CN101039808B - 磷酸锡在激光可写性热塑材料中的应用 - Google Patents

磷酸锡在激光可写性热塑材料中的应用 Download PDF

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CN101039808B
CN101039808B CN2005800353727A CN200580035372A CN101039808B CN 101039808 B CN101039808 B CN 101039808B CN 2005800353727 A CN2005800353727 A CN 2005800353727A CN 200580035372 A CN200580035372 A CN 200580035372A CN 101039808 B CN101039808 B CN 101039808B
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laser
tin
phosphoric acid
thermoplastic materials
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CN101039808A (zh
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J·马克曼
R·维森博斯基
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Chemische Fabrik Budenhiem KG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/267—Marking of plastic artifacts, e.g. with laser

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Glass Compositions (AREA)
  • Paints Or Removers (AREA)
  • Optical Filters (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
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Abstract

为了改善激光篆文的可写性，采用残留水分含量最大为1重量％的磷酸锡化合物用作热塑性材料的颜料。

Description

磷酸锡在激光可写性热塑材料中的应用
本发明涉及激光对塑料制品的可写性或可标记性。
很早就知道可在塑料制品上做标记和书写，多年以来也已知大多数塑料材料不吸收激光，因此不能用激光在塑料材料上书写。因为这个原因，细碎分离的颜料被添加到塑料材料中，这些颜料吸收激光并在激光影响下改变颜色。在这方面，颜色改变这一概念被看做是独立于机制的。此外，这里术语“颜色改变”包括产生了与最初颜色不同的颜色，或形成了相同或类似的颜色但明亮度水平不同。此处，颜色改变也可表示一种溶液最初是无色的，由于激光而获得了某种颜色，或者表示在塑料材料中发生了颜色改变。
这方面的一个主要问题是，清楚易读的激光篆刻需要一方面激光照射之前和另一方面激光照射之后两种状态之间强烈的颜色对比，因为两种状态中类似的颜色色调将在阅读篆刻的塑料材料时产生严重的问题。
也已知采用金属盐用于该目的，例如磷酸氢氧化铜，但该化合物有时仍然不能满足工业的需要，因此仍然在研究能增加某些状态的颜色对比或实际上所有塑料材料在激光照射之前和之后的颜色对比并因此有助于阅读的化合物。
出乎意料地，现在已发现通过采用至少一种磷酸锡盐，具体是采用磷酸三锡作为热塑性材料的颜料，实现了这一目的，热塑性材料的激光可写性得到了意想不到的改善。除磷酸三锡之外，也可单独采用焦磷酸盐或缩合程度更高的多磷酸的锡盐，或它们的混合物。应理解，也可在磷酸盐中加入改善某些性能的常规添加剂，或者这些常规添加剂作为生产过程中引入的杂质而存在于磷酸盐中。
用于实现和改善激光可写性的颜料必须尽可能均匀地分散在待写的塑料制品中，分散在全部制品中或制品的某些区域，如表面区域。对该目的而言，颜料应该是微粒，并且精细分离，其平均粒径(d50)在20μm以下，优选5μm以下。平均颗粒细度对性能影响很大，因此对颗粒是否适宜用作(改善)激光可写性的颜料也影响很大。
锡化合物，具体是磷酸三锡具有很高的容积密度。低平均颗粒细度对激光可写性影响很大。较高的颗粒细度水平将增加所需的能量，而过低的颗粒细度水平导致形成塑料材料上层区域的不良泡沫。
明亮度值，称为L-值，介于92-110，从而该材料可判定几乎为白色，当该材料掺入亮色的塑料材料时具有显著优点。可将所述产品迅速干燥至低含水量。用KarlFischer水测定法测定残留水分水平低于0.5重量％、
本发明磷酸三锡的平均颗粒细度d50为8-20μm，优选为8-10μm，L-值优选在94-98范围内，残留水分水平优选低于0.5重量％。激光照射之前和激光照射之后的状态之间颜色比对显著。
磷酸锡的生产可见“Gmelin，Handbuch der Anorganischen Chemie：Zinn，C部分，第2版-第8版-Springer-Verlag，Berlin，1975，245-259页。
磷酸三锡掺入塑料基质的量为0.1-1.0重量％，优选约0.5重量％。除正磷酸锡之外，也可掺入其它颜料，例如磷酸铜，或改善具体性能的其它物质。
实施例
实施例1
按下述生产的正磷酸锡按本发明以0.5重量％的量掺入聚酰胺基质中，加工模塑材料以形成注塑片，然后通过1046nm波长的Nd-YAG激光提供K值大于4的标记。其中所用的正磷酸锡如下制备：
将正磷酸三钠溶解在水中，室温下与氯化锡等份反应。反应后等候30分钟。然后吸掉反应液，产生的磷酸三锡(tertiary tin phosphate)沉淀用水洗涤，以除去氯。然后小心地用P2O5干燥并破碎。
也可如下制备其中所用的磷酸三锡：
硫酸锡溶解在水中，与磷酸盐等份混合，从而产生磷酸三锡。用氢氧化钠调整pH值为9，分离产生的磷酸三锡并洗涤。然后然后小心地用P2O5干燥并破碎。
实施例2
将0.5重量％的磷酸锡加入聚酰胺基质中，再加入0.5重量％的亚磷酸铁，然后加工塑料材料以形成片材，用1064或532nm波长的Nd-YAG激光照射，产生K值大于3.5的篆刻。

Claims (2)

1.残留水分含量低于0.5重量％，明亮度相当于L值92-110，且平均颗粒细度d50为8-20μm的磷酸锡化合物作为热塑性材料中颜料的应用，以提高热塑性材料的激光可写性/可标记性。
2.如权利要求1所述的应用，其特征在于，所述磷酸锡化合物的平均颗粒细度d50为8-10μm。
CN2005800353727A 2004-10-15 2005-10-14 磷酸锡在激光可写性热塑材料中的应用 Expired - Fee Related CN101039808B (zh)

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DE102004050481A DE102004050481A1 (de) 2004-10-15 2004-10-15 Verwendung von Zinnphosphaten
PCT/EP2005/055283 WO2006042831A1 (de) 2004-10-15 2005-10-14 Verwendung von zinnphosphaten in laserbeschriftbaren thermoplastichen kunstoffen

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DE102006038043A1 (de) 2006-08-14 2008-02-21 Chemische Fabrik Budenheim Kg Laserbeschriftbares Polymermaterial
US10256009B2 (en) 2014-06-19 2019-04-09 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
US9881714B2 (en) 2014-06-19 2018-01-30 Saint-Gobain Performance Plastics Corporation Laser-markable insulation material for wire or cable assemblies
DE102016210160A1 (de) 2016-06-08 2017-12-14 Weilburger Coatings Gmbh Wässrige Zusammensetzung zur Erzeugung einer lasermarkierbaren Beschichtung und lasermarkierte Beschichtung
DE102016219858A1 (de) 2016-10-12 2018-04-12 Weilburger Coatings Gmbh Verfahren zur Herstellung einer Beschichtung mit Markierungen auf einer Oberfläche oder einem Teil einer Oberfläche eines Gegenstandes

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US6214916B1 (en) * 1998-04-29 2001-04-10 General Electric Company Composition for laser marking
DE19905358A1 (de) * 1999-02-10 2000-08-17 Budenheim Rud A Oetker Chemie Verwendung von Alkalikupferdiphosphat
DE10252007A1 (de) * 2002-11-06 2004-05-27 Merck Patent Gmbh Lasermarkierbare Pigmente
WO2004050766A1 (en) * 2002-12-04 2004-06-17 Dsm Ip Assets B.V. Laser light absorbing additive

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AU2005296849B2 (en) 2011-01-27
CN101039808A (zh) 2007-09-19
AU2005296849C1 (en) 2012-01-19
DE102004050481A1 (de) 2006-04-27
WO2006042831A1 (de) 2006-04-27
US20090016945A1 (en) 2009-01-15
EP1819522A1 (de) 2007-08-22
KR20070063038A (ko) 2007-06-18
JP4960243B2 (ja) 2012-06-27
DE502005010246D1 (de) 2010-10-21
HK1110554A1 (en) 2008-07-18
JP2008538785A (ja) 2008-11-06
ATE480408T1 (de) 2010-09-15
EP1819522B1 (de) 2010-09-08
KR101234802B1 (ko) 2013-02-20
TWI373491B (en) 2012-10-01
AU2005296849A1 (en) 2006-04-27

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