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EP0835185A1 - Utilisation de matieres moulables polymeres pour la modification chromatique partielle par energie laser afin de produire des informations optiques a contraste eleve - Google Patents

Utilisation de matieres moulables polymeres pour la modification chromatique partielle par energie laser afin de produire des informations optiques a contraste eleve

Info

Publication number
EP0835185A1
EP0835185A1 EP96922802A EP96922802A EP0835185A1 EP 0835185 A1 EP0835185 A1 EP 0835185A1 EP 96922802 A EP96922802 A EP 96922802A EP 96922802 A EP96922802 A EP 96922802A EP 0835185 A1 EP0835185 A1 EP 0835185A1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
use according
polymer
contain
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.)
Withdrawn
Application number
EP96922802A
Other languages
German (de)
English (en)
Inventor
Aziz El Sayed
Frank Gerling
Salvatore Messina
Herbert Magerstedt
Karsten-Josef Idel
Edgar Ostlinning
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0835185A1 publication Critical patent/EP0835185A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties

Definitions

  • the invention relates to the use of polymer molding compositions for partial color changes by laser energy, in particular for generating optical information, e.g. Letters, numbers, patterns and / or pictures etc. with very good contrasts.
  • Components, keycaps, housings and ID cards are a classic application for laser marking.
  • a polymer matrix is colored with light colorants - pigments or dyes.
  • the polymer matrix / colorant is partially carbonized by absorption of the laser energy. This creates a dark discoloration of the light polymer matrix. This behavior is limited to polymers that tend to carbonize.
  • Contrast ratio has proven to be insufficient.
  • the present invention relates to polymer molding compositions which, when the laser energy is absorbed, give bright characters on a dark background with a very high contrast ratio.
  • the invention relates to the use of polymer molding compositions consisting of:
  • polymer selected from the group of polyamides polyolefins, graft polymer of the ABS type, polyacrylates, polymethacrylates or a mixture of polycarbonate, graft polymer of the ABS type and optionally
  • Another object of the invention is the use of the colored polymers for the production of molded articles by means of laser beam recorders can be labeled, labeled or provided with visual representations.
  • the polymer moldings used according to the invention can be produced on commercially available single-shaft and twin-shaft extruders.
  • the soot is dosed as a color concentrate.
  • Commercially available injection molding machines can be used to produce the molded parts.
  • Thermoplastic polyamides suitable according to the invention are generally aliphatic polyamides or polyamides with a predominantly aliphatic content.
  • Polyamide 6 or polyamide 66 or copolyamides of polyamide 6 with diamines (preferably C 4 -C ] 6 -, in particular C 4 -C 8 -alkylenediamines) and dicarboxylic acids (preferably C 4 -C ] 2 -, in particular C 4, are preferred -C 8 -alkylene dicarboxylic acids) or polyamide 66 with a comonomer content of at most 20% by weight.
  • Polyolefins according to the invention are polymers of aliphatic unsaturated hydrocarbons, such as, for example, ethylene, propylene, butylene or isobutylene, which are obtained by customary processes, for example radical polymerization, and average weight-average molecular weights lvL ⁇ , (measured by gel chromatography methods) between 5,000 and have 3,000,000. Both high pressure polyolefin and low pressure polyolefin are useful.
  • the unsaturated hydrocarbons can also be copolymerized in a known manner with other vinyl monomers such as, for example, vinyl acetate, acrylic acid or acrylic acid esters, the proportion of vinyl monomers being at most 30% by weight, preferably up to 25% by weight. Polyethylene and polypropylene are preferred.
  • polymers of alkyl esters of (meth) acrylic acid are preferably those having a C j -C] 8 alkyl ester used of the (meth) acrylic acid.
  • the C j -C] 8 alkyl ester are generally as Me ⁇ thyl-, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl , tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, lauryl or stearyl acrylate, preferably methyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures of these monomers , used.
  • the esters of methacrylic acid are generally the C 1 -C 4 -alkyl esters, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert. -Butyl-, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, lauryl or stearyl acrylate, preferably methyl methacrylate, and mixtures of these monomers are used.
  • Thermoplastic, aromatic polycarbonates suitable in accordance with the invention in a mixture with graft polymer and optionally copolymer are those based on the diphenols of the formula I.
  • A is a single bond, C r C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -S- or -SO 2 -.
  • Suitable diphenols of the formula (I) are, for example, hydroquinone, resorcinol,
  • Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane.
  • the diphenols of the formula (I) are either known from the literature or can be prepared by processes known from the literature.
  • the preparation of the polycarbonates suitable according to the invention is known from the literature and can be carried out, for example, with phosgene according to the interfacial process or with phosgene according to the process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being known by a corresponding amount of known Chain breakers is achieved.
  • Suitable chain terminators are, for example, monophenols such as phenol itself, p-cresol, p-tert-butylphenol and p-isooctylphenol.
  • the polycarbonates suitable according to the invention have average weight molecular weights measured for example by ultracentrifugation or by scattered light measurement) from 10,000 to 200,000, preferably from 20,000 to 80,000.
  • the polycarbonates suitable according to the invention are both homopolycarbonates and copolycarbonates.
  • the polycarbonates suitable according to the invention can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of three- or more than three-functional compounds, for example those with three or more than three phenolic OH groups.
  • Suitable graft polymers of the ABS type, alone or in a mixture with polycarbonate, are:
  • C j -C 8 alkyl methacrylates especially methyl methacrylate, C j -C 8 alkyl acrylate, especially methacrylate, maleic anhydride, C j -C 4 alkyl or phenyl-N-substituted maleimides or mixtures of these compounds
  • Preferred graft bases are polybutadienes, butadiene / styrene copolymers and acrylate rubbers.
  • the graft base is particulate and generally has an average particle diameter (d 50 ) of 0.05 to 5 ⁇ m, preferably 0.1 to 0.8 ⁇ m.
  • the graft base can contain up to 50% by weight of residues of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, esters of acrylic or methacrylic acid with 1 to 4 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate) , Vinyl ester and / or contain vinyl ether.
  • the preferred graft base consists of pure polybutadiene.
  • Preferred graft polymers are e.g. Bases K.2 grafted with styrene and / or acrylonitrile and / or (meth) acrylic acid alkyl esters such as polybutadienes, butadiene / styrene copolymers, i.e. Copolymers of DE-OS 1 694 173
  • graft polymers are also understood according to the invention to mean those products which are obtained by polymerizing the graft monomers in the presence of the graft base.
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).
  • graft polymer of the ABS type and, if appropriate, copolymer, 50 to 96.5, in particular 60 to, are preferably used
  • Carbon black B) of the molding compositions used according to the invention are very finely divided carbon blacks.
  • the carbon black can be used as pure carbon black (particle size 13 to 20 nm), in pearl shapes or as a concentrate, for example in Microlen Schwarz B® from Ciba Geigy (Basel).
  • reinforcement C) of the molding compositions used according to the invention are up to
  • elastomer modifier D Up to 20% by weight of commercially available EP (D) M rubbers, graft rubbers based on butadiene styrene, acrylonitrile (see above), acrylate rubbers, polyurethanes or EVA are used as elastomer modifier D) according to this invention. Copolymers with or without functional coupling groups are used.
  • Flame retardant additives such as Mg hydroxide or Ca-Mg carbonate hydrate can be used.
  • the processing additives E) consist of up to 2% by weight of commercially available lubricants, stabilizers, mold release agents and nucleating agents.
  • the wavelength can be between 193 nm and 10600 nm, preferably 1064 nm.
  • the molding compositions used according to the invention can be used to apply optical information in the form of patterns, graphics, numbers, letters, characters, images (e.g. passport photos, portraits, photos) etc.
  • Laser energy e.g. can be used by laser beam recorders.
  • photographic images can be transferred to the molding compositions used according to the invention.
  • Polyamide 6 Durethan B 3 ISK ® from Bayer AG
  • Polyamide 6 glass fiber and glass ball reinforced Durethan BG 30 X ® from Bayer AG
  • Polyamide Durethan T 40 ® from Bayer AG
  • ABS Novodur P2H ® from Bayer AG
  • PMMA Plexiglas 7N ® from Röhm GmbH Darmstadt
  • the dyes were premixed with the granules and extruded and granulated using a twin-screw mixer.
  • the granules obtained were injection-molded into plates on an Arburg injection molding machine and labeled with a FOBALLAS ND-YAG laser.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dot-Matrix Printers And Others (AREA)
  • Laser Beam Printer (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

L'invention concerne des matières moulables constituées d'un polymère choisi dans le groupe comprenant les polyamides, les polyoléfines, un polymère greffé de type ABS, les polyacrylates, les polyméthacrylates ou un mélange comprenant un polycarbonate, un polymère greffé de type ABS ainsi qu'éventuellement un copolymère. Lesdites matières moulables contiennent également du noir de carbone, des matériaux de renfort, un modificateur élastomère, des additifs ignifugeants et des additifs de mise en ÷uvre. Ces matières moulables sont utilisées pour la production de signes clairs ou gris sur un fond sombre par gravure au laser, notamment pour la production d'informations optiques à contraste élevé, par exemple lettres, chiffres, motifs et/ou images etc.
EP96922802A 1995-06-26 1996-06-13 Utilisation de matieres moulables polymeres pour la modification chromatique partielle par energie laser afin de produire des informations optiques a contraste eleve Withdrawn EP0835185A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19523086 1995-06-26
DE19523086A DE19523086A1 (de) 1995-06-26 1995-06-26 Verwendung von Polymerformmassen zur partiellen farblichen Veränderung durch Laserenergie zur Erzeugung von optischen Informationen mit sehr guten Kontrasten
PCT/EP1996/002551 WO1997001446A1 (fr) 1995-06-26 1996-06-13 Utilisation de matieres moulables polymeres pour la modification chromatique partielle par energie laser afin de produire des informations optiques a contraste eleve

Publications (1)

Publication Number Publication Date
EP0835185A1 true EP0835185A1 (fr) 1998-04-15

Family

ID=7765226

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96922802A Withdrawn EP0835185A1 (fr) 1995-06-26 1996-06-13 Utilisation de matieres moulables polymeres pour la modification chromatique partielle par energie laser afin de produire des informations optiques a contraste eleve

Country Status (7)

Country Link
EP (1) EP0835185A1 (fr)
JP (1) JPH11508202A (fr)
KR (1) KR19990028386A (fr)
CA (1) CA2225717A1 (fr)
DE (1) DE19523086A1 (fr)
TW (1) TW404963B (fr)
WO (1) WO1997001446A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7058961B2 (en) 2000-12-21 2006-06-06 Samsung Electronics Co., Ltd. Disk player, and self-compensating-dynamic-balancer (SCDB) integrated turntable, SCDB integrated clamper and SCDB integrated spindle motor employed in the same

Families Citing this family (16)

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Publication number Priority date Publication date Assignee Title
DE19531332C2 (de) * 1995-08-25 1998-07-16 Beiersdorf Ag Verwendung von Etiketten zur Kennzeichnung von Gummiteilen, insbesondere Reifen
JPH09100390A (ja) * 1995-10-05 1997-04-15 Japan Synthetic Rubber Co Ltd レーザーマーキング用樹脂組成物
MY121337A (en) * 1997-10-14 2006-01-28 Shinetsu Polymer Co Method for forming pad character in push button switch and method for manufacturing cover member for push button switch
JP4176877B2 (ja) 1998-07-27 2008-11-05 ダイセル化学工業株式会社 レーザーマーク可能な樹脂組成物、マーキング方法及びマーキングが施された成形品
US6207344B1 (en) * 1999-09-29 2001-03-27 General Electric Company Composition for laser marking
EP1467834A4 (fr) 2001-12-24 2005-04-06 Digimarc Id Systems Llc Elements de securite grave au laser destines a des documents d'identification et procedes de fabrication de ces elements
WO2003088144A2 (fr) 2002-04-09 2003-10-23 Digimarc Id Systems, Llc Techniques de traitement d'images pour imprimer des cartes et des documents d'identification
JP4114417B2 (ja) * 2002-07-05 2008-07-09 東洋インキ製造株式会社 感熱記録組成物の製造方法および感熱記録方法
NL1022081C2 (nl) * 2002-12-04 2004-06-07 Dsm Nv Laserlicht absorberend additief.
WO2004050766A1 (fr) * 2002-12-04 2004-06-17 Dsm Ip Assets B.V. Additif absorbeur de lumiere laser
JP4527481B2 (ja) * 2004-09-14 2010-08-18 テクノポリマー株式会社 レーザーマーキング用熱可塑性樹脂組成物及びこれを用いた樹脂成形品並びにレーザーマーキング方法
WO2009003976A1 (fr) * 2007-06-29 2009-01-08 Dsm Ip Assets B.V. Microsphère comprenant un cœur polymère, une écorce et un absorbeur
WO2011152449A1 (fr) * 2010-06-01 2011-12-08 株式会社カネカ Composition de résine et produit moulé associé
DE102010035392A1 (de) * 2010-08-25 2012-03-01 Siemens Aktiengesellschaft Betätigungselement der Gebäudeinstallationstechnik
CN103059557A (zh) * 2011-10-20 2013-04-24 合肥杰事杰新材料股份有限公司 一种具有激光标识功能的pa/abs合金及其制备方法
WO2019223007A1 (fr) * 2018-05-25 2019-11-28 Evonik Degussa Gmbh Matériaux pouvant etre marqués au laser, comprenant un composant polyamide et du noir de carbone

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0710570A1 (fr) * 1994-11-04 1996-05-08 Quantum Chemical Corporation Composition polymèrique et procédé pour l'impression de la surface de cette composition par laser

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU597240B2 (en) * 1985-02-05 1990-05-31 Ciba-Geigy Ag Laser marking of pigmented systems
DE3805056A1 (de) * 1988-02-18 1989-08-31 Bayer Ag Laser-beschriftbares material
DE3819081A1 (de) * 1988-06-04 1989-12-07 Bayer Ag Flammwidrige, schlagzaehe polycarbonat-formmassen
EP0739933B1 (fr) * 1990-11-07 1999-03-03 Teijin Limited Composition de résine polyester
JP3102822B2 (ja) * 1992-05-29 2000-10-23 日本ジーイープラスチックス株式会社 レーザーマーキング用樹脂組成物
DE4419847A1 (de) * 1994-06-07 1995-12-14 Basf Ag Verwendung von Mischungen aus Polymethylmethacrylat und Styrol/Acrylnitril-Copolymeren zur Herstellung laserbeschrifteter Formteile
JP3024495B2 (ja) * 1994-10-21 2000-03-21 ジェイエスアール株式会社 レーザーマーキング用樹脂組成物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0710570A1 (fr) * 1994-11-04 1996-05-08 Quantum Chemical Corporation Composition polymèrique et procédé pour l'impression de la surface de cette composition par laser

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7058961B2 (en) 2000-12-21 2006-06-06 Samsung Electronics Co., Ltd. Disk player, and self-compensating-dynamic-balancer (SCDB) integrated turntable, SCDB integrated clamper and SCDB integrated spindle motor employed in the same

Also Published As

Publication number Publication date
WO1997001446A1 (fr) 1997-01-16
KR19990028386A (ko) 1999-04-15
DE19523086A1 (de) 1997-01-02
CA2225717A1 (fr) 1997-01-16
JPH11508202A (ja) 1999-07-21
TW404963B (en) 2000-09-11

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