JPH0457705B2 - - Google Patents
Info
- Publication number
- JPH0457705B2 JPH0457705B2 JP61129940A JP12994086A JPH0457705B2 JP H0457705 B2 JPH0457705 B2 JP H0457705B2 JP 61129940 A JP61129940 A JP 61129940A JP 12994086 A JP12994086 A JP 12994086A JP H0457705 B2 JPH0457705 B2 JP H0457705B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- graft
- graft copolymer
- 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
- 229920000578 graft copolymer Polymers 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 46
- 238000010559 graft polymerization reaction Methods 0.000 claims description 26
- 238000007747 plating Methods 0.000 claims description 25
- 239000011342 resin composition Substances 0.000 claims description 25
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000000178 monomer Substances 0.000 description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 31
- 229920002554 vinyl polymer Polymers 0.000 description 26
- 229920000126 latex Polymers 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000005060 rubber Substances 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 229920003051 synthetic elastomer Polymers 0.000 description 11
- 239000005061 synthetic rubber Substances 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012784 inorganic fiber Substances 0.000 description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000008121 dextrose Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- -1 1,3-butylene Chemical group 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、透光性に優れ、かつメツキ可能な新
規な耐衝撃性可塑性熱樹脂組成物に関する。
〔従来の技術〕
近年、オーデイオ部品、自動車フロントパネル
等の分野で、機能の作動状態をより明確に確認で
きるように、文字や図形をLEDランプ等を使用
して内側から照らし出す表示方法を用いたスイツ
チ類が採用されている。このような材料にはデザ
インの自由度の点から熱可塑性樹脂を用いること
が好ましいが、透光性に加え金属感を出す目的で
メツキを施すことが不可欠である。
従来、このような製品には透光性を有するポリ
スチレンあるいはアクリル樹脂等とメツキ性の優
れたABS樹脂等の二重成形品が使用されていた
が、このものは、特殊な金型を必要とするため多
様化されたデザインに対応することができず、成
形操作が煩雑であり、さらにポリスチレンあるい
はアクリル樹脂とABS樹脂の境界面でメツキ不
良の問題がある。また。従来のABS樹脂はメツ
キ性に優れているものの、透光性が劣つている。
従つてこれらの問題を一挙に解決できる透光性に
優れ、かつメツキ可能な耐衝撃性熱可塑性樹脂の
出現が望まれていた。
一方、ABS樹脂の特殊グレードとして透明
ABS樹脂が知られている（米国特許第2843561
号、同第3029223号明細書及び特公昭35−4889号
公報参照）。しかしこれらの樹脂は、ゴムとマト
リツクス樹脂の屈折率を一致させる目的でメチル
メタクリレートモノマーが使用されており、メツ
キ性が劣つているので、前記の用途には使用でき
ない。
〔発明が解決しようとする問題点〕
本発明者らは上述した如き現状に鑑み、透光性
に優れ、かつ高温成形時においてもメツキ性能に
優れた耐衝撃性熱可塑性樹脂組成物を得るべく鋭
意検討した結果、使用するゴムの粒径ならびに架
橋構造、さらにはグラフト率を特定の範囲に設定
した場合に初期の目的が達成せられることを見出
した。
〔問題点を解決するための手段〕
本発明の要旨は、１，３−ブタジエン50〜100
重量％及びスチレン０〜50重量％から得られるゲ
ル分率60％以上で、かつ0.04〜0.15μの平均粒子
径を有する合成ゴム(A)ラテツクス15〜80重量部
（固形分として）に対し、芳香族ビニルモノマー
60〜80重量％及びシアン化ビニルモノマー20〜40
重量％からなるモノマー混合物(B)20〜85重量％
〔(A)と(B)の合計量は100重量部〕をグラフト重合さ
せて得られる20〜180％のグラフト率を有するグ
ラフト共重合体（）と、芳香族ビニルモノマー
60〜80重量％及びシアン化ビニルモノマー20〜40
重量％から得られた共重合体（）とが、グラフ
ト共重合体（）と共重合体（）の合計量中の
合成ゴム(A)の含有量が５〜30重量％となるように
配合された配合物と、0.2〜0.4μの平均粒子径を
有するブタジエン系ゴム(C)ラテツクス15〜75重量
部（固形分として）に対し、芳香族ビニルモノマ
ー60〜80重量％及びシアン化ビニルモノマー20〜
40重量％からなるモノマー混合物(D)25〜85重量部
〔(C)と(D)の合計量は100重量部〕をグラフト重合さ
せて得られる20〜100％のグラフト率を有するグ
ラフト共重合体（）とが、全組成物中のブタジ
エン系ゴム(C)の含有量が４〜15重量％になるよう
に配合されてなる良好な透 性及びメツキ性を有
する耐衝撃性熱可塑性樹脂組成物である。
本発明において、合成ゴム(A)のゲル分率及びグ
ラフト共重合体（）及び（）のグラフト率
は、次のように定義される。
ゲル分率：
凝集し乾燥したゴムを一定量秤取し（W0）、50
倍量のトルエン中で30℃で48時間放置する。トル
エン不溶の凝集ゴムを物別し、これを乾燥し、秤
量する（W1）。ゲル分率は下記の式で示される。
ゲル分率（％）＝W1／W0×100
グラフト率：
凝集し乾燥したグラフトゴムを一定量秤取し
（W0）、50倍量のアセトン中で60℃で２時間還流
する。遠心分離によりアセトン不溶のグラフトゴ
ムを分別し、これを乾燥し、秤量する（W1）。グ
ラフトゴム中の合成ゴム(A)の含量をＡ％とすると
グラフト率は次式により算出される。
グラフト率（％）＝W1−〔W0×Ａ／100〕／W0×Ａ／100
×100
本発明におけるグラフト共重合体（）を構成
する合成ゴム(A)は、１，３−ブタジエン50〜100
重量％及びスチレン０〜50重量％から構成される
ものであり、60％以上のゲル分率ならびに0.04〜
0.15μの平均粒子径を有する。これらの合成ゴム
は、通常は公知の乳化重合により製造することが
できる。その粒子径が0.15μを超えると透光性が
著しく低下し、また粒子径が0.04μ未満になると
衝撃強度が低下するので好ましくない。さらにゲ
ル分率が60％未満であると成形時にゴムの変形が
生じやすく、表面光沢が悪化する。
グラフト重合において、合成ゴム(A)15〜80重量
％、好ましくは30〜65重量部に対してグラフト重
合用モノマー混合物(B)は20〜85重量部、好ましく
は35〜70重量部〔(A)と(B)の合計量は100重量部〕
の量で使用される。合成ゴム(A)が15重量部未満で
あると生産性に乏しく実用的でなく、また80重量
部を超えるとグラフト共重合体（）を芳香族ビ
ニルモノマーシアン化ビニルモノマー共重合体
（）及び所望によりグラフト共重合体（）と
溶融混合して得られる樹脂組成物中でグラフト共
重合体（）が一部凝集したままで分散し、成形
外観、透光性、メツキ特性が低下するおそれがあ
り好ましくない。
グラフト重合用モノマー混合物(B)は芳香族ビニ
ルモノマー及びシアン化ビニルモノマーの混合物
であり、芳香族ビニルモノマー60〜80重量部、好
ましくは65〜75重量％及びシアン化ビニルモノマ
ー20〜40重量％、好ましくは25〜35重量％の混合
比でグラフト重合に用いられる。
芳香族ビニルモノマーとしては、例えばスチレ
ン、α−メチルスチレン、アルキル核置換スチレ
ン等が挙げられ、スチレンが好ましい。またシア
ン化ビニルモノマーとしては、例えばアクリロニ
トリル、メタクリロニトリル等が挙げられ、アク
リロニトリルが好ましい。シアン化ビニルモノマ
ーが40重量％を超える混合比でグラフト重合を行
うと、グラフト重合の際にシアン化ビニル単独重
合体が生成し、得られる組成物の着色の原因とな
り好ましくない。またシアン化ビニルモノマーが
20重量％未満の混合比でグラフト重合を行うと、
得られる組成物のメツキ特性が低下するため好ま
しくない。
この乳化グラフト重合に際しては、通常は公知
の乳化剤、開始剤及び連鎖移動剤が使用される。
なおグラフト重合用モノマー混合物(B)はゴムラテ
ツクス中に一度に加えてもよく、分割添加又は連
続添加を行うこともできるが、分割添加又は連続
添加が好ましい。乳化剤、開始剤、連鎖移動剤等
の種類、添加量ならびにモノマーの添加方法につ
いては、得られるグラフト共重合体（）のグラ
フト率が20〜180％となるように選ばれる。グラ
フト率が20％未満であると透光性が著しく低下し
たり、メツキ密着強度も悪くなる傾向となりやす
いため好ましくない。またグラフト率が180％を
超えると衝撃強度が著しく低下し、また流動性も
悪くなることからグラフト共重合体（）のグラ
フト率を20〜180％の範囲に制御すことが必要で
ある。
芳香族ビニルモノマー−シアン化ビニルモノマ
ー共重合体（）は、芳香族ビニルモノマー60〜
80重量％、好ましくは65〜75重量％及びシアン化
ビニルモノマー20〜40重量％、好ましくは25〜35
重量％を重合させて得られる共重合体である。芳
香族ビニルモノマーとしては、例えばスチレン、
α−メチルスチレン、アルキル核置換スチレンが
挙げられ、スチレンが好ましい。またシアン化ビ
ニルモノマーとしては、アルリロニトリル、メタ
クリロニトリル等が挙げられ、アクリロニトリル
が好ましい。グラフト重合用モノマー混合物の場
合と同様にシアン化ビニルモノマーの量が40重量
％を超えると着色しやすく、また20重量％未満で
はメチキ性が低下するため好ましくない。この芳
香族ビニルモノマー−シアン化ビニルモノマー共
重合体（）の重合方法は特に限定されるもので
はなく、公知の塊状重合法、懸濁重合法又は乳化
重合法が用いられる。
本発明の熱可塑性樹脂組成物は上記グラフト共
重合体（）と芳香族ビニルモノマー−シアン化
ビニルモノマー共重合体（）を上記特定の範囲
となるように配合したものを基本構成とするが、
さらにこの配合物に、0.2〜0.4μの平均粒子径を
有するブタジエン系ゴム(C)ラテツクス15〜75重量
部（固形分として）に対し、芳香族ビニルモノマ
ー60〜80重量％及びシアン化ビニルモノマー20〜
40重量％からなるモノマー混合物(D)25〜85重量部
〔(C)と(D)の合計量は100重量部〕をグラフト重合さ
せて得られる20〜100％のグラフト率を有するグ
ラフト共重合体（）を、グラフト共重合体
（）、芳香族ビニルモノマー−シアン化ビニルモ
ノマー共重合体（）及びグラフト共重合体
（）からなる全組成物中におけるグラフト共重
合体（）を構成するブタジエン系ゴム(C)の含有
量が４〜15重量％になるように所望により配合す
ることにより、熱可塑性樹脂組成物の特性、特に
耐衝撃性をより高めることができる。
グラフト共重合体（）を構成するブタジエン
系ゴム(C)としてはポリブタジエン、ブタジエン−
スチレン共重合体、ブタジエン−アクリロニトリ
ル共重合体、ブタジエン−アクリル酸アルキルエ
ステル共重合体及びブタジエン−メタクリル酸ア
ルキルエステル共重合体等が挙げられる。これら
のブタジエン系ゴムは、通常は公知の乳化重合に
より製造することができる。その粒子径が0.2μ未
満では充分な衝撃強度が得られず、また粒子径が
0.4μを超えると透光性が低下するので好ましくな
い。
グラフト重合において、ブタジエン系ゴム(C)15
〜75重量部に対してグラフト重合用モノマー混合
物(D)は25〜85重量部〔(C)と(D)の合計量は100重量
部〕の量で使用される。ブタジエン系ゴム(C)が15
重量部未満では衝撃強度発現性に乏しく、75重量
部を超えるとグラフト共重合体（）及び芳香族
ビニルモノマー−シアン化ビニルモノマー共重合
体（）の配合物への分散不良を起し成形外観が
悪くなるので好ましくない。
グラフト重合用モノマー混合物(D)は芳香族ビニ
ルモノマー及びシアン化ビニルモノマーの混合物
であり、芳香族ビニルモノマー60〜80重量％、好
ましくは65〜75重量％及びシアン化ビニルモノマ
ー20〜40重量％、好ましくは25〜35重量％の混合
比でグラフト重合に用いられる。
芳香族ビニルモノマーとしては、例えばスチレ
ン、α−メチルスチレン、アルキル核置換スチレ
ン等が挙げられ、スチレンが好ましい。またシア
ン化ビニルモノマーとしては、例えばアクリロニ
トリル、メタクリロニトリル等が挙げられ、アク
リロニトリルが好ましい。シアン化ビニルモノマ
ーが40重量％を超える混合比でグラフト重合を行
うと、グラフト重合の際にシアン化ビニル単独重
合体が生成し、得られる組成物の着色の原因とな
り好ましくない。またシアン化ビニルモノマーが
20重量％未満の混合比でグラフト重合を行うと、
得られる組成物のメツキ特性が低下するため好ま
しくない。
この乳化グラフト重合に際しては、通常は公知
の乳化剤、開始剤及び連鎖移動剤が使用される。
なおグラフト重合用モノマー混合物(D)はゴムラテ
ツクス中に一度に加えてもよく、分割添加又は連
続添加を行うこともできるが、分割添加又は連続
添加が好ましい。乳化剤、開始剤、連鎖移動剤等
の種類、添加量ならびにモノマーの添加方法につ
いては、得られるグラフト共重合体（）のグラ
フト率が20〜100％となるように選ばれる。グラ
フト率が20％未満であると透光性が低下しやすく
なるため好ましくない。またグラフト率が100％
を超えると衝撃強度が低下することからグラフト
共重合体（）のグラフト率を20〜100％の範囲
に制御することが必要である。なおグラフト率の
定義はグラフト共重合体（）の場合と同じであ
る。
こうして得られたグラフト共重合体（）と、
芳香族ビニルモノマー−シアン化ビニルモノマー
共重合体（）とが、グラフト共重合体（）と
共重合体（）の合計量中の合成ゴム(A)の含有量
が５〜30重量％となるように配合され、かつこの
配合物にさらにグラフト共重合体（）が全組成
物〔グラフト共重合体（）と共重合体（）及
びグラフト共重合体（）の合計〕中のブタジエ
ンゴム(C)の含有量が４〜15重量％になるように配
合されることにより透光性、メツキ性に優れる耐
衝撃性熱可塑性樹脂組成物が得られる。
グラフト共重合体（）と共重合体（）の合
計量中の合成メツキ(A)の含有量が５重量％未満に
なると、メツキ性が低下し耐衝撃性が低くなるた
め実用的価値はなくなる。また30重量％を超える
と透光性及びメツキ性が低下し、流動性及び加工
性も悪化するので好ましくない。さらにグラフト
共重合体（）は所望により配合されるが、全組
成物〔グラフト共重合体（）と共重合体（）
及びグラフト共重合体（）の合計〕中のブタジ
エンゴム(C)の含有量が４重量％未満になると耐衝
撃性が低下し好ましくなく、また15重量％を超え
ると曇価が上昇し実用上好ましくない。
グラフト共重合体（）は単独で、あるいはゴ
ムのゲル分率及び粒子径、グラフト重合用モノマ
ーの種類及び量、グラフト率等が前記の特定の範
囲内にある２種以上のグラフト共重合体（）の
混合物として使用することができる。芳香族ビニ
ルモノマー−シアン化ビニルモノマー共重合体
（）も２種以上併用してもよい。さらにグラフ
ト共重合体（）は単独で、あるいはゴムの粒子
径、グラフト重合用モノマーの種類及び量、グラ
フト率等が前記の特定の範囲内にある２種以上の
グラフト共重合体（）の混合物として使用する
ことができる。
グラフト共重合体（）と芳香族ビニルモノマ
ー−シアン化ビニルモノマー共重合体（）及び
グラフト共重合体（）とを配合するには、共重
合体（）が乳化重合により製造される場合は三
者をエマルジヨンの状態で配合することが可能で
ある。そのほか三者を粉体として、あるいは粉体
とビーズ、ペレツト等との組み合わせにより、ヘ
ンシエルミキサー、押出機、バンバリーミキサ
ー、加熱ロール等の各種機器を使用して混練配合
することもできる。
本発明の樹脂組成物には、必要により抗酸化
剤、滑剤、着色剤、帯電防止剤、分散剤、充填剤
等の普通の助剤を添加することができる。
〔実施例〕
下記実施例中の「部」及び「％」はそれぞれ重
量部及び重量％を意味する。衝撃強度はASTM
Ｄ−256により、光学特性はASTM Ｄ−1003−
61に準じ板厚1.5mmの試料について日本精密光学
製の積分球式ヘーズメーターを用いて測定した。
成形外観及びメツキ特性は下記の方法によりそれ
ぞれ測定した。
成形外観：
５オンスのスクリユー型射出成形機（山城製
機株式会社製）を用い、シリンダー温度250℃
及び290℃、金型温度60℃の条件で板厚３mmの
平板を成形し、色調、光沢を観察した。
メツキ特性：
成形外観判定用平板試片を用い、膜厚約35μの
電気銅メツキを施したのち、表面外観を観察し、
メツキ膜を30mm／分の速度で直角方向に剥離する
ことにより密着強度を測定した。
流動性、成形外観及びメツキ表面外観の評価：
◎：非常に良好
○：良好
△：やや不良
×：不良
メツキ密着強度の評価：
◎：1.5Kg／cm以上
○：1.0〜1.5Kg／cm
△：0.5〜1.0mm／cm
×：０〜0.5cm／cm
実施例 １
合成ゴム（Ａ−１）の合成：
1.3−ブタジエン 75部
スチレン 25部
１，３−ブチレンメジタクリレート 0.5部
オレイン酸カリウム 1.0部
不均化ロジン酸カリウム 1.0部
ジイソプロピルベンゼンパーオキシド 0.2部
硫酸第１鉄 0.005部
ピロリン酸ソーダ 0.5部
デキストローズ 0.3部
水 200部
上記組成に従つて100オートクレーブを用い、
50℃で重合を行つた。９時間でほぼ重合は完結
し、重合率98％、粒子径0.092μ、ゲル分率99％の
ゴムラテツクスが得られた。
グラフト共重合体（Ｇ−１）の合成：
ゴムラテツクス（Ａ−１）30（固形分として）
スチレン 49部
アクリロニトリル 21部
不均化ロジン酸カリウム 1.0部
クメンヒドロパーオキシド 0.35部
硫酸第１鉄 0.01部
ピロリン酸ソーダ 0.2部
デキストローズ 0.35部
ｔ−ドデシルメルカプタン 0.7部
水 200部（ゴムラテツクス中の水を含む）
ゴムラテツクス（Ａ−１）を用いて、上記組成
に従つてグラフト共重合体（Ｇ−１）を合成し
た。重合温度は70℃、重合時間は４時間である。
スチレン、アクリロニトリルにクメンヒドロパー
オキシド及びｔ−ドデシルメルカプタンを混合溶
解し、これをゴムラテツクス（Ａ−１）に２時間
で滴下した。重合率は97.2％、グラフト率は51％
であつた。得られたグラフト共重合体ラテツクス
に抗酸化剤としてブチル化ヒドロキシトルエン２
部及びジラウリルチオプロピオネート0.5部を加
え、５％硫酸水溶液で凝固し、洗浄し、乾燥して
白色粉末を得た。
スチレン−アクリロニトリル共重合体（Ｍ−
１）の合成：
スチレン 70部
アクリロニトリル 30部
リン酸カルシウム 1.0部
GAFAC GB520（分散助剤、東邦化学(株)製）
0.003部
ラウリルパ−オキシド 0.6部
ｔ−ドデシルメルカプタン 0.5部
水 200部
上記組成に従つてスチレン−アクリロニトリル
共重合体を合成した。重合温度は80℃、重合時間
は６時間である。重合率は98％であつた。
[Industrial Application Field] The present invention relates to a novel impact-resistant plastic thermoresin composition that has excellent translucency and is plateable. [Conventional technology] In recent years, display methods have been used in the fields of audio parts, automobile front panels, etc. in which characters and figures are illuminated from the inside using LED lamps, etc., in order to more clearly confirm the operating status of functions. The existing switches are used. It is preferable to use a thermoplastic resin for such a material from the point of view of freedom of design, but it is essential to apply plating for the purpose of creating a metallic feel in addition to translucency. Traditionally, such products have been made of double-molded products made of translucent polystyrene or acrylic resin and ABS resin with excellent plating properties, but this requires a special mold. Therefore, it is not possible to respond to diversified designs, the molding operation is complicated, and there is also the problem of poor plating at the interface between polystyrene or acrylic resin and ABS resin. Also. Although conventional ABS resin has excellent plating properties, it has poor translucency.
Therefore, it has been desired to develop an impact-resistant thermoplastic resin that has excellent translucency and is plateable, which can solve these problems all at once. On the other hand, it is transparent as a special grade of ABS resin.
ABS resin is known (US Patent No. 2843561
No. 3029223 and Japanese Patent Publication No. 35-4889). However, these resins contain a methyl methacrylate monomer for the purpose of matching the refractive index of the rubber and the matrix resin, and have poor plating properties, so they cannot be used for the above-mentioned purposes. [Problems to be Solved by the Invention] In view of the above-mentioned current situation, the present inventors set out to obtain an impact-resistant thermoplastic resin composition that has excellent translucency and excellent plating performance even during high-temperature molding. As a result of extensive research, it was discovered that the initial objective could be achieved if the particle size and crosslinked structure of the rubber used, as well as the grafting ratio, were set within specific ranges. [Means for solving the problem] The gist of the present invention is that 1,3-butadiene 50 to 100
For 15 to 80 parts by weight (as solid content) of synthetic rubber (A) latex having a gel fraction of 60% or more obtained from 0 to 50 weight % of styrene and an average particle size of 0.04 to 0.15 μ, aromatic vinyl monomer
60-80% by weight and vinyl cyanide monomer 20-40%
Monomer mixture (B) consisting of 20-85% by weight
[The total amount of (A) and (B) is 100 parts by weight] A graft copolymer () having a grafting ratio of 20 to 180% obtained by graft polymerization and an aromatic vinyl monomer
60-80% by weight and vinyl cyanide monomer 20-40%
The copolymer () obtained from the weight% is blended so that the content of the synthetic rubber (A) in the total amount of the graft copolymer () and the copolymer () is 5 to 30% by weight. 60-80% by weight of aromatic vinyl monomer and vinyl cyanide monomer based on 15-75 parts by weight (as solid content) of butadiene-based rubber (C) latex having an average particle size of 0.2-0.4μ. 20〜
A graft copolymer having a graft ratio of 20 to 100% obtained by graft polymerizing 25 to 85 parts by weight of a monomer mixture (D) consisting of 40% by weight [the total amount of (C) and (D) is 100 parts by weight] An impact-resistant thermoplastic resin composition having good permeability and plating property, in which the butadiene rubber (C) content in the entire composition is 4 to 15% by weight. It is a thing. In the present invention, the gel fraction of the synthetic rubber (A) and the graft ratio of the graft copolymers () and () are defined as follows. Gel fraction: Weigh out a certain amount of aggregated and dried rubber (W 0 ), 50
Leave in double volume of toluene at 30°C for 48 hours. Separate the toluene-insoluble aggregated rubber, dry it, and weigh it (W 1 ). The gel fraction is expressed by the following formula. Gel fraction (%) = W 1 /W 0 ×100 Grafting ratio: A certain amount of the aggregated and dried graft rubber is weighed out (W 0 ) and refluxed in 50 times the volume of acetone at 60°C for 2 hours. Acetone-insoluble graft rubber is separated by centrifugation, dried, and weighed (W 1 ). When the content of synthetic rubber (A) in the grafted rubber is A%, the grafting rate is calculated by the following formula. Grafting rate (%) = W 1 - [W 0 × A/100] / W 0 × A/100
×100 The synthetic rubber (A) constituting the graft copolymer () in the present invention contains 1,3-butadiene 50 to 100
% by weight and 0-50% by weight of styrene, with a gel fraction of 60% or more and 0.04-50% by weight.
It has an average particle size of 0.15μ. These synthetic rubbers can usually be produced by known emulsion polymerization. If the particle size exceeds 0.15μ, the light transmittance will be significantly reduced, and if the particle size is less than 0.04μ, the impact strength will decrease, which is not preferable. Further, if the gel fraction is less than 60%, the rubber is likely to be deformed during molding, resulting in poor surface gloss. In the graft polymerization, the monomer mixture for graft polymerization (B) is 20 to 85 parts by weight, preferably 35 to 70 parts by weight [(A ) and (B) total amount is 100 parts by weight]
used in amounts of If the amount of synthetic rubber (A) is less than 15 parts by weight, productivity is poor and it is not practical, and if it exceeds 80 parts by weight, the graft copolymer () is mixed with the aromatic vinyl monomer cyanated vinyl monomer copolymer () and If desired, the graft copolymer (2) may be dispersed while remaining partially aggregated in the resin composition obtained by melt-mixing with the graft copolymer (2), which may deteriorate the molded appearance, translucency, and plating properties. Yes, it's not good. The monomer mixture (B) for graft polymerization is a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer, and contains 60 to 80 parts by weight of the aromatic vinyl monomer, preferably 65 to 75 parts by weight, and 20 to 40 parts by weight of the vinyl cyanide monomer. , preferably used in graft polymerization at a mixing ratio of 25 to 35% by weight. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and alkyl-substituted styrene, with styrene being preferred. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. If the graft polymerization is carried out at a mixing ratio of vinyl cyanide monomers exceeding 40% by weight, vinyl cyanide homopolymer will be produced during the graft polymerization, which will cause discoloration of the resulting composition, which is undesirable. Also, vinyl cyanide monomer
When graft polymerization is carried out at a mixing ratio of less than 20% by weight,
This is not preferred because the plating properties of the resulting composition deteriorate. In this emulsion graft polymerization, known emulsifiers, initiators and chain transfer agents are usually used.
The monomer mixture (B) for graft polymerization may be added to the rubber latex all at once, or may be added in portions or continuously, but preferably added in portions or continuously. The types and amounts of emulsifiers, initiators, chain transfer agents, and the like, as well as the method of adding monomers, are selected so that the resulting graft copolymer () has a graft ratio of 20 to 180%. If the grafting ratio is less than 20%, it is not preferable because the light transmittance tends to decrease significantly and the plating adhesion strength tends to deteriorate. Furthermore, if the grafting ratio exceeds 180%, the impact strength will drop significantly and the fluidity will also deteriorate, so it is necessary to control the grafting ratio of the graft copolymer () within the range of 20 to 180%. Aromatic vinyl monomer-cyanated vinyl monomer copolymer () is an aromatic vinyl monomer 60~
80% by weight, preferably 65-75% by weight and vinyl cyanide monomer 20-40% by weight, preferably 25-35%
It is a copolymer obtained by polymerizing % by weight. Examples of aromatic vinyl monomers include styrene,
Examples include α-methylstyrene and alkyl-substituted styrene, with styrene being preferred. Examples of vinyl cyanide monomers include allylonitrile and methacrylonitrile, with acrylonitrile being preferred. As in the case of the monomer mixture for graft polymerization, if the amount of the vinyl cyanide monomer exceeds 40% by weight, coloring tends to occur, and if it is less than 20% by weight, the methicity deteriorates, which is not preferable. The method of polymerizing this aromatic vinyl monomer-vinyl cyanide monomer copolymer () is not particularly limited, and a known bulk polymerization method, suspension polymerization method, or emulsion polymerization method can be used. The basic composition of the thermoplastic resin composition of the present invention is a mixture of the above-mentioned graft copolymer () and the aromatic vinyl monomer-vinyl cyanide monomer copolymer () within the above-mentioned specific range.
Furthermore, this blend contains 60-80% by weight of an aromatic vinyl monomer and a cyanide vinyl monomer based on 15-75 parts by weight (as solid content) of a butadiene-based rubber (C) latex having an average particle size of 0.2-0.4μ. 20～
A graft copolymer having a graft ratio of 20 to 100% obtained by graft polymerizing 25 to 85 parts by weight of a monomer mixture (D) consisting of 40% by weight [the total amount of (C) and (D) is 100 parts by weight] The butadiene constituting the graft copolymer () in the total composition consisting of the graft copolymer (), the aromatic vinyl monomer-cyanated vinyl monomer copolymer (), and the graft copolymer () By blending the thermoplastic resin composition as desired so that the content of the rubber (C) is 4 to 15% by weight, the properties of the thermoplastic resin composition, particularly the impact resistance, can be further improved. As the butadiene rubber (C) constituting the graft copolymer (), polybutadiene, butadiene-
Examples include styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic acid alkyl ester copolymer, and butadiene-methacrylic acid alkyl ester copolymer. These butadiene rubbers can usually be produced by known emulsion polymerization. If the particle size is less than 0.2μ, sufficient impact strength cannot be obtained;
If it exceeds 0.4μ, the light transmittance will decrease, which is not preferable. In graft polymerization, butadiene rubber (C)15
75 parts by weight, the monomer mixture (D) for graft polymerization is used in an amount of 25 to 85 parts by weight [the total amount of (C) and (D) is 100 parts by weight]. Butadiene rubber (C) is 15
If the amount is less than 75 parts by weight, the impact strength property will be poor, and if it exceeds 75 parts by weight, the graft copolymer () and the aromatic vinyl monomer-vinyl cyanide monomer copolymer () will be poorly dispersed in the blend, resulting in poor molded appearance. This is not preferable because it worsens the condition. The monomer mixture (D) for graft polymerization is a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer, and contains 60 to 80% by weight, preferably 65 to 75% by weight of the aromatic vinyl monomer and 20 to 40% by weight of the vinyl cyanide monomer. , preferably used in graft polymerization at a mixing ratio of 25 to 35% by weight. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, and alkyl-substituted styrene, with styrene being preferred. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred. If the graft polymerization is carried out at a mixing ratio of vinyl cyanide monomers exceeding 40% by weight, vinyl cyanide homopolymer will be produced during the graft polymerization, which will cause discoloration of the resulting composition, which is undesirable. Also, vinyl cyanide monomer
When graft polymerization is carried out at a mixing ratio of less than 20% by weight,
This is not preferred because the plating properties of the resulting composition deteriorate. In this emulsion graft polymerization, known emulsifiers, initiators and chain transfer agents are usually used.
The monomer mixture (D) for graft polymerization may be added all at once to the rubber latex, or may be added in portions or continuously, but addition in portions or continuous addition is preferred. The types and amounts of emulsifiers, initiators, chain transfer agents and the like, as well as the method of adding monomers, are selected so that the resulting graft copolymer () has a graft ratio of 20 to 100%. If the grafting ratio is less than 20%, the translucency tends to decrease, which is not preferable. Also, the graft rate is 100%
Since the impact strength decreases if the ratio exceeds 100%, it is necessary to control the grafting ratio of the graft copolymer (20) to within a range of 20 to 100%. Note that the definition of the graft ratio is the same as in the case of the graft copolymer (). The graft copolymer () obtained in this way,
Aromatic vinyl monomer-vinyl cyanide monomer copolymer (), the content of synthetic rubber (A) in the total amount of graft copolymer () and copolymer () is 5 to 30% by weight. In addition, the graft copolymer () is added to this blend to add butadiene rubber (C ) is blended so that the content is 4 to 15% by weight, an impact-resistant thermoplastic resin composition with excellent translucency and plating properties can be obtained. If the content of the synthetic plating (A) in the total amount of the graft copolymer () and the copolymer () is less than 5% by weight, the plating property will decrease and the impact resistance will decrease, so there will be no practical value. . Moreover, if it exceeds 30% by weight, the light transmittance and plating properties will decrease, and the fluidity and processability will also deteriorate, which is not preferable. Furthermore, the graft copolymer () is blended as desired, but the total composition [graft copolymer () and copolymer ()
If the content of butadiene rubber (C) in the total of 4% by weight and the total of Undesirable. The graft copolymer () may be used alone or in combination of two or more graft copolymers () in which the gel fraction and particle size of the rubber, the type and amount of the monomer for graft polymerization, the grafting ratio, etc. are within the above-mentioned specific ranges. ) can be used as a mixture. Two or more aromatic vinyl monomer-cyanated vinyl monomer copolymers () may also be used in combination. Furthermore, the graft copolymer () may be used alone or as a mixture of two or more graft copolymers () in which the particle size of the rubber, the type and amount of the monomer for graft polymerization, the grafting ratio, etc. are within the above-mentioned specific ranges. It can be used as In order to blend the graft copolymer () with the aromatic vinyl monomer-vinyl cyanide monomer copolymer () and the graft copolymer (), if the copolymer () is produced by emulsion polymerization, three steps are required. It is possible to blend the ingredients in the form of an emulsion. In addition, it is also possible to knead and blend the three materials as powder, or in combination with powder, beads, pellets, etc., using various equipment such as a Henschel mixer, an extruder, a Banbury mixer, or a heating roll. If necessary, common auxiliary agents such as antioxidants, lubricants, colorants, antistatic agents, dispersants, and fillers can be added to the resin composition of the present invention. [Example] In the following examples, "parts" and "%" mean parts by weight and % by weight, respectively. Impact strength is ASTM
D-256, optical properties are ASTM D-1003-
61, a sample with a plate thickness of 1.5 mm was measured using an integrating sphere haze meter manufactured by Nippon Seimitsu Kogaku.
The molded appearance and plating characteristics were measured by the following methods. Molding appearance: Using a 5-ounce screw type injection molding machine (manufactured by Yamashiro Seiki Co., Ltd.), cylinder temperature 250℃
A flat plate with a thickness of 3 mm was molded under conditions of 290°C and a mold temperature of 60°C, and the color tone and gloss were observed. Plating characteristics: After applying electrolytic copper plating to a film thickness of approximately 35μ using a flat specimen for molded appearance evaluation, the surface appearance was observed.
The adhesion strength was measured by peeling the plating film in the right angle direction at a speed of 30 mm/min. Evaluation of fluidity, molded appearance, and plating surface appearance: ◎: Very good ○: Good △: Slightly poor ×: Poor Evaluation of plating adhesion strength: ◎: 1.5 Kg/cm or more ○: 1.0 to 1.5 Kg/cm △: 0.5-1.0mm/cm ×: 0-0.5cm/cm Example 1 Synthesis of synthetic rubber (A-1): 1.3-butadiene 75 parts Styrene 25 parts 1,3-butylene meditacrylate 0.5 parts Potassium oleate 1.0 parts Disproportionated potassium rosinate 1.0 parts Diisopropylbenzene peroxide 0.2 parts Ferrous sulfate 0.005 parts Sodium pyrophosphate 0.5 parts Dextrose 0.3 parts Water 200 parts Using a 100 autoclave according to the above composition,
Polymerization was carried out at 50°C. The polymerization was almost completed in 9 hours, and a rubber latex with a polymerization rate of 98%, a particle size of 0.092 μm, and a gel fraction of 99% was obtained. Synthesis of graft copolymer (G-1): Rubber latex (A-1) 30 (as solid content) Styrene 49 parts Acrylonitrile 21 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide 0.35 parts Ferrous sulfate 0.01 parts Sodium pyrophosphate 0.2 parts Dextrose 0.35 parts t-dodecyl mercaptan 0.7 parts Water 200 parts (including water in rubber latex) Using rubber latex (A-1), graft copolymer (G-1) was prepared according to the above composition. was synthesized. The polymerization temperature was 70°C and the polymerization time was 4 hours.
Cumene hydroperoxide and t-dodecyl mercaptan were mixed and dissolved in styrene and acrylonitrile, and this was added dropwise to rubber latex (A-1) over 2 hours. Polymerization rate is 97.2%, grafting rate is 51%
It was hot. Butylated hydroxytoluene 2 was added to the resulting graft copolymer latex as an antioxidant.
1 part and 0.5 part of dilaurylthiopropionate were added, coagulated with a 5% aqueous sulfuric acid solution, washed, and dried to obtain a white powder. Styrene-acrylonitrile copolymer (M-
Synthesis of 1): Styrene 70 parts Acrylonitrile 30 parts Calcium phosphate 1.0 parts GAFAC GB520 (dispersion aid, manufactured by Toho Chemical Co., Ltd.)
0.003 parts lauryl peroxide 0.6 parts t-dodecyl mercaptan 0.5 parts water 200 parts A styrene-acrylonitrile copolymer was synthesized according to the above composition. The polymerization temperature was 80°C and the polymerization time was 6 hours. The polymerization rate was 98%.
【表】
上記第１表に示す組成及び重合条件に従つてグ
ラフト共重合体（−１）〜（−５）を合成し
た。なお上記グラフト重合時の滴下は上記所定量
のスチレン、アクリロニトリルにクメンヒドロパ
ーオキシド及びｔ−ドデシルメルカプタンを混合
溶解したものをポリ１，３−ブタジエンラテツク
スに所定の滴下時間で行つた。得られたグラフト
共重合体の各ラテツクスにブチル化ヒドロキシト
ルエン２部、ジラウリルチオプロピオネート0.5
部をそれぞれ加え、５％硫酸水溶液で凝固し、洗
浄し、乾燥して白色粉末を得た。
樹脂組成物の調整及び物性評価：
前記のグラフト共重合体（Ｇ−１）とスチレン
−アクリロニトル共重合体（Ｍ−１）を第２表に
示すように合成ゴム（Ａ−１）の含有量が15％と
なるように配合した配合物に、上記の方法によつ
て得たグラフト共重合体（−２）を第２表に示
すように全組成物中のグラフト共重合体（−
２）に基づくゴム含有量を７％としヘンシエルミ
キサー3000rpmで５分間ブレンドし、しかる後押
出機によりペレツト賦型した。
これらのペレツトを用い射出成形機により試験
片を作成し諸物性を評価した。これらの結果を第
２表に示す。
実施例 ２
グラフト共重合体（Ｇ−２）の合成：
ゴムラテツクス（Ａ−１）
45部（固形分として）
スチレン 38.5部
アクリロニトリル 16.5部
不均化ロジン酸カリウム 1.0部
クメンヒドロパーオキシド 0.2部
硫酸第１鉄 0.008部
ピロリン酸ソーダ 0.2部
デキストローズ 0.4部
ｔ−ドデシルメルカプタン 0.5部
水 160（ゴムラテツクス中の水を含む）
実施例１で得たゴムラテツクス（Ａ−１）を用
いて、上記組成に従つてグラフト共重合体（Ｇ−
２）を合成した。重合温度は65℃、重合時間は５
時間である。なおグラフト重合時には上記スチレ
ン、アクリロニトリルにクメンヒドロパーオキシ
ド及びｔ−ドデシルメルカプタンを混合溶解し、
これをゴムラテツクス（Ａ−１）に３時間で滴下
した。重合率は97.5％、グラフト率は83％であつ
た。得られたグラフト共重合体ラテツクスに抗酸
化剤としてブチル化ヒドロキシトルエン２部及び
ジラウリルチオプロピオネート0.5部を加え、５
％硫酸水溶液で凝固し、洗浄し、乾燥して白色粉
末を得た。
上記グラフト共重合体（Ｇ−２）とスチレン−
アクリロニトリル共重合体（Ｍ−１）を第２表に
示すように配合し、第１表に示すような方法によ
つて得たグラフト共重合体（−１）を第２表に
示すように配合した以外は、全て実施例１と同様
の条件で樹脂組成物の調整及び物性評価を行つ
た。これらの結果を第２表に示す。
実施例 ３
グラフト共重合体（−２）を第２表に示すよ
うに配合した以外は全て実施例２と同様の条件で
樹脂、組成物の調製及び物性評価を行つた。これ
らの結果を第２表に示す。
実施例 ４
グラフト重合体（−３）を第２表に示すよう
に配合した以外は全て実施例３と同様の条件で樹
脂組成物の調製及び物性評価を行つた。これらの
結果を第２表に示す。
実施例 ５
グラフト共重合体（Ｇ−３）の合成：
実施例１で得たゴムラテツクス（Ａ−１）を用
いて下記の組成及び重合条件に従つてグラフト共
重合体（Ｇ−３）を合成した。
ゴムラテツクス（Ａ−１）
45部（固形分として）
スチレン 38.5部
アクリロニトリル 16.5部
不均化ロジン酸カリウム 1.0部
クメンヒドロパーオキシド 0.2部
硫酸第１鉄 0.01部
ピロリン酸ソーダ 0.2部
デキストローズ 0.4部
ｔ−ドデシルメルカプタン 0.15部
水 160部（ゴムラテツクス中の水を含む）
重合温度 65℃
重合時間 ５時間
滴下時間 ３時間
重合率 97.3％
グラフト率 150％
なお上記のグラフト重合時の滴下は上記所定量
のスチレン、アクリロニトリルにクメンヒドロパ
ーオキシド及びｔ−ドデシルメルカプタンを混合
溶解し、これをゴムラテツクス（Ａ−１）に所定
の滴下時間で行つた。得られたグラフト共重合体
ラテツクスはグラフト共重合体（Ｇ−２）と同様
に処理し、白色粉末を得た。
上記グラフト共重合体（Ｇ−３）を第２表に示
すように配合した以外は全て実施例１と同様の条
件で樹脂組成物の調製及び物性評価を行つた。こ
れらの結果を第２表に示す。
実施例 ６
全組成物のグラフト重合体（−２）に基づく
ゴム含有量を４％に変えた以外は全て実施例３と
同様の条件で樹脂組成物の調製及び物性評価を行
つた。これらの結果を第２表に示す。
実施例 ７
全組成物のグラフト重合体（−２）に基づく
ゴム含有量を10％に変えた以外は全て実施例６と
同様の条件で樹脂組成物の調製及び物性評価を行
つた。これらの結果を第２表に示す。
実施例 ８
グラフト共重合体（Ｇ−２）とスチレン−アク
リロニトリル共重合体（Ｍ−１）を第２表に示す
ように配合し、配合物中の合成ゴム（Ａ−１）の
含有量を20％に変え、全組成物のグラフト共重合
体（−２）に基づくゴム含有量を13％に変えた
以外は、全て実施例７と同様の条件で樹脂組成物
の調製及び物性評価を行つた。これらの結果を第
２表に示す。
比較例 １
グラフト共重合体（）の添加をなしにした以
外は全て実施例１と同様の条件で樹脂組成物の調
製及び物性評価を行つた。これらの結果を第２表
に示す。
比較例 ２
グラフト共重合体（Ｇ−２）を第２表に示すよ
うに配合した以外は全て比較例１と同様の条件で
樹脂組成物の調製及び物性評価を行つた。これら
の結果を第２表に示す。
比較例 ３
グラフト共重合体（Ｇ−３）を第２表に示すよ
うに配合した以外は全て比較例２と同様の条件で
樹脂組成物の調製及び物性評価を行つた。これら
の結果を第２表に示す。
比較例 ４
グラフト共重合体（−５）を第２表に示すよ
うに配合した以外は全て比較例３と同様の条件で
樹脂組成物の調製及び物性評価を行つた。これら
の結果を第２表に示す。
比較例 ５
グラフト共重合体（−４）を第２表に示すよ
うに配合した以外は全て比較例４と同様の条件で
樹脂組成物の調製及び物性評価を行つた。これら
の結果を第２表に示す。
比較例 ６
グラフト共重合体（−２）を第２表に示すよ
うに配合した以外は全て比較例５と同様の条件で
樹脂組成物の調製及び物性評価を行つた。これら
の結果を第２表に示す。
第２表の結果から明らかなように実施例１〜８
はアイゾツト衝撃強度、透光性及びメツキ性に優
れることがわかる。比較例４ではグラフト共重合
体（−５）のグラフト率が130％と高いため流
動性がやや悪く充分な衝撃強度が得られない。比
較例５ではグラフト共重合体（−４）のグラフ
ト率が15％と低いため表面光沢がやや悪く透光性
に劣る。また比較例６では全組成物中でのグラフ
ト共重合体（−２）を構成するブタジエンゴム
含有量が20％と高いため衝撃強度は充分であるが
光学特性が悪くなることがわかる。[Table] Graft copolymers (-1) to (-5) were synthesized according to the compositions and polymerization conditions shown in Table 1 above. In the graft polymerization, a mixture of cumene hydroperoxide and t-dodecyl mercaptan in the predetermined amounts of styrene and acrylonitrile was added dropwise to the poly-1,3-butadiene latex for a predetermined time. 2 parts of butylated hydroxytoluene and 0.5 parts of dilaurylthiopropionate were added to each latex of the resulting graft copolymer.
The mixture was coagulated with a 5% aqueous sulfuric acid solution, washed, and dried to obtain a white powder. Preparation of resin composition and evaluation of physical properties: The graft copolymer (G-1) and the styrene-acrylonitrile copolymer (M-1) were mixed with the content of the synthetic rubber (A-1) as shown in Table 2. The graft copolymer (-2) obtained by the above method was added to a blend containing 15% of the graft copolymer (-2) in the total composition as shown in Table 2.
The rubber content based on 2) was set to 7%, and the mixture was blended for 5 minutes using a Henschel mixer at 3000 rpm, and then formed into pellets using an extruder. Test pieces were made from these pellets using an injection molding machine and their physical properties were evaluated. These results are shown in Table 2. Example 2 Synthesis of graft copolymer (G-2): Rubber latex (A-1)
45 parts (as solids) Styrene 38.5 parts Acrylonitrile 16.5 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide 0.2 parts Ferrous sulfate 0.008 parts Sodium pyrophosphate 0.2 parts Dextrose 0.4 parts t-dodecyl mercaptan 0.5 parts Water 160 (Contains water in the rubber latex) Using the rubber latex (A-1) obtained in Example 1, a graft copolymer (G-1) was prepared according to the above composition.
2) was synthesized. Polymerization temperature was 65℃, polymerization time was 5
It's time. During graft polymerization, cumene hydroperoxide and t-dodecyl mercaptan are mixed and dissolved in the styrene and acrylonitrile,
This was added dropwise to rubber latex (A-1) over a period of 3 hours. The polymerization rate was 97.5% and the grafting rate was 83%. To the obtained graft copolymer latex were added 2 parts of butylated hydroxytoluene and 0.5 parts of dilaurylthiopropionate as antioxidants, and 5 parts of dilaurylthiopropionate were added.
% aqueous sulfuric acid solution, washed and dried to obtain a white powder. The above graft copolymer (G-2) and styrene
Acrylonitrile copolymer (M-1) was blended as shown in Table 2, and graft copolymer (-1) obtained by the method shown in Table 1 was blended as shown in Table 2. Except for the above, the resin composition was prepared and the physical properties were evaluated under the same conditions as in Example 1. These results are shown in Table 2. Example 3 A resin and a composition were prepared and their physical properties were evaluated under the same conditions as in Example 2, except that the graft copolymer (-2) was blended as shown in Table 2. These results are shown in Table 2. Example 4 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Example 3, except that the graft polymer (-3) was blended as shown in Table 2. These results are shown in Table 2. Example 5 Synthesis of graft copolymer (G-3): Graft copolymer (G-3) was synthesized using the rubber latex (A-1) obtained in Example 1 according to the following composition and polymerization conditions. did. Rubber latex (A-1)
45 parts (as solid content) Styrene 38.5 parts Acrylonitrile 16.5 parts Disproportionated potassium rosinate 1.0 parts Cumene hydroperoxide 0.2 parts Ferrous sulfate 0.01 parts Sodium pyrophosphate 0.2 parts Dextrose 0.4 parts t-dodecyl mercaptan 0.15 parts Water 160 (including water in the rubber latex) Polymerization temperature 65°C Polymerization time 5 hours Dripping time 3 hours Polymerization rate 97.3% Grafting rate 150% The above-mentioned amount of styrene, acrylonitrile, and cumene hydroperoxide are added during the above-mentioned graft polymerization. and t-dodecylmercaptan were mixed and dissolved, and this was added dropwise to rubber latex (A-1) for a predetermined time. The obtained graft copolymer latex was treated in the same manner as graft copolymer (G-2) to obtain a white powder. A resin composition was prepared and its physical properties were evaluated under the same conditions as in Example 1, except that the graft copolymer (G-3) was blended as shown in Table 2. These results are shown in Table 2. Example 6 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Example 3, except that the rubber content based on graft polymer (-2) in the entire composition was changed to 4%. These results are shown in Table 2. Example 7 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Example 6 except that the rubber content based on graft polymer (-2) in the entire composition was changed to 10%. These results are shown in Table 2. Example 8 Graft copolymer (G-2) and styrene-acrylonitrile copolymer (M-1) were blended as shown in Table 2, and the content of synthetic rubber (A-1) in the blend was The resin composition was prepared and the physical properties were evaluated under the same conditions as in Example 7, except that the rubber content based on the graft copolymer (-2) of the entire composition was changed to 20% and 13%. Ivy. These results are shown in Table 2. Comparative Example 1 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Example 1 except that the graft copolymer () was not added. These results are shown in Table 2. Comparative Example 2 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Comparative Example 1, except that the graft copolymer (G-2) was blended as shown in Table 2. These results are shown in Table 2. Comparative Example 3 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Comparative Example 2, except that the graft copolymer (G-3) was blended as shown in Table 2. These results are shown in Table 2. Comparative Example 4 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Comparative Example 3, except that the graft copolymer (-5) was blended as shown in Table 2. These results are shown in Table 2. Comparative Example 5 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Comparative Example 4, except that the graft copolymer (-4) was blended as shown in Table 2. These results are shown in Table 2. Comparative Example 6 A resin composition was prepared and its physical properties were evaluated under the same conditions as in Comparative Example 5, except that the graft copolymer (-2) was blended as shown in Table 2. These results are shown in Table 2. As is clear from the results in Table 2, Examples 1 to 8
It can be seen that the material has excellent Izot impact strength, translucency and plating property. In Comparative Example 4, the grafting ratio of the graft copolymer (-5) was as high as 130%, so the fluidity was rather poor and sufficient impact strength could not be obtained. In Comparative Example 5, the grafting rate of the graft copolymer (-4) was as low as 15%, so the surface gloss was rather poor and the translucency was poor. Furthermore, in Comparative Example 6, the content of butadiene rubber constituting the graft copolymer (-2) in the entire composition was as high as 20%, so that although the impact strength was sufficient, the optical properties were deteriorated.
【表】【table】
本発明の熱可塑性樹脂組成物は従来公知の熱可
塑性樹脂組成物と比較して、特に次の利点により
優れている。
(1) 従来の透明ABS樹脂では良好なメツキ性が
得られないのに対し、通常のABS樹脂と同等
の優れたメツキ性を保持しながら大幅に向上し
た透明性を有する。
(2) 金属感を有する光表示スイツチ類の成形に従
来用いられるポリスチレンとABS樹脂の二重
成形品の場合は、成形金型が複雑で成形操作も
煩雑なため成形加工価格が高く、デザインの多
様化に対応できなかつたのに対し、成形加工価
格を低減でき、デザインの多様化にも対応でき
る。
The thermoplastic resin composition of the present invention is particularly superior to conventionally known thermoplastic resin compositions due to the following advantages. (1) While conventional transparent ABS resins do not have good plating properties, this product has significantly improved transparency while maintaining excellent plating properties equivalent to those of regular ABS resins. (2) In the case of double-molded products of polystyrene and ABS resin, which are conventionally used to mold optical display switches with a metallic feel, the molding mold is complex and the molding operation is complicated, resulting in high molding costs and design problems. Whereas it was not possible to respond to diversification, it is possible to reduce molding processing costs and respond to diversification of designs.
１ 平均繊維径(d)が0.5μ以下、平均繊維長(l)が5μ
以下かつｌ／ｄが３〜10の無機繊維を下記式を満
足する割合で含有するポリエステルからなり、フ
イルム平均表面粗さ（Ra）が0.005〜0.05μである
ことを特徴とする二軸配向ポリエステルフイル
ム。
0.005≦ｄ×ｌ×ｗ≦１
〔但しｄ：無機繊維の平均繊維径（μ）
ｌ：無機繊維の平均繊維長（μ）
ｗ：無機繊維の含有量（重量％）〕
２ 無機繊維がチタン酸カリウム、炭酸カルシウ
ム及びハイシリカゼオライトからなる群から選ば
れる少なくとも１種であることを特徴とする特許
請求の範囲第１項記載の二軸配向ポリエステルフ
イルム。
1 Average fiber diameter (d) is 0.5μ or less, average fiber length (l) is 5μ
A biaxially oriented polyester consisting of polyester containing inorganic fibers with l/d of 3 to 10 in a proportion satisfying the following formula, and having a film average surface roughness (Ra) of 0.005 to 0.05μ. film. 0.005≦d×l×w≦1 [However, d: Average fiber diameter of inorganic fiber (μ) l: Average fiber length of inorganic fiber (μ) w: Content of inorganic fiber (% by weight)] 2 The inorganic fiber is titanium 2. The biaxially oriented polyester film according to claim 1, wherein the biaxially oriented polyester film is at least one selected from the group consisting of potassium acid, calcium carbonate, and high silica zeolite.
Claims (1)
れる20〜100％のグラフト率を有するグラフト共
重合体（）とが、全組成物中のブタジエン系ゴ
ム(C)の含有量が４〜15重量％になるように配合さ
れてなる良好な透光性及びメツキ性を有する耐衝
撃性熱可塑性樹脂組成物。A graft copolymer () having a graft ratio of 20 to 100% obtained by graft polymerizing [total amount is 100 parts by weight] is obtained by graft polymerization in which the content of butadiene rubber (C) in the entire composition is 4 to 15%. An impact-resistant thermoplastic resin composition having good translucency and plating properties, which is blended in such a manner that the weight of the resin composition is adjusted to % by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-122063 | 1985-06-05 | ||
| JP12206385 | 1985-06-05 | ||
| JP60-260916 | 1985-11-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62201959A JPS62201959A (en) | 1987-09-05 |
| JPH0457705B2 true JPH0457705B2 (en) | 1992-09-14 |
Family
ID=14826706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12994086A Granted JPS62201959A (en) | 1985-06-05 | 1986-06-04 | Impact-resistant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62201959A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4741202B2 (en) * | 2004-06-10 | 2011-08-03 | ユーエムジー・エービーエス株式会社 | Thermoplastic resin composition and molded article thereof |
| JP2006111764A (en) * | 2004-10-15 | 2006-04-27 | Umg Abs Ltd | Thermoplastic resin composition for direct vapor deposition, and molded article and lamp |
| JP6218347B1 (en) * | 2017-07-21 | 2017-10-25 | ユーエムジー・エービーエス株式会社 | Thermoplastic resin composition for plating, resin molded product and plated product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5357293A (en) * | 1976-11-04 | 1978-05-24 | Asahi Chem Ind Co Ltd | Preparation of impact resistant thermoplastic resin |
| JPS5743097A (en) * | 1980-08-26 | 1982-03-10 | Mitsubishi Heavy Ind Ltd | Low-temperature underground tank |
| JPS5751710A (en) * | 1980-07-14 | 1982-03-26 | Toray Ind Inc | Production of impact-resistant thermoplastic resin |
| JPS61236849A (en) * | 1985-04-15 | 1986-10-22 | Mitsubishi Rayon Co Ltd | Impact-resistant thermoplastic resin composition having improved light transmission property and plating |
-
1986
- 1986-06-04 JP JP12994086A patent/JPS62201959A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5357293A (en) * | 1976-11-04 | 1978-05-24 | Asahi Chem Ind Co Ltd | Preparation of impact resistant thermoplastic resin |
| JPS5751710A (en) * | 1980-07-14 | 1982-03-26 | Toray Ind Inc | Production of impact-resistant thermoplastic resin |
| JPS5743097A (en) * | 1980-08-26 | 1982-03-10 | Mitsubishi Heavy Ind Ltd | Low-temperature underground tank |
| JPS61236849A (en) * | 1985-04-15 | 1986-10-22 | Mitsubishi Rayon Co Ltd | Impact-resistant thermoplastic resin composition having improved light transmission property and plating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62201959A (en) | 1987-09-05 |
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