JP3585542B2 - Colored body composition - Google Patents

Description

【００６３】
（２）斑点模様の判定：射出成形で得られた着色熱可塑性樹脂成形体（９０ｍｍ×５０ｍｍ×３ｍｍの平板成形体）の斑点模様輪郭の明瞭さを目視で判定し、平均粒子径（円相当径の平均値）を画像処理装置〔旭化成（株）社製ＩＰ−１０００〕を用い測定する。
【００６４】
（３）落錘衝撃強度：デュポン式落錘衝撃試験法に従い測定する。即ち、まず、直径１５．２ｍｍの半球形状の凹所を有するテーブルに、凹所を覆うように上記平板成形体をねかせる。重量１ｋｇで樹脂成形体に接触する先端部分が直径１／２インチ（１２．７ｍｍ）の半球形状を有する鋼鉄錘を、テーブル上に置いた上記平板成形体の、テーブルの凹所に対応する部分に高さＨｃｍ（鋼鉄錘の先端から成形体表面までの距離）より落下させ、５０％の確率で亀裂が発生する際の衝撃強度〔Ｈ（ｋｇ・ｃｍ）〕を求める。
【００６５】
（参考例Ａ）水添ブロック共重合体の製法
（Ａ−１） ；ポリブタジエン−ポリスチレン−ポリブタジエン−ポリスチレンの構造を有し、結合スチレン量３５％、数平均分子量１６６，０００、分子量分布１．０４、ポリブタジエン部の１，２−ビニル結合量３７％のスチレン−ブタジエン共重合エラストマーにつき、ポリブタジエン部を特公昭６３−４８４１号公報（米国特許第４５０１８５７号に対応）に記載の方法により水添し、ポリブタジエン部の水添率９９％の水添スチレン−ブタジエン共重合エラストマーを得る。
【００６６】
（Ａ−２） ；ポリブタジエン−ポリスチレン−ポリブタジエン−ポリスチレンの構造を有し、結合スチレン量２２％、数平均分子量６４，０００、分子量分布１．０３、ポリブタジエン部の１，２−ビニル結合量５５％のスチレン−ブタジエン共重合エラストマーを用いるほかは（Ａ−１）と同様の手順を行い、ポリブタジエン部の水添率９８％の水添スチレン−ブタジエン共重合エラストマーを得る。
【００６７】
（参考例Ｂ）変性（水添）ブロック共重合体の製法
（Ｂ−１） ；（Ａ−１）で得られる水添ブロック共重合体１００重量部あたり、無水マレイン酸２．０重量部、２，５−ジメチル−２，５−ジ（第３ブチルパーオキシ）ヘキサン０．２重量部を混合し、３０ｍｍφ径の二軸押出機にて２５０℃の温度で溶融混錬して付加変性反応を行う。得られる変性水添ブロック共重合体は、重合体１００重量部あたり１．５重量部の無水マレイン酸が付加したものである。
【００６８】
（Ｂ−２） ；（Ａ−２）で得られる水添ブロック共重合体１００重量部あたり、無水マレイン酸２．５重量部、ジクミルパーオキサイド０．２５重量部を混合し、３０ｍｍφ径の二軸押出機にて２５０℃の温度で溶融混錬して付加変性反応を行う。得られる変性水添ブロック共重合体は、重合体１００重量部あたり１．８重量部の無水マレイン酸が付加したものである。
【００６９】
（Ｂ−３） ；（Ａ−１）の原料であるポリブタジエン−ポリスチレン−ポリブタジエン−ポリスチレンの構造を有するブロック共重合体１００重量部あたり、無水マレイン酸２．０重量部、２，５−ジメチル−２，５−ジ（第３ブチルパーオキシ）ヘキサン０．２重量部を混合し、３０ｍｍφ径の二軸押出機にて２５０℃の温度で溶融混錬して付加変性反応を行う。得られる変性ブロック共重合体は、重合体１００重量部あたり１．７重量部の無水マレイン酸が付加したものである。
【００７０】
（参考例Ｃ）着色変性（水添）ブロック共重合体の製法
（Ｃ−１） ；（Ｂ−１）で得られる変性水添ブロック共重合体１００重量部あたり、カーボンブラック粉末１．０重量部を混合し、３０ｍｍφ二軸押出機にて２２０℃で溶融混錬着色する。得られる着色変性水添ブロック共重合体は黒色となる。
（Ｃ−２） ；（Ｂ−２）で得られる変性水添ブロック共重合体１００重量部あたり、ペリレン系赤色染料（スイス国チバガイギー社製ＩＲＧＡＺＩＮ ＲｅｄＢＰＴ）０．３重量部を混合し、３０ｍｍφ二軸押出機にて２２０℃で溶融混錬着色する。得られる着色変性水添ブロック共重合体は鮮やかな赤色となる。
【００７１】
（Ｃ−３） ；（Ｂ−１）で得られる変性水添ブロック共重合体１００重量部あたり、アンスラキノン系黄色顔料（チバガイギー社製ＣＲＯＭＯＰＨＴＡＬ Ｙｅｌｌｏｗ ＡＧＲ）０．２重量部を混合し、３０ｍｍφ二軸押出機にて２２０℃で溶融混錬着色する。得られる着色変性水添ブロック共重合体は鮮やかな黄色となる。
（Ｃ−４） ；（Ｂ−１）で得られる変性水添ブロック共重合体１００重量部あたり、酸化チタン系白色顔料（英国ＩＣＩ社製ＴＩＯＸＩＤＥ Ｒ−ＴＣ３０ＰＷ ６）２．０重量部を混合し、３０ｍｍφ二軸押出機にて２２０℃で溶融混錬着色する。得られる着色変性水添ブロック共重合体は白色となる。
【００７２】
（Ｃ−５） ；（Ｂ−３）で得られる変性ブロック共重合体１００重量部あたり、アルミニウム粒子〔ダイヤ工業（株）製スーパーミラーＳＰ−３１０〕５．０重量部を混合し、３０ｍｍφ二軸押出機にて２２０℃で溶融混錬着色する。得られる着色変性ブロック共重合体は灰色となる。
（Ｃ−６） ；（Ｂ−１）で得られる変性ブロック共重合体１００重量部あたり、スチレン−無水マレイン酸（重量比９２／８）共重合体１００重量部、カーボンブラック粉末２．０重量部を混合し、３０ｍｍφ二軸押出機にて２３０℃で溶融混錬着色する。得られる着色変性ブロック共重合体は黒色となる。
【００７３】
（Ｃ−７） ；（Ｂ−１）で得られる変性ブロック共重合体１００重量部あたり、スチレン−無水マレイン酸（重量比９２／８）共重合体１５００重量部、カーボンブラック粉末１６．０重量部を混合し、３０ｍｍφ二軸押出機にて２３０℃で溶融混錬着色する。得られる着色変性ブロック共重合体は黒色となる。
（Ｃ−８） ；（Ｂ−１）で得られる変性ブロック共重合体１００重量部あたり、スチレン−無水マレイン酸（重量比９２／８）共重合体２５００重量部、カーボンブラック粉末２６．０重量部を混合し、３０ｍｍφ二軸押出機にて２４０℃で溶融混錬着色する。得られる着色変性ブロック共重合体は黒色となる。
【００７４】
（Ｃ−９） ；（Ｂ−１）で得られる変性ブロック共重合体１００重量部あたり、スチレン−アクリル酸−無水マレイン酸共重合体〔旭化成工業（株）製デルペット９８０Ｎ〕１００重量部、カーボンブラック粉末２．０重量部を混合し、３０ｍｍφ二軸押出機にて２３０℃で溶融混錬着色する。得られる着色変性ブロック共重合体は黒色となる。
（Ｃ−１０） ；（Ｂ−１）で得られる変性ブロック共重合体１００重量部あたり、スチレン−アクリル酸−無水マレイン酸共重合体〔旭化成工業（株）製デルペット９８０Ｎ〕２４００重量部、カーボンブラック粉末２５．０重量部を混合し、３０ｍｍφ二軸押出機にて２３０℃で溶融混錬着色する。得られる着色変性ブロック共重合体は黒色となる。
【００７５】
（参考例Ｄ）変性水添ブロック共重合体の架橋
（Ｄ−１） ；（Ｂ−２）で得られる変性水添ブロック共重合体１００重量部あたり、架橋剤（ジアミノポリエチレングリコール：米国テキサコケミカル社製ジェファーミンＥＤＲ−１４８）３．０重量部、及びパラフィン系オイル〔出光興産（株）製ダイアナプロセスオイルＰＷ−３８０〕２０重量部を混合し、ブラベンダーを用いて２２０℃で溶融混錬を行い（Ｂ−２）の架橋物を得る。
【００７６】
得られる架橋水添ブロック共重合体をキシレン中で６時間振とうし、溶解物の抽出を行い残留物に対し赤外吸収スペクトルの測定を行った。
図１に（Ｂ−２）で得られる変性水添ブロック共重合体の赤外吸収スペクトル、図２に架橋水添ブロック共重合体の赤外吸収スペクトルを示す。図１には，付加した無水マレイン酸のＣ＝Ｏ伸縮振動に由来する吸収帯（１７７８ｃｍ−１）が見られる。図２では、架橋構造（イミド結合、アミド結合）のＣ＝Ｏ伸縮振動に由来する吸収帯（１７４３ｃｍ−１）が見られる。
【００７７】
（参考例Ｅ）着色体組成物の製法
（Ｅ−１） ；（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリスチレン〔旭化成工業（株）製旭化成ポリスチレン４０３Ｒ〕５重量部を混合し、ブラベンダーを用い２３０℃で１０分間溶融混錬を行い着色体組成物を得る。
（Ｅ−２） ；（Ｃ−２）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及び高密度ポリエチレン〔旭化成工業（株）製サンテックＨＤ−Ｊ３１１〕５重量部を混合し、ブラベンダーを用い２３０℃で１０分間溶融混錬を行い着色体組成物を得る。
【００７８】
（Ｅ−３） ；（Ｃ−３）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及び低密度ポリエチレン〔旭化成工業（株）製サンテックＬＤ−Ｍ６５２５〕５重量部を混合し、ブラベンダーを用い２３０℃で１０分間溶融混錬を行い着色体組成物を得る。
（Ｅ−４） ；（Ｃ−４）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリプロピレン樹脂〔旭化成工業（株）製旭化成ポリプロ−Ｍ７５４６〕５重量部を混合し、ブラベンダーを用い２３０℃で１０分間溶融混錬を行い着色体組成物を得る。
【００７９】
（Ｅ−５） ；（Ｃ−５）で得られる着色変性ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びアクリル樹脂〔旭化成工業（株）製デルペット５６０Ｆ〕５重量部を混合し、ブラベンダーを用い２３０℃で１０分間溶融混錬を行い着色体組成物を得る。
（Ｅ−６） ；（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びＡＢＳ樹脂〔旭化成工業（株）製スタイラックＡＢＳ−１２１Ｂ〕５重量部を混合し、ブラベンダーを用い２５０℃で１０分間溶融混錬を行い着色体組成物を得る。
（Ｅ−７） ；（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリアセタール樹脂〔旭化成工業（株）製テナック４５１０〕５重量部を混合し、ブラベンダーを用い２００℃で１０分間溶融混錬を行い着色体組成物を得る。
【００８０】
（参考例Ｆ）着色体組成物の製法
（Ｆ−１）；（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリスチレン〔旭化成工業（株）製旭化成ポリスチレン４０３Ｒ〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２２０℃で溶融混錬を行い着色体組成物を得る。
（Ｆ−２）；（Ｃ−２）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及び高密度ポリエチレン〔旭化成工業（株）製サンテックＨＤ−Ｊ３１１〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２００℃で溶融混錬を行い着色体組成物を得る。
【００８１】
（Ｆ−３）；（Ｃ−３）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及び低密度ポリエチレン〔旭化成工業（株）製サンテックＬＤ−Ｍ６５２５〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２００℃で溶融混錬を行い着色体組成物を得る。
（Ｆ−４）；（Ｃ−４）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリプロピレン樹脂〔旭化成工業（株）製旭化成ポリプロ−Ｍ７５４６〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２２０℃で溶融混錬を行い着色体組成物を得る。
【００８２】
（Ｆ−５）；（Ｃ−５）で得られる着色変性ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びアクリル樹脂〔旭化成工業（株）製デルペット５６０Ｆ〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２３０℃で溶融混錬を行い着色体組成物を得る。
（Ｆ−６）；（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びＡＢＳ樹脂〔旭化成工業（株）製スタイラックＡＢＳ−１２１Ｂ〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２４０℃で溶融混錬を行い着色体組成物を得る。
【００８３】
（Ｆ−７）；（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリアセタール樹脂〔旭化成工業（株）製テナック４５１０〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２００℃で溶融混錬を行い着色体組成物を得る。
（Ｆ−８）〜（Ｆ−１０）；（Ｃ−６）〜（Ｃ−８）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びポリスチレン〔旭化成工業（株）製旭化成ポリスチレン４０３Ｒ〕４００重量部を混合し、３０ｍｍφ２軸押出機にて２３０℃で溶融混錬を行い着色体組成物を得る。
【００８４】
（Ｆ−１１）〜（Ｆ−１２）；（Ｃ−９）〜（Ｃ−１０）で得られる着色変性水添ブロック共重合体１００重量部あたり、１，４−ブタンジオール３．０重量部、及びＡＢＳ樹脂〔旭化成工業（株）製旭化成スタイラックＡＢＳ−１２１Ｂ〕４００重量部を混合し、３０ｍｍφ２軸押出機を用い２５０℃で溶融混錬を行い着色体組成物を得る。
【００８５】
（参考例Ｇ）熱可塑性樹脂組成物の製法
（Ｇ−１）〜（Ｇ−１２）；（参考例Ｆ）の（Ｆ−１）〜（Ｆ−１２）で得られる着色体組成物１００重量部あたり、（Ｆ−１）〜（Ｆ−１２）で用いたのと同様の希釈ポリマー１，９００重量部を混合し、３０ｍｍφ２軸押出機で（Ｆ−１）〜（Ｆ−１２）と同様の押出温度で溶融混錬を行い（Ｇ−１）〜（Ｇ−１２）の熱可塑性樹脂組成物を得る。
【００８６】
（参考例Ｈ）熱可塑性樹脂成形体の製法
（Ｈ−１）〜（Ｈ−１２）；（参考例Ｇ）の（Ｇ−１）〜（Ｇ−１２）で得られる熱可塑性樹脂組成物を用いて射出成型を行なう。即ち、フィルムゲート金型（ゲートサイズ：０．９ｍｍ×２．０ｍｍ）と型締め圧１００トンの射出成形機を用いて（Ｆ−１）〜（Ｆ−１２）の押出温度と同様の温度で射出成形を行い（Ｈ−１）〜（Ｈ−１２）の熱可塑性樹脂成形体（９０ｍｍ×５０ｍｍ×３ｍｍ大の平板状成形体）を得る。
【００８７】
（参考例Ｉ）比較着色体組成物の製法
（Ｉ−１） ；下記のように、特開平２−１０３２５４号公報中の実施例Ｂ−１と同様の方法で着色体組成物を得る。即ち、ｏ−クレゾールノボラックグリシジルエーテル化合物１００重量部、フェノールホルムアルデヒド系ノボラック５０重量部（硬化剤）、２−エチル、４−メチルイミダゾール１重量部（硬化促進剤）及びカーボンブラック０．１重量部を混合後、１００℃で加熱混練硬化し、さらに１７０℃で１５分間プレスしたものを粉砕・分級して平均粒子径３００μｍの硬化エポキシ樹脂着色体組成物を得る。
【００８８】
（Ｉ−２） ；下記のように、特開平３−２８１４８号公報中の実施例１と同様の方法で着色体組成物を得る。即ち、メチルメタクリレート１００重量部、炭酸カルシウム１５０重量部、ＴＭＰＴ（トリメチロールプロパントリメタクリレート）１重量部、ベンゾイルパーオキサイド１重量部、カーボンブラック３重量部を混合後、８０℃で加熱混錬硬化したものを粉砕・分級して平均粒子径５００μｍの着色体組成物を得る。
【００８９】
（Ｉ−３） ；下記のように、特開平３−２００８４１号公報中の実施例１と同様の方法で着色体組成物を得る。即ち、ポリプロピレン系シラン架橋性ポリマー（三菱油化社製リンクロンＸＰＭ７００Ｂ）１００重量部に、プロピレンエチレンブロック共重合体（三菱油化社製三菱ポリプロ−ＢＣ３）１００重量部、ジブチル錫ジラウレート１重量部とからなるマスターバッチ５重量部、ステアリン酸マグネシウム０．１重量部、ステアリン酸亜鉛０．１重量部、カーボンブラック０．３重量部を混合後、２１０℃で加熱混練する。得られたペレットを９０℃の熱湯中に５時間浸漬することにより架橋したものを脱水後、粉砕・分級し、平均粒子径５００μｍの着色体組成物を得る。
【００９０】
（Ｉ−４） ；スチレン−無水マレイン酸（重量比９２／８）共重合体１００重量部にカーボンブラック粉末１．０重量部を混合し、３０ｍｍφ二軸押出機を用い２４０℃で溶融混合着色する。得られる着色体１００重量部に対し、１，４−ブタンジオール３重量部およびポリスチレン樹脂〔旭化成社製旭化成ポリスチレン４０３Ｒ〕９００重量部を混合し、３０ｍｍφ二軸押出機を用い２４０℃で溶融混合着色し、着色体組成物を得る。
【００９１】
（参考例Ｊ）熱可塑性樹脂組成物の製法
（Ｊ−１） ；（Ｉ−４）で得られる着色体組成物１００重量部に対し、ポリスチレン樹脂〔旭化成社製旭化成ポリスチレン４０３Ｒ〕１，９００重量部を混合し、熱可塑性樹脂組成物を得る。
【００９２】
（実施例１〜６及び比較例１〜３）
（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部に対し、表１記載の架橋剤３．０重量部、ポリスチレン樹脂〔旭化成工業（株）製旭化成ポリスチレン−６６６〕５重量部を混合し、ブラベンダーを用い２３０℃で１０分間溶融混練を行い着色体組成物を得る。得られた着色体組成物に対しゲル含有率（Ｇｅｌ％）を求める。また、この着色体組成物を液体窒素で冷凍した後粉砕したもの１００重量部に上記ポリスチレン樹脂を１０，０００重量部添加し、参考例Ｈと同様の成型機とフィルムゲート金型（ゲートサイズ：０．９ｍｍ×２．０ｍｍ）を用いて２２０℃で射出成形を行い熱可塑性樹脂成形体（９０ｍｍ×５０ｍｍ×３ｍｍの平板成形体）を得、斑点模様の判定を行う。表１から明らかなように、実施例１〜６においては着色体組成物のゲル含有率は比較例１〜３よりもはるかに大きい値を示し、成形体は輪郭が明瞭な斑点模様を示す。結果を表１に示す。
【００９３】
【表１】

【００９４】
（実施例７〜８及び比較例４〜６）
（Ｃ−１）で得られる着色変性水添ブロック共重合体１００重量部あたり、架橋剤として１，４−ブタンジオールを用いる。実施例７、８でそれぞれ、１．０重量部及び６．０重量部、比較例４、５、６でそれぞれ、０．１重量部、０重量部及び２００重量部を混合し、実施例１と同様の手法で、着色体組成物を得る。得られる着色体組成物に対し、実施例１と同様にゲル含有率（Ｇｅｌ％）を測定し、実施例１と同様にして熱可塑性樹脂成形体を作成し斑点模様の判定を行う。表２に実施例１を含め結果を示す。
【００９５】
【表２】

【００９６】
（実施例９〜１５）
参考例Ｅの（Ｅ−１）〜（Ｅ−７）で得られる着色体組成物に対しゲル含有率（Ｇｅｌ％）を求め、さらに、着色体組成物各々１００重量部に対し、それぞれ（Ｅ−１）〜（Ｅ−７）で用いたのと同じ熱可塑性樹脂５０００重量部と混合して熱可塑性樹脂組成物を得て、実施例１と同様にして熱可塑性樹脂成形体を作成し、斑点模様の判定を行う。表３に結果を示す。表３から明らかなように、ゲル含有率は他の実施例と同様良好な値を示す。また、熱可塑性樹脂成形体はそれぞれ輪郭が明瞭な斑点模様を呈す。
【００９７】
【表３】

【００９８】
（比較例７〜１２）
表４に示すように、６種類の着色剤を別々に用いる。即ち、参考例（Ｉ−１）〜（Ｉ−４）で得られる着色体組成物（比較例７〜１０）、アルミニウム粒子（日本防湿工業社製アストロフレーク＃４０ＢＬ）（比較例１１）及びマイカ粒子（メルク社製イリオジン１６３）（比較例１２）のそれぞれの１００重量部に対し、ポリスチレン樹脂（旭化成社製旭化成ポリスチレン４０３Ｒ）５０００重量部を溶融混錬してなる熱可塑性樹脂組成物に対し、ゲル含有率（Ｇｅｌ％）を求め、成形体について斑点模様の判定を行う。さらに、実施例９で得た樹脂成形体とともに落錘衝撃試験を行う。結果を表４に示す。比較例７〜１２は実施例９と比較し何れも落錘衝撃強度が大きく劣り、また、比較例９は着色体組成物よりマトリックス樹脂中に顔料が拡散し、輪郭が明瞭な斑点模様とならない。
【００９９】
【表４】

【０１００】
（実施例１６〜２２）
参考例Ｆの（Ｆ−１）〜（Ｆ−７）で得られる希釈着色体組成物に対しゲル含有率（Ｇｅｌ％）を求める。さらに、各々の着色体組成物１００重量部に対し、それぞれ（Ｆ−１）〜（Ｆ−７）で用いたのと同じ熱可塑性樹脂５００重量部を混合して熱可塑性樹脂組成物を調製し、実施例１と同様にして熱可塑性樹脂成形体を得る。表５に結果を示す。ゲル含有率は良好な値を示し、熱可塑性樹脂成形体は輪郭が明瞭な斑点模様を呈す。
【０１０１】
【表５】

【０１０２】
（実施例２３〜２９）
参考例Ｇの（Ｇ−１）〜（Ｇ−７）で得られる着色熱可塑性樹脂組成物に対しゲル含有率（Ｇｅｌ％）を求める。さらに、参考例Ｈの（Ｈ−１）〜（Ｈ−７）で得られる熱可塑性樹脂成形体に対し、ゲル含有率、斑点模様の判定、平均粒子径の測定を行う。表６に結果を示す。Ｇｅｌ％は良好な値を示し、熱可塑性樹脂成形体は輪郭が明瞭な斑点模様を呈す。
【０１０３】
【表６】

【０１０４】
（実施例３０〜３２、比較例１３〜１４）
実施例４の着色体組成物を液体窒素で冷凍した後粉砕したもの１００重量部にポリスチレン樹脂（旭化成ポリスチレン４０３Ｒ）を５，０００重量部添加した熱可塑性樹脂組成物（実施例３０）、実施例１６の熱可塑性樹脂組成物（実施例３１）、実施例２３の熱可塑性樹脂組成物（実施例３２）、アルミニウム粒子〔日本防湿工業社製アストロフレーク＃７０ＢＬ（粒子径１ｍｍ×１ｍｍ）〕１００重量部と上記ポリスチレン樹脂５０００重量部を溶融混錬してなる熱可塑性樹脂組成物（比較例１３）、マイカ粒子〔レプコ社製マイカＳ２０（粒子径７００μｍ）〕１００重量部と上記ポリスチレン樹脂５０００重量部を溶融混錬してなる熱可塑性樹脂組成物（比較例１４）を用い、成形条件はゲート径８００μｍのピンゲート金型を用いる他は実施例１と同様にして平板状熱可塑性樹脂成形体を得る。表７から明らかなように本発明の着色体組成物使用する場合は、熱可塑性樹脂成形体中の最大粒子径はゲート径より大きく、輪郭が明瞭な斑点模様を呈す。これに対し、比較例１３ではアルミニウム粒子が変形し、また、比較例１４ではマイカ粒子が粉砕し平均粒径が減少する。比較例１３と１４には、ゲート径より大きな粒子はない。
【０１０５】
【表７】

【０１０６】
（実施例３３〜３５、比較例１５〜１７）
実施例３３〜３５では参考例（Ｈ−８）、（Ｈ−９）及び（Ｈ−１１）、比較例１５、１６では参考例（Ｈ−１０）、（Ｈ−１２）で得られる熱可塑性樹脂成形体に対し、また、比較例１７では参考例（Ｊ−１）で得られる熱可塑性樹脂組成物を実施例１と同様にして成型して得られる熱可塑性樹脂成形体に対し、実施例９及び比較例７〜１２と同様にＧｅｌ％、斑点模様の判定及び落錘衝撃試験を行う。結果を実施例９と合わせて、表８に示す。比較例１５、１７は実施例９、３３、３４と比較し何れも落錘衝撃強度が大きく劣り、比較例１６は実施例３５と比較し落錘衝撃強度が大きく劣る。
【０１０７】
【表８】

【０１０８】
【発明の効果】
本発明の着色体組成物より成る石目調等の装飾模様剤は射出成形時の形状安定性、熱安定性が良好である。また、着色体組成物の周囲にあるマトリックス樹脂等への染顔料の拡散がない。従って、本発明により、熱可塑性エラストマーを主な原料とする熱可塑性樹脂用模様剤を提供できるようになった。
【０１０９】
また、本発明の着色体組成物は伸度、熱可塑性樹脂との溶融接着特性に優れる。このため、本発明の着色熱可塑性樹脂成形体は従来技術と比較し、引張特性、衝撃強度等樹脂の重要な物性が極めて向上する。
さらに、本発明の着色体組成物は変形能と形状復原性に優れる。このため、成形時に模様剤の粒子が破断せず、成形体内の斑点模様は模様剤粒子本来の大きさを保つ。また、射出成形機射出口内径より大きな粒子径の装飾剤を含む成形体も成形可能であり、従来技術では不可能な装飾模様を付与することができる。
【図面の簡単な説明】
【図１】参考例Ｂの（Ｂ−２）で得られる変性水添ブロック共重合体の赤外吸収スペクトルを示す。
【図２】参考例Ｄにおいて上記（Ｂ−２）の変性水添ブロック共重合体を架橋することによって得られた架橋水添ブロック共重合体（Ｄ−１）の赤外吸収スペクトルを示す。[0001]
[Industrial applications]
TECHNICAL FIELD The present invention relates to a colored body composition (that is, a decorative composition). More specifically, a base composed mainly of at least one polymer block (A) mainly composed of vinyl aromatic monomer units and at least one polymer block (B) mainly composed of conjugated diene monomer units. A gel comprising a crosslinked block copolymer component (1) comprising a molecular chain of a block copolymer; and at least one colorant component (2) selected from organic pigments, inorganic pigments, and organic dyes. A colored composition having a content of 60% by weight or more, wherein the molecular chain of the base block copolymer contains at least one type of bond selected from an imide bond, an amide bond, an ester bond, and a urethane bond. The present invention relates to a colored body composition which is cross-linked through a cross-linking portion. Furthermore, the present invention provides a colored thermoplastic resin composition containing a thermoplastic resin and the above-mentioned colored body composition (decorative body composition), and a colored thermoplastic resin molded article produced from the above colored thermoplastic resin composition About. Since the colored body composition of the present invention is excellent in melt adhesion with a thermoplastic resin, heat resistance, shape stability, etc., using the thermoplastic resin composition of the present invention containing this colored body composition, For example, when molding such as injection molding, it is possible to obtain clear spot patterns and stone-grain patterns with excellent decorativeness, such as exterior parts such as home electric appliances and OA equipment, furniture, wash basins, bathtubs, and musical instruments. Various colored thermoplastic resin molded articles having excellent mechanical strength can be obtained.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, many techniques have been disclosed for imparting decorative properties such as spotted patterns and stone-like patterns to a molded article of a thermoplastic resin. As a technique of spotting, JP-A-49-17831 discloses a method of dispersing mica particles as a decorating agent in a thermoplastic resin and dispersing a short fibrous substance as a reinforcing agent. Also, as an example of the grain tone, Japanese Patent Application Laid-Open No. 2-153971 discloses a method of dispersing colored aluminum particles in a specific amount of resin, and discloses a method of obtaining a wood grain / stone grain pattern. As an example, Japanese Patent Application Laid-Open No. 55-142613 discloses a method in which a colored grafted polyphenylene ether resin is used as a decorating agent, mixed with the resin, and injection-molded at a specific temperature. Further, as a method of using a crosslinked polymer as a decorating agent, JP-A-50-105760 discloses a method in which a fine particle polymer crosslinked using divinylbenzene is used as a graining agent to give a PMMA resin a grainy tone. A method is disclosed. Japanese Patent Application Laid-Open No. 2-103254 discloses a technique related to a stone-grained resin composition using epoxy resin particles, which are cured with a non-amine-based curing agent and contain a dye and a pigment, as a stone-graining agent, Japanese Patent Application Laid-Open No. 3-200841 (corresponding to U.S. Pat. No. 5,151,324) discloses a technique using a crosslinked polyolefin containing a pigment as a coloring material for a synthetic resin. Further, JP-A-3-28148 discloses a technique in which a crosslinked methacrylate resin containing an inorganic filler and a colorant is used as a graining agent for methyl methacrylate resin.
However, in the method disclosed in Japanese Patent Application Laid-Open No. 55-142613, molding conditions are extremely limited in order to maintain the decorative pattern and to suppress the transfer of dyes and pigments from the graining agent to the resin. Problem. That is, in the technology of this document, for example, when an impact-resistant polystyrene resin is used as a thermoplastic resin mixed with a decorating agent, the optimum temperature range of injection molding is limited to a narrow range of 180 to 210 ° C. Further, since this temperature range is too low, the obtained molded body is inferior in surface finish and reproducibility of the cavity shape of the mold. In the methods of JP-A-50-105760, JP-A-2-103254 and JP-A-3-200841, the impact resistance and tensile elongation of the graining agent itself are insufficient. Therefore, the physical properties of the resin decrease. Further, in the method disclosed in JP-A-3-28148, since a radical initiator is used as a cross-linking agent, molecular deterioration of the resin constituting the graining agent is inevitable. Does not have sufficient physical properties. Therefore, the conventional resin decoration techniques described in these publications have a problem that the molding conditions are extremely limited, and also the interface adhesion between the decoration agent and the resin and the elongation of the decoration agent are insufficient. In addition, due to the deterioration of the physical properties of the graining agent due to the deterioration of the constituent molecules at the time of crosslinking, the obtained molded article has problems such as poor impact resistance and tensile elongation. Is not satisfactory.
[0003]
Furthermore, in the technology disclosed in the above-mentioned JP-A-49-17831 and JP-A-2-153971, that is, in the technology using mica, aluminum or the like as a resin decorating agent, a resin injection port such as a pin gate mold is used. In the injection molding using a mold having a small diameter, it is extremely difficult to give a decorative pattern larger than the inner diameter of the injection port to the resin molded body. Further, the patterning agent smaller than the inner diameter of the injection port also has a problem that the patterning agent in the molded body cannot maintain its original shape due to deformation and breakage due to a shear force or the like at the time of resin injection.
[0004]
On the other hand, as a means for improving the physical properties of a thermoplastic resin, a technique of adding a thermoplastic elastomer having good compatibility with the thermoplastic resin is widely used. There is no prior art which provides a thermoplastic resin molded article having a decorative pattern such as a spot pattern. That is, the conventional thermoplastic elastomer has insufficient shape stability of the patterning agent particles at the time of melt processing, and is unsuitable as a resin decoration agent such as stone texture.
[0005]
Further, when a conventional thermoplastic elastomer is colored and used as a decorating agent, there is a problem in that, during melt-kneading, a dye or a pigment diffuses into surrounding components that come into contact with the decorating agent, such as a matrix resin, and the opacity becomes cloudy.
[0006]
[Problems to be solved by the invention]
Under these circumstances, the present inventors have conducted intensive studies in order to solve the above-mentioned problems of the prior art, and as a result, surprisingly, at least one polymer block (A) mainly composed of a vinyl aromatic monomer unit and A crosslinked block copolymer component (1) composed of a molecular chain of a base block copolymer composed mainly of at least one polymer block (B) composed mainly of conjugated diene monomer units; and a colorant component (2). A) wherein the gel content is 60% by weight or more, wherein the molecular chain of the base block copolymer is selected from an imide bond, an amide bond, an ester bond, and a urethane bond. It has been found that the colored body composition crosslinked via a crosslinked portion containing at least one kind of bond is extremely excellent in melt adhesion with a thermoplastic resin, heat resistance, shape stability and the like. In addition, when molding such as injection molding is performed using the thermoplastic resin composition containing the colored body composition, the colorant component does not diffuse into the surrounding contact components such as the matrix resin during the injection molding. It has been found that, even when resin molding conditions are used, not only a molded article having a clear decorative pattern can be obtained, but also the obtained thermoplastic resin molded article is excellent in important physical properties such as impact strength.
[0007]
Furthermore, the colored body composition of the present invention is excellent in deformability and shape stability after deformation, and enables the production of a resin molded body having a decorative pattern larger than the gate diameter of a mold, which was conventionally impossible to mold. I found something. Based on these findings, the present invention has been completed.
Therefore, one object of the present invention is to provide an excellent colored body composition that solves various problems of the conventional resin decoration technology, that is, a molding composition which does not deteriorate the physical properties of the thermoplastic resin to be colored and decorated. It is an object of the present invention to provide a colored composition (that is, a decorative composition) which has a wide width, does not cause breakage or permanent deformation at the time of molding, and has a large degree of freedom of a pattern that can be applied to a resin molded article.
[0008]
Another object of the present invention is to provide a colored thermoplastic resin composition having excellent moldability, comprising a thermoplastic resin and the above-mentioned colored composition.
Still another object of the present invention is to provide a colored thermoplastic resin molded article which is produced from the above-mentioned colored thermoplastic resin composition and is excellent in both decorativeness and mechanical strength.
The above and other objects, features, and advantages of the present invention will become apparent from the following detailed description and the appended claims, with reference to the accompanying drawings.
[0009]
[Means for Solving the Problems]
That is, according to the present invention, it is composed of at least one polymer block (A) mainly composed of a vinyl aromatic monomer unit and at least one polymer block (B) mainly composed of a conjugated diene monomer unit. 100 parts by weight of a crosslinked block copolymer component (1) comprising a molecular chain of a base block copolymer to be used; and at least one colorant component (2) 0 selected from organic pigments, inorganic pigments, and organic dyes 0.001 to 20.0 parts by weight; a gel composition having a gel content of 60% by weight or more, wherein the molecular chain of the base block copolymer is an imide bond, an amide bond, or an ester bond. Cross-linked via a cross-linking section containing at least one bond selected from urethane bonds Characterized in that the colorant component is incorporated in the crosslinked product A colored body composition is provided.
[0010]
In the colored composition of the present invention, the polymer block (B) is particularly preferably a polymer block mainly composed of a hydrogenated conjugated diene monomer unit.
The colored body composition of the present invention may further contain a diluent, if desired, and have a gel content of 10 to 80% by weight, preferably 30 to 60% by weight. Dilution It may be a colored composition.
Also, a thermoplastic resin and the colored composition of the present invention Or diluted coloring composition The colored thermoplastic resin composition of the present invention having a gel content of 0.1 to 50% by weight is obtained by molding a colored thermoplastic resin molded article which has been decorated into a fleck pattern such as a stone pattern by molding. Obtainable. When molding is performed using the colored thermoplastic resin composition of the present invention, molding under a wide range of molding conditions is possible.
[0011]
In the colored thermoplastic resin molded article of the present invention produced from the colored thermoplastic resin composition having a gel content of 0.1 to 50% by weight, the colored composition has an average particle diameter of 10 to 30 in the thermoplastic resin. 2,000 μm, and the colored thermoplastic resin molded article exhibits an excellent decorative pattern such as a clear stone grain.
Furthermore, the above-mentioned colored body composition and colored thermoplastic resin composition of the present invention can be produced using an extruder.
Hereinafter, the present invention will be described in more detail.
[0012]
The block copolymer that can be used for producing the crosslinked block copolymer component (1) of the colored composition of the present invention includes at least one polymer block (A) mainly composed of a vinyl aromatic monomer unit, A molecular chain of a base block copolymer (hereinafter often simply referred to as a “block copolymer”) mainly composed of at least one polymer block (B) mainly composed of a conjugated diene monomer unit, or the base block copolymer. A modified block copolymer in which at least one type of functional group is introduced into the molecular chain of a hydrogenated base block copolymer obtained by hydrogenating a polymer (hereinafter often simply referred to as “hydrogenated block copolymer”). It is a polymer. Examples of the method for introducing a functional group include a method of introducing a functional group by graft addition to a block copolymer, and a method of introducing a functional group into a main chain by copolymerizing with a polymer block (A) or (B). . The type of the functional group to be introduced is not particularly limited, but at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a carboxylic acid group, and a carboxylic anhydride group is advantageous.
[0013]
As the modified block copolymer used in the present invention, a graft modified block copolymer in which a molecular unit having at least one group selected from a carboxylic acid group and a carboxylic anhydride group is bonded to a base block copolymer, A graft-modified hydrogenated block copolymer obtained by performing similar grafting on a hydrogenated base block copolymer is particularly preferably used. That is, if the polymer block (A) mainly composed of vinyl aromatic monomer units is "A" and the polymer block (B) mainly composed of conjugated diene monomer units is "B", for example,
AB
ABA,
ABAB,
ABBABA,
(AB) ₄ Si,
(ABA) ₄ Si
Graft-modified block copolymer produced by adding an unsaturated carboxylic acid to a vinyl aromatic compound-conjugated diene compound block copolymer having such a structure, and / or hydrogenating the above block copolymer A graft-modified hydrogenated block copolymer produced by subjecting the obtained vinyl aromatic compound-hydrogenated conjugated diene compound block copolymer to an addition reaction with an unsaturated carboxylic acid is particularly preferably used.
[0014]
The block copolymer in the present invention contains 5 to 60% by weight, preferably 10 to 55% by weight of a vinyl aromatic monomer unit and 40 to 50% by weight of a conjugated diene monomer unit or a hydrogenated conjugated diene monomer unit. It contains 95% by weight, preferably 45 to 90% by weight.
Further, the polymer block (A) mainly composed of vinyl aromatic monomer units in the block copolymer has a structure of a homopolymer block of vinyl aromatic monomer units or a vinyl aromatic monomer unit. A vinyl aromatic monomer unit and a conjugated diene monomer unit or a hydrogenated conjugated diene monomer unit containing 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more of a monomer unit Having the structure of a copolymer block.
[0015]
The polymer block (B) mainly composed of a conjugated diene monomer unit or a hydrogenated conjugated diene monomer unit has a homopolymer block structure of a conjugated diene monomer unit or a hydrogenated conjugated diene monomer unit. Or a conjugated diene monomer unit or water containing 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more of a conjugated diene monomer unit or a hydrogenated conjugated diene monomer unit. It has a structure of a copolymer block of a conjugated diene monomer unit and a vinyl aromatic monomer unit.
[0016]
In the polymer block (A) mainly composed of vinyl aromatic monomer units and the polymer block (B) mainly composed of conjugated diene monomer units or hydrogenated conjugated diene monomer units, The distribution of the vinyl aromatic monomer unit and the conjugated diene monomer unit or the hydrogenated conjugated diene monomer unit is not particularly limited, and even if the distribution is random, the distribution may be tapered (the monomer component along the longitudinal direction of the molecular chain). The content may be continuously increasing or decreasing), may be block-like, or may consist of any combination thereof.
[0017]
In addition, the blocks of both the polymer block (A) mainly composed of vinyl aromatic monomer units and the polymer block (B) mainly composed of conjugated diene monomer units or hydrogenated conjugated diene monomer units are formed. When there are two or more, each polymer block may have the same structure or different structures.
Examples of the vinyl aromatic compound that provides a vinyl aromatic monomer unit in the block copolymer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, p-tert-butylstyrene, and 1,1 ′. One or more of diphenylethylene and the like are selected, and styrene is particularly preferred.
[0018]
Further, as the conjugated diene compound for providing a conjugated diene monomer unit or a conjugated diene monomer unit for obtaining a hydrogenated conjugated diene monomer unit in the block copolymer, for example, butadiene, isoprene, One or more of 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable.
Furthermore, in the polymer block (B), the microstructure in the block is not particularly limited. For example, in a polybutadiene block, the amount of 1,2-vinyl bond is 10 to 65%, preferably 20 to 55%. Is preferred.
[0019]
Further, the block copolymer or hydrogenated block copolymer having the above-mentioned structure and used in the present invention generally has a number average molecular weight of 5,000 to 1,000,000, preferably 10,000 to 500,000. From the viewpoint of maintaining the balance between the crosslinking efficiency in producing the composition of the present invention, the physical properties of the composition, and the processability, 30,000 to 300,000 is a more preferable range, and the molecular weight distribution [weight] The ratio (Mw / Mn) between the average molecular weight (Mw) and the number average molecular weight (Mn)] is preferably 10 or less. The weight average molecular weight and the number average molecular weight can be determined by a gel permeation chromatogram method. In this case, standard polystyrene is used as a molecular weight standard. Further, the molecular structure of the block copolymer or hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.
[0020]
As an example of a method for producing the above hydrogenated block copolymer, a block copolymer is synthesized in an inert solvent using a lithium catalyst or the like by a method described in JP-B-40-23798, and then, for example, JP-B-42-8704 (corresponding to Australian Patent Application Publication No. 6453173 and Canadian Patent Application Publication No. 815575) and JP-B-43-6636 (corresponding to U.S. Pat. No. 3,333,024). The hydrogenation block used in the present invention is preferably subjected to hydrogenation in an inert solvent in the presence of a hydrogenation catalyst by a method described in JP-B-63-5401 (corresponding to U.S. Pat. No. 4,501,857). A copolymer can be produced. At this time, it is preferable to hydrogenate at least 80% of the aliphatic double bonds based on the conjugated diene monomer unit of the block copolymer. If the hydrogenation rate is less than 80%, weather resistance and heat discoloration resistance Is not enough. This hydrogenation rate may be 100%.
[0021]
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic monomer unit of the polymer block (A) and the vinyl aromatic monomer unit optionally copolymerized with the polymer block (B) is particularly important. Although there is no limitation, the hydrogenation rate is preferably 20% or less. If the hydrogenation rate exceeds 20%, the compatibility with the thermoplastic resin and the physical properties of the block copolymer deteriorate.
The amount of unhydrogenated aliphatic double bonds and the amount of unhydrogenated aromatic double bonds contained in the hydrogenated block copolymer can be determined by infrared spectroscopy, nuclear magnetic resonance spectroscopy, etc. it can.
[0022]
Then, an unsaturated carboxylic acid or a derivative thereof is added to the above-mentioned block copolymer or hydrogenated block copolymer in a solution state or a molten state, with or without the use of a radical initiator, to thereby obtain a carboxylic acid. An acid addition block copolymer (hereinafter often referred to as "modified block copolymer") or a carboxylic acid addition hydrogenated block copolymer (hereinafter often referred to as "modified hydrogenated block copolymer") is obtained. Any of the block copolymers or hydrogenated block copolymers that can be subjected to addition modification can be used as long as they are as defined above.
[0023]
Examples of the unsaturated carboxylic acid added to the block copolymer or the hydrogenated block copolymer include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, Examples include endo-cis-bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid and anhydrides of these dicarboxylic acids. Among these, maleic anhydride is particularly effective.
[0024]
The method of performing the modification reaction for producing these modified block copolymers or modified hydrogenated block copolymers is not particularly limited in the present invention. A production method that involves undesirable components such as a polymer gel or the like, or a problem that the melt viscosity is remarkably increased and processability is deteriorated is not preferable. Preferred methods include, for example, radicals in an extruder. There is a method in which a block copolymer or a hydrogenated block copolymer is reacted with an unsaturated carboxylic acid in the presence of an initiator.
[0025]
The amount of the unsaturated carboxylic acid added to the block copolymer or the hydrogenated block copolymer is preferably 20 parts by weight or less, more preferably 10 parts by weight or less per 100 parts by weight of the block copolymer or the hydrogenated block copolymer. preferable. Even if the added amount exceeds 20 parts by weight, the effect of the improvement is hardly increased as compared with the amount less than 20 parts by weight. The unsaturated carboxylic acids used in the present invention can be used alone or in combination of two or more.
[0026]
A softening agent can be added to the modified block copolymer or modified hydrogenated block copolymer for use. Softeners are softeners generally used for rubber and plastics, and include various compounds such as petroleum softeners, aliphatic softeners, and synthetic organic compounds. Specifically, for example, paraffinic process oil , Naphthene-based process oil, aroma-based process oil, vaseline, paraffin, polyethylene wax, polybutene, linseed oil, soybean oil, epoxidized soybean oil, dioctyl phthalate, stearic acid ester, ester plasticizers such as dioctyl adipate, and the like. In addition, depending on the purpose, a thermoplastic resin or a thermoplastic elastomer can be used as a softening agent.
[0027]
The above-mentioned softener is optionally added to impart flexibility and fluidity to the colored composition of the present invention. The amount is not particularly limited, but is preferably 200 parts by weight or less based on 100 parts by weight of the modified block copolymer or the modified hydrogenated block copolymer. If the amount exceeds 200 parts by weight, the softener may bleed out on the surface of the molded product containing the obtained composition or the mechanical properties may be deteriorated. However, when a thermoplastic resin or a thermoplastic elastomer is used as the softener, the amount of the softener is preferably 900 parts by weight based on 100 parts by weight of the modified block copolymer or the modified hydrogenated block copolymer. It is as follows.
[0028]
Further, a compatibilizing aid with the thermoplastic resin to be decorated may be added to the modified block copolymer or the modified hydrogenated block copolymer. The compatibilizing aid is a compatibilizing aid generally used for rubber, plastics, and the like, and a thermoplastic resin, a thermoplastic elastomer, or another polymer compound can be used as the compatibilizing aid. The compatibilizing aid improves the melt adhesion properties between the colored composition of the present invention and the thermoplastic resin to be decorated. The amount is not particularly limited, but is preferably 1900 parts by weight or less based on 100 parts by weight of the modified block copolymer or the modified hydrogenated block copolymer. If the amount exceeds 1900 parts by weight, bleed-out occurs in the obtained molded article, the original impact resistance and tensile elongation of the colored composition are reduced, and the mechanical properties of the molded article are reduced.
[0029]
The compatibilizing aid that can be used in the present invention is, for example, when the thermoplastic resin to be decorated is polystyrene, a rubber-reinforced polystyrene resin, or a modified polyphenylene ether resin, polystyrene, or styrene and a carboxylic acid group, or a maleic anhydride group. A vinyl compound having a functional group which does not react with the modified block copolymer and the modified hydrogenated block copolymer, which is appropriately selected from epoxy group, amide group, hydroxyl group and the like according to the type of the modifying agent of the modified block copolymer ( For example, when the functional group of the modified (hydrogenated) block copolymer is a carboxylic acid group, a vinyl compound containing a carboxylic acid group) or a copolymer with an olefin compound is preferably used. Further, when the thermoplastic resin to be decorated is polyethylene, a polyolefin resin such as polypropylene, or a polyacetal resin, a polyolefin or a copolymer of an olefin and a compound containing the above functional group is preferably used as a compatibilizing aid. You. When the thermoplastic resin to be decorated is ABS, AS resin, acrylic resin, polycarbonate resin, styrene and acrylonitrile, acrylic acid, acrylate, olefin, or vinyl compound containing the above functional group in the structure Among them, a copolymer composed of at least one kind can be preferably used as a compatibilizing aid.
[0030]
Further, when the thermoplastic resin to be decorated is a polyester resin, styrene and acrylonitrile, acrylic acid, acrylic acid ester, olefin, or a vinyl compound containing at least one of the above functional groups in the structure are commonly used. A mixture of a polymer and a polycarbonate resin can be preferably used. When used for decoration of other thermoplastic resins, a polymer compound or the like that is compatible and adhesive with the thermoplastic resin can be preferably used as a compatibilizing aid. As described above, the compatibilizing aids for the colorant composition have been exemplified, but these may be used alone or in combination of two or more. In addition, as long as it is one that improves or retains the melt adhesion with the thermoplastic resin, it can be used as a compatibilizing aid other than those exemplified.
[0031]
As the colorant component (2), one or more selected from desired organic pigments, inorganic pigments, and organic dyes can be used. The preferred amount of the colorant component (2) is such that the colorant component (2) is added in an amount of 100 parts by weight of the modified vinyl aromatic compound-conjugated diene compound block copolymer or the modified hydrogenated block copolymer. 0.001 to 20.0 parts by weight.
[0032]
Examples of pigments and dyes include organic pigments such as monoazo and condensed azo-based, anthraquinone-based, isoindolinone-based, heterocyclic-based, perinone-based, quinacridone-based, perylene-based, thioindigo-based, dioxazine-based, and phthalocyanine-based pigments. Titanium, carbon black, titanium yellow, iron oxide, ultramarine, cobalt blue, calcined pigments, metallic pigments such as metal particles such as aluminum particles, mica, inorganic pigments such as pearl pigments, anthraquinone-based, heterocyclic-based, perinone-based, etc. And organic dyes. The above pigments and dyes may be arbitrarily mixed for coloring.
[0033]
As the coloring method of the modified block copolymer or the modified hydrogenated block copolymer, an ordinary resin or thermoplastic elastomer coloring method can be adopted. That is, 0.1 to 20% by weight of a pigment or dye is preferably mixed with the modified block copolymer or modified hydrogenated block copolymer, and then melt-kneaded using an extruder, a Brabender, a heating stirrer, or the like. Then, a colored modified block copolymer or a colored modified hydrogenated block copolymer is obtained.
[0034]
As a method of crosslinking the color-modified block copolymer or the color-modified hydrogenated block copolymer, when the functional group introduced into the base block copolymer is, for example, a carboxylic acid group or a carboxylic anhydride group, There is a method of reacting with a cross-linking agent containing two or more functional groups that react with carboxylic acid or carboxylic anhydride or a chemical bond that exchanges with these groups in one molecule.
[0035]
In the present invention, as the crosslinking agent, a compound having two or more functional groups selected from an amino group, an isocyanate group, a hydroxyl group, an epoxy group, a carboxylic acid group, and a carboxylic anhydride group is particularly effectively used. Specifically, for example, ethylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,5-dimethyl-3-hexyne-2,5-diol, etc. Aliphatic diols, bisphenol-A, aromatic hydroxy compounds such as 2,3,5-trimethylhydroquinone, polyols such as trimethylolpropanediglycerol, pentaerythritol, resorcinol, ethylenediamine, 1,4-diaminobutane, Aliphatic diamines such as hexamethylenediamine, alicyclic diamines such as 1,3-diaminocyclohexane, p, p'-diaminocyclohexylmethane, and aromatics such as o, m, p-phenylenediamine, m-xylylenediamine Aliphatic diamines, diethyltriamine, f Polyamines such as xamethylenetetramine; diisocyanates such as hexamethylene diisocyanate and diphenylmethane diisocyanate; diglycidyl compounds such as neopentyl glycol diglycidyl ether and glycerol diglycidyl ether; Glycidyl compounds, alkylethanol such as N, N, -diethylethanolamine, aminoethylethanolamine, N-methylethanolamine, N-methyl-N, N'-dibutylethanolamine, mono-, di-, and tri-ethanolamine Amines, isopropanolamine, 3-aminopropanol, 2-hydroxyethylaminopropylamine, 2-amino-4-chlorophenol And leuco-1,4-diaminoanthraquinone.
[0036]
Further, as a polymer compound containing two or more functional groups selected from a hydroxyl group, an amino group, an isocyanate group, an epoxy group, a carboxylic acid group, and a carboxylic anhydride group, a monomer having the above functional group may be used. Or a functional group-containing polymer obtained by radical polymerization of another vinyl compound copolymerizable with the monomer, and a polymer obtained by polyaddition or polycondensation of a functional compound. Yes, a polymer main chain, a side chain or a functional group capable of undergoing a cross-linking reaction at a terminal position, preferably a hydroxyl group, an amino group, an isocyanate group, an epoxy group, a carboxylic acid group, or a carboxylic acid anhydride group. It is a polymer having two or more functional groups. For example, polyethylene glycol, polyglycols such as polybutylene glycol, ethylene-vinyl acetate copolymer of ethylene-vinyl acetate copolymer in which the vinyl acetate unit is saponified, liquid polybutadiene having hydroxyl groups at both ends, epoxy resin, ethylene And glycidyl methacrylate copolymers, and one or more of the above-mentioned polymers can be used.
[0037]
When using the above crosslinking agent, a compound having a small molecular weight is preferable from the viewpoint of crosslinking efficiency, and in terms of prevention of damage to health and safety in the production work of the colored thermoplastic resin composition and the colored thermoplastic resin molded article. Therefore, a compound having a large molecular weight is preferred, and therefore the molecular weight of the crosslinking agent is preferably in the range of 40 to 30,000. More preferably, the molecular weight is in the range of 50 to 2,000, and still more preferably, the molecular weight is in the range of 100 to 500.
[0038]
The amount of the crosslinking agent is 0.01 to 50 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the colored modified block copolymer or the colored modified hydrogenated block copolymer. The degree of crosslinking is selected from the range, and the degree of crosslinking of the crosslinked modified block copolymer component (1) can be adjusted.
When the color-modified block copolymer or the color-modified hydrogenated block copolymer is crosslinked as described above, the molecular chain of the block copolymer becomes at least one kind selected from imide bond, amide bond, ester bond, and urethane bond. Crosslinking is carried out via a crosslinking portion containing a bond, and thus a crosslinked colored block copolymer or a crosslinked colored hydrogenated block copolymer, that is, the colored composition of the present invention is obtained.
[0039]
As a means for effectively promoting the crosslinking of the color-modified block copolymer or the color-modified hydrogenated block copolymer, the color-modified block copolymer or the color-modified hydrogenated block copolymer is mixed with a cross-linking agent and melted or melted. After dissolution, a method of stirring or kneading at a temperature sufficient for the reaction can be adopted.
In the present invention, a cross-linking method using a melt kneader such as an extruder or a kneader is effective, and in order to prevent clogging of the extruder due to cross-linking, a resin or a thermoplastic elastomer containing no functional group in the structure, It is more effective to perform melt-kneading with a diluent such as a softener.
[0040]
As a method of qualifying the type of cross-linking, a cross-linked product after dissolving and removing a softener component and an extractable compatibilizing aid with a solvent, or a copolymer in which the cross-linked product is further swollen to remove pigments and dyes In contrast, methods such as infrared absorption spectroscopy and NMR spectroscopy are used.
As described above, the details of the preparation and the production method of the colored body composition of the present invention have been described.However, the method for introducing a functional group into the block copolymer or the hydrogenated block copolymer, the coloring method, the crosslinking method, etc. are as described above. There is no particular limitation, and it goes without saying that any production method can be used as long as the colored body composition of the present invention can be obtained.
[0041]
The colored body composition of the present invention has a gel content (Gel%) in the composition of 60% by weight or more, preferably 70% by weight or more, and particularly preferably 80% by weight or more. The upper limit of the gel content of the colored body composition of the present invention is 100% by weight.
When the gel content is 60% by weight or more, the colored composition of the present invention has good shape stability and thermal stability at the time of injection molding, and dyes matrix resin and the like around the colored composition. Substantially no pigment diffusion occurs, and therefore, the colored composition exhibits an excellent effect as a patterning agent for thermoplastic resin.
[0042]
The colored composition of the present invention has excellent melt adhesion properties with a thermoplastic resin, and is particularly good for polystyrene resin, polyethylene resin, polypropylene resin, polyamide resin, polyester resin, acrylic resin, polyphenylene ether resin, and polyacetal resin. Shows melt adhesion. In addition, the colored body composition exhibits a tensile elongation at break of 100% or more, and furthermore, the colored body composition of the present invention exhibits good melt adhesion to resin and deformability, shape stability, and elongation. A colored thermoplastic resin molded article having decorative properties obtained from a colored thermoplastic resin composition containing the above-described thermoplastic resin and the colored body composition of the present invention is colored by a conventional resin decoration technique. Mechanical properties such as tensile elongation, Izod impact strength, and dart impact strength are significantly improved as compared with resin molded articles.
[0043]
Furthermore, when the colored body composition of the present invention is used as a decorating agent, since the colored body composition is excellent in deformability and shape stability, a decorative pattern larger than the pin gate inner diameter of the mold can be formed, In addition, deformation and breakage of the patterning agent due to shear stress or the like do not occur, and the patterning agent in the molded body can maintain its original size, and thus the problem of the conventional resin decoration technology can be solved.
[0044]
The colored body composition of the present invention obtained by the above-described method is, if desired, diluted with a diluent such as a resin, a thermoplastic elastomer, a plasticizer, a fat or oil, a surfactant, an adhesive, an organic solvent, an aqueous solution, or a lubricant. Alternatively, a thermoplastic resin, a thermosetting resin, a varnish, or the like processed so as to be easily colored may be used.
The colored composition of the present invention containing a diluent is particularly preferred as a coloring agent for thermoplastic resins, thermoplastic elastomers, and thermosetting resins. In this case, the diluent is preferably a resin, a thermoplastic elastomer, a plasticizer, or a fat, and more preferably a thermoplastic resin or a thermoplastic elastomer.
[0045]
The thermoplastic resin that can be used as a diluent for the colored composition is a thermoplastic resin that can be used for general injection molding, for example, styrene resins, polyethylene, olefin polymers such as polypropylene, modified polyphenylene ether resins, polyacetal resins. Injection molding of vinyl chloride polymer or its copolymer, polycarbonate resin, polyamide resin, polyester resin, polyacrylate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, liquid crystal resin, etc. The thermoplastic resin used for the above can be used.
[0046]
Further, the thermoplastic elastomer that can be used as a diluent, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, urethane-based thermoplastic elastomer, PVC-based thermoplastic elastomer, Other examples include syndiotactic 1,2-polybutadiene, trans 1,4-polyisoprene, and ionomers.
[0047]
Further, as the plasticizer that can be used as a diluent, a plasticizer added for the purpose of imparting fluidity to an ordinary thermoplastic resin can be widely used, and examples thereof include a phosphate ester plasticizer, Phthalate plasticizers, aliphatic monobasic ester plasticizers (eg, zinc stearylate, sodium stearylate, etc.), dihydric alcohol plasticizers, oxyester plasticizers, other chlorinated paraffins, dinonyl And naphthalene.
[0048]
Examples of the thermosetting resin that can be used as a diluent include epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, furan resin, polyimide, poly-p- Thermosetting resins such as hydroxybenzoic acid, polyurethane, maleic acid resin, melamine resin, and urea resin are exemplified.
[0049]
Further, examples of fats and oils that can be used as a diluent include soybean oil, coconut oil, linseed oil, castor oil, whale oil, hydrogenated oil, other fatty acids and their esters, higher alcohols, glycerin compounds and the like.
When a styrene-based resin or a styrene-based thermoplastic elastomer is used as a diluent, the characteristics of the colored composition of the present invention are particularly good.
[0050]
As described above, the diluents that can be added to the coloring composition have been exemplified. However, these diluents can be used alone or in combination of two or more, and other diluents other than the above do not depart from the gist of the present invention. Can also be used.
Furthermore, the colored body composition of the present invention may be a mixture of two or more kinds of colored body compositions manufactured separately.
As a method for producing a colored body composition containing a diluent, a method in which a diluent is mixed with the colored body composition of the present invention and then melt-kneaded using an extruder, a Brabender, a kneader, or the like can be used. Particularly effective in the invention is a method of melt-kneading using an extruder.
[0051]
In addition, the gel content of the colored composition containing the diluent is preferably 10 to 80% by weight. In this case, the shape stability and heat stability of the decorative pattern such as stone-like pattern formed by the colored composition are improved. The properties are improved, and the pigments and dyes are not diffused from the colored composition to the surrounding thermoplastic resin and the like, and thus, after the colored composition is added to the thermoplastic resin and the like, it is preferably decorated when molded and processed. A colored resin molded product can be easily obtained. A more preferred gel content of the colored composition containing a diluent is 15 to 50% by weight, in which case a more preferred decorative molded article is obtained.
[0052]
The thermoplastic resin contained in the colored thermoplastic resin composition of the present invention is a thermoplastic resin that can be used for general injection molding, for example, a styrene-based resin, polyethylene, an olefin polymer such as polypropylene, a modified polyphenylene ether resin, Polyacetal resin, vinyl chloride polymer or their copolymer, polycarbonate resin, polyamide resin, polyester resin, polyacrylate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, liquid crystal resin, etc. A thermoplastic resin generally used for injection molding can be used. Of these thermoplastic resins, styrene resins are preferred.
[0053]
Styrene-based resins include polystyrene resin, AS resin, etc., rubber-reinforced polystyrene, ABS resin, AAS resin (acrylate / styrene / acrylonitrile resin), MBS resin (methyl (Methacrylate, butadiene, styrene resin).
[0054]
Rubber-reinforced polystyrene is a resin in which a rubber phase such as polybutadiene and SBR is dispersed in an island shape in a resin phase of a polymer mainly composed of styrene, and an ABS resin is a copolymer mainly composed of styrene and acrylonitrile. Is a resin phase in which a rubber phase such as polybutadiene and SBR is dispersed in the form of islands. AAS resin is a resin phase of a copolymer mainly composed of styrene and acrylonitrile. MBS resin is a resin in which a rubber phase of polybutadiene is dispersed in an island shape in a resin phase composed of a copolymer mainly composed of styrene and methyl methacrylate.
The above resins can be used alone or in combination.
[0055]
As a method for producing the colored thermoplastic resin composition of the present invention, a method of mixing one or more of the colored body compositions of the present invention with the thermoplastic resin can be employed. A more preferred method is a method of mixing one or more of the coloring composition of the present invention with a thermoplastic resin and then melt-kneading the mixture using an extruder, a Brabender, a kneader, or the like. A particularly effective method is extrusion. This is a method of melting and kneading using a machine.
[0056]
When the gel content of the colored thermoplastic resin composition of the present invention is 0.1 to 50% by weight, a colored thermoplastic resin molded article exhibiting a good and stable decorative pattern is obtained, and the gel content is 0%. When the content is 0.5 to 30% by weight, a more preferable decorative resin molded product is obtained.
[0057]
The colored thermoplastic resin composition of the present invention can be directly injection molded using an ordinary plastic molding injection molding machine. Further, a molded article such as an exterior part having a good pattern can be obtained by mixing the colored thermoplastic resin composition obtained by the present invention with a conventional resin composition and injection molding. The molding method of the colored thermoplastic resin composition obtained in the present invention is not limited to the injection molding method, and a molded article can be obtained by any other known molding methods such as a compression molding method and a hollow molding method.
[0058]
In the colored thermoplastic resin molded article of the present invention produced from the colored thermoplastic resin composition having a gel content of 0.1 to 50% by weight, the colored composition has an average particle diameter of 10 to 30,000 μm in the thermoplastic resin. Are dispersed as particles.
This colored thermoplastic resin molded article exhibits an excellent decorative pattern such as a clear stone tone, has a stable pattern shape, and substantially obscure contours of a speckle pattern due to diffusion of dyes and pigments. There is nothing. In particular, when the gel content of the colored thermoplastic resin composition to be used is 0.5 to 30% by weight, a more preferable decorative molded article is obtained.
[0059]
The use of the colored thermoplastic resin molded article of the present invention is not limited, and the colored thermoplastic resin molded article of the present invention may be, for example, an electric device, an electronic device, an OA device, an audio product, an automobile, a toy, furniture, It can be preferably used as a wash basin, bathtub, toilet bowl, interior and exterior parts of musical instruments, and the like.
The colored thermoplastic resin molded article of the present invention includes an air conditioner exterior part, a vacuum cleaner exterior part, a television exterior part, a computer exterior part, a CRT exterior part, a facsimile exterior part, a copier exterior part, an electric refrigerator exterior part, and an electric washing machine. It can be particularly preferably used as exterior parts, hanger parts, planters, tableware, musical instruments, toilet seats, washbasin exterior parts, furniture and the like.
[0060]
Further, known additives can be added to the colored body composition and the colored thermoplastic resin composition of the present invention. For example, additives such as antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, flame retardants, mold release agents, reinforcing materials such as glass fiber, asbestos, calcium carbonate, talc, calcium sulfate, and wood powder And fillers can be arbitrarily compounded.
[0061]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to the following examples.
The evaluation of various basic physical properties in the examples was performed by the following methods.
(1) Gel content (Gel%): Measure the weight (composition weight) of the colored body composition, the colored thermoplastic resin composition, and the colored thermoplastic resin molded article, and then diluent constituting the composition And a solvent for the thermoplastic resin, for example, xylene when the thermoplastic resin is a styrene resin, an acrylic resin, a modified PPE resin, etc., trichlorobenzene for the olefin resin, a polyacetal resin, hexafluoroisopropanol for the polyamide resin, etc. The solvent is extracted by the Soxhlet extraction method using the above solvent for 24 hours. The residue is washed with acetone, vacuum dried at 140 ° C., and the weight of the dried product (dry weight after extraction) is measured, and the gel content (%) is determined according to the following equation.
[0062]
(Equation 1)

[0063]
(2) Judgment of spot pattern: The clarity of the spot pattern of the colored thermoplastic resin molded article (90 mm × 50 mm × 3 mm flat molded article) obtained by injection molding was visually judged, and the average particle diameter (equivalent to a circle) (Mean value of diameter) is measured using an image processing apparatus [IP-1000 manufactured by Asahi Kasei Corporation].
[0064]
(3) Drop weight impact strength: Measured according to the Dupont drop weight impact test method. That is, first, the flat plate-shaped molded product is set on a table having a hemispherical recess having a diameter of 15.2 mm so as to cover the recess. A portion corresponding to the recess of the table of the flat plate molded body, in which a steel weight having a hemispherical shape with a diameter of 1/2 inch (12.7 mm) and a tip portion contacting the resin molded body having a weight of 1 kg is placed on the table. At a height of Hcm (the distance from the tip of the steel weight to the surface of the compact), and the impact strength [H (kg · cm)] when a crack occurs with a probability of 50% is determined.
[0065]
(Reference Example A) Method for producing hydrogenated block copolymer
(A-1); having a structure of polybutadiene-polystyrene-polybutadiene-polystyrene, having a bound styrene content of 35%, a number average molecular weight of 166,000, a molecular weight distribution of 1.04, and a 1,2-vinyl bond content of the polybutadiene portion of 37% Styrene-butadiene copolymerized elastomer, the polybutadiene portion was hydrogenated by the method described in JP-B-63-4841 (corresponding to U.S. Pat. No. 4,501,857), and the hydrogenated styrene-polybutadiene portion was 99% hydrogenated. A butadiene copolymer elastomer is obtained.
[0066]
(A-2); having a structure of polybutadiene-polystyrene-polybutadiene-polystyrene, having a bound styrene content of 22%, a number average molecular weight of 64,000, a molecular weight distribution of 1.03, and a 1,2-vinyl bond content of polybutadiene portion of 55% Except for using the styrene-butadiene copolymer elastomer of (A-1), a hydrogenated styrene-butadiene copolymer elastomer having a hydrogenation ratio of 98% in the polybutadiene portion is obtained.
[0067]
(Reference Example B) Method for producing modified (hydrogenated) block copolymer
(B-1): 2.0 parts by weight of maleic anhydride, 2,5-dimethyl-2,5-di (tertiary butyl par) per 100 parts by weight of the hydrogenated block copolymer obtained in (A-1) 0.2 parts by weight of oxy) hexane are mixed and melt-kneaded at a temperature of 250 ° C. by a twin-screw extruder having a diameter of 30 mm to carry out an addition modification reaction. The resulting modified hydrogenated block copolymer is obtained by adding 1.5 parts by weight of maleic anhydride per 100 parts by weight of the polymer.
[0068]
(B-2): 2.5 parts by weight of maleic anhydride and 0.25 parts by weight of dicumyl peroxide are mixed with 100 parts by weight of the hydrogenated block copolymer obtained in (A-2) to obtain a 30 mmφ diameter. The mixture is melt-kneaded at a temperature of 250 ° C. in a twin-screw extruder to perform an addition modification reaction. The resulting modified hydrogenated block copolymer is obtained by adding 1.8 parts by weight of maleic anhydride per 100 parts by weight of the polymer.
[0069]
(B-3): 2.0 parts by weight of maleic anhydride, 2,5-dimethyl-, per 100 parts by weight of a block copolymer having a polybutadiene-polystyrene-polybutadiene-polystyrene structure as a raw material of (A-1). 0.2 parts by weight of 2,5-di (tert-butylperoxy) hexane is mixed and melt-kneaded at a temperature of 250 ° C. by a twin-screw extruder having a diameter of 30 mm to perform an addition modification reaction. The resulting modified block copolymer is obtained by adding 1.7 parts by weight of maleic anhydride per 100 parts by weight of the polymer.
[0070]
(Reference Example C) Method for producing colored modified (hydrogenated) block copolymer
(C-1); 1.0 part by weight of carbon black powder is mixed with 100 parts by weight of the modified hydrogenated block copolymer obtained in (B-1), and melt-blended at 220 ° C. with a 30 mmφ twin screw extruder. Alchemy. The resulting colored modified hydrogenated block copolymer is black.
(C-2): per 100 parts by weight of the modified hydrogenated block copolymer obtained in (B-2), 0.3 part by weight of a perylene-based red dye (IRGAZIN RedBPT manufactured by Ciba Geigy, Switzerland) was mixed, and mixed with 30 mmφ Melt kneading and coloring at 220 ° C in a screw extruder. The resulting colored modified hydrogenated block copolymer has a bright red color.
[0071]
(C-3): 100 parts by weight of the modified hydrogenated block copolymer obtained in (B-1) was mixed with 0.2 part by weight of an anthraquinone-based yellow pigment (CROMOPHTAL Yellow AGR manufactured by Ciba-Geigy), and mixed with 30 mmφ Melt kneading and coloring at 220 ° C in a screw extruder. The resulting colored modified hydrogenated block copolymer becomes bright yellow.
(C-4): 2.0 parts by weight of a titanium oxide-based white pigment (TIOXIDE R-TC30PW 6 manufactured by ICI UK) is mixed with 100 parts by weight of the modified hydrogenated block copolymer obtained in (B-1). And melt kneading and coloring at 220 ° C. with a 30 mmφ twin screw extruder. The resulting colored modified hydrogenated block copolymer becomes white.
[0072]
(C-5); 5.0 parts by weight of aluminum particles (Supermirror SP-310 manufactured by Dia Kogyo Co., Ltd.) were mixed with 100 parts by weight of the modified block copolymer obtained in (B-3), and the mixture was mixed with 30 mmφ Melt kneading and coloring at 220 ° C in a screw extruder. The resulting colored modified block copolymer turns gray.
(C-6); 100 parts by weight of a styrene-maleic anhydride (92/8 by weight) copolymer, 2.0 parts by weight of carbon black powder per 100 parts by weight of the modified block copolymer obtained in (B-1) The parts are mixed and melt-kneaded and colored at 230 ° C. using a 30 mmφ twin screw extruder. The resulting colored modified block copolymer turns black.
[0073]
(C-7); 1500 parts by weight of a styrene-maleic anhydride (92/8 weight ratio) copolymer and 16.0 parts by weight of carbon black powder per 100 parts by weight of the modified block copolymer obtained in (B-1) The parts are mixed and melt-kneaded and colored at 230 ° C. using a 30 mmφ twin screw extruder. The resulting colored modified block copolymer turns black.
(C-8): 2500 parts by weight of a styrene-maleic anhydride (92/8 by weight) copolymer, 26.0 parts by weight of carbon black powder per 100 parts by weight of the modified block copolymer obtained in (B-1) The parts are mixed and melt-kneaded and colored at 240 ° C. with a 30 mmφ twin screw extruder. The resulting colored modified block copolymer turns black.
[0074]
(C-9); 100 parts by weight of a styrene-acrylic acid-maleic anhydride copolymer [Delpet 980N manufactured by Asahi Kasei Kogyo Co., Ltd.] per 100 parts by weight of the modified block copolymer obtained in (B-1); 2.0 parts by weight of carbon black powder are mixed and melt-kneaded and colored at 230 ° C. in a 30 mmφ twin screw extruder. The resulting colored modified block copolymer turns black.
(C-10); 2,400 parts by weight of a styrene-acrylic acid-maleic anhydride copolymer [Delpet 980N manufactured by Asahi Kasei Corporation] per 100 parts by weight of the modified block copolymer obtained in (B-1), 25.0 parts by weight of carbon black powder are mixed and melt-kneaded and colored at 230 ° C. by a 30 mmφ twin screw extruder. The resulting colored modified block copolymer turns black.
[0075]
(Reference Example D) Crosslinking of modified hydrogenated block copolymer
(D-1); 3.0 parts by weight of a crosslinking agent (diaminopolyethylene glycol: Jeffamine EDR-148 manufactured by Texaco Chemical Company, USA) per 100 parts by weight of the modified hydrogenated block copolymer obtained in (B-2); And 20 parts by weight of a paraffin oil [Diana Process Oil PW-380 manufactured by Idemitsu Kosan Co., Ltd.] are mixed and melt-kneaded at 220 ° C. using a Brabender to obtain a crosslinked product of (B-2).
[0076]
The resulting cross-linked hydrogenated block copolymer was shaken in xylene for 6 hours to extract the dissolved product, and the residue was measured for infrared absorption spectrum.
FIG. 1 shows an infrared absorption spectrum of the modified hydrogenated block copolymer obtained in (B-2), and FIG. 2 shows an infrared absorption spectrum of the crosslinked hydrogenated block copolymer. FIG. 1 shows an absorption band (1778 cm −1) derived from the C ＝ O stretching vibration of the added maleic anhydride. In FIG. 2, an absorption band (1743 cm −1) derived from C 伸縮 O stretching vibration of a crosslinked structure (an imide bond or an amide bond) is seen.
[0077]
(Reference Example E) Production Method of Colored Body Composition
(E-1); 3.0 parts by weight of 1,4-butanediol and polystyrene [Asahi Kasei polystyrene manufactured by Asahi Kasei Kogyo Co., Ltd.] per 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-1) 403R], and melt-knead at 230 ° C. for 10 minutes using a Brabender to obtain a colored body composition.
(E-2): 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-2), and high-density polyethylene [manufactured by Asahi Chemical Industry Co., Ltd.] Suntech HD-J311], and melt-knead at 230 ° C. for 10 minutes using a Brabender to obtain a colored body composition.
[0078]
(E-3); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of low-density polyethylene per 100 parts by weight of the color-modified hydrogenated block copolymer obtained in (C-3) [manufactured by Asahi Chemical Industry Co., Ltd.] 5 parts by weight of Suntec LD-M6525] and melt-kneaded at 230 ° C. for 10 minutes using a Brabender to obtain a colored body composition.
(E-4); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of polypropylene resin per 100 parts by weight of the color-modified hydrogenated block copolymer obtained in (C-4) [Asahi Kasei Co., Ltd. Polypro-M7546] is melt-kneaded at 230 ° C. for 10 minutes using a Brabender to obtain a colored body composition.
[0079]
(E-5); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of an acrylic resin per 100 parts by weight of the colored modified block copolymer obtained in (C-5) [Delpet 560F manufactured by Asahi Chemical Industry Co., Ltd.] 5 parts by weight and melt kneading at 230 ° C. for 10 minutes using a Brabender to obtain a colored composition.
(E-6); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of an ABS resin per 100 parts by weight of the colored and modified hydrogenated block copolymer obtained in (C-1) [Stylish manufactured by Asahi Kasei Kogyo Co., Ltd.] Rack ABS-121B], and melt kneading at 250 ° C. for 10 minutes using a Brabender to obtain a colored body composition.
(E-7); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of polyacetal resin per 100 parts by weight of the color-modified hydrogenated block copolymer obtained in (C-1) [Tenac, manufactured by Asahi Chemical Industry Co., Ltd.] 4510], and melt-kneading at 200 ° C. for 10 minutes using a Brabender to obtain a colored body composition.
[0080]
(Reference Example F) Method for producing colored body composition
(F-1); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of polystyrene [Asahi Kasei Polystyrene manufactured by Asahi Kasei Kogyo Co., Ltd.] per 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-1) 403R] and melt-kneaded at 220 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
(F-2): 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of a colored modified hydrogenated block copolymer obtained in (C-2), and a high-density polyethylene [manufactured by Asahi Kasei Corporation Suntech HD-J311] and melt-knead at 200 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
[0081]
(F-3); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of low-density polyethylene per 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-3) [manufactured by Asahi Chemical Industry Co., Ltd.] 400 parts by weight of Suntec LD-M6525] and melt-kneaded at 200 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
(F-4); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of polypropylene resin per 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-4) [Asahi Kasei Co., Ltd. Polypropylene-M7546], and melt-knead at 220 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
[0082]
(F-5); 3.0 parts by weight of 1,4-butanediol and acrylic resin [Delpet 560F manufactured by Asahi Kasei Kogyo Co., Ltd.] per 100 parts by weight of the colored modified block copolymer obtained in (C-5) 400 parts by weight, and melt-kneaded at 230 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
(F-6); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of ABS resin [100% by weight of the colored modified hydrogenated block copolymer obtained in (C-1)] Rack ABS-121B] and melt-knead at 240 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
[0083]
(F-7); 3.0 parts by weight of 1,4-butanediol and 100 parts by weight of a polyacetal resin per 100 parts by weight of the color-modified hydrogenated block copolymer obtained in (C-1) [Tenac manufactured by Asahi Kasei Kogyo Co., Ltd.] 4510] 400 parts by weight are mixed and melt-kneaded at 200 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
(F-8) to (F-10); 3.0 parts by weight of 1,4-butanediol per 100 parts by weight of the colored modified hydrogenated block copolymer obtained from (C-6) to (C-8) And 400 parts by weight of polystyrene [Asahi Kasei Kogyo Co., Ltd. Asahi Kasei Polystyrene 403R] are mixed and melt-kneaded at 230 ° C. with a 30 mm φ twin screw extruder to obtain a colored body composition.
[0084]
(F-11) to (F-12); 3.0 parts by weight of 1,4-butanediol per 100 parts by weight of the colored modified hydrogenated block copolymer obtained from (C-9) to (C-10) And 400 parts by weight of an ABS resin (Asahi Kasei Styrac ABS-121B manufactured by Asahi Kasei Kogyo Co., Ltd.) are mixed and melt-kneaded at 250 ° C. using a 30 mm φ twin screw extruder to obtain a colored body composition.
[0085]
(Reference Example G) Method for producing thermoplastic resin composition
(G-1) to (G-12); (F-1) to (F-12) per 100 parts by weight of the colored composition obtained in (F-1) to (F-12) in Reference Example F. 1,900 parts by weight of the same diluted polymer as used in 12) was mixed, and melt-kneaded with a 30 mm φ twin screw extruder at the same extrusion temperature as (F-1) to (F-12) (G- 1) to (G-12) thermoplastic resin compositions are obtained.
[0086]
(Reference Example H) Manufacturing method of thermoplastic resin molded article
(H-1) to (H-12): Injection molding is performed using the thermoplastic resin compositions obtained in (G-1) to (G-12) in (Reference Example G). That is, using a film gate mold (gate size: 0.9 mm × 2.0 mm) and an injection molding machine with a mold clamping pressure of 100 tons, at the same temperature as the extrusion temperature of (F-1) to (F-12). Injection molding is performed to obtain a thermoplastic resin molded product (90 mm × 50 mm × 3 mm large flat molded product) of (H-1) to (H-12).
[0087]
(Reference Example I) Production Method of Comparative Colored Body Composition
(I-1): As described below, a colored composition is obtained in the same manner as in Example B-1 in JP-A-2-103254. That is, 100 parts by weight of an o-cresol novolak glycidyl ether compound, 50 parts by weight of a phenol formaldehyde-based novolak (curing agent), 1 part by weight of 2-ethyl and 4-methylimidazole (curing accelerator) and 0.1 part by weight of carbon black. After mixing, the mixture is heated, kneaded and cured at 100 ° C., and further pressed at 170 ° C. for 15 minutes, and pulverized and classified to obtain a cured epoxy resin colored body composition having an average particle diameter of 300 μm.
[0088]
(I-2): As described below, a colored composition is obtained in the same manner as in Example 1 in JP-A-3-28148. That is, 100 parts by weight of methyl methacrylate, 150 parts by weight of calcium carbonate, 1 part by weight of TMPT (trimethylolpropane trimethacrylate), 1 part by weight of benzoyl peroxide, and 3 parts by weight of carbon black were mixed and then heated and kneaded and cured at 80 ° C. The product is pulverized and classified to obtain a colored composition having an average particle size of 500 μm.
[0089]
(I-3): As described below, a colored composition is obtained in the same manner as in Example 1 in JP-A-3-200841. That is, 100 parts by weight of a polypropylene-based silane crosslinkable polymer (Linklon XPM700B manufactured by Mitsubishi Yuka), 100 parts by weight of a propylene ethylene block copolymer (Mitsubishi Polypro-BC3 manufactured by Mitsubishi Yuka), and 1 part by weight of dibutyltin dilaurate After mixing 5 parts by weight of a master batch consisting of 0.1 parts by weight of magnesium stearate, 0.1 parts by weight of zinc stearate, and 0.3 parts by weight of carbon black, the mixture is heated and kneaded at 210 ° C. The obtained pellets were immersed in hot water at 90 ° C. for 5 hours, crosslinked, dehydrated, pulverized and classified to obtain a colored composition having an average particle diameter of 500 μm.
[0090]
(I-4): 1.0 part by weight of carbon black powder is mixed with 100 parts by weight of a styrene-maleic anhydride (92/8 by weight) copolymer, and melt-mixed and colored at 240 ° C. using a 30 mmφ twin screw extruder. I do. 3 parts by weight of 1,4-butanediol and 900 parts by weight of a polystyrene resin (Asahi Kasei Polystyrene 403R manufactured by Asahi Kasei Corporation) were mixed with 100 parts by weight of the obtained colored body, and melt-mixed and colored at 240 ° C. using a 30 mmφ twin-screw extruder. Then, a colored body composition is obtained.
[0091]
(Reference Example J) Method for producing thermoplastic resin composition
(J-1); 1,900 parts by weight of a polystyrene resin [Asahi Kasei Polystyrene 403R] is mixed with 100 parts by weight of the colored body composition obtained in (I-4) to obtain a thermoplastic resin composition. .
[0092]
(Examples 1 to 6 and Comparative Examples 1 to 3)
With respect to 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-1), 3.0 parts by weight of a crosslinking agent shown in Table 1 and 5 parts by weight of a polystyrene resin [Asahi Kasei Kogyo Co., Ltd. Asahi Kasei Polystyrene-666]. The parts are mixed and melt-kneaded at 230 ° C. for 10 minutes using a Brabender to obtain a colored composition. The gel content (Gel%) is determined for the obtained colored body composition. Further, 10,000 parts by weight of the above polystyrene resin was added to 100 parts by weight of the colored body composition frozen in liquid nitrogen and pulverized, and the same molding machine and film gate mold as in Reference Example H (gate size: Injection molding is performed at 220 ° C. using 0.9 mm × 2.0 mm) to obtain a thermoplastic resin molded body (a flat molded body having a size of 90 mm × 50 mm × 3 mm), and a spot pattern is determined. As is clear from Table 1, in Examples 1 to 6, the gel content of the colored body composition shows a value much larger than that of Comparative Examples 1 to 3, and the molded article shows a spot pattern with a clear contour. Table 1 shows the results.
[0093]
[Table 1]

[0094]
(Examples 7 to 8 and Comparative Examples 4 to 6)
1,4-butanediol is used as a crosslinking agent per 100 parts by weight of the colored modified hydrogenated block copolymer obtained in (C-1). Example 1 was mixed with 1.0 part by weight and 6.0 parts by weight in Examples 7 and 8, respectively, and 0.1 part by weight, 0 parts by weight and 200 parts by weight in Comparative Examples 4, 5, and 6 were mixed. A colored body composition is obtained in the same manner as described above. The gel content (Gel%) of the obtained colored body composition is measured in the same manner as in Example 1, and a thermoplastic resin molded body is prepared in the same manner as in Example 1 to determine a spot pattern. Table 2 shows the results including Example 1.
[0095]
[Table 2]

[0096]
(Examples 9 to 15)
The gel content (Gel%) was determined for the colored compositions obtained in (E-1) to (E-7) of Reference Example E, and the (E) was further determined for each 100 parts by weight of the colored compositions. -1) to 5,000 parts by weight of the same thermoplastic resin as used in (E-7) to obtain a thermoplastic resin composition, and to form a thermoplastic resin molded body in the same manner as in Example 1, The spot pattern is determined. Table 3 shows the results. As is clear from Table 3, the gel content shows a good value as in the other examples. Further, each of the thermoplastic resin moldings has a spot pattern with a clear outline.
[0097]
[Table 3]

[0098]
(Comparative Examples 7 to 12)
As shown in Table 4, six colorants are used separately. That is, the colored composition obtained in Reference Examples (I-1) to (I-4) (Comparative Examples 7 to 10), aluminum particles (Astroflake # 40BL, manufactured by Nippon Moisture Co., Ltd.) (Comparative Example 11) and mica For a thermoplastic resin composition obtained by melt-kneading 5000 parts by weight of a polystyrene resin (Asahi Kasei Polystyrene 403R) with respect to 100 parts by weight of each of the particles (Iriodin 163 manufactured by Merck Ltd.) (Comparative Example 12), The gel content (Gel%) is determined, and a spot pattern is determined for the molded body. Further, a falling weight impact test is performed together with the resin molded body obtained in Example 9. Table 4 shows the results. In Comparative Examples 7 to 12, the falling weight impact strength was significantly inferior to that of Example 9, and in Comparative Example 9, the pigment was diffused into the matrix resin from the colored composition, and the spot pattern did not have a clear outline. .
[0099]
[Table 4]

[0100]
(Examples 16 to 22)
Obtained in (F-1) to (F-7) of Reference Example F Dilution The gel content (Gel%) is determined for the colored body composition. Further, 500 parts by weight of the same thermoplastic resin as used in (F-1) to (F-7) were mixed with 100 parts by weight of each colored body composition to prepare a thermoplastic resin composition. In the same manner as in Example 1, a thermoplastic resin molded body is obtained. Table 5 shows the results. The gel content shows a good value, and the thermoplastic resin molded article shows a spot pattern with a clear outline.
[0101]
[Table 5]

[0102]
(Examples 23 to 29)
Obtained in (G-1) to (G-7) of Reference Example G Coloring The gel content (Gel%) is determined for the thermoplastic resin composition. Further, for the thermoplastic resin molded products obtained in (H-1) to (H-7) of Reference Example H, determination of gel content, spot pattern, and measurement of average particle size are performed. Table 6 shows the results. Gel% shows a good value, and the thermoplastic resin molded article exhibits a spot pattern with a clear outline.
[0103]
[Table 6]

[0104]
(Examples 30 to 32, Comparative Examples 13 to 14)
A thermoplastic resin composition (Example 30) in which 5,000 parts by weight of a polystyrene resin (Asahi Kasei Polystyrene 403R) was added to 100 parts by weight of the colored body composition of Example 4 frozen in liquid nitrogen and then pulverized. 16 thermoplastic resin compositions (Example 31), the thermoplastic resin composition of Example 23 (Example 32), and aluminum particles [Astroflake # 70BL manufactured by Nippon Moisture Shield Co., Ltd. (particle diameter 1 mm x 1 mm)] 100 weight Parts and the thermoplastic resin composition obtained by melt-kneading 5,000 parts by weight of the polystyrene resin (Comparative Example 13), 100 parts by weight of mica particles [Mica S20 (particle size: 700 μm, manufactured by REPCO)] and 5000 parts by weight of the polystyrene resin Is molded using a thermoplastic resin composition (Comparative Example 14), and the molding condition is to use a pin gate mold having a gate diameter of 800 μm. Obtaining a flat thermoplastic resin molded article in the same manner as in Example 1. As is clear from Table 7, when the colored composition of the present invention is used, the maximum particle diameter in the thermoplastic resin molded article is larger than the gate diameter, and a clear spot pattern is exhibited. On the other hand, in Comparative Example 13, the aluminum particles are deformed, and in Comparative Example 14, the mica particles are pulverized to reduce the average particle diameter. Comparative Examples 13 and 14 have no particles larger than the gate diameter.
[0105]
[Table 7]

[0106]
(Examples 33 to 35, Comparative Examples 15 to 17)
In Examples 33 to 35, the thermoplastic resins obtained in Reference Examples (H-8), (H-9) and (H-11), and in Comparative Examples 15 and 16, thermoplastic resins obtained in Reference Examples (H-10) and (H-12). In Comparative Example 17, the thermoplastic resin composition obtained in Reference Example (J-1) was molded in the same manner as in Example 1. As in the case of Comparative Example 9 and Comparative Examples 7 to 12, the determination of Gel%, the spot pattern, and the falling weight impact test are performed. The results are shown in Table 8 together with Example 9. Comparative Examples 15 and 17 are all significantly inferior in falling weight impact strength as compared with Examples 9, 33 and 34, and Comparative Example 16 is significantly inferior in falling weight impact strength compared to Example 35.
[0107]
[Table 8]

[0108]
【The invention's effect】
The decorative patterning agent having a stone-grain tone or the like comprising the colored composition of the present invention has good shape stability and heat stability during injection molding. Further, there is no diffusion of the dye / pigment into the matrix resin or the like around the colorant composition. Therefore, according to the present invention, it has become possible to provide a patterning agent for a thermoplastic resin using a thermoplastic elastomer as a main raw material.
[0109]
Further, the colored composition of the present invention is excellent in elongation and melt adhesion to a thermoplastic resin. For this reason, the colored thermoplastic resin molded article of the present invention significantly improves important physical properties of the resin, such as tensile properties and impact strength, as compared with the prior art.
Further, the colored composition of the present invention is excellent in deformability and shape stability. For this reason, the particles of the patterning agent do not break at the time of molding, and the spot pattern in the molded body maintains the original size of the patterning agent particles. Also, a molded article containing a decorating agent having a particle diameter larger than the inner diameter of the injection port of the injection molding machine can be molded, and it is possible to impart a decorative pattern which cannot be achieved by the conventional technology.
[Brief description of the drawings]
FIG. 1 shows an infrared absorption spectrum of a modified hydrogenated block copolymer obtained in Reference Example B (B-2).
FIG. 2 shows an infrared absorption spectrum of a crosslinked hydrogenated block copolymer (D-1) obtained by crosslinking the modified hydrogenated block copolymer (B-2) in Reference Example D.

Claims (8)

A base block copolymer mainly composed of at least one polymer block (A) mainly composed of vinyl aromatic monomer units and at least one polymer block (B) mainly composed of conjugated diene monomer units. crosslinked block copolymer component consisting of molecular chains (1) 100 parts by weight; and organic pigments, inorganic pigments, at least one coloring agent component selected from the group consisting of organic dyes (2) from 0.001 to 20.0 parts by weight A colorant composition having a gel content of 60% by weight or more, wherein the molecular chain of the base block copolymer is selected from an imide bond, an amide bond, an ester bond, and a urethane bond. A colored composition which is crosslinked via a crosslinking portion containing at least one type of bond, and wherein the colorant component is incorporated in the crosslinked product. The colored composition according to claim 1, wherein the polymer block (B) is a polymer block mainly composed of a hydrogenated conjugated diene monomer unit. 3. The colored composition according to claim 1, which is produced using an extruder. A diluted colorant composition having a gel content of 10 to 80% by weight obtained by adding a diluent to the colorant composition according to claim 1 or 2. The diluted colorant composition according to claim 4, which is produced using an extruder. Coloring having a gel content of 0.1 to 50% by weight obtained by containing a thermoplastic resin and the colored composition according to claim 1 or a thermoplastic resin and a diluted colored composition according to claim 4. Thermoplastic resin composition. The colored thermoplastic resin composition according to claim 6, which is produced using an extruder. A colored thermoplastic resin molded article produced from the colored thermoplastic resin composition according to claim 6, wherein the colored composition is dispersed in the thermoplastic resin as particles having an average particle diameter of 10 to 30,000 μm. Colored thermoplastic resin molding.

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