JPH0227378B2 - TAISHOGEKISEINETSUKASOSEIJUSHISOSEIBUTSU - Google Patents
TAISHOGEKISEINETSUKASOSEIJUSHISOSEIBUTSUInfo
- Publication number
- JPH0227378B2 JPH0227378B2 JP5691681A JP5691681A JPH0227378B2 JP H0227378 B2 JPH0227378 B2 JP H0227378B2 JP 5691681 A JP5691681 A JP 5691681A JP 5691681 A JP5691681 A JP 5691681A JP H0227378 B2 JPH0227378 B2 JP H0227378B2
- Authority
- JP
- Japan
- Prior art keywords
- monomers
- acid ester
- rubbery polymer
- ester monomers
- copolymer
- 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.)
- Expired - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 106
- 229920001971 elastomer Polymers 0.000 claims description 77
- 239000002245 particle Substances 0.000 claims description 48
- -1 vinyl cyanide compound Chemical class 0.000 claims description 42
- 229920001577 copolymer Polymers 0.000 claims description 23
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 21
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 229920005992 thermoplastic resin Polymers 0.000 claims description 19
- 239000011342 resin composition Substances 0.000 claims description 17
- 229920000578 graft copolymer Polymers 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000007423 decrease Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 230000004931 aggregating effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
［産業上の利用分野］
本発明は、断熱箱体の壁材として使用されるフ
ロンガス、例えばフロン−11、フロン−12等に対
する耐ストレスクラツク性に優れ、かつ剛性、外
観特性に優れた耐衝撃性熱可塑性樹脂組成物に関
するものであ。
［従来の技術］
従来、電気冷蔵庫等の断熱箱体の内面の壁材と
してはゴム補強ポリスチレン（以下HIPSと略
す）シート、又はアクリロニトリル−ブタジエン
−スチレン共重合体（以下ABSと略す）シート
の熱成形品が用いられている。
一般に、HIPSシートを用いた場合には断熱材
のウレタンフオームの発泡に用いられているフロ
ンガスにより白化、亀裂等が生ずるため、その防
止策としてポリエチレンフイルム等の保護フイル
ムで成形品を被覆する方法が採用されているが、
その為、一工程増し、生産能率、作業性に悪影響
を与えている。
一方、ABSシートを用いた場合にはHIPSシー
トを用いた場合に比較しフロンガスに対する耐ス
トレスクラツク性は改良されるが、それでも完全
に満足すべきレベルではない。又、熱成形による
内部歪、あるいは冷却時の断熱箱体の外壁である
鉄板等と、ウレタンフオームに密着したABSシ
ートとの線膨張係数の差により発生する内部歪が
ある場合、フロンガスの影響により白化、亀裂等
が発生する。
従来の射出成形用ABS樹脂又は押出成形用
ABS樹脂の場合、フロンガスに対する耐ストレ
スクラツク性を向上させるにはゴム質重合体の含
有量を増加させることにより達成されることは良
く知られている。しかるに、ゴム質重合体含有量
を増加させることは、成形品の剛性を低下させ
る。これを防ぐにはシート厚みを厚くしなければ
ならない。又、ゴム質重合体の含有量を増加させ
ることは成形品の外観を低下させるという欠点を
有している。
また特定の構造にゴム質重合体を凝集させ、強
度と外観を向上させる技術（特開昭53−57257号
公報）も開示されているが、フロンガスに対する
耐ストレスクラツク性は十分なレベルに達してい
ない。
［発明が解決しようとする問題点］
近年、電気冷蔵庫が大型化し、シート厚みを薄
くしたいとの要望が強い。従来のABS樹脂では
前述の問題点を解決することがますます困難にな
つた。かかる観点から、本発明者らはフロンガス
に対する耐ストレスクラツク性に優れ、かつ剛
性、外観特性に優れた耐衝撃性熱可塑性樹脂組成
物について鋭意研究を重ねた結果、本発明に到達
した。
［問題点を解決するための手段及び作用］
即ち、本発明の要旨とするところは、ビニルシ
アン化合物単量体、メタアクリル酸エステル単量
体及びアクリル酸エステル単量体の群より選ばれ
る１種以上の単量体とビニル芳香族化合物単量体
よりなる共重合体と、ビニルシアン化合物単量
体、メタアクリル酸エステル単量体及びアクリル
酸エステル単量体の群より選ばれる１種以上の単
量体とビニル芳香族化合物単量体がゴム質重合体
にグラフトしたグラフト率が25〜80％のグラフト
共重合体とよりなる熱可塑性樹脂組成物におい
て、熱可塑性樹脂組成物中のゴム質重合体の重量
分率が10〜25％の範囲にあり、(イ)平均粒子径が
0.2μ以下のゴム質重合体粒子が平均粒子径0.5〜
2.0μの大きさの範囲に凝集しているゴム質重合体
の重量分率が全体のゴム質重合体量に対して25〜
80％の範囲にあり、(ロ)平均粒子径が0.5μ以上の凝
集していないゴム質重合体の重量分率が全体のゴ
ム質重合体量に対して10〜60％の範囲にある耐衝
撃性熱可塑性樹脂組成物である。
ここでいうゴム質重合体粒子の平均粒子径はジ
ヤーナル・オブ・エレクトロン・ミクロスコピー
（J.Electron Microscopy）14巻、222頁（1965）
およびポリマー・エンジニアリング・アンド・サ
イエンス（polymer Eng.＆ Sci.）７巻、38頁
（1967）に記載されている四酸化オスミウムによ
る固定染色法によつてゴム質重合体のみを染色
し、電子顕微鏡下に観察し、測定されたものであ
る。
平均粒子径は夫々ゴム質重合体粒子径の長径と
短径の相加平均値を表わす。ゴム質重合体の凝集
体の平均粒子径も長径と短径の相加平均値を表わ
す。
凝集体の重量分率は次式で表わされる。
重量分率（％）＝ΣNiDi3／Σnidi3×100
ここでniは平均粒子径がdiである電子顕微鏡写
真中に存在する粒子の数（すなわちdi、niは、
0.2μ以下のゴム質重合体粒子、凝集によつてでき
たゴム質重合体粒子、及び0.5μ以上で凝集に関与
していないゴム質重合体粒子を含んだそれぞれの
平均粒子径とその数である。）である。Niは平均
粒子径がDi（Diは凝集ゴム質重合体の平均粒子径
で、かつ0.5〜2.0μの範囲にあるゴム質重合体の
平均粒子径）である電子顕微鏡写真中に存在する
ゴム質重合体粒子の数である。
平均粒子径0.5μ以上の凝集していないゴム質重
合体の重量分率は次式で表わされる。
重量分率（％）＝ΣMiRi3／Σnidi3×100
ここでMiは平均粒子径がRi（Riは平均粒子径が
0.5μ以上で凝集に関与していないゴム質重合体粒
子の平均粒子径）である電子顕微鏡写真中に存在
するゴム質重合体粒子の数である。
電子顕微鏡写真により読み取るゴム質重合体粒
子の数は500個以上が好ましい。
熱可塑性樹脂組成物は、平均粒子径0.2μ以下の
ゴム質重合体にシアン化ビニル化合物単量体、メ
タクリル酸エステル単量体及びアクリル酸エステ
ル単量体の群より選ばれる１種以上の単量体とビ
ニル芳香族化合物単量体とよりなる共重合体をグ
ラフト共重合してなるグラフト共重合体(A)と、
0.5μ以上の粒子を含むゴム質重合体に(A)と同様の
グラフト共重合を施してなるグラフト共重合体(B)
を混合使用する処に特徴がある。平均粒子径0.2μ
以下のゴム質重合体が凝集して得られる0.5〜2μ
の凝集ゴム粒子(イ)は、主としてグラフト共重合体
(A)に由来し、平均粒子径0.5μ以上の凝集していな
いゴム粒子(ロ)は、主としてグラフト共重合体(B)に
由来する。しかし、(A)(B)ともに原料となるゴム質
重合体粒子径に分布があるため、必ずしも(A)＝
(イ)、(B)＝(ロ)とならない。
また熱可塑性樹脂組成物を構成するシアン化ビ
ニル化合物の単量体、メタアクリル酸エステル単
量体及びアクリル酸エステル単量体の群より選ば
れる１種以上の単量体とビニル芳香族化合物単量
体よりなる共重合体は、(A)(B)作成時にゴム質重合
体にグラフトせずに生じたもの、或いは、上記共
重合体をゴム質重合体へのグラフト反応とは別途
に作成したもの(C)を(A)(B)に加えてなるものであ
る。
ゴム質重合体粒子は、ビニルシアン化合物単量
体、メタアクリル酸エステル単量体及びアクリル
酸エステル単量体の群より選ばれる１種以上の単
量体とビニル芳香族化合物単量体とよりなる共重
合体を少量粒子中にオクルージヨン成分として含
むことがあり得る。
本発明で言うグラフト率とは、一定重量の樹脂
をアセトンに溶解し、アセトン不溶分を遠心分離
器を用いて分離し、乾燥、秤量して次式より求め
られる。
グラフト率（％）
＝（アセトン不溶分重量／ゴム質重合体重量−１）
×100
また、上記式は、以下に書き替え可能である。
●グラフト共重合体量（％）＝
ゴム質重合体量（％）×（１＋グラフト率／100）
●共重合体量（％）
＝100−グラフト共重合体量（％）
すなわち、ビニルシアン化合物単量体、メタア
クリル酸エステル単量体及びアクリル酸エステル
単量体の群より選ばれる１種以上の単量体とビニ
ル芳香族化合物単量体よりなる共重合体は、必ず
しも(C)成分のみに由来するものではなく、(A)(B)成
分共重合反応時に生成するが、グラフト率測定時
に、同時に該共重合体含有量を知ることができ
る。
次に本発明の構成要件を詳細に説明する。
本発明にいうゴム質重合体は、ポリブタジエン
及びブタジエンを主成分とするブタジエン共重合
体、好ましくはポリブタジエンである。ブタジエ
ン共重合体を用いる場合は、低温での耐衝撃性向
上の観点から、ブタジエンを70重量％以上含有す
る共重合体が好ましい。
ゴム質重合体は現在知られている重合法、例え
ば乳化重合法、溶液重合法、イオン重合法等によ
り得られるゴム質重合体が使用できる。
本発明におけるビニルシアン化合物単量体、メ
タアクリル酸エステル単量体及びアクリル酸エス
テル単量体の群より選ばれる１種以上の単量体と
ビニル芳香族化合物単量体がゴム質重合体にグラ
フトしたグラフト共重合体（以下グラフト共重合
体と略す）は、前記ゴム質重合体にビニルシアン
化合物単量体、メタアクリル酸エステル単量体及
びアクリル酸エステル単量体の群より選ばれる１
種以上の単量体とビニル芳香族化合物単量体の混
合物をグラフト重合させて得られる。重合体中の
ゴム質重合体の重量分率は５〜60％が好ましく、
10〜50％がより好ましい。
グラフトゴム質重合体は現在知られている重合
方法、例えば乳化重合法、溶液重合法、塊状重合
法、乳化−懸濁重合法、塊状−懸濁重合法等いず
れの方法によつたものであつてもよい。
平均粒子径0.2μ以下のゴム質重合体の凝集方法
は現在知られている方法、例えばゴム質重合体ラ
テツクスに電解質あるいは酸無水物を添加して凝
集させる方法、ゴム質重合体ラテツクスと凍結さ
せて凝集させる方法、ゴム質重合体にビニルシア
ン化合物単量体、メタアクリル酸エステル単量体
及びアクリル酸エステル単量体の群より選ばれる
１種以上の単量体とビニル芳香族化合物単量体の
混合物をグラフト重合させたラテツクスを塩析、
脱水、乾燥後、溶融混練して凝集させる方法等い
ずれの方法によつてもよい。
平均粒子径0.5μ以上の凝集していないゴム質重
合体と平均粒子径0.5〜2.0μの範囲に凝集したゴ
ム質重合体を配合する方法は、例えば凝集したゴ
ム質重合体ラテツクスと平均粒子径0.5μ以上の凝
集していないゴム質重合体ラテツクスをブレンド
する方法、個々のゴム質重合体ラテツクスにビニ
ルシアン化合物単量体、メタアクリル酸エステル
単量体及びアクリル酸エステル単量体の群より選
ばれる１種以上の単量体とビニル芳香族化合物単
量体の混合物をグラフト重合させたラテツクスを
ブレンドする方法、個々のゴム質重合体を含有す
る熱可塑性樹脂をペレツト化し、ペレツト同志を
配合する方法等が含まれる。
本発明にいうビニル芳香族化合物単量体は例え
ばスチレン、メチルスチレン、ビニルトルエン、
エチルスチレン、ジメチルスチレン、ブチルスチ
レン、ジクロルスチレン等が含まれる。又、これ
らの二種又はそれ以上の混合物も使用できる。
本発明にいうビニルシアン化合物単量体は例え
ばアクリロニトリル、メタアクリロニトリル等が
含まれる。メタアクリル酸エステル単量体として
は、メタアクリル酸のメチル、エチル、プロピル
ブチル及びフエニルエステル等が挙げられる。ア
クリル酸エステル単量体としてはアクリル酸のメ
チル、エチル、プロピル、ブチル及びフエニルエ
ステル等が挙げられる。
ビニルシアン化合物単量体、メタアクリル酸エ
ステル単量体及びアクリル酸エステル単量体の群
より選ばれる１種以上の単量体とビニル芳香族化
合物単量体よりなる共重合体は、ゴム質重合体に
ビニルシアン化合物単量体、メタアクリル酸エス
テル単量体及びアクリル酸エステル単量体の群よ
り選ばれる１種以上の単量体とビニル芳香族化合
物単量体をグラフト重合させる時につくられる。
又、現在知られている方法、例えば乳化重合法、
溶液重合法、塊状重合法、懸濁重合法、塊状−懸
濁重合法等によりビニルシアン化合物単量体、メ
タアクリル酸エステル単量体及びアクリル酸エス
テル単量体の群より選ばれる１種以上の単量体と
ビニル芳香族化合物単量体とよりなる共重合体を
作り、グラフト共重合体を含有する熱可塑性樹脂
とゴム質重合体の重量分率が10〜25％の範囲にな
るように配合してもよい。
配合方法は例えばラテツクス同志、フレーク同
志、ペレツト同志、ペレツト−フレーク等いずれ
の方法によつても良い。
本発明の特徴はゴム質重合体として、小粒子ゴ
ム質重合体を凝集させたゴム質重合体と平均粒子
径0.5μ以上の凝集していないゴム質重合体の混合
物を用いた点にある。
熱可塑性樹脂組成物中のゴム質重合体の重量分
率は10〜25％の範囲が使用できる。10％未満の場
合は衝撃強度、フロンガスに対する耐ストレスク
ラツク性が著しく低下し電気冷蔵庫等の壁材とし
て使用に耐え得ない。重量分率が25％を超える場
合は剛性が低下し、外観特性も低下するので好ま
しくない。
ゴム質重合体中の平均粒子径が0.2μ以下のゴム
質重合体が平均粒子径0.5〜2.0μの大きさの範囲
に凝集しているゴム質重合体の重量分率が25〜80
％の範囲にあるものが使用できる。重量分率が25
％未満の場合はフロンガスに対する耐ストレスク
ラツク性が低下し、80％を超える場合は衝撃強度
が低下、外観特性が低下し好ましくない。
凝集体の大きさが2.0μを超える場合は、凝集体
の個数が減少するためフロンガスに対する耐スト
レスクラツク性が低下する。又、外観特性も著し
く低下するので電気冷蔵庫等の壁材として使用に
耐え得ない。0.5μ未満の場合もフロンガスに対す
る耐ストレスクラツク性が低下し好ましくない。
凝集体を構成するゴム質重合体の平均粒子径が
0.2μを超える場合は、凝集体を構成するゴム質重
合体粒子の数が少なくなる結果、フロンガスに対
する耐ストレスクラツク性が低下し好ましくな
い。
ゴム質重合体中の0.5μ以上の凝集していないゴ
ム質重合体の重量分率が10〜60％の範囲で使用で
きる。10％未満の場合は衝撃強度の低下、外観特
性の低下が大きく使用に耐え得ない。60％を超え
る場合はフロンガスに対する耐ストレスクラツク
性が低下し使用に耐え得ない。
上記要件を満足すれば0.5μ以下のゴム質重合体
粒子が凝集しないで組成物中に分散していてもよ
い。
本発明の組成物において、ゴム質重合体に上記
単量体がグラフトしたグラフト共重合体のグラフ
ト率は25〜80％である。この範囲内であれば、外
観特性、衝撃強度等の特性が極めて良好で、電気
冷蔵庫の壁材として使用するのに好適である。
本発明の組成物においてビニルシアン化合物単
量体、メタアクリル酸エステル単量体及びアクリ
ル酸エステル単量体の群より選ばれる１種以上の
単量体とビニル芳香族化合物単量体よりなる共重
合体中のビニルシアン化合物単量体、メタアクリ
ル酸エステル単量体及びアクリル酸エステル単量
体の群より選ばれる１種以上の単量体の重量分率
は20〜40％の範囲が好ましい。20〜40％の範囲内
であれば、薬品（食用油、アルコール等）に対す
る耐ストレスクラツク性に優れ、電気冷蔵庫の壁
材として好適に使用され、又、加工流動性も良好
でシート成形、真空成形も容易である。
熱可塑性樹脂組成物の分子量は、ゴム質重合体
にグラフト結合していないビニルシアン化合物単
量体、メタアクリル酸エステル単量体及びアクリ
ル酸エステル単量体の群より選ばれる１種以上の
単量体のビニル芳香族化合物単量体よりなる共重
合体の固有粘度により知ることができる。(A)、
(B)、(C)で生成するゴム質重合体にグラフト結合し
ていない共重合体の分子量は、最終樹脂組成物の
アセトン可溶分の固有粘度で0.3以上好ましくは
0.35以上であれば、本発明の効果が発現するので
特に分子量を限定する必要はない。熱可塑性樹脂
組成物に求められる加工性と耐衝撃性に応じ、当
業者公知の値に任意に設定すれば良い。
ここでいう固有粘度とは、メチルエチルケトン
中で測定した固有粘度の値である。
［実施例］
以下に実施例によつて本発明をさらに具体的に
説明するが、本発明の範囲はその要旨を越えない
限りこれらの実施例によつて限定されるものでは
ない。
なお、以下の実施例、比較例において部及び％
は特にことわらない限り重量部、重量％を意味す
る。
実施例及び比較例
−グラフト重合体（Ａ−１〜Ａ−９、Ｂ−１〜Ｂ
−５）−
表−１、表−２に示される組成物の全量又は一
部を反応器に仕込み、70℃で撹拌しながら重合を
行い、組成物の残りを逐次添加しながら重合を行
い、反応性単量体の転化率が99％以上になる迄重
合する。
重合完了後、塩析、脱水、乾燥を行い、二軸押
出機でペレツト化される。この時、小粒子径を有
するＡシリーズの重合体はグラフト率に応じて凝
集する。
ペレツト化された熱可塑性樹脂の物性を表−
３、表−４に示す。
−共重合体（Ｃ−１、Ｃ−２）−
表−５に示される組成物を反応器に仕込み、70
℃で撹拌しながら重合を行い、反応性単量体の転
化率が99％以上になる迄重合する。重合完了後、
塩析、脱水、乾燥後、単軸押出機でペレツトし
た。
Ｃ−１、Ｃ−２をメチルエチルケトンに溶解
し、30℃における固有粘度を測定したところそれ
ぞれ0.56、0.57であつた。
−熱可塑性樹脂組成物−
グラフト重合体（Ａ−１〜Ａ−９）ペレツトと
グラフト重合体（Ｂ−１〜Ｂ−５）ペレツトと共
重合体（Ｃ−１〜Ｃ−２）ペレツトを表−６、表
−７に示すように配合し、単軸押出機でペレツト
化した。混練後の主なる組成比を表−８、表−９
に示す。
尚、熱可塑性樹脂組成物中のゴム質重合体の重
量分率は、赤外線分光光度計を用い実測可能であ
り、これは表−６、表−７に示した各成分配合比
に基く計算値とよく一致した。
[Industrial Application Field] The present invention provides a material that has excellent stress cracking resistance against fluorocarbon gases such as fluorocarbon-11 and fluorocarbon-12, and has excellent rigidity and appearance characteristics, and is used as a wall material for insulating boxes. The present invention relates to an impact thermoplastic resin composition. [Prior art] Conventionally, heat-reinforcing polystyrene (hereinafter referred to as HIPS) sheets or acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS) sheets have been used as inner wall materials for insulating boxes such as electric refrigerators. Molded products are used. Generally, when HIPS sheets are used, whitening and cracking occur due to the fluorocarbon gas used to foam the urethane foam of the insulation material, so as a preventive measure, it is recommended to cover the molded product with a protective film such as polyethylene film. Although it has been adopted,
As a result, one step is added, which has a negative impact on production efficiency and workability. On the other hand, when an ABS sheet is used, the stress crack resistance against fluorocarbon gas is improved compared to when a HIPS sheet is used, but it is still not at a completely satisfactory level. In addition, if there is internal strain due to thermoforming or due to the difference in linear expansion coefficient between the steel plate, etc. that is the outer wall of the insulation box during cooling, and the ABS sheet that is in close contact with the urethane foam, it may be caused by the influence of fluorocarbon gas. Whitening, cracking, etc. occur. For traditional injection molding ABS resin or extrusion molding
In the case of ABS resin, it is well known that improving stress cracking resistance against fluorocarbon gas can be achieved by increasing the content of rubbery polymer. However, increasing the rubbery polymer content reduces the rigidity of the molded article. To prevent this, the sheet thickness must be increased. Furthermore, increasing the content of the rubbery polymer has the disadvantage of deteriorating the appearance of the molded product. In addition, a technology has been disclosed (Japanese Patent Laid-Open No. 53-57257) that improves strength and appearance by agglomerating rubbery polymers into a specific structure, but the stress cracking resistance against fluorocarbon gas has not reached a sufficient level. Not yet. [Problems to be Solved by the Invention] In recent years, electric refrigerators have become larger and there is a strong desire to reduce the thickness of the sheets. It has become increasingly difficult to solve the above-mentioned problems with conventional ABS resin. From this point of view, the present inventors have conducted extensive research into impact-resistant thermoplastic resin compositions that have excellent stress cracking resistance against fluorocarbon gas, as well as excellent rigidity and appearance characteristics, and as a result, have arrived at the present invention. [Means and effects for solving the problems] That is, the gist of the present invention is to provide a monomer selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers. A copolymer consisting of at least one type of monomer and a vinyl aromatic compound monomer, and one or more types selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers. In a thermoplastic resin composition comprising a graft copolymer in which a vinyl aromatic compound monomer is grafted onto a rubbery polymer and the graft ratio is 25 to 80%, the rubber in the thermoplastic resin composition is The weight fraction of the quality polymer is in the range of 10 to 25%, and (a) the average particle size is
Rubbery polymer particles of 0.2μ or less have an average particle size of 0.5~
The weight fraction of the rubbery polymer that aggregates within the size range of 2.0μ is 25 to 25% of the total amount of rubbery polymer.
(b) The weight fraction of non-agglomerated rubbery polymer with an average particle size of 0.5μ or more is in the range of 10 to 60% of the total amount of rubbery polymer. It is an impact thermoplastic resin composition. The average particle diameter of the rubbery polymer particles referred to here is based on the Journal of Electron Microscopy, Vol. 14, p. 222 (1965).
Only the rubbery polymer was stained by the fixation staining method using osmium tetroxide, which is described in Polymer Eng. & Sci., Vol. 7, p. 38 (1967). This is what was observed and measured below. The average particle diameter represents the arithmetic average value of the major axis and minor axis of the rubbery polymer particle diameter. The average particle diameter of the rubbery polymer aggregate also represents the arithmetic average value of the major axis and the minor axis. The weight fraction of the aggregate is expressed by the following formula. Weight fraction (%) = ΣNiDi 3 /Σnidi 3 ×100 where ni is the number of particles present in the electron micrograph with an average particle diameter of di (i.e. di, ni is
The average particle size and number of rubbery polymer particles of 0.2 μ or less, rubbery polymer particles formed by agglomeration, and rubbery polymer particles of 0.5 μ or more and not involved in aggregation. be. ). Ni is a rubber substance present in electron micrographs whose average particle size is Di (Di is the average particle size of the aggregated rubbery polymer, and the average particle size of the rubbery polymer is in the range of 0.5 to 2.0μ). is the number of polymer particles. The weight fraction of the non-agglomerated rubbery polymer with an average particle diameter of 0.5μ or more is expressed by the following formula. Weight fraction (%) = ΣMiRi 3 /Σnidi 3 ×100 Here, Mi is the average particle diameter Ri (Ri is the average particle diameter
This is the number of rubbery polymer particles present in an electron micrograph with an average particle diameter of 0.5μ or more and not involved in aggregation. The number of rubbery polymer particles read by electron micrograph is preferably 500 or more. The thermoplastic resin composition comprises a rubbery polymer having an average particle size of 0.2μ or less and one or more monomers selected from the group consisting of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers. a graft copolymer (A) obtained by graft copolymerization of a copolymer consisting of a vinyl aromatic compound monomer and a vinyl aromatic compound monomer;
Graft copolymer (B) obtained by performing the same graft copolymerization as (A) on a rubbery polymer containing particles of 0.5μ or more.
It is distinctive in that it is used in combination. Average particle size 0.2μ
0.5 to 2μ obtained by agglomerating the following rubbery polymers
The aggregated rubber particles (a) are mainly made of graft copolymer
Non-agglomerated rubber particles (b) derived from (A) and having an average particle diameter of 0.5 μ or more are mainly derived from the graft copolymer (B). However, since there is a distribution in the particle size of the rubbery polymer that is the raw material for both (A) and (B), it is not always the case that (A) =
(B) and (B) do not hold. In addition, one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers and vinyl aromatic compound monomers constituting the thermoplastic resin composition. The copolymer consisting of polymers (A) and (B) is produced without being grafted onto the rubbery polymer, or the copolymer is created separately from the grafting reaction of the above copolymer onto the rubbery polymer. It is obtained by adding (C) to (A) and (B). The rubbery polymer particles are made of one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers, and a vinyl aromatic compound monomer. The particles may contain a small amount of a copolymer as an occlusion component. The graft ratio in the present invention is determined by the following formula by dissolving a certain weight of resin in acetone, separating the acetone-insoluble content using a centrifuge, drying, and weighing. Grafting rate (%) = (weight of acetone insoluble matter/weight of rubbery polymer - 1)
×100 Moreover, the above formula can be rewritten as follows. ●Amount of graft copolymer (%) = Amount of rubbery polymer (%) x (1 + graft ratio/100) ●Amount of copolymer (%) = 100 - Amount of graft copolymer (%) In other words, vinyl cyanide compound A copolymer consisting of a vinyl aromatic compound monomer and one or more monomers selected from the group of monomers, methacrylic acid ester monomers, and acrylic acid ester monomers does not necessarily contain component (C). Although it is generated during the copolymerization reaction of components (A) and (B), it is possible to know the copolymer content at the same time when measuring the graft ratio. Next, the constituent elements of the present invention will be explained in detail. The rubbery polymer referred to in the present invention is polybutadiene and a butadiene copolymer containing butadiene as a main component, preferably polybutadiene. When using a butadiene copolymer, a copolymer containing 70% by weight or more of butadiene is preferred from the viewpoint of improving impact resistance at low temperatures. As the rubbery polymer, rubbery polymers obtained by currently known polymerization methods, such as emulsion polymerization, solution polymerization, and ionic polymerization, can be used. In the present invention, one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers and the vinyl aromatic compound monomer are combined into a rubbery polymer. The grafted copolymer (hereinafter abbreviated as graft copolymer) is a rubbery polymer containing one selected from the group consisting of a vinyl cyanide compound monomer, a methacrylic acid ester monomer, and an acrylic acid ester monomer.
It is obtained by graft polymerization of a mixture of more than one type of monomer and a vinyl aromatic compound monomer. The weight fraction of the rubbery polymer in the polymer is preferably 5 to 60%,
More preferably 10-50%. The grafted rubbery polymer can be produced by any of the currently known polymerization methods, such as emulsion polymerization, solution polymerization, bulk polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. It's okay. There are currently known methods for aggregating rubbery polymers with an average particle size of 0.2μ or less, such as adding an electrolyte or an acid anhydride to a rubbery polymer latex and aggregating it, or freezing the rubbery polymer latex. A method of aggregating a rubbery polymer with one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers and vinyl aromatic compound monomers. Salting out the latex obtained by graft polymerization of the body mixture,
Any method may be used, such as a method of dehydrating, drying, melt-kneading, and aggregating. A method of blending a non-agglomerated rubbery polymer with an average particle size of 0.5μ or more and an agglomerated rubbery polymer with an average particle size in the range of 0.5 to 2.0μ is, for example, a method of blending an agglomerated rubbery polymer latex with an average particle size of A method of blending a non-agglomerated rubbery polymer latex with a size of 0.5μ or more, in which each rubbery polymer latex is blended with a group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers. A method of blending a latex obtained by graft polymerization of a mixture of one or more selected monomers and a vinyl aromatic compound monomer, a method of pelletizing a thermoplastic resin containing individual rubbery polymers, and blending the pellets with each other. This includes how to do so. Vinyl aromatic compound monomers referred to in the present invention include, for example, styrene, methylstyrene, vinyltoluene,
Includes ethylstyrene, dimethylstyrene, butylstyrene, dichlorostyrene, etc. Moreover, a mixture of two or more of these can also be used. The vinyl cyanide compound monomer referred to in the present invention includes, for example, acrylonitrile, methacrylonitrile, and the like. Examples of the methacrylic acid ester monomer include methyl, ethyl, propyl butyl, and phenyl esters of methacrylic acid. Examples of acrylic acid ester monomers include methyl, ethyl, propyl, butyl, and phenyl esters of acrylic acid. A copolymer consisting of a vinyl aromatic compound monomer and one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers has a rubbery property. Formed when a vinyl aromatic compound monomer is graft-polymerized with one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers. It will be done.
Also, currently known methods such as emulsion polymerization method,
One or more types selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers by solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, etc. A copolymer consisting of a monomer and a vinyl aromatic compound monomer is made, and the weight fraction of the thermoplastic resin containing the graft copolymer and the rubbery polymer is in the range of 10 to 25%. It may be added to. The blending method may be any method such as latex-on-latex, flake-on-flake, pellet-on-pellet, pellet-flake, etc. The feature of the present invention is that the rubbery polymer is a mixture of a rubbery polymer obtained by agglomerating small particle rubbery polymers and a non-agglomerated rubbery polymer having an average particle size of 0.5 μm or more. The weight fraction of the rubbery polymer in the thermoplastic resin composition can range from 10 to 25%. If it is less than 10%, the impact strength and stress crack resistance against chlorofluorocarbon gas will be significantly reduced, making it unusable as a wall material for electric refrigerators, etc. If the weight fraction exceeds 25%, the rigidity and appearance characteristics will deteriorate, which is not preferable. Rubber polymers with an average particle diameter of 0.2 μ or less are aggregated in a size range of 0.5 to 2.0 μ.The weight fraction of the rubber polymer is 25 to 80.
% range can be used. Weight fraction is 25
If it is less than 80%, the stress crack resistance against fluorocarbon gas will decrease, and if it exceeds 80%, the impact strength will decrease and the appearance characteristics will deteriorate, which is not preferable. If the size of the aggregates exceeds 2.0μ, the number of aggregates decreases, resulting in a decrease in stress crack resistance against fluorocarbon gas. In addition, the appearance characteristics are significantly deteriorated, so that it cannot be used as a wall material for electric refrigerators, etc. If it is less than 0.5 μm, the stress crack resistance against fluorocarbon gas is also lowered, which is not preferable. The average particle size of the rubbery polymer constituting the aggregate is
If it exceeds 0.2μ, the number of rubbery polymer particles constituting the aggregate decreases, resulting in a decrease in stress crack resistance against fluorocarbon gas, which is not preferable. The rubbery polymer can be used in a range of 10 to 60% by weight of non-agglomerated rubbery polymer with a size of 0.5μ or more. If it is less than 10%, the impact strength and appearance properties are greatly reduced and cannot be used. If it exceeds 60%, the stress crack resistance against fluorocarbon gas decreases and it cannot withstand use. As long as the above requirements are satisfied, rubbery polymer particles of 0.5 μm or less may be dispersed in the composition without agglomerating. In the composition of the present invention, the graft copolymer obtained by grafting the above monomer onto a rubbery polymer has a grafting ratio of 25 to 80%. Within this range, properties such as appearance and impact strength are extremely good, and it is suitable for use as a wall material for an electric refrigerator. In the composition of the present invention, a copolymer comprising one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers and a vinyl aromatic compound monomer. The weight fraction of one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers in the polymer is preferably in the range of 20 to 40%. . If it is within the range of 20 to 40%, it has excellent stress crack resistance against chemicals (edible oil, alcohol, etc.) and is suitable for use as a wall material for electric refrigerators.It also has good processing fluidity and can be used for sheet forming, Vacuum forming is also easy. The molecular weight of the thermoplastic resin composition is determined by one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers that are not graft-bonded to the rubbery polymer. It can be determined from the intrinsic viscosity of a copolymer made of a vinyl aromatic compound monomer. (A),
The molecular weight of the copolymer not grafted to the rubbery polymer produced in (B) and (C) is preferably 0.3 or more based on the intrinsic viscosity of the acetone soluble portion of the final resin composition.
As long as it is 0.35 or more, the effect of the present invention is exhibited, so there is no need to particularly limit the molecular weight. It may be arbitrarily set to a value known to those skilled in the art, depending on the processability and impact resistance required of the thermoplastic resin composition. The intrinsic viscosity here is the value of intrinsic viscosity measured in methyl ethyl ketone. [Examples] The present invention will be explained below in more detail with reference to Examples, but the scope of the present invention is not limited by these Examples unless the scope of the present invention goes beyond the gist thereof. In addition, in the following examples and comparative examples, parts and %
means parts by weight or weight % unless otherwise specified. Examples and Comparative Examples - Graft polymers (A-1 to A-9, B-1 to B
-5)- Charge all or part of the compositions shown in Tables 1 and 2 into a reactor, perform polymerization while stirring at 70°C, and perform polymerization while sequentially adding the rest of the composition, Polymerization is carried out until the conversion rate of the reactive monomer reaches 99% or more. After completion of polymerization, salting out, dehydration, and drying are performed, followed by pelletization using a twin-screw extruder. At this time, the A series polymers having small particle diameters aggregate depending on the grafting rate. Table of physical properties of pelletized thermoplastic resin.
3. Shown in Table-4. - Copolymer (C-1, C-2) - Charge the composition shown in Table 5 into a reactor, and
Polymerization is carried out at °C with stirring until the conversion of the reactive monomer reaches 99% or more. After polymerization is complete,
After salting out, dehydration, and drying, it was pelletized using a single screw extruder. When C-1 and C-2 were dissolved in methyl ethyl ketone and their intrinsic viscosities at 30°C were measured, they were 0.56 and 0.57, respectively. - Thermoplastic resin composition - Graft polymer (A-1 to A-9) pellets, graft polymer (B-1 to B-5) pellets, and copolymer (C-1 to C-2) pellets are shown below. -6, the mixture was blended as shown in Table-7 and pelletized using a single screw extruder. The main composition ratios after kneading are shown in Table-8 and Table-9.
Shown below. The weight fraction of the rubbery polymer in the thermoplastic resin composition can be measured using an infrared spectrophotometer, and this is a calculated value based on the compounding ratio of each component shown in Tables 6 and 7. agreed well.
【表】
単位は部数
【table】
Unit is number of copies
【表】【table】
【表】【table】
【表】【table】
【表】
単位は部数
[Table] Unit is number of copies
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
電気冷蔵庫等の断熱箱体の壁材として使用でき
る基準は衝撃強度、耐フロン性、耐薬品性は〇で
あること、流動性、引張強度、外観は△以上であ
ること、である。表−10より明らかなように、本
発明組成物はフロンガスに対する耐ストレスクラ
ツク性に優れ、かつ剛性、外観特性に優れた耐衝
撃性樹脂である。
表−11よりわかるように、凝集したゴム質重合
体の量が増加するにつれて、フロンガスに対する
耐ストレスクラツク性は向上するが、外観、衝撃
強度が低下する。又、凝集したゴム質重合体の量
が25％未満では、フロンガスに対する耐ストレス
クラツク性が低下する。
本発明組成物は工業的観点からも有用である。[Table] Standards for use as wall materials for insulated boxes such as electric refrigerators are that impact strength, fluorocarbon resistance, and chemical resistance must be ○, and fluidity, tensile strength, and appearance must be △ or higher. . As is clear from Table 10, the composition of the present invention is an impact-resistant resin that has excellent stress crack resistance against fluorocarbon gas, as well as excellent rigidity and appearance characteristics. As can be seen from Table 11, as the amount of aggregated rubbery polymer increases, stress crack resistance against fluorocarbon gas improves, but appearance and impact strength decrease. Furthermore, if the amount of aggregated rubbery polymer is less than 25%, the stress crack resistance against fluorocarbon gas will decrease. The composition of the present invention is also useful from an industrial standpoint.
Claims (1)
エステル単量体及びアクリル酸エステル単量体の
群より選ばれる１種以上の単量体とビニル芳香族
化合物単量体よりなる共重合体と、ビニルシアン
化合物単量体、メタアクリル酸エステル単量体及
びアクリル酸エステル単量体の群より選ばれる１
種以上の単量体とビニル芳香族化合物単量体がポ
リブタジエン又はブタジエンを主成分とするブタ
ジエン共重合体（以下ゴム質重合体と略す）にグ
ラフトしたグラフト率が25〜80％のグラフト共重
合体とよりなる熱可塑性樹脂組成物において、熱
可塑性樹脂組成物中のゴム質重合体の重量分率が
10〜25％の範囲にあり、(イ)平均粒子径が0.2μ以下
のゴム質重合体粒子が平均粒子径0.5〜2.0μの大
きさの範囲に凝集しているゴム質重合体の重量分
率が全体のゴム質重合体量に対して25〜80％の範
囲にあり、(ロ)平均粒子径が0.5μ以上の凝集してい
ないゴム質重合体の重量分率が全体のゴム質重合
体量に対して10〜60％の範囲にあることを特徴と
する耐衝撃性熱可塑性樹脂組成物。 ２ ビニルシアン化合物単量体、メタアクリル酸
エステル単量体及びアクリル酸エステル単量体の
群より選ばれる１種以上の単量体とビニル芳香族
化合物単量体よりなる共重合体中のビニルシアン
化合物単量体、メタアクリル酸エステル単量体及
びアクリル酸エステル単量体の群より選ばれる１
種以上の単量体の重量分率が20〜40％の範囲にあ
る特許請求の範囲第１項記載の耐衝撃性熱可塑性
樹脂組成物。[Scope of Claims] 1 Consisting of one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers and a vinyl aromatic compound monomer copolymer, and 1 selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers.
Graft copolymer with a graft ratio of 25 to 80%, in which more than one type of monomer and a vinyl aromatic compound monomer are grafted onto polybutadiene or a butadiene copolymer (hereinafter referred to as rubbery polymer) whose main component is butadiene. In a thermoplastic resin composition consisting of coalescence, the weight fraction of the rubbery polymer in the thermoplastic resin composition is
The weight of the rubbery polymer is in the range of 10 to 25%, and (a) rubbery polymer particles with an average particle size of 0.2μ or less are aggregated in the size range of 0.5 to 2.0μ. (b) The weight fraction of non-agglomerated rubbery polymers with an average particle size of 0.5μ or more is in the range of 25 to 80% of the total rubbery polymer weight. An impact-resistant thermoplastic resin composition characterized in that the amount of the resin is in the range of 10 to 60% based on the combined amount. 2 Vinyl in a copolymer consisting of a vinyl aromatic compound monomer and one or more monomers selected from the group of vinyl cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers 1 selected from the group of cyanide compound monomers, methacrylic acid ester monomers, and acrylic acid ester monomers
The impact-resistant thermoplastic resin composition according to claim 1, wherein the weight fraction of one or more monomers is in the range of 20 to 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5691681A JPH0227378B2 (en) | 1981-04-17 | 1981-04-17 | TAISHOGEKISEINETSUKASOSEIJUSHISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5691681A JPH0227378B2 (en) | 1981-04-17 | 1981-04-17 | TAISHOGEKISEINETSUKASOSEIJUSHISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57172947A JPS57172947A (en) | 1982-10-25 |
| JPH0227378B2 true JPH0227378B2 (en) | 1990-06-15 |
Family
ID=13040794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5691681A Expired - Lifetime JPH0227378B2 (en) | 1981-04-17 | 1981-04-17 | TAISHOGEKISEINETSUKASOSEIJUSHISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0227378B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2596634B2 (en) * | 1990-08-03 | 1997-04-02 | 宇部サイコン株式会社 | Insulation box |
| KR100396402B1 (en) * | 2000-12-21 | 2003-09-02 | 제일모직주식회사 | Thermoplastic Resin Composition Having Excellent Chemical Resistance And Easy Vacuum Formability |
-
1981
- 1981-04-17 JP JP5691681A patent/JPH0227378B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57172947A (en) | 1982-10-25 |
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