JPS6214576B2 - - Google Patents
Info
- Publication number
- JPS6214576B2 JPS6214576B2 JP53102743A JP10274378A JPS6214576B2 JP S6214576 B2 JPS6214576 B2 JP S6214576B2 JP 53102743 A JP53102743 A JP 53102743A JP 10274378 A JP10274378 A JP 10274378A JP S6214576 B2 JPS6214576 B2 JP S6214576B2
- Authority
- JP
- Japan
- Prior art keywords
- black
- pigment
- component
- weight
- ethylene
- 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
Links
- 239000000049 pigment Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- -1 polyethylene Polymers 0.000 description 11
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 2
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明はエチレン・プロピレン−ブロツク共重
合体と黒色成分を含む多成分系顔料との組成物に
関するものである。
ポリエチレン、ポリプロピレンまたはそれらの
ブレンド品等のポリオレフインを多成分顔料で中
間色に着色する場合、カーボンブラツク、フアー
ネスブラツク、アセチレンブラツク、ボーンブラ
ツク、ランプブラツク、グラフアイト等の炭素系
顔料、鉄、銅、クロム等の金属の酸化物である焼
成顔料またはフタロシアニン系顔料（シアニンブ
ラツク）、アニリンブラツク等の有機顔料が黒色
成分顔料として用いられ、とりわけ経済性の点か
ら一般にカーボンブラツクが用いられる。
一方、製品として要求される性能は種々多様化
して来ており、これらの要求をみたすには従来の
ポリオレフインあるいはそれらのブレンドでは不
充分であり、共重合型特にブロツク共重合型のポ
リオレフインが要求されることが多い。
一般にポリオレフインを着色する場合、金属石
けん等で分散処理した顔料とポリオレフインとを
ミキサー等でブレンドし、そのまゝ成形するか、
あるいはブレンド物を溶解押出しし、カツテイン
グしたカラーペレツトを用いて成形する。
ところがエチレン・プロピレンブロツク共重合
体を黒色顔料、特に経済性の点から通常用いられ
るカーボンブラツクを黒色成分として含有する多
成分系顔料で着色した場合カーボンブラツクの偏
在による色むらが生じ易く、殊に製品の成形に際
して用いられる射出成形において溶融樹脂に摩擦
力またはせん断力を受ける部分例えばピンゲート
附近や製品の薄肉部に色むらを生じ易い。例えば
エチレン・プロピレンブロツク共重合体にカーボ
ンブラツクとベンガラ赤を配合して茶色に着色し
て射出成形した場合ピンゲート周辺にカーボンブ
ラツクの濃度の低い部分、即ち黒色度の薄い部分
を生じ赤の縞模様が現れる。
この色むらは製品価値に対して極めて大きな問
題であり、特にその特性上エチレン・プロピレン
ブロツク共重合体の適用される大型部品にあつて
は色むらの存在は極めて目立ち易いため致命的で
ある。
また最近はポリマー自体の性質改良と共に寸法
安定性向上、難燃化、燃焼性改善、力学特性改良
その他種々の要求から炭酸カルシウム、タルク、
硫酸バリウム、ガラス繊維等の充填材が配合され
る場合が多くなつて来た。このような充填材を含
有する系を着色する場合には、充填材自体の有す
る着色力を打消すために顔料の使用濃度は充填材
を含まない系に対するよりも大となることが多
い。顔料の使用濃度が大きくなると、その色むら
は一層顕著に現れる傾向があり、この点からもエ
チレン・プロピレン−ブロツク共重合体の着色に
おける色むらの解消は特に重要である。
このような多成分系顔料による色むらはポリエ
チレン、ポリプロピレン等のホモポリマーにおい
ては生ぜず、共重合型樹脂特にエチレン・プロピ
レン−ブロツク共重合体において黒色顔料が多成
分顔料中10乃至80重量％程度配合された場合に生
じ易く、その原因については必ずしも明かではな
い。前記の如くエチレン・プロピレン−ブロツク
共重合体はそのすぐれた特性から自動車内装部品
等の大型成形部品に用いられ、その色むら解消は
極めて重要な問題である。この色むらの大きな原
因の１つは着色に用いる多成分系顔料の黒色成分
の偏在に起因するところから、各種の黒色顔料に
ついて検討した結果特定の黒色顔料を多成分系顔
料の黒色成分として用いることにより、この色む
らを生じないポリオレフイン樹脂組成物を得るこ
とができた。
即ち本発明はエチレン・プロピレン−ブロツク
共重合体99.9乃至95重量％と、黒色成分として鉄
黒10乃至80重量％含有する多成分系顔料0.1乃至
５重量％とからなる顔料含有ポリオレフイン組成
物である。
本発明に用いられるエチレン・プロピレン−ブ
ロツク共重合体はエチレン含量が１乃至50重量
％、プロピレン含量が99乃至50重量％のブロツク
共重合体である。この共重合体の製造方法につい
ては例えば特公昭40−11623、同43−11230または
同44−16668に記載されている。本発明における
ブロツク共重合体は前記エチレン又はプロピレン
の一部がC4乃至C6のオレフインに置換えられた
ものであつても使用し得る。
本発明において多成分系顔料の黒色成分として
用いられる鉄黒は一般式Fe3O4で表わされる酸化
鉄（）鉄（）（四三酸化鉄）を95％以上含
む、平均粒径が0.1乃至1.0の黒色顔料である。
この鉄黒が多成分系顔料中に黒色成分として使
用される量は、多成分系顔料の10乃至80重量％で
あり、所望する色調によつて変化する。即ち量が
多いほど黒みが強くなる。また上記範囲外、即ち
黒色顔料が一方的に多いか少ない場合には色むら
は生じない。
この黒色顔料と併用される他成分系顔料の他の
成分である顔料は一般にポリオレフインの着色用
に使用される顔料で、特に制限はないが、無機顔
料としてはベンガラ、酸化チタン、カドミイエロ
ー、カドミレツド、亜鉛華、群青、コバルトブル
ー、炭酸カルシウム、チタンイエロー、鉛白、鉛
丹、黄鉛、紺青等である。また有機顔料としては
キナクリドン、ポリアゾイエロー、アンスラキノ
ンイエロー、ポリアゾレツド、アゾレーキイエロ
ー、ペリレン、フタロシアニンブルー、フタロシ
アニングリーン、イソインドリノンイエロー等が
ある。
鉄黒を10乃至80重量％含有する多成分系顔料
は、エチレン・プロピレン−ブロツク共重合体と
配合された場合の全体に対して一般に0.1乃至５
重量％用いられる。５重量％以上では一般にこれ
以上使用しても色調に変化はなく0.1重量％以下
では色が弱すぎる。通常0.4乃至2.5重量％が使用
される。
本発明の組成物には所望に応じて適当量の他の
樹脂、充填材、あるいは分散剤、酸化防止剤、滑
剤等の添加剤を配合することができる。即ち、ポ
リエチレン、ポリプロピレン等のポリオレフイ
ン、エチレン−プロピレンゴム、スチレン−ブタ
ジエンゴム、ポリイソブチレン等のゴム成分、タ
ルク、クレー、シリカ、硫酸バリウム、炭酸カル
シウム、ガラス繊維、木粉等の無機、有機充填材
または強化材、および種々の添加剤である。この
ように本発明の組成物に他の成分が配合された場
合でも、エチレン・プロピレン−ブロツク共重合
体に対する多成分系顔料の配合比は前述の範囲で
選ばれる。
本発明による顔料含有ポリオレフイン組成物を
作るための顔料のポリオレフインへの配合および
成形は常法により行なわれ、例えば粉末のまゝ
（ドライカラー法）、カラーコンセントレートとし
て（マスターバツチ法）、液状で（リキドカラー
法）、あるいはカラーコンパウンドを経て押出機
または射出成形機で成形される。
本発明によるポリオレフイン樹脂組成物は成形
加工時の熱あるいはせん断力等にも拘らず、成形
品とした場合に均一な顔料分散が得られ、色むら
現象を生じないのですぐれた外観を有する製品が
得られる。
実施例１〜５および比較例１〜４
平均粒径約２μのアニリンブラツク、平均粒径
約0.27μで四三酸化鉄96重量％含有の鉄黒、平均
粒径約３μのシアニンブラツク、フアーネスカー
ボン、クロム酸化物系焼成顔料、ベンガラレツド
および有機混合顔料（フタロシアニングリーン：
イソインドリノンイエロー＝１：６の混合物）の
各顔料の所定配合比とエチレン含量８重量％、
MFR1.8のエチレン・プロピレン−ブロツク共重
合体とをスーパーミキサー（川田製作所製）にて
混合した後、一軸押出機（三菱重工製）で造粒
し、着色ペレツトを得た。
次に射出成形機（多機製作所製）にて上記ペレ
ツトを用いて所定量の顔料成分を含有する350mm
×100mm×２mmの板状成形品（ゲートは１mmφの
ピンゲート）を成形し、その色むら発生の状況を
観察した。結果は第１表に示す。
この結果から、本発明で用いるエチレン・プロ
ピレン−ブロツク共重合体を多成分系顔料で着色
する場合、黒色顔料成分としてカーボンブラツク
に代えて鉄黒を用いた材料は成形品の色むら発生
を防止した優れた材料であることが判る。
なお、参考のためにポリプロピレン
（MFR2.0）を、カーボンブラツクを黒色顔料成
分とした多成分系顔料で着色した材料についても
実験したが（第１表中の参考例１）、この場合色
むらは発生せず、従つて色むらは共重合体型ポリ
マーに特有のものであることを観認した。
実施例６〜９および比較例５、６
前記各実施例および比較例と同様の方法で各種
着色ペレツトを得、射出成形する際に各種顔料お
よび他の樹脂成分に加えて無機充填材として平均
粒径１μの沈降性硫酸バリウムを所定量配合し、
第１表の如き組成成分となした成形品の色むら発
生状況を観察した。結果は第１表に示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition of an ethylene-propylene block copolymer and a multicomponent pigment containing a black component. When polyolefins such as polyethylene, polypropylene, or blends thereof are colored with multi-component pigments, carbon-based pigments such as carbon black, furnace black, acetylene black, bone black, lamp black, graphite, iron, copper, A fired pigment which is an oxide of a metal such as chromium or an organic pigment such as a phthalocyanine pigment (cyanine black) or an aniline black is used as the black component pigment, and carbon black is generally used from the viewpoint of economical efficiency. On the other hand, the performance required for products has become increasingly diverse, and conventional polyolefins or their blends are insufficient to meet these demands, and copolymer type polyolefins, especially block copolymer type polyolefins, are required. Often. Generally, when coloring polyolefin, pigments dispersed with metal soap etc. and polyolefin are blended in a mixer etc., and then molded as is, or
Alternatively, the blend is melt extruded and molded using cut color pellets. However, when an ethylene-propylene block copolymer is colored with a black pigment, especially a multi-component pigment containing carbon black as a black component, which is commonly used from an economic point of view, color unevenness is likely to occur due to the uneven distribution of carbon black. In injection molding used to mold products, color unevenness is likely to occur in areas where the molten resin is subjected to frictional force or shearing force, such as near pin gates or in thin-walled areas of the product. For example, when ethylene-propylene block copolymer is blended with carbon black and red red red and colored brown and injection molded, a region with a low concentration of carbon black, that is, a region with a low degree of blackness, appears around the pin gate, resulting in a red striped pattern. appears. This color unevenness is an extremely serious problem in terms of product value, and is especially fatal for large parts to which ethylene-propylene block copolymers are applied because the presence of color unevenness is extremely noticeable. Recently, calcium carbonate, talc,
Fillers such as barium sulfate and glass fiber are increasingly being added. When coloring systems containing such fillers, the concentration of pigment used is often higher than for systems without fillers in order to counteract the coloring power of the fillers themselves. As the concentration of pigment used increases, the color unevenness tends to become more pronounced, and from this point of view as well, it is particularly important to eliminate color unevenness when coloring ethylene-propylene block copolymers. Such color unevenness due to multi-component pigments does not occur in homopolymers such as polyethylene and polypropylene, and in copolymer resins, especially ethylene-propylene block copolymers, the black pigment is about 10 to 80% by weight of the multi-component pigments. This is likely to occur when the drug is mixed with other substances, and the cause is not necessarily clear. As mentioned above, ethylene-propylene-block copolymers are used for large molded parts such as automobile interior parts because of their excellent properties, and eliminating color unevenness is an extremely important problem. One of the major causes of this color unevenness is due to the uneven distribution of the black component of the multi-component pigment used for coloring, so after studying various black pigments, a specific black pigment is used as the black component of the multi-component pigment. By doing so, it was possible to obtain a polyolefin resin composition that does not cause this color unevenness. That is, the present invention is a pigment-containing polyolefin composition comprising 99.9 to 95% by weight of an ethylene-propylene block copolymer and 0.1 to 5% by weight of a multicomponent pigment containing 10 to 80% by weight of iron black as a black component. . The ethylene/propylene block copolymer used in the present invention is a block copolymer having an ethylene content of 1 to 50% by weight and a propylene content of 99 to 50% by weight. The method for producing this copolymer is described, for example, in Japanese Patent Publications No. 40-11623, No. 43-11230, and No. 44-16668. In the block copolymer of the present invention, a part of the ethylene or propylene may be replaced with a C 4 to C 6 olefin. The iron black used as the black component of the multi-component pigment in the present invention contains 95% or more of iron oxide () iron () (triiron tetroxide) represented by the general formula Fe 3 O 4 and has an average particle size of 0.1 to 1. 1.0 black pigment. The amount of iron black used as a black component in a multi-component pigment ranges from 10 to 80% by weight of the multi-component pigment and varies depending on the desired color tone. That is, the larger the amount, the stronger the blackness. Further, outside the above range, that is, when the black pigment is unilaterally large or small, color unevenness does not occur. Pigments that are other components of the other component pigments used in combination with this black pigment are pigments that are generally used for coloring polyolefins, and are not particularly limited, but examples of inorganic pigments include red iron oxide, titanium oxide, cadmium yellow, and cadmium red. , zinc white, ultramarine blue, cobalt blue, calcium carbonate, titanium yellow, lead white, red lead, yellow lead, and navy blue. Examples of organic pigments include quinacridone, polyazo yellow, anthraquinone yellow, polyazole, azo lake yellow, perylene, phthalocyanine blue, phthalocyanine green, and isoindolinone yellow. Multi-component pigments containing 10 to 80% by weight of iron black generally contain 0.1 to 5% by weight of iron black when blended with the ethylene-propylene block copolymer.
% by weight is used. If it is more than 5% by weight, there is generally no change in color tone even if it is used more than this, and if it is less than 0.1% by weight, the color is too weak. Usually 0.4 to 2.5% by weight is used. The composition of the present invention may contain appropriate amounts of other resins, fillers, or additives such as dispersants, antioxidants, and lubricants, as desired. That is, polyolefins such as polyethylene and polypropylene, rubber components such as ethylene-propylene rubber, styrene-butadiene rubber, and polyisobutylene, and inorganic and organic fillers such as talc, clay, silica, barium sulfate, calcium carbonate, glass fiber, and wood flour. or reinforcing materials, and various additives. Even when other components are blended into the composition of the present invention, the blending ratio of the multicomponent pigment to the ethylene/propylene block copolymer is selected within the above-mentioned range. The blending and molding of the pigment into the polyolefin to produce the pigment-containing polyolefin composition according to the present invention can be carried out by conventional methods, for example, as a powder (dry color method), as a color concentrate (masterbatch method), or as a liquid ( (liquid color method), or molded with a color compound using an extruder or injection molding machine. When the polyolefin resin composition of the present invention is made into a molded product, it can achieve uniform pigment dispersion and do not cause color unevenness, despite the heat or shearing force during the molding process, resulting in a product with an excellent appearance. can get. Examples 1 to 5 and Comparative Examples 1 to 4 Aniline black with an average particle size of about 2μ, iron black containing 96% by weight of triiron tetroxide with an average particle size of about 0.27μ, cyanine black with an average particle size of about 3μ, furnace Carbon, chromium oxide fired pigments, red iron and organic mixed pigments (phthalocyanine green:
A mixture of isoindolinone yellow = 1:6) with a predetermined blending ratio of each pigment and an ethylene content of 8% by weight,
After mixing with an ethylene/propylene block copolymer having an MFR of 1.8 using a super mixer (manufactured by Kawada Seisakusho), the mixture was granulated using a single screw extruder (manufactured by Mitsubishi Heavy Industries) to obtain colored pellets. Next, using an injection molding machine (manufactured by Taki Seisakusho), the pellets were molded into a 350 mm molding machine containing a predetermined amount of pigment components.
A plate-shaped molded product measuring 100 mm x 2 mm (the gate was a pin gate with a diameter of 1 mm) was molded, and the occurrence of color unevenness was observed. The results are shown in Table 1. From this result, when the ethylene propylene block copolymer used in the present invention is colored with a multi-component pigment, materials using iron black instead of carbon black as the black pigment component prevent color unevenness in molded products. It is clear that it is an excellent material. For reference, we also experimented with a material in which polypropylene (MFR2.0) was colored with a multi-component pigment containing carbon black as the black pigment component (Reference Example 1 in Table 1), but in this case, color unevenness was observed. It was observed that the color unevenness was unique to copolymer-type polymers. Examples 6 to 9 and Comparative Examples 5 and 6 Various colored pellets were obtained in the same manner as in the above Examples and Comparative Examples, and during injection molding, average particles were added to various pigments and other resin components as an inorganic filler. A predetermined amount of precipitated barium sulfate with a diameter of 1μ is blended,
The occurrence of color unevenness in molded products made with the composition components shown in Table 1 was observed. The results are shown in Table 1. 【table】
Claims (1)
ン・プロピレン−ブロツク共重合体99.9乃至95重
量％と、黒色成分として鉄黒を10乃至80重量％含
有する多成分系顔料0.1乃至５重量％とからなる
ことを特徴とする顔料含有ポリオレフイン組成
物。1 Consists of 99.9 to 95% by weight of an ethylene/propylene block copolymer with a propylene content of 99 to 50% by weight, and 0.1 to 5% by weight of a multicomponent pigment containing 10 to 80% by weight of iron black as a black component. A pigment-containing polyolefin composition characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10274378A JPS5531801A (en) | 1978-08-25 | 1978-08-25 | Pigment-containing polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10274378A JPS5531801A (en) | 1978-08-25 | 1978-08-25 | Pigment-containing polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5531801A JPS5531801A (en) | 1980-03-06 |
| JPS6214576B2 true JPS6214576B2 (en) | 1987-04-02 |
Family
ID=14335706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10274378A Granted JPS5531801A (en) | 1978-08-25 | 1978-08-25 | Pigment-containing polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5531801A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0536590U (en) * | 1991-05-28 | 1993-05-18 | 株式会社タカラ | Commodity vending machine |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5934601B2 (en) * | 2012-07-31 | 2016-06-15 | 日本ピグメント株式会社 | Automotive underhood parts |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4833255A (en) * | 1971-09-06 | 1973-05-08 | ||
| JPS50160519A (en) * | 1974-05-18 | 1975-12-25 | ||
| JPS5130486A (en) * | 1974-07-04 | 1976-03-15 | Siemens Ag | Handotaidebaisuto sonoseizohoho |
| JPS523684A (en) * | 1975-06-27 | 1977-01-12 | Showa Denko Kk | Process for preparing ropylene copolymer |
| JPS5239623A (en) * | 1975-09-20 | 1977-03-28 | Katayama Chem Works Co Ltd | Process for preparation of bromoacetic acid esters |
| JPS547447A (en) * | 1977-06-20 | 1979-01-20 | Fuji Photo Film Co Ltd | Coloring of high polymer |
-
1978
- 1978-08-25 JP JP10274378A patent/JPS5531801A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4833255A (en) * | 1971-09-06 | 1973-05-08 | ||
| JPS50160519A (en) * | 1974-05-18 | 1975-12-25 | ||
| JPS5130486A (en) * | 1974-07-04 | 1976-03-15 | Siemens Ag | Handotaidebaisuto sonoseizohoho |
| JPS523684A (en) * | 1975-06-27 | 1977-01-12 | Showa Denko Kk | Process for preparing ropylene copolymer |
| JPS5239623A (en) * | 1975-09-20 | 1977-03-28 | Katayama Chem Works Co Ltd | Process for preparation of bromoacetic acid esters |
| JPS547447A (en) * | 1977-06-20 | 1979-01-20 | Fuji Photo Film Co Ltd | Coloring of high polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0536590U (en) * | 1991-05-28 | 1993-05-18 | 株式会社タカラ | Commodity vending machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5531801A (en) | 1980-03-06 |
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