of electric wire coating materials, there has been an increasing demand for soft vinyl chloride resins that have excellent layer abrasion resistance. Regarding soft vinyl chloride resin, a known method for improving the abrasion resistance is to blend a resin with excellent abrasion resistance such as polyurethane, or to obtain sufficient abrasion resistance, a highly abrasion resistant resin is used. Since it is necessary to use a large amount of , there is a problem that other desirable physical properties are lost as a result.
本発明は、軟質塩化ビニル樹脂の経済性および機械的性
質なとの特性を損なうことなく、耐摩耗性を改良し得る
改質剤を提供しようとするものである。The present invention aims to provide a modifier that can improve the abrasion resistance of soft vinyl chloride resin without impairing its economic efficiency and mechanical properties.
（ロ）発明の構成
〔課題を解決する為の手段〕
本発明者らは、上記課題を解決する方法につき鋭意検討
した結果、特定の化学構造を有するグラフト共重合体が
、軟質塩化ビニル樹脂の機械的特性を維持したまま耐磨
耗性を著しく向上させる添加剤として有用であることを
見出し、本発明を完成するに至った。(B) Structure of the Invention [Means for Solving the Problems] As a result of intensive study on methods for solving the above problems, the present inventors discovered that a graft copolymer having a specific chemical structure is a flexible vinyl chloride resin. We have discovered that it is useful as an additive that significantly improves abrasion resistance while maintaining mechanical properties, and have completed the present invention.
即ち本発明は、全構成単位の合計量を規準として、（ａ
）メタクリル酸メチル単量体単位を主成分とする重合体
の片末端にラジカル重合性基を有する、数平均分子量か
２．０００〜２０．０００のマクロモノマー単位か３〜
５０重量％、（ｂ）スチレン単量体単位か５０〜９７重
量％、および（ｃ）その他のビニル単量体単位か０〜３
０重量％であるグラフト共重合体からなる軟質塩化ビニ
ル樹脂用の耐摩耗性改質剤である。That is, in the present invention, (a
) A macromonomer unit with a number average molecular weight of 2.000 to 20.000 or 3 to 3, which has a radically polymerizable group at one end of a polymer mainly composed of methyl methacrylate monomer units.
50% by weight, (b) 50 to 97% by weight of styrene monomer units, and (c) 0 to 3 other vinyl monomer units.
This is an abrasion resistance modifier for soft vinyl chloride resin consisting of a graft copolymer of 0% by weight.
以下、本発明について更に詳しく説明する。The present invention will be explained in more detail below.
本発明におけるグラフト共重合体は、（ａ）メタクリル
酸メチル単量体単位（以下ＭＭＡ単量体単位という）を
主成分とする重合体の片末端にラジカル重合性基を有す
る、数平均分子量か２．０００〜２０、０００のマクロ
モノマー、（ｂ）スチレンおよび所望により（ｃ）その
他のビニル単量体をラジカル重合して得られるグラフト
共重合体である。The graft copolymer in the present invention has a radically polymerizable group at one end of a polymer mainly composed of (a) methyl methacrylate monomer units (hereinafter referred to as MMA monomer units), and has a number average molecular weight. It is a graft copolymer obtained by radical polymerization of a macromonomer of 2,000 to 20,000, (b) styrene, and optionally (c) other vinyl monomers.
マクロモノマーの数平均分子量か２．０００未満である
と、得られるグラフト共重合体における枝成分の分子鎖
長か短すぎ、ポリ塩化ビニルへのアンカー効果か不十分
となり、一方２０．０００を越えるとスチレンとの共重
合に劣り、未反応のマクロモノマーか残存したり、マク
ロモノマーの単独重合体かグラフト共重合体中に混在し
、高純度のグラフト共重合体か得られ難い。If the number average molecular weight of the macromonomer is less than 2.000, the molecular chain length of the branch component in the resulting graft copolymer will be too short and the anchoring effect to polyvinyl chloride will be insufficient, while if it exceeds 20.000. Copolymerization with styrene is poor, and unreacted macromonomers may remain or be mixed in the homopolymer or graft copolymer of the macromonomer, making it difficult to obtain a highly pure graft copolymer.
なお、本発明における数平均分子量とは、ゲルパーミェ
ーションクロマトグラフィー（以下ＧＰＣという）によ
って測定されるポリスチレン換算の数平均分子量である
。Note that the number average molecular weight in the present invention is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC).
本発明において使用するマクロモノマーを構成する重合
体におけるＭＭＡ単量体単位の量は、該重合体骨格を形
成する単量体単位の合計量を基準にして８０重量％以上
であることが好ましい。ＭＭＡ単量体単位の量か８０重
量％未満であると、得られるグラフト共重合体の技部分
のポリ塩化ビニルに対する相溶性が劣る。The amount of MMA monomer units in the polymer constituting the macromonomer used in the present invention is preferably 80% by weight or more based on the total amount of monomer units forming the polymer skeleton. If the amount of MMA monomer units is less than 80% by weight, the compatibility of the technical part of the resulting graft copolymer with polyvinyl chloride will be poor.
またマクロモノマーのラジカル重合性基としては、（メ
タ）アクリロイル基、スチリル基、アリル基、ビニルエ
ーテル基等が挙げられ、（メタ）アクリロイル基および
スチリル基か好ましく、特に好ましくは（メタ）アクリ
ロイル基である。Examples of the radical polymerizable group of the macromonomer include (meth)acryloyl group, styryl group, allyl group, vinyl ether group, etc., with (meth)acryloyl group and styryl group being preferred, and (meth)acryloyl group being particularly preferred. be.
上記マクロモノマーは、アニオンリビング重合法、グル
ープトランスファー重合法もしくはインモータル重合法
なとのリビング重合法、または以下に概略を示すラジカ
ル重合法によって合成できるが、不純物の影響を受けに
くく工業的に容易に製造できるという理由からラジカル
重合法か好ましい。The above macromonomer can be synthesized by a living polymerization method such as anionic living polymerization method, group transfer polymerization method, or immortal polymerization method, or by a radical polymerization method outlined below, but it is not easily affected by impurities and is industrially easy. The radical polymerization method is preferable because it can be produced in a number of steps.
ラジカル重合法によるポリメタクリル酸メチルマクロモ
ノマーの製造について説明すると、エポキシ基と反応性
基例えばカルボキシル基とメルカプト基を併せ有するメ
ルカプタン化合物を連鎖移動剤として使用して、メタク
リル酸メチルをラジカル重合し、分子の片末端にカルボ
キシル基を有するポリメタクリル酸メチルを得、次いで
分子中にエポキシ基と（メタ）アクリロイル基を有する
化合物を付加反応させることにより、マクロモノマーを
得ることかできる。To explain the production of polymethyl methacrylate macromonomer by a radical polymerization method, methyl methacrylate is radically polymerized using a mercaptan compound having both an epoxy group and a reactive group, such as a carboxyl group and a mercapto group, as a chain transfer agent. A macromonomer can be obtained by obtaining polymethyl methacrylate having a carboxyl group at one end of the molecule, and then subjecting it to an addition reaction with a compound having an epoxy group and a (meth)acryloyl group in the molecule.
本発明において、上記マクロモノマーおよびスチレンと
共重合させることができる、その他のビニル単量体とし
ては、芳香環置換スチレン類、α−メチルスチレン、塩
化ビニリデン等のハロケン化ビニリデン類、酢酸ビニル
等のビニルエステル類、ｎ−ブチルビニルエーテル等の
ビニルエーテル類、アクリル酸ブチル等のアクリル酸エ
ステル類、メタクリル酸２−エチルへキシル等のメタク
リル酸エステル類、アクリル酸、メタクリル酸、無水マ
レイン酸、Ｎ−置換マレイミド類等が挙げられる。In the present invention, other vinyl monomers that can be copolymerized with the macromonomer and styrene include aromatic ring-substituted styrenes, α-methylstyrene, vinylidene halides such as vinylidene chloride, and vinyl acetate. Vinyl esters, vinyl ethers such as n-butyl vinyl ether, acrylic esters such as butyl acrylate, methacrylic esters such as 2-ethylhexyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, N-substituted Examples include maleimides.
本発明の軟質塩化ビニル樹脂用の耐摩耗性改質剤として
用いられるグラフト共重合体の構成は、グラフト共重合
体の全構成単位の合計量を規準にして、前記マクロモノ
マー単位３〜５０重量％、スチレン単量体単位５０〜９
７重量％および上記その他のビニル単量体単位０〜３０
重量％であり、より好ましくは、マクロモノマー単位５
〜４０重量％、スチレン単量体単位６０〜９５重量％お
よびその他のビニル単量体単位０〜２０重量％である。The structure of the graft copolymer used as the abrasion resistance modifier for the soft vinyl chloride resin of the present invention is based on the total amount of all the structural units of the graft copolymer, and the macromonomer units are 3 to 50% by weight. %, styrene monomer units 50-9
7% by weight and 0 to 30 of the other vinyl monomer units listed above
% by weight, more preferably macromonomer units 5
-40% by weight, 60-95% by weight of styrene monomer units and 0-20% by weight of other vinyl monomer units.
マクロモノマーの量か３重量％未満であると、グラフト
共重合体への枝成分の導入量か少なすぎ、ポリ塩化ビニ
ルへの相溶性に劣り、一方５０重量％を越えると、グラ
フト共重合体の合成時にゲル化か起こり易い。マクロモ
ノマーおよびスチレン以外のビニル単量体の量か、３０
重量％を越えると、軟質塩化ビニル樹脂の耐磨耗性を向
上させることかできない。If the amount of the macromonomer is less than 3% by weight, the amount of branch components introduced into the graft copolymer will be too small, resulting in poor compatibility with polyvinyl chloride, while if it exceeds 50% by weight, the graft copolymer will have poor compatibility with polyvinyl chloride. gelation is likely to occur during the synthesis of The amount of macromonomer and vinyl monomer other than styrene, 30
If the amount exceeds % by weight, the abrasion resistance of the soft vinyl chloride resin cannot be improved.
グラフト共重合体は、溶液重合、塊状重合、懸濁重合、
乳化重合または分散重合なとの重合形態を採用し、ラジ
カル重合法で製造できる。好ましい重合形態である懸濁
重合を採用する場合の概略を説明すると、ポリビニルア
ルコールなどの懸濁剤を溶解した蒸留水を攪拌・加熱し
ておき、その中に、マクロモノマー、スチレン、その他
ビニル単量体および重合開始剤の混合液を加え、反応温
度５０〜９０°Ｃで３〜１５時間程度重合させ、重合終
了後、濾過・水洗・乾燥することによりグラフト共重合
体の粉末か得ることができる。Graft copolymers can be produced by solution polymerization, bulk polymerization, suspension polymerization,
It can be produced by radical polymerization using emulsion polymerization or dispersion polymerization. To explain briefly when suspension polymerization, which is the preferred polymerization form, is used, distilled water in which a suspending agent such as polyvinyl alcohol is dissolved is stirred and heated, and macromonomers, styrene, and other vinyl monomers are added to the mixture. A mixed solution of polymer and polymerization initiator is added, polymerized at a reaction temperature of 50 to 90°C for about 3 to 15 hours, and after the polymerization is completed, a powder of the graft copolymer can be obtained by filtering, washing with water, and drying. can.
上記グラフト共重合体は、軟質塩化ビニル樹脂用の耐摩
耗性改質剤として有用である。The above graft copolymer is useful as an abrasion resistance modifier for soft vinyl chloride resins.
本発明の改質剤を用いて育効な軟質塩化ビニル樹脂とし
ては、ポリ塩化ビニル１００重量部当たり、可塑剤が２
０〜２００重量部配合された軟質塩化ビニル樹脂か好ま
しく、さらに好ましくは可塑剤か３０〜１００重量部配
合された軟質塩化ビニル樹脂であり、該軟質塩化ビニル
樹脂には、通常軟質塩化ピじル樹脂に使用される安定剤
すなわちステアリン酸鉛、ステアリン酸バリウム等の金
属石鹸類、バリウム−亜鉛系安定剤、ジプチル錫ジラウ
レート等の有機錫系安定剤などが単独あるいは複数併用
して添加されいても良く、またそれ以外に、加工助剤、
紫外線吸収剤、酸化防止剤、顔料および炭酸カルシウム
等の無機充填剤などが適量添加されていても良い。The soft vinyl chloride resin that can be grown using the modifier of the present invention contains 2 plasticizers per 100 parts by weight of polyvinyl chloride.
A soft vinyl chloride resin containing 0 to 200 parts by weight is preferred, and more preferably a soft vinyl chloride resin containing 30 to 100 parts by weight of a plasticizer. Stabilizers used in resins, such as metal soaps such as lead stearate and barium stearate, barium-zinc stabilizers, and organotin stabilizers such as diptyltin dilaurate, may be added singly or in combination. In addition, processing aids,
Appropriate amounts of ultraviolet absorbers, antioxidants, pigments, and inorganic fillers such as calcium carbonate may be added.
可塑剤としては、ジオクチルフタレートまたはジブチル
フタレートなどのフタル酸エステル類、トリメリット酸
トリアルキルエステル類およびアジピン酸ジアルキルエ
ステルなどの低分子量可塑剤、ならびに各種の脂肪族ポ
リエステルおよび熱可塑性ポリウレタンなどの高分子可
塑剤が上げられる。Plasticizers include phthalate esters such as dioctyl phthalate or dibutyl phthalate, low molecular weight plasticizers such as trialkyl trimellitates and dialkyl adipate, and polymers such as various aliphatic polyesters and thermoplastic polyurethanes. Plasticizers are mentioned.
ポリ塩化ビニルの平均重合度としては、８００〜１５０
０か好ましい。ポリ塩化ビニルの平均重合度か８００未
満であると、機械的強度か不足し易く、一方１５００を
越えると成形性か劣る。The average degree of polymerization of polyvinyl chloride is 800 to 150.
0 is preferable. When the average degree of polymerization of polyvinyl chloride is less than 800, mechanical strength tends to be insufficient, while when it exceeds 1500, moldability is poor.
上記ポリ塩化ビニルは、懸濁重合、溶液重合、塊状重合
または乳化重合などによって、塩化ビニル単量体を単独
重合するか、または以下に示す共重合単量体を３０重量
％以下の割合で塩化ビニル単量体と併用して共重合する
ことにより得ることかできる。好ましい重合方法は懸濁
重合であり、例えば部分ケン化ポリビニルアルコールな
どの懸濁剤、アゾ化合物または有機過酸化物なとの重合
開始剤、さらに所望によりメルカプタン化合物などの連
鎖移動剤を使用して、水媒体中で重合温度３０〜７０°
Ｃて重合すればよい。The above polyvinyl chloride can be obtained by homopolymerizing vinyl chloride monomers by suspension polymerization, solution polymerization, bulk polymerization, or emulsion polymerization, or by chlorinating the following copolymerized monomers at a ratio of 30% by weight or less. It can be obtained by copolymerizing it in combination with a vinyl monomer. A preferred polymerization method is suspension polymerization, for example using a suspending agent such as partially saponified polyvinyl alcohol, a polymerization initiator such as an azo compound or an organic peroxide, and optionally a chain transfer agent such as a mercaptan compound. , polymerization temperature 30-70° in aqueous medium
C and polymerization.
上記共重合単量体としてはエチレン、プロピレン等のオ
レフィン類、塩化ビニリデン等のハロゲン化ビニリデン
類、酢酸ビニル等のビニルエステル類、ｎ−ブチルビニ
ルエーテル等のビニルエーテル類、アクリル酸ブチル等
のアクリル酸エステル類、メタクリル酸２−エチルヘキ
シル等のメタクリル酸エステル類等か挙げられる。The above-mentioned comonomers include olefins such as ethylene and propylene, vinylidene halides such as vinylidene chloride, vinyl esters such as vinyl acetate, vinyl ethers such as n-butyl vinyl ether, and acrylic esters such as butyl acrylate. and methacrylic acid esters such as 2-ethylhexyl methacrylate.
軟質塩化ビニル樹脂に対するグラフト共重合体の好まし
い配合割合は、軟質塩化ビニル樹脂におけるポリ塩化ビ
ニルと可塑剤との合計量１００重量部当たり、グラフト
共重合体３〜３０重量部であり、更に好ましくはグラフ
ト共重合体５〜２０重量部である。The preferred blending ratio of the graft copolymer to the soft vinyl chloride resin is 3 to 30 parts by weight, more preferably 3 to 30 parts by weight of the graft copolymer per 100 parts by weight of the total amount of polyvinyl chloride and plasticizer in the soft vinyl chloride resin. The amount of graft copolymer is 5 to 20 parts by weight.
軟質塩化ビニル樹脂へのグラフト共重合体の配合は、例
えばバンバリーミキサ−、ロールまたは押出機などの混
練り機を使用して、１２０〜２００°Ｃで溶融混練りす
ることによってなされる。The graft copolymer is blended into the soft vinyl chloride resin by melt-kneading it at 120 to 200°C using a kneader such as a Banbury mixer, roll or extruder.
以下に参考例、実施例及び比較例を挙げ本発明を更に具
体的に説明する。なお、各個における％はすべて重量％
であり、部は重量部である。The present invention will be explained in more detail by referring to Reference Examples, Examples and Comparative Examples below. All percentages for each item are by weight.
and parts are parts by weight.
参考例１
撹拌機、還流冷却器、滴下ロート及温度計を取りつけた
ガラスフラスコに、蒸留水４００部、ポリビニルアルコ
ール（クラレ■製ポバール４２０）の５％水溶液 ４部
、燐酸カルシウム懸濁液（日本化学工業■製スーパータ
イト１０）１０部、ドデシルベンゼンスルホン酸ナトリ
ウム（花王（ａ）製エマール２Ｆ）０．２部を仕込んだ
。Reference Example 1 In a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 400 parts of distilled water, 4 parts of a 5% aqueous solution of polyvinyl alcohol (Poval 420 manufactured by Kuraray ■), and a suspension of calcium phosphate (Japanese) were added. 10 parts of Supertite 10) manufactured by Kagaku Kogyo ■ and 0.2 parts of sodium dodecylbenzenesulfonate (Emar 2F manufactured by Kao (a)) were charged.
次に、末端メタクリロイル基型のポリメチルメタクリレ
ートマクロモノマー（東亜合成化学工業■製マクロモノ
マーＡＡ−６）１０部、アブヒスイソブチロニトリル１
．５部をスチレン９０部に溶解した溶液を滴下ロートに
入れ、フラスコを加熱・撹拌して内液の温度を７５°Ｃ
に設定した後、上記滴下ロートより単量体混合物を１分
間かけて滴下した。Next, 10 parts of a polymethyl methacrylate macromonomer having a terminal methacryloyl group (Macromonomer AA-6 manufactured by Toagosei Kagaku Kogyo ■), 1 part of Abhis isobutyronitrile,
．． A solution of 5 parts dissolved in 90 parts of styrene was placed in the dropping funnel, and the flask was heated and stirred to bring the temperature of the internal liquid to 75°C.
The monomer mixture was then added dropwise from the above-mentioned dropping funnel over a period of 1 minute.
７５°Ｃて７時間維持し重合を完結させ、その後濾過・
水洗・脱水・乾燥して、固形のスチレン−メタクリル酸
メチル系グラフト共重合体を９０部を得た。得られたグ
ラフト共重合体の数平均分子量は、ＧＰＣによるスチレ
ン換算て、Ｍｎ＝３５．０００であった。The temperature was maintained at 75°C for 7 hours to complete the polymerization, and then filtered.
The mixture was washed with water, dehydrated, and dried to obtain 90 parts of a solid styrene-methyl methacrylate graft copolymer. The number average molecular weight of the obtained graft copolymer was Mn=35.000 in terms of styrene by GPC.
参考例２
末端メタクリロイル基型のポリメチルメタクリレートマ
クロモノマーの量を１５重量部へ、またスチレンの量を
８５重量部へ、それぞれ変更した以外は参考例１と同様
の方法により、Ｍｎ＝３７，０００のスチレン−メタク
リル酸メチル系グラフト共重合体９１部を得た。Reference Example 2 Mn=37,000 was prepared in the same manner as in Reference Example 1, except that the amount of polymethyl methacrylate macromonomer with a terminal methacryloyl group was changed to 15 parts by weight, and the amount of styrene was changed to 85 parts by weight. 91 parts of a styrene-methyl methacrylate graft copolymer was obtained.
参考例３
末端メタクリロイル基型のポリメチルメタクリレートマ
クロモノマーの量を２５重量部へ、またスチレンの量を
７５重量部へ、それぞれ変更した以外は参考例１と同様
の方法により、Ｍｎ＝３６，０００のスチレン−メタク
リル酸メチル系グラフト共重合体９２部を得た。Reference Example 3 Mn=36,000 was prepared in the same manner as in Reference Example 1, except that the amount of polymethyl methacrylate macromonomer with a terminal methacryloyl group was changed to 25 parts by weight, and the amount of styrene was changed to 75 parts by weight. 92 parts of a styrene-methyl methacrylate graft copolymer was obtained.
参考例４
以下に示す配合物をヘンシェルミキサーで混合し、軟質
塩化ビニル樹脂を得た。Reference Example 4 The formulation shown below was mixed in a Henschel mixer to obtain a soft vinyl chloride resin.
塩化ビニル樹脂（東亜合成化学工業■製ＴＳ−１１００
） １００部ジオクチルフタレート
５０部炭酸カルシウム ２５部
エポキシ化大豆油 ５部Ｂａ−Ｚｎ系
液状安定剤 １部実施例１〜６及び比較
例１〜３
参考例４て製造した軟質塩化ビニル樹脂に、参考例１〜
３て製造したグラフトポリマー、または市販のポリスチ
レン樹脂、ポリメタクリル酸メチル樹脂を表１に示す割
合で使用して、２軸スクリユ一押出機（ベント式同方向
回転、直径２９ｍｍ Ｌ／Ｄ＝２５）により樹脂温度１
６５°Ｃて溶融混合して、ペレット状の樹脂組成物を得
た。得られた樹脂組成物について、引張試験およびスク
レープ試験を行い、その結果を表１に併記した。Vinyl chloride resin (TS-1100 manufactured by Toagosei Chemical Industry Co., Ltd.)
) 100 parts dioctyl phthalate
50 parts Calcium carbonate 25 parts Epoxidized soybean oil 5 parts Ba-Zn liquid stabilizer 1 part Examples 1 to 6 and Comparative Examples 1 to 3 Reference Examples 1 to 3 were added to the soft vinyl chloride resin produced in Reference Example 4.
Using the graft polymer produced in Step 3 or commercially available polystyrene resin or polymethyl methacrylate resin in the proportions shown in Table 1, a twin-screw single extruder (vented co-rotating, diameter 29 mm L/D = 25) was used. Resin temperature 1
The resin compositions were melt-mixed at 65°C to obtain pellet-shaped resin compositions. The obtained resin composition was subjected to a tensile test and a scrape test, and the results are also listed in Table 1.
なお、各試験方法の詳細は、以下のとおりである。The details of each test method are as follows.
樹脂組成物を小型プレス機にて、１８０°Ｃて５分間プ
レスし、１００ Ｘ１００ Ｘ １ ｍｍのシートを作
成した。このシートからダンベル型試験片に打ち抜いて
、ＪＡＳ Ｋ７１１３に準じ引張り速度２００ｍｍ／分
て試験した。The resin composition was pressed using a small press at 180°C for 5 minutes to create a sheet of 100 x 100 x 1 mm. A dumbbell-shaped test piece was punched out from this sheet and tested at a tensile speed of 200 mm/min according to JAS K7113.
上記と同様の方法で厚さ１ｍｍのシートを作成した。こ
のシートを第１図に示す如く、シートと刃とか直角にな
るような配置てスクレープ試験装置に取りつけ、荷重Ｉ
Ｋｇ、刃幅２ｍｍ、ストローク５０ｍｍおよび毎分２５
回の速度の条件で、刃を往復運動させ、５０回往復後の
摩耗量を評価した。A sheet with a thickness of 1 mm was created in the same manner as above. As shown in Figure 1, this sheet was placed in a scrape tester with the sheet and blade at right angles, and a load of I
Kg, blade width 2mm, stroke 50mm and 25 per minute
The blade was reciprocated at a speed of 50 times, and the amount of wear after reciprocating 50 times was evaluated.
表１に示された結果から明らかなとおり、本発明の耐摩
耗性改質剤を添加した実施例によれは、軟質塩化ビニル
樹脂製シートは、耐摩耗性か向上しており、しかも機械
的強度か殆ど低下していないのに対して、ポリスチレン
やポリメタクリル酸メチルを配合した比較例のシートで
は、耐磨耗性か改良されていないかまたは機械的強度か
低下している。As is clear from the results shown in Table 1, in the examples in which the abrasion resistance modifier of the present invention was added, the soft vinyl chloride resin sheets had improved abrasion resistance and mechanical In contrast to the comparative sheets containing polystyrene and polymethyl methacrylate, the abrasion resistance was not improved or the mechanical strength was decreased.
（ハ）発明の効果
本発明における特定の構造を存するグラフト共重合体は
、それを軟質塩化ビニル樹脂に加えることにより、軟質
塩化ビニル樹脂の引張強度・伸びなどの機械的強度を損
なうことなく、該樹脂の耐摩耗性を向上させることがで
きる。(c) Effects of the Invention By adding the graft copolymer having a specific structure to a soft vinyl chloride resin, the graft copolymer of the present invention can be used without impairing the mechanical strength such as tensile strength and elongation of the soft vinyl chloride resin. The abrasion resistance of the resin can be improved.
従って、本発明の改質剤によって耐摩耗性か改良された
軟質塩化ビニル樹脂は、例えば電線被覆材などの用途に
好適に使用される。Therefore, the soft vinyl chloride resin whose abrasion resistance has been improved by the modifier of the present invention is suitably used for applications such as electric wire coating materials.
第１図は、スクレープ試験装置の概念図であり、刃部ｌ
は、その先端か試料３の表面を擦りなから水平方向に往
復運動する。また第２図は、第１図における刃部ｌの先
端拡大図である。
なお図中の番号は、それぞれ次のものを示す。
ｌ・・・・・・・・・・刃部 、 ２−・・・−
・荷重３ ・−・・−・−・試料シート、 ４ −
−−−一支持具５ ・−・−・・駆動装置 、 ６
−−−−−−支持台ノ 特許出願人 東亜合成化
学工業株式会社第１図Figure 1 is a conceptual diagram of the scrape test device, and the blade part l.
moves back and forth in the horizontal direction without rubbing its tip against the surface of the sample 3. FIG. 2 is an enlarged view of the tip of the blade l in FIG. 1. The numbers in the figure indicate the following, respectively. l......Blade part, 2-...-
・Load 3 ・−・・−・−・Sample sheet, 4 −
---One support tool 5 --- Drive device, 6
−−−−−−Support stand Patent applicant Toagosei Chemical Industry Co., Ltd. Figure 1
Claims (1)
合体の片末端にラジカル重合性基を有する、数平均分子
量が２，０００〜２０，０００のマクロモノマー単位が
３〜５０重量％、 （ｂ）スチレン単量体単位が５０〜９７重量％、および （ｃ）その他のビニル単量体単位が０〜３０重量％であ
るグラフト共重合体からなる軟質塩化ビニル樹脂用の耐
摩耗性改質剤。[Claims] 1. Based on the total amount of all structural units, (a) a polymer mainly composed of methyl methacrylate monomer units has a radically polymerizable group at one end, and has a number average molecular weight of 3-50% by weight of 2,000-20,000 macromonomer units, (b) 50-97% by weight of styrene monomer units, and (c) 0-30% by weight of other vinyl monomer units. A wear resistance modifier for soft vinyl chloride resin made of a graft copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30068590A JPH04173818A (en) | 1990-11-06 | 1990-11-06 | Wear resistance modifier for non-rigid vinyl resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30068590A JPH04173818A (en) | 1990-11-06 | 1990-11-06 | Wear resistance modifier for non-rigid vinyl resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04173818A true JPH04173818A (en) | 1992-06-22 |
Family
ID=17887845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30068590A Pending JPH04173818A (en) | 1990-11-06 | 1990-11-06 | Wear resistance modifier for non-rigid vinyl resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04173818A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002022715A2 (en) | 2000-09-14 | 2002-03-21 | Rohm And Haas Company | A method of improving the melt processing of thermoplastic polymers and compositions produced thereby |
| KR100344893B1 (en) * | 1999-11-04 | 2002-07-20 | 삼성전자 주식회사 | Styrene Based Terpolymer Having Excellent Melt Flowability and Impact Strength and Method of Preparing the Same |
| WO2004003042A1 (en) * | 2002-06-28 | 2004-01-08 | Kaneka Corporation | Vinyl chloride copolymer resin for paste, composition, and process for producing resin |
| WO2006103806A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride copolymer resin composition and vinyl chloride injection molded article produced from the same |
| WO2006103808A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Stain-proof vinyl chloride film |
| WO2006103807A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride sheet |
| WO2006103809A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Gamma-ray-resistant, flexible vinyl chloride molded article |
| WO2006112076A1 (en) * | 2005-03-31 | 2006-10-26 | Kaneka Corporation | Vinyl chloride resin dope composition |
-
1990
- 1990-11-06 JP JP30068590A patent/JPH04173818A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100344893B1 (en) * | 1999-11-04 | 2002-07-20 | 삼성전자 주식회사 | Styrene Based Terpolymer Having Excellent Melt Flowability and Impact Strength and Method of Preparing the Same |
| WO2002022715A3 (en) * | 2000-09-14 | 2002-07-11 | Rohm & Haas | A method of improving the melt processing of thermoplastic polymers and compositions produced thereby |
| US6797775B2 (en) | 2000-09-14 | 2004-09-28 | Rohm And Haas Company | Method of improving the melt processing of thermoplastic polymers and compositions produced thereby |
| WO2002022715A2 (en) | 2000-09-14 | 2002-03-21 | Rohm And Haas Company | A method of improving the melt processing of thermoplastic polymers and compositions produced thereby |
| KR101015077B1 (en) * | 2002-06-28 | 2011-02-16 | 카네카 코포레이션 | Vinyl chloride copolymer resin for paste, composition, and process for producing resin |
| WO2004003042A1 (en) * | 2002-06-28 | 2004-01-08 | Kaneka Corporation | Vinyl chloride copolymer resin for paste, composition, and process for producing resin |
| JP2004083854A (en) * | 2002-06-28 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | Polyvinyl chloride-based copolymer resin for paste, composition and method for producing the same resin |
| KR101014584B1 (en) * | 2002-06-28 | 2011-02-16 | 카네카 코포레이션 | Vinyl chloride copolymer resin for paste, composition, and process for producing resin |
| WO2006103806A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride copolymer resin composition and vinyl chloride injection molded article produced from the same |
| WO2006103809A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Gamma-ray-resistant, flexible vinyl chloride molded article |
| WO2006103807A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Vinyl chloride sheet |
| WO2006103808A1 (en) * | 2005-03-25 | 2006-10-05 | Kaneka Corporation | Stain-proof vinyl chloride film |
| WO2006112076A1 (en) * | 2005-03-31 | 2006-10-26 | Kaneka Corporation | Vinyl chloride resin dope composition |
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