JP7184869B2 - プラスチック用の添加剤混合物、それらを含むレーザー標識ポリマー組成物およびそれらの使用 - Google Patents
プラスチック用の添加剤混合物、それらを含むレーザー標識ポリマー組成物およびそれらの使用 Download PDFInfo
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- JP7184869B2 JP7184869B2 JP2020500698A JP2020500698A JP7184869B2 JP 7184869 B2 JP7184869 B2 JP 7184869B2 JP 2020500698 A JP2020500698 A JP 2020500698A JP 2020500698 A JP2020500698 A JP 2020500698A JP 7184869 B2 JP7184869 B2 JP 7184869B2
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Classifications
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Description
- 成分Aとして、式(I)のホスフィン酸塩
MはAl、Fe、TiOpまたはZnであり、
mは2~3、好ましくは2または3であり、
p=(4-m)/2であり、
- 成分Bとして、エチルブチルホスフィン酸、ジブチルホスフィン酸、エチルヘキシルホスフィン酸、ブチルヘキシルホスフィン酸、および/またはジヘキシルホスフィン酸のAl、Fe、TiOpまたはZn塩の群から選択される化合物
- 成分Cとして、式IIのホスフィン酸塩
R3がエチルであり、
MetがAl、Fe、TiOqまたはZnであり、
nが2~3、好ましくは2または3であり、
qが(4~n)/2であり、
- 成分Dとして、アンチモン、スズおよび/またはインジウム。
- 成分Aの割合が5~85質量%、
- 成分Bの割合が0.01~10質量%、
- 成分Cの割合が0.01~10質量%、
- 成分Dの割合が0.0001~3質量%である
添加剤混合物が好ましい。
- 成分Aの割合が10~60質量%、
- 成分Bの割合が0.1~2.5質量%、
- 成分Cの割合が0.1~2.5質量%、
- 成分Dの割合が0.1~2質量%である
添加剤混合物が好ましい。
[(HO)PO2]2- p/2 Katp+ (IV)
[(HO)2PO]- p Katp+ (V)
ここで、Katはp価カチオン、特にアルカリ金属、アルカリ土類金属、アンモニウムカチオンおよび/またはFe、Znのカチオン、特にAl(OH)またはAl(OH)2を含むAlのカチオン、ならびにpは1、2、3または4である。
Al2(HPO3)3x(H2O)q (VI)、
ここでqは0~4、
Al2.00Mz(HPO3)y(OH)vx(H2O)w (VII)、
ここでMはアルカリ金属カチオン、zは0.01~1.5、yは2.63~3.5、およびvは0~2、wは0~4であり;
Al2.00(HPO3)u(H2PO3)tx(H2O)s (VIII),
ここで、uは2~2.99、tは2~0.01、sは0~4であり、
および/または
亜リン酸アルミニウム[Al(H2PO3)3]、第二級亜リン酸アルミニウム[Al2(HPO3)3]、塩基性亜リン酸アルミニウム[Al(OH)(H2PO3)2 *2aq]、亜リン酸アルミニウム四水和物[Al2(HPO3)3 *4aq]リン酸アルミニウム、Al7(HPO3)9(OH)6(1,6-ヘキサンジアミン)1.5×12H2O、Al2(HPO3)3*xAl2O3×nH2Oであり、ここでx=2.27-1および/またはAl4H6P16O18)である。
MeがFe、TiOr、Znまたは特にAlであり、
oは2~3、好ましくは2または3、
r=(4-o)/2である。
1. モノ-およびジオレフィン、例えば、ポリプロピレン、ポリイソブチレン、ポリブチレン-1、ポリイソプレンまたはポリブタジエン、およびシクロオレフィンの付加ポリマー、例えばシクロペンテンまたはノルボルネン;および、任意に架橋され得るポリエチレン;例えば、高密度ポリエチレン(HDPE)、高モル質量の高密度ポリエチレン(HDPE-HMW)、高密度および超モル質量の高密度ポリエチレン(HDPE-UHMW)、中密度ポリエチレン(MDPE)、低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(LLDPE)、分枝低密度ポリエチレン(VLDPE)。
さらに、エチレン-アルキルアクリレート共重合体、エチレン-酢酸ビニル共重合体および一酸化炭素とのそれらの共重合体、またはエチレン-アクリル酸共重合体およびそれらの塩(イオノマー)、並びにエチレンとプロピレンおよびジエン、例えば、ヘキサジエン、ジシクロペンタジエンまたはエチリデンノルボルネンのターポリマー;
また、このような共重合体と相互の混合物および1.で言及したポリマーとの混合物、例えば、
ポリプロピレン/エチレン-プロピレンコポリマー、LDPE/エチレン-酢酸ビニルコポリマー、LDPE/エチレン-アクリル酸コポリマー、LLDPE/エチレン-酢酸ビニルコポリマー、LLDPE/エチレン-アクリル酸コポリマー、および交互またはランダムのポリアルキレン/一酸化炭素コポリマーおよびそれらの他のポリマー、例えば、ポリアミドとの混合物。
ポリブタジエン上のスチレン、アクリロニトリルおよびメタクリル酸メチル;
ポリブタジエン上のスチレンおよび無水マレイン酸;
ポリブタジエン上のスチレン、アクリロニトリルおよび無水マレイン酸またはマレイミド;
ポリブタジエン上のスチレンおよびマレイミド;
ポリブタジエン上のスチレンおよびアルキルアクリレート/アルキルメタクリレート、エチレン-プロピレン-ジエンターポリマー上のスチレンおよびアクリロニトリル;
ポリアルキルアクリレートまたはポリアルキルメタクリレート上のスチレンおよびアクリロニトリル;
アクリレート-ブタジエン共重合体上のスチレンおよびアクリロニトリルおよびこれらと5.に記載のポリマーとの混合物、例えば、ABS、MBS、ASAまたはAESポリマーとして知られているポリマー。
1. 使用成分
難燃性FM1(成分A):
DE19607635A1の実施例1と同様に調製したジエチルホスフィン酸のアルミニウム塩
難燃性FM2(成分AおよびB):
DE102014001222A1の実施例1と同様に生成された0.9mol%のアルミニウムエチルブチルホスフィナートを含むジエチルホスフィン酸のアルミニウム塩
難燃性FM3(成分A、B、C):
US7,420,007B2の実施例3に従い調製された0.9mol%のアルミニウムエチルブチルホスフィナートおよび0.5mol%のアルミニウムエチルホスホネートを含むジエチルホスフィン酸のアルミニウム塩
難燃性FM4(成分A、B、C):
US7,420,007B2の実施例4に従い調製された2.7mol%アルミニウムエチルブチルホスフィナートおよび0.8mol%のアルミニウムエチルホスホネートを含むジエチルホスフィン酸のアルミニウム塩
難燃性FM5(成分A、B、C):
US7,420,007B2に準拠した方法で製造された0.5mol%のアルミニウムエチルブチルホスフィナートと0.05mol%のアルミニウムエチルホスホネートを含有するジエチルホスフィン酸のアルミニウム塩
難燃性FM6(成分A、B、C):
US7,420,007B2に準拠した方法で製造された10mol%のアルミニウムエチルブチルホスフィネートおよび5mol%のアルミニウムエチルホスホネートを含むジエチルホスフィン酸のアルミニウム塩
難燃性FM7(成分F):
DE102011120218A1の実施例1に従って製造したホスホン酸のアルミニウム塩
難燃性FM8(成分I):
WO2000/002869A1の実施例に従って製造されたメラミンポリリン酸塩
レーザー添加剤L1(成分D):
DE102014016286A1の実施例1に従って製造された、比表面積(BET)が52m2/gのアンチモンドープ酸化スズ
レーザー添加剤L2(成分D):
DE102014016286A1の実施例3に従って製造された、比表面積(BET)38m2/gのアンチモンドープ酸化スズ
レーザー添加剤L3(成分D):
比表面積(BET)20m2/gのNanoniMaterials&TechnologyからのITOナノ粉末を、450°Cにおいて形成ガス下でアニールした後、粉砕した。
色素FP(成分E):
有機緑色顔料、PV Fast True Green GG01(クラリアント)
市販のポリマー(成分G):
ポリアミド6.6(PA6.6-GV;融点範囲255~260℃):Ultramid(登録商標)A27(BASF)
ポリブチレンテレフタレート(PBT):Ultradur(登録商標)4500(BASF)
ガラス繊維(成分H):
ガラス繊維PPGHP3610、10μm径、長さ4.5mm(PPG,NLより)、
2.1 ポリアミド成形化合物
添加剤成分を表に示した比率で混合し、二軸押し出し機(LeistritzZSE型27/44D)の側面取入口を介して260~310℃の温度でPA6.6に組み込んだ。ガラス繊維は第2側面取入口を介して添加した。ホモジナイズしたポリマー鎖を引き出し、水浴中で冷却した後、ペレット化した。
1=非常に明確で詳細な線のマーキング
2=試験グリッドの軽微な撮像エラー
3=試験グリッドの重大な撮像エラー
その手順はポリアミド成形化合物の場合と同様である。添加成分は、240~280°Cの温度で二軸押し出し機器中のポリマーにのみ取り込まれた。
PA6.6成形組成物を用いた試験の結果を、下表に列挙した実施例を示す。全ての量は質量%で与えられ、添加剤および補強材料を含むポリアミド成形化合物に関連する。
PBT成形組成物を用いた試験の結果を下表に列挙した実施例を示した。全ての量は質量%で与えられ、添加剤および補強材料を含むポリエステル成形組成に関連する。
Claims (22)
- - 成分Aとして、式(I)のホスフィン酸塩
MはAl、Fe、TiOpまたはZnであり、
mは2~3であり、
p=(4-m)/2であり、
- 成分Bとして、エチルブチルホスフィン酸、ジブチルホスフィン酸、エチルヘキシルホスフィン酸、ブチルヘキシルホスフィン酸、および/またはジヘキシルホスフィン酸のAl、Fe、TiOpまたはZn塩の群から選択される化合物
- 成分Cとして、式IIのホスホン酸塩
R3がエチルであり、
MetがAl、Fe、TiOqまたはZnであり、
nが2~3であり、
qが(4~n)/2であり、
- 成分Dとして、アンチモンまたはフッ素でドープした酸化スズ、インジウムスズ酸化物および/または酸化アンチモンである、アンチモン、スズおよび/またはインジウム、
並びに、
着色剤E
を含む、プラスチック用添加剤混合物。 - MおよびMetがAlであり、mおよびnが3であり、成分Bがアルミニウム塩であることを特徴とする、請求項1に記載の添加剤混合物。
- 添加剤混合物の総量に基づく割合で、
- 成分Aの割合が5~85質量%、
- 成分Bの割合が0.01~10質量%、
- 成分Cの割合が0.01~10質量%、
- 成分Dの割合が0.0001~3質量%、
であることを特徴とする、
請求項1~2の少なくとも1項に記載の添加剤混合物。 - 添加剤混合物の総量に基づく割合で、
- 成分Aの割合が10~60質量%、
- 成分Bの割合が0.1~2.5質量%、
- 成分Cの割合が0.1~2.5質量%、
- 成分Dの割合が0.1~2質量%、
であることを特徴とする、
請求項3に記載の添加剤混合物。 - 成分Dとして、0.0001~2.6質量%のアンチモン、および/または0.0001~1.5質量%のスズ、および/または0.0001~1.5質量%のインジウムを含むことを特徴とする、請求項1~3の少なくとも1項に記載の添加剤混合物。
- 成分Dがアンチモンドープ酸化スズ、フッ化物ドープ酸化スズおよびインジウムスズ酸化物からなる群より選択され、酸化スズ中のドーパントの含有量が1~15モル%であり、インジウムスズ酸化物中のスズの含量は5~15モル%である、請求項1~5の少なくとも1項に記載の添加剤混合物。
- 成分Dが0.0001~2.6質量%のアンチモンおよび/または0.0001~1.5質量%のスズを含有するアンチモンドープ酸化スズであるか、または成分Dが0.0001~1.5質量%のインジウムおよび/または0.0001~1.5質量%のスズを含有するインジウムスズ酸化物であるか、または、成分Dが15~30質量%のスズおよび0.3~2質量%のアンチモンを含む二酸化スズ-ダイアンチモン三酸化スズでコーティングされた雲母であるか、または、成分Dが酸化アンチモンであることを特徴とする請求項1~6に記載の添加剤混合物。
- 有機染料および顔料から選択される着色剤Eを含むことを特徴とする、請求項1~7の少なくとも1項に記載の添加剤混合物。
- 成分Fとして無機ホスホネートを含むことを特徴とする、請求項1~8の少なくとも1項に記載の添加剤混合物。
- 成分Iとして平均縮合度が2~200のメラミンポリリン酸を含むことを特徴とする請求項1~10の少なくとも1項に記載の添加剤混合物。
- 熱可塑性ポリマーおよび/または熱硬化性ポリマーおよび請求項1~11の少なくとも1つに記載の添加剤混合物を含むポリマー組成物。
- 成分Gとして、ポリアミドまたはポリエステルから選択される熱可塑性ポリマーを含有することを特徴とする請求項12に記載のポリマー組成物。
- ポリマー組成物の総量に基づく割合で、
成分Gの割合が25~95質量%であり、成分Aの割合が1~35質量%であり、成分Bの割合が0.01~3%質量%であり、成分Cの割合が0.001~1質量%であり、成分Dの割合が0.005~2質量%であり、成分Eの割合が0~25質量%であり、成分Fの割合が0~10質量%であることを特徴とする、請求項12~13の少なくとも1つに記載のポリマー組成物。 - 500ボルト以上の国際電気技術委員会基準(InternationalElectrotechnicalCommissionStandard)IEC-60112/3に従って測定された比較トラッキングインデックス(トラッキングインデックス)を有することを特徴とする請求項12~14に記載のポリマー組成物。
- 厚さ3.2mm~0.4mmの成形物に関して測定し、UL-94によるV0基準を達成することを特徴とする請求項12~15の少なくとも1つに記載のポリマー組成物。
- 厚さ0.75~3mmの成形物に関して測定し、960°C以上のIEC-60695-2-12によるグローワイヤ難燃性インデックスを有することを特徴とする請求項12~16の少なくとも1つに記載のポリマー組成物。
- 少なくとも775℃のIEC-60695-2-13によるグローワイヤ発火温度(GWIT)を有することを特徴とする請求項12~17の少なくとも1項に記載のポリマー組成物。
- 成分Hとしてさらに添加剤を含有し、さらに当該添加剤が、抗酸化剤、UV安定剤、ガンマ線安定剤、加水分解安定剤、抗酸化剤のための補助安定剤、帯電防止剤、乳化剤、有核剤、可塑剤、加工助剤、衝撃修飾剤、成分DおよびEと異なる染料または顔料、充填剤、補強材料および/または成分A、B、C、FおよびIとは異なる他の難燃剤からなる群から選択されることを特徴とする請求項12~18の少なくとも1項に記載のポリマー組成物。
- ガラス繊維を含むことを特徴とする、請求項12~19の少なくとも1項に記載のポリマー組成物。
- 電気・電子・自動車産業における成形組成物、半完成品または完成品としての、食品部門または玩具部門における包装に対する、または、医療技術におけるラベル画像としての、または、動物の個体識別のためのプラスチックマークとしての、請求項12~20の少なくとも1項に記載のポリマー組成物の使用。
- 回路板、ハウジング、フィルム、電線、スイッチ、分配器、リレー、抵抗器、コンデンサ、コイル、ランプ、ダイオード、LED、トランジスタ、コネクタ、レギュレータ、メモリおよびセンサの一部を、大面積の構成要素、制御キャビネット用のハウジングの形態で、かつ要求された高度な形状で精巧な形状を有する構成要素の形態で製造するために使用されることを特徴とする請求項21に記載のポリマー組成物の使用。
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PCT/EP2018/068322 WO2019011791A1 (de) | 2017-07-14 | 2018-07-06 | Additivmischungen für kunststoffe, lasermarkierbare polymerzusammensetzungen enthaltend diese und deren verwendung |
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US20200165415A1 (en) | 2020-05-28 |
US11739195B2 (en) | 2023-08-29 |
CN109251355B (zh) | 2021-01-05 |
DE102017212099A1 (de) | 2019-01-17 |
KR20200032142A (ko) | 2020-03-25 |
KR102546392B1 (ko) | 2023-06-26 |
EP3652241A1 (de) | 2020-05-20 |
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