JPS624417B2 - - Google Patents
Info
- Publication number
- JPS624417B2 JPS624417B2 JP3963481A JP3963481A JPS624417B2 JP S624417 B2 JPS624417 B2 JP S624417B2 JP 3963481 A JP3963481 A JP 3963481A JP 3963481 A JP3963481 A JP 3963481A JP S624417 B2 JPS624417 B2 JP S624417B2
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- parts
- deformation
- molded
- specific surface
- 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 50
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims description 16
- 239000003086 colorant Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920005672 polyolefin resin Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- -1 polyethylene Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリオレフイン系樹脂特にポリエチ
レンの溶融着色成形時、成形品に収縮による変形
を生じさせないイソインドリノン系顔料を含有す
るポリオレフイン系樹脂用着色剤に関するもので
ある。
イソインドリノン系顔料は耐候性、耐熱性等各
種の顔料特性が優れているため各種のプラスチツ
ク材料の着色に広く使用されているが、ポリオレ
フイン系樹脂、特にポリエチレンの着色剤として
使用した場合には、該樹脂の熔融着色成形加工時
に成形品に歪み、反り、等の変形を生じせしめる
ために実用に供することが困難であつた。
この変形の現象は、一般に加熱熔融されたポリ
オレフイン系樹脂の冷却に伴う結晶化の際、着色
剤として使用した有機顔料の粒子が結晶核として
働き、樹脂の結晶化を促進することにより、不均
一な収縮を引き起し、全体として成形品の歪み、
反り、等の変形を生じさせると考えられている。
また、チタンホワイト、カドミユウムレツド、カ
ドミユウムイエロー等の無機顔料の使用時にはこ
の様な成形品の変形現象が発生せずイソインドリ
ノン系顔料等多くの有機顔料がこの成形品の変形
を惹起する理由は、有機顔料の粒子の形状と樹脂
との親和性に関連があると推定される。
従来、ポリオレフインの着色には、カドミウム
系、クロム系、鉛系など毒性の強い重金属顔料が
使用されてきたが、公害防止等の見地から、これ
ら重金属顔料の使用の規制と自粛により有機顔料
を採用する必要が生じ、色相、耐候性、褪色性、
耐熱性等において秀れた特性を有する無害なイソ
インドリノン系顔料について、ポリオレフイン系
樹脂の成形品に変形を生じさせない顔料の開発が
要望されていた。
本発明者等は、上記の知見に基づき種々研究し
た結果、BET法による比表面積が40m2／ｇ以上
の一般式（）で示される微細なイソインドリノ
ン系顔料
（式中、Ｘは塩素原子又は臭素原子、Ｒは芳香
族基又は複素環基、ｎは０又は１〜４の整数をそ
れぞれ表わす。）
を、親水性の有機溶剤100重量部（以下単に部と
記す）に対し水５乃至200部を混合した水性有機
溶媒中で加熱処理することにより得られる比表面
積40m2／ｇ以下のイソインドリノン系顔料は、ポ
リオレフイン系樹脂の着色剤として使用した場
合、着色成形品の成形収縮に伴う変形が殆んど生
じない事実を見いだし、本発明を完成するに至つ
た。
前記一般式（）で示されるイソインドリノン
系顔料は、既に米国特許第2573352号明細書、特
公昭34−4488号明細書その他の文献より公知であ
るが、式中Ｒで示される芳香族基及び複素環基に
ついて、その代表的なものを例示すると、１，２
−、１，３−又は１，４−フエニレン基、２，
2′−又は４，4′−ジフエニレン基、４，4′−ジフ
エニレンスルフイド基、４，4′−ジフエニレン尿
素基、スチルベン−４，4′−イレン基、ベンゾイ
ルアニリン−４，4′−イレン基、アゾベンゼン−
４，4′−イレン基、４，4′−ジフエニレンエーテ
ル基、４，4′−ジフエニレンメタン基、１，４−
ナフチレン基等の芳香族基、ピリジン−２，６−
又は−２，５−イレン基、カルバゾール−３，６
−イレン基等の複素環基が挙げられる。これらの
基は、低級アルキル基、低級アルコキシ基、ハロ
ゲン原子等の置換基を有していてもよい。
比表面積40m2／ｇ（BET法）以上の前記一般
式（）で表わされるイソインドリノン系顔料を
得る方法は、ニーダー等による機械的磨砕法、顔
料を硫酸に溶解後水中に注入析出させて微細な粒
子として取り出す方法、顔料を親水性有機溶剤中
で塩基と塩を形成させた後、酸もしくは水で加水
分解する方法（特公昭47−39565）等がすでに公
知である。
本発明の着色剤に用いる顔料の製造方法におい
て、微細なイソインドリノン系顔料を加熱処理す
るための親水性溶剤としては、メタノール、エタ
ノール、プロパノール、エチレングライコール等
のアルコール類、アセトン、メチルエチルケトン
等のケトン類、エチレングライコールモノメチル
エーテル、ジエチレングライコールモノアセテー
ト等のエチレングライコールのエステル、エーテ
ル類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチル
スルホキシド、Ｎ−メチルピロリドン、アセトニ
トリル、トリエタノールアミン、THF等があげ
られ、これらが単独で、または２種以上混合して
用いられる。
本発明の着色剤に用いる顔料の製造方法におい
て親水性有機溶剤に対して混合する水の添加比率
は、有機溶剤100重量部に対して水５〜200重量部
であり、好ましくは10〜50重量部の範囲である。
水性有機溶媒の使用量には特に制限がなく、処
理される顔料を容易に撹拌し得る程度の量であれ
ばよい。好ましくは顔料の５〜10倍量である。
親水性有機溶剤一水の混合水性有機溶媒中での
イソインドリノン系顔料の加熱処理温度は使用す
る有機溶剤の種類、水との混合比率によつて異る
が、通常30℃以上200℃以下が適しており、好ま
しくは50〜90℃の範囲である。加熱処理時間は、
使用する有機溶剤の種類、加熱温度によつて異る
が１〜５時間で十分である。
以上のような本発明の着色剤となる顔料の製造
法において原料となるイソインドリノン系顔料の
比表面積が40m2／ｇ以下であつても、また処理さ
れた顔料の比表面積が40m2／ｇ以上であつても、
前記の如く処理された結果、その比表面積がある
程度減少された顔料は成形収縮による歪をいくら
か改善することが確認された。しかしながら、実
用上満足すべき着色成形品を得るためには、比表
面積40m2／ｇ以上の顔料を40m2／ｇ以下に処理す
ることが必要である。
本発明のポリオレフイン系樹脂用着色剤は、前
記の如くして得られるイソインドリノン系顔料を
含有するものであり、成形品の色相や物理的強
度、耐久性等を改善するため、また成形加工工程
上の必要性等から、一般に使用される他の顔料、
体質顔料、各種添加剤例えば界面活性剤、可塑
剤、分散剤、分散助剤、賦型剤、帯電防止剤、酸
化防止剤、紫外線吸収剤等と配合して使用するこ
とができ、更に被着色樹脂や低分子量のポリエチ
レン、ポリプロピレン等と予め混練して使用する
こともできる。従つて、本発明に係る着色剤は、
粉末状、粒状、ペレツド状、ビース状、フレーク
状、ペースト状等種々の形態で使用される。
被着色樹脂であるポリオレフイン系樹脂として
は、種々のグレードのポリエチレン、ポリプロピ
レン、ポリスチレン及びこれらの変性或いは共重
合樹脂等が挙げられるが、本発明に係る着色剤
は、特にポリエチレン用として重要である。
次に本発明に用いられるイソインドリノン系顔
料の製造例を挙げる。
製造例 １
比表面積68m2／ｇ（BET法）のビス−（４，
５，６，７−テトラクロルイソインドリン−１オ
ン−３−インデン）−フエニレンジアミン（1.4）
100部をＮ−メチルピロリドン700部、メタノール
100部及び水200部の混合溶剤中に分散させ、80℃
で３時間加熱した後、熱時濾過し、十分水洗後乾
燥して、比表面積29m2／ｇ（BET法）の赤味黄
色顔料990部を得た。
製造例 ２
比表面積54m2／ｇのビス−（４，５，６，７−
テトラクロルイソインドリン−１−オン−３−イ
ンデン）−トルエンジアミン（2.6）100部をNN−
ジメチルホルムアミド80部、水200部の混合溶剤
中に分散し、90℃で１時間加熱する。熱時濾過し
十分水洗後乾燥すると、比表面積25m2／ｇの青味
黄色顔料98.2部が得られた。
製造例 ３
比表面積72m2／ｇ（BET法）のビス−（４，
５，６，７−テトラクロルイソインドリン−１−
オン−３−インデン）−３，3′−ジメトキシビフ
エニレンジアミン−（４，4′）100部をエチレング
ライコール700部、ピリジン100部及び水200部の
混合溶剤中に分散させ、50℃で５時間撹拌後、熱
時濾過し、十分乾燥すると比表面積（BET法）
36m2／ｇの赤色顔料97.5部が得られた。
この様にして得られた顔料を着色剤としてポリ
オレフイン系樹脂に添加着色成形したときの収縮
変形について以下に例をあげて説明する。尚各例
中に於いて用いられる変形度及び収縮率、収縮比
は次の方法により測定した。
(1) 変形度
直径120mm、厚さ２mmの円板状の金型を用
い、３オンス インライン式射出成形機によ
り、成形温度220℃で円板を成形する。この円
板を25℃で48時間放置した後、平面上に置いた
円板の片方を軽くおさえ、その反対側の反りが
最大になる部位の平面からの高さｍ／ｍを変形
度とする。
(2) 収縮率及び収縮比
縦140mm、横80mm、厚さ２mmの平板状の金型
を用い、３オンス インラインスクリユー式射
出成形機により、成形温度220℃で平板を成形
する。この平板を25℃で48時間放置した後、縦
方向（樹脂の流れ方向）及び横方向（樹脂の流
れに直角の方向）の長さを測定し、次式に基づ
き縦方向及び横方向の収縮率を求め、更にそれ
らの比である収縮比を求める。
縦方向の収縮率
＝縦方向の金型寸法一縦方向の成形品寸法／縦方向の金
型寸法×100
横方向の収縮率は、上式に準ずる。
収縮比＝縦方向の収縮率／横方向の収縮率
実施例 １
製造例１で得られた顔料１部とステアリン酸亜
鉛１部とから成るドライカラーを高密度ポリエチ
レン（MI6、密度0.970ｇ／cm3）1000部とドライ
ブレンドし、これを射出成形機で円板及び平板状
の成形品に成形し、変形度等を測定した。結果を
表−に示す。
比較例 １−ａ
製造例１で原料として使用した比表面積68m2／
ｇの顔料を用いるほかは実施例１と同様にして円
板及び平板状の成形品を成形し、変形度等を測定
した。結果を表−に示す。
比較例 １−ｂ
実施例１の顔料と同一化学構造を有する比表面
積25m2／ｇの市販顔料を用いるほかは実施例１と
同様にして円板及び平板状の成形品を成形し、変
形度等を測定した。結果を表−に示す。
The present invention relates to a coloring agent for polyolefin resins containing an isoindolinone pigment that does not cause deformation due to shrinkage in molded products during melt color molding of polyolefin resins, particularly polyethylene. Isoindolinone pigments have excellent pigment properties such as weather resistance and heat resistance, so they are widely used for coloring various plastic materials.However, when used as a colorant for polyolefin resins, especially polyethylene, However, it has been difficult to put this resin into practical use because it causes deformations such as distortion and warping in the molded product when the resin is melt-colored and molded. This deformation phenomenon is generally caused by the non-uniformity of the polyolefin resin, which is caused by the particles of the organic pigment used as a coloring agent acting as crystal nuclei and promoting the crystallization of the resin when it crystallizes as it cools. This causes significant shrinkage and distortion of the molded product as a whole.
It is believed that this causes deformations such as warping.
Furthermore, when using inorganic pigments such as titanium white, cadmium red, and cadmium yellow, this deformation phenomenon of molded products does not occur, and many organic pigments such as isoindolinone pigments cause this deformation of molded products. The reason for this is presumed to be related to the particle shape of the organic pigment and its affinity with the resin. Traditionally, highly toxic heavy metal pigments such as cadmium-based, chromium-based, and lead-based pigments have been used to color polyolefins, but from the perspective of pollution prevention, the use of these heavy metal pigments has been regulated and refrained from being used, and organic pigments have been adopted. The need arises, hue, weather resistance, fading resistance,
Regarding harmless isoindolinone pigments that have excellent properties such as heat resistance, there has been a desire to develop pigments that do not cause deformation in polyolefin resin molded products. As a result of various studies based on the above findings, the present inventors found that a fine isoindolinone pigment represented by the general formula () with a specific surface area of 40 m 2 /g or more by the BET method. (wherein, X represents a chlorine atom or a bromine atom, R represents an aromatic group or a heterocyclic group, and n represents an integer of 0 or 1 to 4, respectively), 100 parts by weight of a hydrophilic organic solvent (hereinafter simply "parts") When used as a coloring agent for polyolefin resins, isoindolinone pigments with a specific surface area of 40 m 2 /g or less obtained by heating in an aqueous organic solvent containing 5 to 200 parts of water They discovered the fact that almost no deformation occurs due to molding shrinkage of colored molded products, and completed the present invention. The isoindolinone pigment represented by the general formula () is already known from U.S. Pat. Typical examples of heterocyclic groups include 1, 2
-, 1,3- or 1,4-phenylene group, 2,
2'- or 4,4'-diphenylene group, 4,4'-diphenylene sulfide group, 4,4'-diphenylene urea group, stilbene-4,4'-ylene group, benzoylaniline-4,4' -Ylene group, azobenzene-
4,4'-ylene group, 4,4'-diphenylene ether group, 4,4'-diphenylenemethane group, 1,4-
Aromatic groups such as naphthylene groups, pyridine-2,6-
or -2,5-ylene group, carbazole-3,6
Examples include heterocyclic groups such as -ylene group. These groups may have a substituent such as a lower alkyl group, a lower alkoxy group, or a halogen atom. The isoindolinone pigment represented by the general formula () having a specific surface area of 40 m 2 /g or more (BET method) can be obtained by mechanical grinding using a kneader or the like, or by dissolving the pigment in sulfuric acid and then pouring it into water to precipitate it. A method of extracting the pigment as fine particles, a method of forming a salt with a base in a hydrophilic organic solvent, and then hydrolyzing the pigment with acid or water (Japanese Patent Publication No. 39565/1983) are already known. In the method for producing pigments used in the colorant of the present invention, hydrophilic solvents for heat-treating fine isoindolinone pigments include alcohols such as methanol, ethanol, propanol, and ethylene glycol, acetone, and methyl ethyl ketone. Ketones, esters of ethylene glycol such as ethylene glycol monomethyl ether and diethylene glycol monoacetate, ethers, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile, triethanolamine, THF, etc. These can be used alone or in combination of two or more. In the method for producing pigments used in the colorant of the present invention, the ratio of water added to the hydrophilic organic solvent is 5 to 200 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the organic solvent. This is within the scope of the department. The amount of the aqueous organic solvent to be used is not particularly limited, and may be an amount that allows the pigment to be treated to be easily stirred. The amount is preferably 5 to 10 times that of the pigment. A mixture of hydrophilic organic solvent and water The heat treatment temperature of isoindolinone pigments in an aqueous organic solvent varies depending on the type of organic solvent used and the mixing ratio with water, but is usually above 30°C and below 200°C. is suitable, preferably in the range of 50 to 90°C. The heat treatment time is
Although it varies depending on the type of organic solvent used and the heating temperature, 1 to 5 hours is sufficient. Even if the specific surface area of the isoindolinone pigment used as a raw material in the above-described method for producing a pigment serving as a coloring agent of the present invention is 40 m 2 /g or less, the specific surface area of the treated pigment is 40 m 2 /g or less. Even if it is more than g,
It has been confirmed that the pigment whose specific surface area has been reduced to some extent as a result of the treatment described above can somewhat improve the distortion caused by molding shrinkage. However, in order to obtain a colored molded article that is practically satisfactory, it is necessary to process the pigment having a specific surface area of 40 m 2 /g or more to 40 m 2 /g or less. The coloring agent for polyolefin resins of the present invention contains the isoindolinone pigment obtained as described above, and is used to improve the hue, physical strength, durability, etc. of molded products, and also to improve molding processing. Due to process needs, other commonly used pigments,
It can be used in combination with extender pigments and various additives such as surfactants, plasticizers, dispersants, dispersion aids, excipients, antistatic agents, antioxidants, and ultraviolet absorbers. It can also be used by kneading it with a resin, low molecular weight polyethylene, polypropylene, etc. in advance. Therefore, the colorant according to the present invention is
It is used in various forms such as powder, granules, pellets, beads, flakes, and pastes. Examples of polyolefin resins to be colored include various grades of polyethylene, polypropylene, polystyrene, modified or copolymer resins thereof, and the coloring agent according to the present invention is particularly important for polyethylene. Next, an example of manufacturing the isoindolinone pigment used in the present invention will be given. Production example 1 Bis- (4,
5,6,7-tetrachloroisoindolin-1one-3-indene)-phenylenediamine (1.4)
100 parts to 700 parts of N-methylpyrrolidone, methanol
Dispersed in a mixed solvent of 100 parts and 200 parts of water and heated at 80℃
After heating for 3 hours, the mixture was filtered while hot, thoroughly washed with water, and dried to obtain 990 parts of a reddish yellow pigment with a specific surface area of 29 m 2 /g (BET method). Production example 2 Bis-(4,5,6,7-
100 parts of tetrachloroisoindolin-1-one-3-indene)-toluenediamine (2.6)
Disperse in a mixed solvent of 80 parts of dimethylformamide and 200 parts of water and heat at 90°C for 1 hour. After filtering while hot, thoroughly washing with water, and drying, 98.2 parts of a bluish yellow pigment with a specific surface area of 25 m 2 /g was obtained. Production example 3 Bis- (4,
5,6,7-tetrachloroisoindoline-1-
100 parts of (4,4')-3,3-indene)-3,3'-dimethoxybiphenylenediamine-(4,4') was dispersed in a mixed solvent of 700 parts of ethylene glycol, 100 parts of pyridine, and 200 parts of water, and the mixture was heated at 50°C. After stirring for 5 hours, filter while hot, and dry thoroughly to determine the specific surface area (BET method).
97.5 parts of red pigment of 36 m 2 /g were obtained. The shrinkage deformation when the pigment thus obtained is added to a polyolefin resin as a coloring agent and colored and molded will be explained below by giving an example. The degree of deformation, shrinkage rate, and shrinkage ratio used in each example were measured by the following method. (1) Degree of deformation A disk-shaped mold with a diameter of 120 mm and a thickness of 2 mm is used to mold a disk at a molding temperature of 220°C using a 3-ounce in-line injection molding machine. After leaving this disc at 25°C for 48 hours, lightly press one side of the disc placed on a flat surface, and define the degree of deformation as the height (m/m) from the flat surface of the part where the warp on the opposite side is maximum. . (2) Shrinkage rate and shrinkage ratio A flat plate with a length of 140 mm, width of 80 mm, and thickness of 2 mm is used to form a flat plate at a molding temperature of 220°C using a 3-ounce in-line screw injection molding machine. After this flat plate was left at 25℃ for 48 hours, the length in the vertical direction (direction of resin flow) and horizontal direction (direction perpendicular to the flow of resin) was measured, and the shrinkage in the vertical and horizontal directions was calculated based on the following formula. Find the ratio, and then find the contraction ratio, which is their ratio. Vertical shrinkage rate = Vertical mold dimension - Vertical molded product dimension / Vertical mold dimension x 100 The horizontal shrinkage rate is based on the above formula. Shrinkage ratio = longitudinal shrinkage ratio / transverse shrinkage ratio Example 1 A dry color consisting of 1 part of the pigment obtained in Production Example 1 and 1 part of zinc stearate was added to high-density polyethylene (MI6, density 0.970 g/cm 3 ) Dry-blended with 1000 parts, molded into disc and flat molded products using an injection molding machine, and measured the degree of deformation, etc. The results are shown in the table. Comparative Example 1-a Specific surface area used as raw material in Production Example 1: 68 m 2 /
Disc and flat plate-shaped molded products were molded in the same manner as in Example 1, except that pigment (g) was used, and the degree of deformation and the like were measured. The results are shown in the table. Comparative Example 1-b Disc and flat plate shaped products were molded in the same manner as in Example 1 except that a commercially available pigment with a specific surface area of 25 m 2 /g having the same chemical structure as the pigment in Example 1 was used, and the degree of deformation was determined. etc. were measured. The results are shown in the table.
【表】
実施例 ２
製造例２で得られた顔料１部とステアリン酸亜
鉛１部から成るドライカラーを高密度ポリエチレ
ン（MI6、密度0.970ｇ／cm3）1000部とドライブ
レンドし、これを射出成形機で円板及び平板状の
成形品に成形し、その変形度等を測定した。結果
を表−に示す。
比較例 ２−ａ
製造例２で原料として使用した比表面積54m2／
ｇの顔料を用いるほかは実施例２と同様にして円
板及び平板状の成形品を成形し、その変形度等を
測定した。結果を表−に示す。
比較例 ２−ｂ
製造例２と顔料と同一化学構造を有する比表面
積29m2／ｇの市販顔料を用いるほかは実施例２と
同様にして円板及び平板状の成形品を成形し、変
形度等を測定した。結果を表−に示す。[Table] Example 2 A dry color consisting of 1 part of the pigment obtained in Production Example 2 and 1 part of zinc stearate was dry blended with 1000 parts of high-density polyethylene (MI6, density 0.970 g/cm 3 ), and this was injected. The molded products were molded into discs and flat plates using a molding machine, and their degree of deformation was measured. The results are shown in the table. Comparative Example 2-a Specific surface area used as raw material in Production Example 2: 54 m 2 /
Disc and flat plate-shaped molded products were molded in the same manner as in Example 2, except that pigment (g) was used, and the degree of deformation, etc. of the molded products were measured. The results are shown in the table. Comparative Example 2-b Disc and flat plate-shaped products were molded in the same manner as in Example 2, except that a commercially available pigment with a specific surface area of 29 m 2 /g having the same chemical structure as the pigment in Production Example 2 was used, and the degree of deformation was determined. etc. were measured. The results are shown in the table.
【表】
実施例 ３
製造例３で得られた顔料１部とステアリン酸亜
鉛１部から成るドライカラーを高密度ポリエチレ
ン（MI6、密度0.970ｇ／cm3）1000部とドライブ
レンドし、これを射出成形機で円板及び平板状の
成形品に成形し、その変形度等を測定した。結果
を表−に示す。
比較例 ３−ａ
製造例３で原料として使用した比表面積42m2／
ｇの顔料を用いるほかは実施例３と同様にして円
板及び平板状の成形品を成形し、変形度等を測定
した。結果を表−に示す。
比較例 ３−ｂ
製造例３の顔料と同一化学構造を有する比表面
積39m2／ｇの市販顔料を用いるほかは実施例３と
同様にして円板及び平板状の成形品を成形し、そ
の変形度等を測定した。結果を表−に示す。[Table] Example 3 A dry color consisting of 1 part of the pigment obtained in Production Example 3 and 1 part of zinc stearate was dry blended with 1000 parts of high-density polyethylene (MI6, density 0.970 g/cm 3 ), and this was injected. The molded products were molded into discs and flat plates using a molding machine, and their degree of deformation was measured. The results are shown in the table. Comparative Example 3-a Specific surface area used as raw material in Production Example 3: 42 m 2 /
Disc and flat plate-shaped molded products were molded in the same manner as in Example 3, except that pigment (g) was used, and the degree of deformation and the like were measured. The results are shown in the table. Comparative Example 3-b Disc and flat plate shaped products were molded in the same manner as in Example 3, except that a commercially available pigment with a specific surface area of 39 m 2 /g having the same chemical structure as the pigment of Production Example 3 was used, and the deformation thereof was The degree etc. were measured. The results are shown in the table.
【表】
実施例 ４−18
一般式（）で示されるイソインドリノン顔料
のＲが表に示される基である種々の顔料につい
て、製造例１に示した方法と同様な方法で処理を
施し、得られた顔料１部を実施例１と同様にステ
アリン酸亜鉛１部と混合してドライカラーとし
た。これを高密度ポリエチレン（MI6、密度
0.970ｇ／cm3）1000部とドライブレンドし、この
ブレンド物を射出成形機で円板及び平板状の着色
成形品に成形し、その変形度、収縮率、収縮比を
測定した。それぞれの顔料の色相と測定結果を表
−に示す。
[Table] Example 4-18 Various pigments in which R of the isoindolinone pigment represented by the general formula () is a group shown in the table were treated in the same manner as shown in Production Example 1, One part of the obtained pigment was mixed with one part of zinc stearate in the same manner as in Example 1 to obtain a dry color. This is made of high-density polyethylene (MI6, density
The mixture was dry blended with 1000 parts of 0.970 g/cm 3 ), and this blend was molded into disk- and flat-shaped colored molded products using an injection molding machine, and the degree of deformation, shrinkage rate, and shrinkage ratio were measured. The hue and measurement results of each pigment are shown in the table.
【表】【table】
Claims (1)
顔料を親水性の有機溶剤100重量部に対し水５重
量部乃至200重量部を混合した水性有機溶媒中で
加熱処理して得られる、比表面40m2／ｇ以下のイ
ソインドリノン系顔料を含有するポリオレフイン
系樹脂用着色剤。1 Specific surface obtained by heat-treating an isoindolinone pigment with a specific surface area of 40 m 2 /g or more in an aqueous organic solvent containing 100 parts by weight of a hydrophilic organic solvent and 5 to 200 parts by weight of water. A coloring agent for polyolefin resin containing 40 m 2 /g or less of isoindolinone pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3963481A JPS57155242A (en) | 1981-03-20 | 1981-03-20 | Colorant for polyolefin resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3963481A JPS57155242A (en) | 1981-03-20 | 1981-03-20 | Colorant for polyolefin resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57155242A JPS57155242A (en) | 1982-09-25 |
| JPS624417B2 true JPS624417B2 (en) | 1987-01-30 |
Family
ID=12558517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3963481A Granted JPS57155242A (en) | 1981-03-20 | 1981-03-20 | Colorant for polyolefin resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57155242A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266616A (en) * | 1991-07-12 | 1993-11-30 | Phillips Petroleum Company | Polyolefin resin formulation using organic pigments |
| US7077896B2 (en) * | 2003-06-13 | 2006-07-18 | Toyo Ink Mfg. Co., Ltd. | Pigment composition and use thereof in plastic |
| WO2005100349A2 (en) * | 2004-04-13 | 2005-10-27 | Icagen, Inc. | Polycyclic pyridines as potassium ion channel modulators |
| JP5764835B1 (en) | 2014-03-24 | 2015-08-19 | 東洋インキＳｃホールディングス株式会社 | Colorant for plastic, coloring composition using the same, and molded product |
-
1981
- 1981-03-20 JP JP3963481A patent/JPS57155242A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57155242A (en) | 1982-09-25 |
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