JPS6210540B2 - - Google Patents
Info
- Publication number
- JPS6210540B2 JPS6210540B2 JP54145506A JP14550679A JPS6210540B2 JP S6210540 B2 JPS6210540 B2 JP S6210540B2 JP 54145506 A JP54145506 A JP 54145506A JP 14550679 A JP14550679 A JP 14550679A JP S6210540 B2 JPS6210540 B2 JP S6210540B2
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- phosphonic acid
- pigment
- acid ester
- organic phosphonic
- 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
- 229920005668 polycarbonate resin Polymers 0.000 claims description 28
- 239000004431 polycarbonate resin Substances 0.000 claims description 28
- 239000000049 pigment Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- -1 3,5-dibromo-4-hydroxyphenyl Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- AIRJUNVWOGNWPB-UHFFFAOYSA-N 2-diethoxyphosphoryl-2-methylbutanoic acid Chemical compound CCOP(=O)(OCC)C(C)(CC)C(O)=O AIRJUNVWOGNWPB-UHFFFAOYSA-N 0.000 description 1
- JLOFLXNYMHMEIC-UHFFFAOYSA-N 2-dimethoxyphosphoryl-2-methylpropanoic acid Chemical compound COP(=O)(OC)C(C)(C)C(O)=O JLOFLXNYMHMEIC-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic 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
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- BKJJHKROOQVIHY-UHFFFAOYSA-N butyl 2-dibutoxyphosphorylacetate Chemical compound CCCCOC(=O)CP(=O)(OCCCC)OCCCC BKJJHKROOQVIHY-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- PLSFNSJUKGEOSL-UHFFFAOYSA-N dioctoxy(oxo)phosphanium Chemical compound CCCCCCCCO[P+](=O)OCCCCCCCC PLSFNSJUKGEOSL-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer 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
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- SIGOIUCRXKUEIG-UHFFFAOYSA-N methyl 2-dimethoxyphosphorylacetate Chemical compound COC(=O)CP(=O)(OC)OC SIGOIUCRXKUEIG-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は安定化された着色ポリカーボネート樹
脂組成物に関する。さらに詳しくは本発明はポリ
カーボネート樹脂に顔料と有機ホスホン酸エステ
ルとを混合してなる安定化された着色ポリカーボ
ネート樹脂組成物に関する。
ポリカーボネート樹脂は高度の耐衝撃性、透明
性、耐熱性、電気特性、寸法安定性等を具備する
ために、エンジニアリングプラスチツクスとして
広範囲に使用されている。その市販用途によつて
はポリカーボネート樹脂に顔料を加え外観を向上
させる必要があるが、着色成形品はその色相、鮮
明性によつて商品価値が左右される。また、顔料
としては優れた隠蔽力を有する二酸化チタンがよ
く用いられる。しかしながら、二酸化チタン等の
顔料はポリカーボネート樹脂の酸化分解を促進す
るために、顔料で着色されたポリカーボネート樹
脂は顔料を含まないポリカーボネート樹脂に比べ
て、成形過程の間の変色度合や分子量低下の度合
が大きくなる欠点があり、予期した色相や強度の
ものが得られないことがある。ポリカーボネート
樹脂の成形過程の間の変色や分子量低下を防止す
るために、従来よりトリアリールホスフアイトや
トリアルキルホスフアイト等の有機亜リン酸エス
テルが用いられているが、これら安定剤は自然色
ポリカーボネート樹脂に対して有効に作用するも
のの、顔料を含む場合には十分な安定化効果を示
さない。
そこで、顔料を含むポリカーボネート樹脂の熱
安定剤としてリン酸のモノまたはジエステルの使
用が提案されているが、これら安定剤も省資源化
に伴う成形品の薄肉化に対応した300℃以上とい
う厳しい条件下での成形時には変色が大きく、且
つ分子量低下も大きい。
本発明の目的は高温での成形過程の間に劣化や
変色を生じない熱安定性に優れた着色ポリカーボ
ネート樹脂組成物を提供することにある。
本発明者らはこの目的を達成するために鋭意研
究した結果、ポリカーボネート樹脂に顔料と特定
の有機ホスホン酸エステルを添加混合した着色ポ
リカーボネート樹脂組成物が高温成形時に安定し
た色相と分子量を保持することを見い出し、本発
明に到達した。
すなわち、本発明はポリカーボネート樹脂に、
顔料と一般式(1)
（ただし、式中のR1、R2およびR3はそれぞれ炭素
数１乃至18のアルキル基であり、ｎは１または２
である）で表わされる有機ホスホン酸エステルを
含有せしめることを特徴とする安定化された着色
ポリカーボネート樹脂組成物である。
本発明の安定化された着色ポリカーボネート樹
脂組成物は、高温での成形過程の間に変色や分子
量低下に伴う機械的特性の低下を生じないので、
高温で薄肉の成形品に容易に成形でき、且つ成形
品の薄肉化に対する隠蔽性や色相保持のための顔
料の多量添加が可能となる。このような組成物の
優れた効果は、ポリカーボネート樹脂に顔料と特
定の有機ホスホン酸エステルを配合することによ
つて始めて達成されたものであり、有機ホスホン
酸エステルであるがエステル結合を有しないオク
チルホスホン酸ジオクチルが分子量の低下防止に
全く効果を奏さないことを考えると驚くべきこと
である。エステル結合がリン原子から離れるほど
効果が小さくなることから推察すると、本発明で
用いられる有機ホスホン酸エステルの安定化効果
にはエステル結合とリン原子の相互作用が重要な
役割を果していると考えられるが、その作用機構
は明らかではない。
本発明に用いられるポリカーボネート樹脂は酸
受容体および分子量調整剤の存在下での二価フエ
ノールとホスゲン等のカーボネート前駆体との反
応、或いは２価フエノールとジフエニルカーボネ
ート等のカーボネート前駆体とのエステル交換反
応によつて製造される。ここで使用しうる２価フ
エノールは、ビスフエノール類が好ましく、とく
に２・２−ビス（４−ヒドロキシフエニル）プロ
パン（以下ビスフエノールＡと称す）が好まし
い。また、ビスフエノールＡの一部または全部を
他の２価フエノールで置換してもよい。ビスフエ
ノールＡ以外の２価フエノールは、例えばハイド
ロキノン、４・4′−ジヒドロキシジフエニル、ビ
ス（４−ヒドロキシフエニル）アルカン、ビス
（４−ヒドロキシフエニル）シクロアルカン、ビ
ス（４−ヒドロキシフエニル）スルフイツド、ビ
ス（４−ヒドロキシフエニル）スルホン、ビス
（４−ヒドロキシジフエニル）スルホキシド、ビ
ス（４−ヒドロキシフエニル）エーテルの如き化
合物またはビス（３・５−ジブロモ−４−ヒドロ
キシフエニル）プロパンの如きハロゲン化ビスフ
エノール類である。これら２価フエノールのホモ
ポリマーまたは２種以上のコポリマー或いはこれ
らのブレンド物であつてもよい。
本発明に用いられる顔料は例えば神原、井本監
修“プラスチツクおよびゴム用添加剤実用便覧”
第791〜797頁（化学工業社発行）に類別されてい
る如き化合物であり、更に具体的には二酸化チタ
ン、酸化亜鉛のような酸化金属や、カドミニウム
黄、群青、カーボンブラツク等が挙げられるが、
必ずしもこれらに限定されるものでない。これら
顔料は単独で或いは他の顔料や染料とともに用い
られる。これら顔料のうち二酸化チタンが好まし
い。
本発明に用いられる有機ホスホン酸エステル
は、一般式(1)
において、ｎが１または２であることを特徴と
し、R1、R2およびR3のアルキル基の炭素数が18
以下のものであり、好ましくはアルキル基の炭素
数が８以下のものであり、さらに好ましくはアル
キル基の炭素数が２であるものである。かかる有
機ホスホン酸エステルとしては具体的にはメチル
ジメチルホスホノアセテート、メチルジメチルホ
スホノプロピオネート、ブチルジブチルホスホノ
アセテート、ブチルジブチルホスホノプロピオネ
ート、オクチルジオクチルホスホノアセテート、
オクチルジオクチルホスホノプロピオネートなど
を例示することができるが、とくにエチルジエチ
ルホスホノアセテートとエチルジエチルホスホノ
プロピオネートが好ましく用いられる。
本発明における組成物の各成分の配合比はポリ
カーボネート樹脂100重量部に対して、顔料は
0.001〜５重量部、有機ホスホン酸エステルは
0.001〜0.2重量部が好ましい。
本発明の着色ポリカーボネート樹脂組成物の調
製は、任意の従来方法によつて行われうる。その
方法としては例えばポリカーボネート樹脂に顔料
と有機ホスホン酸エステルを直接添加する方法；
高濃度の顔料と有機ホスホン酸エステルを添加、
配合したいわゆるマスターバツチを製造し、これ
を他のポリカーボネート樹脂に配合して、所定の
添加剤濃度とする方法；或いはポリカーボネート
樹脂の塩化メチレン溶液または粉末に有機ホスホ
ン酸エステルをあらかじめ添加したのちに、顔料
を添加する方法などがある。
本発明の組成物には有機亜リン酸エステル等の
他の安定剤やポリカーボネート樹脂の改質を目的
とする添加剤、例えばガラス繊維等の如き強化
剤、酸化防止剤、難然剤、光安定剤、可塑剤、充
填剤、帯電防止剤、離型剤、滑剤、発泡剤などを
添加することができる。また、ポリカーボネート
樹脂に例えばポリエチレン、ポリプロピレン、ポ
リスチレン、ポリメチルメタクリレート、AS樹
脂、ABS樹脂、ポリフエニレンオキサイド等の
他の樹脂を混合してもよい。
以下に本発明を実施例を以つて説明する。な
お、実施例中の部は重量部を示す。また、熱安定
性の評価は下記の方法による。
熱安定性評価法：
ペレツトを射出成形機を用いて、成形温度340
℃で０分または10分滞留せしめたのち70mm×50mm
×２mmの見本板に成形した。得られた見本板のハ
ンターによるＬ、ａ、ｂ値を色差計（スガ試験機
(株)製）にて測定し、色相をｂ値で評価した。ｂ値
は小さい程黄味が少なく色相が良好であることを
表わす。変色の度合はΔＥ＝√（−′）2＋（−
a′）2＋（ｂ−b′）2（ここに、Ｌ、ａ、ｂは340℃滞
留０分の成形見本板の測定値、L′、a′、b′は340
℃滞留10分の成形見本板の測定値である。）で評
価した。ΔＥは小さい程変色が小さく良好である
ことを示す。また、該見本板の分子量を粘度法に
より測定し、分子量低下を評価した。
実施例１〜４及び比較例１〜３
２・２−ビス（４−ヒドロキシフエニル）プロ
パンとホスゲンとの反応で調製した分子量24500
のポリカーボネート樹脂100部に、二酸化チタン
（石原産業(株)製Ｒ−930）0.5部及び有機ホスホン
酸エステル或いはトリス（ノニルフエニル）ホス
フアイトを第１表に示す部だけ添加し、それぞれ
スーパーミキサーを用いて充分に混合したのち、
30mmφ押出機で押出しペレツト化した。得られた
ペレツトは前記の方法で射出成形し、熱安定性を
評価した。その結果を第１表に示す。
The present invention relates to stabilized colored polycarbonate resin compositions. More specifically, the present invention relates to a stabilized colored polycarbonate resin composition comprising a polycarbonate resin mixed with a pigment and an organic phosphonic acid ester. Polycarbonate resins are widely used as engineering plastics because they have high impact resistance, transparency, heat resistance, electrical properties, dimensional stability, etc. Depending on its commercial use, it is necessary to add pigments to the polycarbonate resin to improve its appearance, but the commercial value of colored molded products is determined by their hue and clarity. Furthermore, titanium dioxide, which has excellent hiding power, is often used as a pigment. However, since pigments such as titanium dioxide promote the oxidative decomposition of polycarbonate resins, polycarbonate resins colored with pigments have a lower degree of discoloration and molecular weight reduction during the molding process than polycarbonate resins that do not contain pigments. It has the disadvantage of becoming larger and may not produce the expected hue or intensity. Organic phosphite esters such as triaryl phosphites and trialkyl phosphites have traditionally been used to prevent discoloration and molecular weight reduction during the molding process of polycarbonate resins, but these stabilizers are Although it acts effectively on resins, it does not show a sufficient stabilizing effect when pigments are included. Therefore, the use of phosphoric acid mono- or diesters as heat stabilizers for polycarbonate resins containing pigments has been proposed, but these stabilizers must also be used under strict conditions of 300°C or higher to accommodate the thinning of molded products in line with resource conservation. During molding at the bottom, there is a large discoloration and a large drop in molecular weight. An object of the present invention is to provide a colored polycarbonate resin composition with excellent thermal stability that does not cause deterioration or discoloration during the molding process at high temperatures. As a result of intensive research to achieve this objective, the present inventors have found that a colored polycarbonate resin composition prepared by adding and mixing a pigment and a specific organic phosphonic acid ester to a polycarbonate resin maintains a stable hue and molecular weight during high-temperature molding. They discovered this and arrived at the present invention. That is, the present invention provides polycarbonate resin with
Pigments and general formula (1) (However, R 1 , R 2 and R 3 in the formula are each an alkyl group having 1 to 18 carbon atoms, and n is 1 or 2
This is a stabilized colored polycarbonate resin composition characterized by containing an organic phosphonic acid ester represented by The stabilized colored polycarbonate resin composition of the present invention does not cause discoloration or deterioration of mechanical properties due to molecular weight reduction during the molding process at high temperatures.
It can be easily molded into a thin-walled molded product at high temperatures, and a large amount of pigment can be added to the molded product to hide the thinning of the wall and to maintain the hue. The excellent effects of such a composition were first achieved by blending a pigment and a specific organic phosphonic acid ester with a polycarbonate resin. This is surprising considering that dioctyl phosphonate has no effect on preventing molecular weight reduction. Judging from the fact that the farther the ester bond is from the phosphorus atom, the smaller the effect, it is thought that the interaction between the ester bond and the phosphorus atom plays an important role in the stabilizing effect of the organic phosphonic acid ester used in the present invention. However, its mechanism of action is not clear. The polycarbonate resin used in the present invention is produced by the reaction of divalent phenol with a carbonate precursor such as phosgene in the presence of an acid acceptor and a molecular weight regulator, or the ester reaction of divalent phenol with a carbonate precursor such as diphenyl carbonate. Produced by exchange reaction. The divalent phenol that can be used here is preferably bisphenols, and 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) is particularly preferable. Further, part or all of bisphenol A may be replaced with another divalent phenol. Examples of divalent phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)cycloalkane, and bis(4-hydroxyphenyl). ) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxydiphenyl) sulfoxide, bis(4-hydroxyphenyl) ether or bis(3,5-dibromo-4-hydroxyphenyl) These are halogenated bisphenols such as propane. It may be a homopolymer of these dihydric phenols, a copolymer of two or more types, or a blend thereof. The pigments used in the present invention are described in, for example, "Practical Handbook of Additives for Plastics and Rubber" edited by Kanbara and Imoto.
These are compounds categorized in pages 791 to 797 (published by Kagaku Kogyosha), and more specific examples include metal oxides such as titanium dioxide and zinc oxide, cadmium yellow, ultramarine, and carbon black. ,
It is not necessarily limited to these. These pigments may be used alone or together with other pigments or dyes. Among these pigments, titanium dioxide is preferred. The organic phosphonic acid ester used in the present invention has the general formula (1) , n is 1 or 2, and the alkyl groups of R 1 , R 2 and R 3 have 18 carbon atoms.
They are as follows, preferably those in which the alkyl group has 8 or less carbon atoms, and more preferably those in which the alkyl group has 2 carbon atoms. Specific examples of such organic phosphonic acid esters include methyldimethylphosphonoacetate, methyldimethylphosphonopropionate, butyldibutylphosphonoacetate, butyldibutylphosphonopropionate, octyldioctylphosphonoacetate,
Examples include octyldioctylphosphonopropionate, and ethyldiethylphosphonoacetate and ethyldiethylphosphonopropionate are particularly preferably used. The blending ratio of each component of the composition in the present invention is as follows: 100 parts by weight of polycarbonate resin, pigment:
0.001 to 5 parts by weight, organic phosphonic acid ester
0.001 to 0.2 parts by weight is preferred. Preparation of the colored polycarbonate resin compositions of the present invention may be carried out by any conventional method. For example, a method of directly adding a pigment and an organic phosphonic acid ester to a polycarbonate resin;
Added high concentration of pigment and organic phosphonic acid ester,
A method of producing a so-called blended master batch and blending it with other polycarbonate resin to achieve a predetermined additive concentration; Alternatively, after adding an organic phosphonate ester to a methylene chloride solution or powder of a polycarbonate resin in advance, pigment There are methods such as adding . The composition of the present invention may contain other stabilizers such as organic phosphites, additives for the purpose of modifying the polycarbonate resin, reinforcing agents such as glass fiber, antioxidants, retardant agents, and light stabilizers. Agents, plasticizers, fillers, antistatic agents, mold release agents, lubricants, foaming agents, etc. can be added. Further, other resins such as polyethylene, polypropylene, polystyrene, polymethyl methacrylate, AS resin, ABS resin, and polyphenylene oxide may be mixed with the polycarbonate resin. The present invention will be explained below using examples. Note that parts in the examples indicate parts by weight. In addition, thermal stability was evaluated by the following method. Thermal stability evaluation method: Pellets were molded using an injection molding machine at a molding temperature of 340°C.
70mm x 50mm after staying at ℃ for 0 or 10 minutes
It was molded into a 2 mm sample plate. The L, a, and b values of the obtained sample board were measured by Hunter using a color difference meter (Suga Test Instruments).
Co., Ltd.), and the hue was evaluated by the b value. The smaller the b value, the less yellow and the better the hue. The degree of discoloration is ΔE=√(−′) 2 +(−
a') 2 + (b-b') 2 (Here, L, a, b are the measured values of the molded sample plate at 340℃ residence time 0 minutes, L', a', b' are 340
These are the measured values of a molded sample plate kept at ℃ for 10 minutes. ) was evaluated. The smaller ΔE is, the smaller the discoloration is and the better it is. In addition, the molecular weight of the sample plate was measured by a viscosity method to evaluate the decrease in molecular weight. Examples 1 to 4 and Comparative Examples 1 to 3 Molecular weight 24500 prepared by reaction of 2,2-bis(4-hydroxyphenyl)propane and phosgene
To 100 parts of polycarbonate resin, 0.5 part of titanium dioxide (R-930 manufactured by Ishihara Sangyo Co., Ltd.) and the parts shown in Table 1 of organic phosphonic acid ester or tris(nonylphenyl) phosphite were added, and each was mixed using a super mixer. After mixing thoroughly,
It was extruded into pellets using a 30 mmφ extruder. The obtained pellets were injection molded by the method described above, and their thermal stability was evaluated. The results are shown in Table 1.
【表】
本発明の組成物は第１表より安定した色相と分
子量を保持し、熱安定性に優れていることが判
る。Table 1 shows that the composition of the present invention maintains stable hue and molecular weight and has excellent thermal stability.
Claims (1)
般式(1) （ただし、式中のR1、R2およびR3はそれぞれ炭素
数１乃至18のアルキル基であり、ｎは１または２
である）で表わされる有機ホスホン酸エステルを
含有せしめることを特徴とする安定化された着色
ポリカーボネート樹脂組成物。 ２ 前記顔料が二酸化チタンであることを特徴と
する特許請求の範囲第１項記載の組成物。 ３ 前記有機ホスホン酸エステルが下記一般式(2) （ただし、式中のｎは１または２である）で表わ
される化合物であることを特徴とする特許請求の
範囲第１項記載の組成物。[Claims] 1 Polycarbonate resin, pigment and the following general formula (1) (However, R 1 , R 2 and R 3 in the formula are each an alkyl group having 1 to 18 carbon atoms, and n is 1 or 2
A stabilized colored polycarbonate resin composition containing an organic phosphonic acid ester represented by 2. The composition according to claim 1, wherein the pigment is titanium dioxide. 3 The organic phosphonic acid ester has the following general formula (2) (However, n in the formula is 1 or 2.) The composition according to claim 1, wherein the composition is a compound represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14550679A JPS5670054A (en) | 1979-11-12 | 1979-11-12 | Stabilized colored polycarbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14550679A JPS5670054A (en) | 1979-11-12 | 1979-11-12 | Stabilized colored polycarbonate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5670054A JPS5670054A (en) | 1981-06-11 |
| JPS6210540B2 true JPS6210540B2 (en) | 1987-03-06 |
Family
ID=15386819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14550679A Granted JPS5670054A (en) | 1979-11-12 | 1979-11-12 | Stabilized colored polycarbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5670054A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176547A (en) * | 1984-09-21 | 1986-04-19 | Teijin Chem Ltd | Molded article for transmitting diffused light |
| US6475588B1 (en) | 2001-08-07 | 2002-11-05 | General Electric Company | Colored digital versatile disks |
| US6475589B1 (en) | 2001-12-17 | 2002-11-05 | General Electric Company | Colored optical discs and methods for making the same |
| WO2023228768A1 (en) * | 2022-05-24 | 2023-11-30 | 帝人株式会社 | Thermoplastic resin composition and molded article formed from same |
| WO2023243350A1 (en) * | 2022-06-17 | 2023-12-21 | 帝人株式会社 | Polycarbonate resin composition and molded article comprising same |
-
1979
- 1979-11-12 JP JP14550679A patent/JPS5670054A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5670054A (en) | 1981-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0023291B2 (en) | Stabilized thermoplastic moulding compositions based on polycarbonates, abs polymers and phosphites | |
| DE10083568B3 (en) | Polycarbonate resin composition and casings and parts formed therefrom | |
| EP0014322B1 (en) | Polycarbonate composition containing a metal salt of an aromatic sulfonamide as an ignition depressant | |
| DE19960316A1 (en) | Flame retarding thermoplastic composition, for thin walled injection molded products, comprises styrene, polycarbonate, red phosphorus and talc | |
| KR101316581B1 (en) | Polycarbonate resin composition and molded article thereof | |
| US4097547A (en) | Stabilized polycarbonates | |
| JP2645741B2 (en) | Antistatic polycarbonate composition | |
| JPS6210263B2 (en) | ||
| JPS6210540B2 (en) | ||
| JPH0150257B2 (en) | ||
| DE2658849A1 (en) | STABILIZED POLYCARBONATE COMPOSITION | |
| JPS6210539B2 (en) | ||
| JPS6210579B2 (en) | ||
| EP0170851A1 (en) | Aryl ester of perfluoroalkane-sulphonic acid as an antidripping agent in flame-resistant compositions based on thermoplastic aromatic polycarbonates | |
| US7662876B2 (en) | Arylalkylsilyls used as flame retardant additives | |
| JPH08311320A (en) | Flame-retardant polycarbonate resin composition | |
| US4254014A (en) | Polycarbonate containing a bis(cyclic phosphite) as a thermal stabilizer | |
| JP3527134B2 (en) | Polycarbonate resin composition and molded article | |
| US3525706A (en) | Stabilized pigmented polycarbonate resin | |
| US3763063A (en) | Color stabilized polycarbonate composition containing a cadmium or cerium salt of an alkanoic acid an alkanoic acid and an organic phosphite | |
| DE2705219A1 (en) | STABILIZED POLYCARBONATE MOLDING COMPOUNDS | |
| DE2206720A1 (en) | Thermostable polycarbonates - contg phosphines opt mixed with epoxides | |
| DE2741064A1 (en) | STABILIZED PIGMENTED POLYCARBONATE COMPOSITION | |
| DE2510463A1 (en) | Colour-stabilising plastics pref polycarbonates - with mixt of neutral phosphite esters and oxetan cpds | |
| JPS6210261B2 (en) |