CN1147227A - 可激光标识的塑料 - Google Patents
可激光标识的塑料 Download PDFInfo
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- CN1147227A CN1147227A CN95192924A CN95192924A CN1147227A CN 1147227 A CN1147227 A CN 1147227A CN 95192924 A CN95192924 A CN 95192924A CN 95192924 A CN95192924 A CN 95192924A CN 1147227 A CN1147227 A CN 1147227A
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- 239000000049 pigment Substances 0.000 claims abstract description 58
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 4
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- 239000013065 commercial product Substances 0.000 description 2
- XJUNRGGMKUAPAP-UHFFFAOYSA-N dioxido(dioxo)molybdenum;lead(2+) Chemical compound [Pb+2].[O-][Mo]([O-])(=O)=O XJUNRGGMKUAPAP-UHFFFAOYSA-N 0.000 description 2
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- ZEHOVWPIGREOPO-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-[2-(4,5,6,7-tetrachloro-1,3-dioxoinden-2-yl)quinolin-8-yl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C(=O)N1C(C1=N2)=CC=CC1=CC=C2C1C(=O)C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C1=O ZEHOVWPIGREOPO-UHFFFAOYSA-N 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- UVOOBSVIDMVALT-UHFFFAOYSA-L copper hydrogen phosphate hydrate Chemical compound P(=O)(O)([O-])[O-].[Cu+2].O UVOOBSVIDMVALT-UHFFFAOYSA-L 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
- B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
-
- 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
-
- 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
- B41M5/24—Ablative recording, e.g. by burning marks; Spark recording
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/22—Removing surface-material, e.g. by engraving, by etching
- B44C1/228—Removing surface-material, e.g. by engraving, by etching by laser radiation
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Abstract
本发明涉及可激光标识的塑料，特别是热塑性聚氨酯，其特征是，它们含有掺杂的二氧化锡涂料的颜料。
Description
本发明涉及可激光标识的塑料，其特点是它们含有掺杂的二氧化锡涂料的颜料。
事实上，在所有工业部门中产品的标识已变得越来越重要。例如，生产日期、使用日期、条形码、公司标志、批号等都必须经常使用。目前，这些标识主要用传统的技术制作，例如印刷、压花、盖章和贴标签等。但是，使用激光进行非接触的，快速和灵活的标识的重要性，特别是在塑料的情况下，不断增加。这一技术使得甚至在非平面上以高的速度进行图形注册如条形码成为可能。因为是在塑料本身上注册，它是经久耐磨的。
许多塑料如聚烯烃和聚苯乙烯到目前为止被认为是很难或甚至根本不可能用激光标识。在聚烯烃和聚苯乙烯的情况下，甚至在很高功率输出下，能产生10.6μm红外区域光的CO2激光也仅能产生很弱的肉眼难以辨认的标识。在聚氨酯和聚醚-酯弹性体的情况下，Nd-YAG激光不产生相互作用，而CO2激光产生刻花。塑料必须不完全反射或透射激光，否则不能发生相互作用。但是，两者都不可能有强的吸收，因为在这种情况下塑料蒸发，仅留下刻花。激光束的吸收从而与塑料材料的相互作用与塑料的化学结构和所用的激光波长有关。在许多情况下，有必要加入适合的添加剂如光吸收剂，使塑料能激光标识。
除了CO激光外，越来越多的使用Nd-YAG激光进行塑料的标识。通常使用的YAG激光发射特征波长为1064nm或532nm的脉冲能量束。吸收剂在这一特定的NIR区域必须显示出明显的吸收能力，以便在快速标识操作过程中有充分的反应。
DE-A2936926公开，通过塑料与暴露到能量辐射中能变色的填充剂如炭黑或石墨混合的方法，可实现用激光给聚合材料标识。
EP0400305A2公开了可用激光标识的高度聚合材料，它们含有磷酸羟铜(II)或二氧化钼(VI)作为变色添加剂。
EP0522370A1公开了基于有机热塑性聚合物并含有黑色颜料的塑料模塑组合物，它通过暴露到激光辐射中可产生这些特征。
但是，背景技术已知的填充剂都有这样一个缺点：它们使要印的塑料长期着色，因此使通常是黑色文字在浅色背景上的激光标识不再有足够高的反差。
所以，填充剂或合格的吸收剂应有很浅的固有颜色或只需使用极少的数量。造影剂三氧化锑满足这样的要求。US4816374将三氧化锑用于Nd-YAG激光对热塑性弹性体的激光标识。使用的浓度为3-8％，它与基材和激光纪录速度有关。用镉和砷化合物进行激光标识是可能的，但是由于它们有毒，这些物质已不再使用。
所以，本发明的目的是寻找可激光标识的塑料。它们在暴露到激光下产生高的反差标识，并且只含有少量重金属。
令人吃惊的是，现已发现，含有锑掺杂的二氧化锡涂料的颜料的热塑性塑料能形成带有锐边的高反差标识。
所以本发明涉及可激光标识的塑料，其特征是热塑性塑料含有掺杂的二氧化锡涂料的颜料。
按塑料体系计，颜料加入浓度为0.1-4％(重)(优选0.5-25％(重)，特别优选0.3-2％(重))时可在激光标识上达到这样的反差，它相当于或甚至优于含SbO3浓度高得多的塑料的反差。但是，颜料在塑料中的浓度取决于所用的塑料体系。少量颜料不会明显改变塑料体系，也不会影响它的加工性能。
颜料中的二氧化锡涂料优选用锑、砷、铋、铜、镓或锗掺杂，特别是锑，或者用相应的氧化物掺杂。按二氧化锡计，掺杂量为0.5-50％(重量)、优选0.5-40％(重)，特别优选0.5-20％(重)。二氧化锡涂料可为导电涂料或非导电涂料。
用这样的纯色颜料掺杂的透明热塑性塑料稍有金属闪光，但仍然是透明的。如果需要，加入0.2-1 0％(重)(优选0.5-3％(重)不透明颜料如二氧化钛可完全掩盖金属光泽，特别是在热塑性聚氨酯的情况下。此外，可将能使所有类型塑料变色的有色颜料加到塑料中，同时保留激光标识。
例如在DE-A3842330和EP0139557中公开了适合于标识的颜料及其制备方法。颜料优选为片晶形状，特别为页硅酸盐的透明或半透明物质，如云母、滑石、高岭土、玻璃、SO2小片、合成的或陶瓷小片或合成的无载体片晶。金属片晶如铝片晶，或片晶状金属氧化物如氧化铁或氯氧化铋也是适合的。特别优选的物质包括用一种或多种金属氧化物涂覆的云母小片。在这里使用的金属氧化物为无色的耐高温金属氧化物如二氧化钛和/或二氧化锆，或者为有色的金属氧化物如氧化铬、氧化镍、氧化铜、氧化钴，特别是氧化铁。
可用已知的方法，如EP0139557中公开的方法将二氧化锡涂料涂到物质上。将用锑、砷、铋、铜、镓或锗掺杂的二氧化锡涂料涂到片晶状物质上，其量为约25-100％，特别是约50-75％。
特别适用于激光标识的颜料是那些片晶状金属氧化物或片晶状物质，特别是用一种或多种金属氧化物涂覆的云母。特别适合的颜料是这样的颜料；其特征是基础物质在用掺杂的二氧化锡涂料涂覆以前先用任选的水合二氧化硅涂覆。在DE3842330中公开了这样的颜料。在这种情况下，先将该物质悬浮在水中，然后在适合的pH值下将可溶性硅酸盐的溶液加入；如果需要，同时加入酸，使pH值保持在适合的范围。在随后的用二氧化锡涂料涂覆和处理前，可将硅酸涂覆的物质从悬浮液中分离出来，或者直接用掺杂的二氧化锡涂料涂覆。
如在Ullmann，Vol.15，pp457ff(VCH出版)描述的所有已知热塑性塑料都可用作激光标识。适合的塑料的例子是聚乙烯、聚丙烯、聚酰胺、聚酯、聚酯酯、聚醚酯、聚苯醚、聚缩醛、聚对苯二甲酸丁二醇酯、聚甲基丙烯酸甲酯、聚乙烯缩醛、聚苯乙烯、丙烯腈-丁二烯-苯乙烯(ABS)、丙烯腈-苯乙烯-丙烯酸酯(ASA)、聚碳酸酯、聚醚砜、聚醚酮和共聚物和/或其混合物。特别适合的是热塑性聚氨酯(TPU)，因为它们有良好的机械性能以及加工方法费用低。热塑性聚氨酯早已从许多专利和其他公开发表物中知道，例如GB1057018和EP0564931。
用塑料颗粒与颜料混合，然后将混合物在升温下模化的方法将颜料加到热塑性塑料中。如果需要，在加入颜料的过程中，可将在工作条件下是热稳定的粘合剂，聚合物相容的有机溶剂、稳定剂和/或表面活性剂加入。通常用将塑料颗粒装入适合的混合器，用任何添加剂润湿颗粒，然后加入和混合颜料的方法来制备塑料颗粒/颜料混合物。通常通过色料浓缩物(母料)或混合料进行塑料着色。生成的混合物然后直接在挤塑机或注塑机中加工。加工中生成的模塑制品有很均匀的颜料分布。然后进行激光标识。
本发明还涉及一种制备新型的可激光标识的塑料的方法，其特征是热塑性塑料与颜料混合，然后在升温下模化。
通过将试验样品放在脉冲激光(优选Nd-YAG激光)射线途径中进行激光标识。用激发物激光标识也是可能的，例如用掩模技术，但是，用其他传统类型的激光也可得到所希望的结果，这些激光对所用的颜料应有高吸收率的波长范围。得到的标识由激光辐照时间(或在脉冲激光的情况下为脉冲数)和激光的辐照输出功率以及所用的塑料体系决定。所用的激光输出功率与特定的应用有关，对于熟悉本专业的技术人员来说，在单个情况下很容易决定。
新型的加颜料塑料可用于迄今印刷法已用于塑料标识的所有领域。例如，新型塑料的模塑品可用于电器、电子和汽车工业。例如在加热、通风和冷却部门中含有新型塑料的电缆、电线、装饰带或功能部件或开关、插头、杠杆和手柄用激光的标识是可能的，甚至在不易达到的地方。由于其重金属含量低，新型塑料体系还可用于食品方面或玩具方面的包装。在包装上的标识其特征是，它们是耐擦和耐刮的，在随后的消毒过程中是稳定的，在标识过程中可用卫生学上纯净的方法标识。对于可重复使用的体系来说，整个标识可长久在包装上。激光标识的另一重要应用领域包括动物单个标识的塑料标识，称为家畜或耳记。通过条形码体系，将对该动物特定的信息贮存，当需要时然后可用扫描仪进行信息检索。由于在某些情况下要求标识在动物上保持数年，所以标识必须很耐久。
因此得到激光标识的塑料制品或含有新型塑料的模塑品是可能的。
以下实施例用来说明本发明，但不是对本发明的限制。百分数为重量百分数。
实施例1
由肖氏硬度为85A的热塑性聚醚-聚氨酯制备黄色注塑品，它基于1000份分子量1000的聚四氢呋喃、600份MDI(亚甲基二苯基4，4’-二异氰酸酯)和126份l，4-丁二醇，含有1％云母颜料Minatec31CM(有锑掺杂二氧化锡涂料的TiO云母颜料，由E.Merck，Darm stadt制造的商业产品)、0.6％二氧化钛和0.25％Quinophtalone〔sic〕Yellow(BASF制造的PaloitholK〔sic〕0691)。在注塑操作以前，将颜料浓缩物加到聚醚-TPU中。在电流强度15安培和纪录速度400mm/s下用Nd-YAG激光标识后，标牌显示出透明耐磨的标识。用PSC快速检测300和670nm读笔测量的反射数值对基质为66％，而在标识区域为21％。条形码很容易读出。
机械性能
| 抗拉强度/MPa | 断裂伸长率/％ | 肖氏A硬度 | 磨损/mm3 |
| DIN53504 | DIN53504 | DIN53505 | DIN53516 |
| 50 | 650 | 85 | 30 |
实施例2
由肖氏硬度为90A的热塑性聚醚-聚氨酯制备橙色注塑品，它基于1000份分子量为1000的聚四氢呋喃、700份MDI和162份1，4-丁二醇，含有1％云母颜料Minatec30CM(有锑掺杂的二氧化锡涂料的SO2涂覆的TiO2云母颜料，由Merck，Darmstadt制造的商业产品)、0.6％二氧化钛和0.5％铬酸铅颜料(Krolor Yellow787D)和0.1％钼酸铅颜料(Krolor Orange789D)。在注塑操作前，将颜料浓缩物加到聚醚-TPU中。
在13安培、脉冲频率5KHz和600mm/s下用Nd-YAG激光方法的标识有高的反差和耐磨性。
用PSC300测量的反射数值对基质为56％，而在标识区域为25％。
实施例3
由肖氏硬度为95A的热塑性聚醚-聚氨酯制得橙色注塑品，它基于1000份分子量1000的聚四氢呋喃、830份MDI和209份1，4-丁二醇以及2％UV稳定剂浓缩物。另外，小片含有1％云母颜料Minatec31CM、0.6％二氧化钛和0.25％Quinophtalone〔sic〕Yellow和0.02％偶氮颜料Paliotol Yellow K2270。在注塑操作前，将颜料浓缩物加到聚醚-TPU中。
在18安培和600mm/s下用Nd-YAG激光方法的标识有高的反差和耐磨性。
用PSC300测量的反射数值对基质为67％，而在标识区域为24％。
实施例4
由肖氏硬度为90A的聚醚-聚氨酯制得白色注塑品，它基于1％云母颜料Minatec31CM和1％二氧化钛。在注塑操作前，将颜料浓缩物加到聚醚TPU中。
在14安培、脉冲频率5KHz和400mm/s下，用Nd-YAG激光方法的标识有高的反差和耐磨性。
用PSC300测量的反射数值对基质为68％，而在标识区域为28％。
实施例5
由肖氏硬度为42D的聚醚酯制得黄色注塑品，它基于聚四氢呋喃和聚对苯二甲酸丁二醇酯。小片含有1％云母颜料Minatec31CM、0.6％二氧化钛和0.25％Quinophtalone〔sic〕Yellow.在注塑操作以前，将颜料浓缩物加入。
用Nd-YAG激光的方法得到高反差的标识。
实施例6
由肖氏硬度为55D的聚酯酯制得黄色注塑品，它基于聚对苯二甲酸丁二醇酯和聚己酸内酯。小片含1.5％云母颜料Minatec31CM，0.6％二氧化钛和0.25％Quinophtalone〔sic〕Yellow。在注塑操作前，将颜料浓缩物加入。
用Nd-YAG激光的方法得到高反差的标识。
实施例7
由肖氏硬度为90A的聚酯-聚氨酯制得橙色注塑品，它基于100份分子量为2000的聚(1，4-丁二醇)己二酸己二醇酯、580份MDI和162份1，4-丁二醇，含有1.5％云母颜料Minatec30CM、0.6％二氧化钛、0.5％铬酸铅颜料(Krolor Yellow787D)和0.1％钼酸铅颜料(Krolor Orange789D)。在注塑操作前，将颜料浓缩物加到聚醚-TPU中。
用Nd-YAG激光方法得到的标识耐久，有高反差。
实施例8
由含有聚酰胺(UltramidA3K BASF，Ludwigshafen)和0.3％Minatec30CM的模塑组合物制得的插头在白色背景上加有黑色标识。用Nd-YAG激光方法得到的标识得到干净和平滑的基本花纹。在聚酰胺中靠近颜料出现的颜色变化是很透明的，聚合物没有任何明显的变化。
实施例9
由含有聚甲醛(HostaformC902，Hoechst公司生产)和1％Minatec31CM的模塑组合物制得的照明开关用Nd-YAG激光在白色背景上产生灰色标识。
实施例10
含有聚丙烯(PPH10，DSM生产)和1％Minatec30CM的薄膜有Nd-YAG激光产生有锐边的标识，衬料未起泡。
对比例1
由肖氏硬度为95A的热塑性聚醚-聚氨酯制得黄色注塑品，它基于1000份分子量为1000的聚四氢呋喃、830份MDI和209份1，4-丁二醇和2％UV稳定剂浓缩物。另外，小片含有0.6％二氧化钛和0.25％Quinophthalone Yellow和0.02％偶氮颜料Paliotol Yellow K2270。在注塑操作前，将颜料浓缩物加到聚醚TPU中。
组成和颜色对应于实施例3，但不含激光显影剂。不可能用Nd-YAG激光标识。
对比例2
由肖氏硬度为95A的热塑性聚醚-聚氨酯制得黄色注塑品，它基于1000份分子量为1000的聚四氢呋喃、830份MDI和209份1，4-丁二醇和2％UV稳定剂浓缩物。另外，小片含有5％三氧化锑、0.6％二氧化钛和0.25％Quinophthalone和0.02％偶氮颜料Paliothol YellowK2270。在注塑操作前，将颜料浓缩物加到聚醚TPU中。
组成和颜色对应于实施例3，不同的是不含激光显影剂，类似对比例1。
在18A和600mm/s下，用Nd-YAG激光进行标识。
用PSC300测量的反射数值对于基质为69％，而在标识区域为22％。
Claims (12)
1.可激光标识的塑料，其特征是，热塑性塑料含有掺杂的二氧化锡涂料的颜料。
2.根据权利要求1的可激光标识的塑料，其特征是，热塑性塑料含有片晶状物质为基础的颜料。
3.根据权利要求1或2的可激光标识的塑料，其特征是，颜料含有云母片晶、SiO2小片或一种或多种金属氧化物涂覆的云母片晶作为片晶状物质。
4.根据权利要求1-3的可激光标识的塑料，其特征是，颜料含有用任选的水合二氧化硅涂料或其他不溶性硅酸盐涂料涂覆的片晶状物质。
5.根据权利要求1-4的可激光标识的塑料，其特征是，按塑料体系计，颜料的比例为0.1-3％(重)。
6.根据权利要求1-5的可激光标识的塑料，其特征是，颜料的二氧化锡涂料用0.5-50％(重)锑、砷、铋、铜、镓、锗或对应的氧化物掺杂。
7.根据权利要求1的可激光标识的塑料，其特征是，塑料为热塑性聚氨酯。
8.根据权利要求1的可激光标识的塑料，其特征是，塑料是聚醚酯或聚酯酯。
9.根据权利要求1的可激光标识的塑料，其特征是，它们还含有染料颜料。
10.一种制备可激光标识的塑料的方法，其特征是，热塑性塑料颗粒与颜料混合，然后在升温下模塑。
11.权利要求1的可激光标识的塑料作为生产可用激光辐照标识的模塑品的材料的应用。
12.含有权利要求1的可激光标识的塑料的模塑品。
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| DE4436897A1 (de) | 1994-10-15 | 1996-04-18 | Elastogran Gmbh | Verfahren zur Beschriftung von Formkörpern |
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- 1995-05-03 BR BR9507704A patent/BR9507704A/pt active Search and Examination
- 1995-05-03 CN CN95192924A patent/CN1077905C/zh not_active Expired - Lifetime
- 1995-05-03 AU AU25239/95A patent/AU690993B2/en not_active Ceased
- 1995-05-03 EP EP95919380A patent/EP0797511B1/de not_active Expired - Lifetime
- 1995-05-03 JP JP52866795A patent/JP3591654B2/ja not_active Expired - Lifetime
- 1995-05-03 KR KR1019960706241A patent/KR100347466B1/ko not_active IP Right Cessation
- 1995-05-03 WO PCT/EP1995/001672 patent/WO1995030546A1/de active IP Right Grant
- 1995-05-03 AT AT95919380T patent/ATE183142T1/de not_active IP Right Cessation
- 1995-05-03 ES ES95919380T patent/ES2138737T3/es not_active Expired - Lifetime
- 1995-05-03 DE DE59506606T patent/DE59506606D1/de not_active Expired - Lifetime
- 1995-05-04 ZA ZA953604A patent/ZA953604B/xx unknown
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1999
- 1999-12-15 US US09/461,032 patent/US6214917B1/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368303C (zh) * | 2001-04-12 | 2008-02-13 | 恩格哈德公司 | 用于yag激光标记的添加剂 |
| CN101044027B (zh) * | 2004-10-15 | 2010-11-03 | 化学制造布敦海姆两合公司 | 用于产生高耐燃性制品的模塑材料、用于该材料的颜料及其用途 |
| CN101423653B (zh) * | 2008-12-01 | 2011-08-17 | 上海金发科技发展有限公司 | 具有激光打印标记功能的玻纤增强聚对苯二甲酸丁二醇酯树脂组合物及其制备方法 |
| CN103443328A (zh) * | 2011-03-18 | 2013-12-11 | 三菱化学欧洲有限公司 | 热塑性树脂组合物、树脂成型品和带镀层的树脂成型品的制造方法 |
| US8933161B2 (en) | 2011-03-18 | 2015-01-13 | Mitsubishi Chemical Europe Gmbh | Thermoplastic resin composition, resin molded article, and method of manufacturing resin molded article with plated layer |
| CN103443328B (zh) * | 2011-03-18 | 2016-02-24 | 三菱化学欧洲有限公司 | 热塑性树脂组合物、树脂成型品和带镀层的树脂成型品的制造方法 |
| CN107075260A (zh) * | 2014-11-05 | 2017-08-18 | 默克专利股份有限公司 | 可激光标记和可激光焊接的聚合物材料 |
| CN107075260B (zh) * | 2014-11-05 | 2020-04-03 | 默克专利股份有限公司 | 可激光标记和可激光焊接的聚合物材料 |
| CN106957522A (zh) * | 2017-03-17 | 2017-07-18 | 姜有为 | 牲畜专用可视耳标材料及其制备方法和耳标 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59506606D1 (de) | 1999-09-16 |
| EP0797511B1 (de) | 1999-08-11 |
| ATE183142T1 (de) | 1999-08-15 |
| AU690993B2 (en) | 1998-05-07 |
| JPH10500149A (ja) | 1998-01-06 |
| US6214917B1 (en) | 2001-04-10 |
| KR100347466B1 (ko) | 2002-12-18 |
| JP3591654B2 (ja) | 2004-11-24 |
| ZA953604B (en) | 1995-12-05 |
| BR9507704A (pt) | 1997-08-19 |
| EP0797511A1 (de) | 1997-10-01 |
| CN1077905C (zh) | 2002-01-16 |
| WO1995030546A1 (de) | 1995-11-16 |
| AU2523995A (en) | 1995-11-29 |
| ES2138737T3 (es) | 2000-01-16 |
| DE4415802A1 (de) | 1995-11-09 |
| KR970702790A (ko) | 1997-06-10 |
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