WO1997001446A1 - Use of polymer molding compounds to produce partial color change using laser energy to generate high-contrast optical information - Google Patents
Use of polymer molding compounds to produce partial color change using laser energy to generate high-contrast optical information Download PDFInfo
- Publication number
- WO1997001446A1 WO1997001446A1 PCT/EP1996/002551 EP9602551W WO9701446A1 WO 1997001446 A1 WO1997001446 A1 WO 1997001446A1 EP 9602551 W EP9602551 W EP 9602551W WO 9701446 A1 WO9701446 A1 WO 9701446A1
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- WIPO (PCT)
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- contain
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Classifications
-
- 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
- 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
- B41M5/36—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.
- 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.
- 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
- 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.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96922802A EP0835185A1 (en) | 1995-06-26 | 1996-06-13 | Use of polymer molding compounds to produce partial color change using laser energy to generate high-contrast optical information |
JP9504126A JPH11508202A (en) | 1995-06-26 | 1996-06-13 | Use of polymer molding compositions to produce partial color changes with laser energy to produce very high contrast optical information |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19523086A DE19523086A1 (en) | 1995-06-26 | 1995-06-26 | Use of polymer molding compounds for partial color changes by laser energy to generate optical information with very good contrasts |
DE19523086.8 | 1995-06-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997001446A1 true WO1997001446A1 (en) | 1997-01-16 |
Family
ID=7765226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/002551 WO1997001446A1 (en) | 1995-06-26 | 1996-06-13 | Use of polymer molding compounds to produce partial color change using laser energy to generate high-contrast optical information |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0835185A1 (en) |
JP (1) | JPH11508202A (en) |
KR (1) | KR19990028386A (en) |
CA (1) | CA2225717A1 (en) |
DE (1) | DE19523086A1 (en) |
TW (1) | TW404963B (en) |
WO (1) | WO1997001446A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000006644A1 (en) * | 1998-07-27 | 2000-02-10 | Daicel Chemical Industries, Ltd. | Resin composition capable of laser marking, marking method, and marked molded article |
KR100413859B1 (en) * | 1995-08-25 | 2004-03-30 | 테사 악티엔게젤샤프트 | How labels are used to label rubber parts, especially tires |
WO2004050767A1 (en) * | 2002-12-04 | 2004-06-17 | Dsm Ip Assets B.V. | Laser writable composition |
CN1312224C (en) * | 2002-12-04 | 2007-04-25 | 帝斯曼知识产权资产管理有限公司 | Laser writable composition |
CN103059557A (en) * | 2011-10-20 | 2013-04-24 | 合肥杰事杰新材料股份有限公司 | PA/ABS alloy with laser identification function, and preparation method thereof |
US8833663B2 (en) | 2002-04-09 | 2014-09-16 | L-1 Secure Credentialing, Inc. | Image processing techniques for printing identification cards and documents |
CN112218921A (en) * | 2018-05-25 | 2021-01-12 | 赢创运营有限公司 | Laser markable material comprising a polyamide component and carbon black |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09100390A (en) * | 1995-10-05 | 1997-04-15 | Japan Synthetic Rubber Co Ltd | Resin composition for laser marking |
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 |
US6207344B1 (en) * | 1999-09-29 | 2001-03-27 | General Electric Company | Composition for laser marking |
KR100396546B1 (en) | 2000-12-21 | 2003-09-02 | 삼성전자주식회사 | Disk player, and turntable incorporating self-compensating dynamic balancer, clamper incorporating self-compensating dynamic balancer and spindle motor incorporating self compensating dynamic balancer adopted for disk player |
JP4114417B2 (en) * | 2002-07-05 | 2008-07-09 | 東洋インキ製造株式会社 | Method for producing thermal recording composition and thermal recording method |
JP4527481B2 (en) * | 2004-09-14 | 2010-08-18 | テクノポリマー株式会社 | Thermoplastic resin composition for laser marking, resin molded product using the same, and laser marking method |
EP2162293B1 (en) * | 2007-06-29 | 2010-10-20 | Merck Patent GmbH | Microsphere comprising a polymer core, a shell and an absorber |
CN102918104A (en) * | 2010-06-01 | 2013-02-06 | 株式会社钟化 | Resin composition and molded product thereof |
DE102010035392A1 (en) * | 2010-08-25 | 2012-03-01 | Siemens Aktiengesellschaft | Operating element e.g. electrical switch for building installation, comprises actuatable control element having surface for manual operation of operating element, where surface of actuatable control element comprises thermoplastic material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0345522A2 (en) * | 1988-06-04 | 1989-12-13 | Bayer Ag | Flame-retardant, impact-resistant polycarbonate moulding compositions |
EP0572178A1 (en) * | 1992-05-29 | 1993-12-01 | Ge Plastics Japan Limited | Resin compositions for laser marking |
EP0708147A1 (en) * | 1994-10-21 | 1996-04-24 | Japan Synthetic Rubber Co., Ltd. | Laser marking resin composition |
Family Cites Families (4)
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 (en) * | 1988-02-18 | 1989-08-31 | Bayer Ag | LASER-STAMPABLE MATERIAL |
EP0485181B1 (en) * | 1990-11-07 | 1998-02-04 | Teijin Limited | Polyester resin composition suitable to be marked with laser. |
DE4419847A1 (en) * | 1994-06-07 | 1995-12-14 | Basf Ag | Use of mixtures of polymethyl methacrylate and styrene / acrylonitrile copolymers for the production of laser-inscribed molded parts |
-
1995
- 1995-06-26 DE DE19523086A patent/DE19523086A1/en not_active Withdrawn
-
1996
- 1996-06-13 KR KR1019970709702A patent/KR19990028386A/en not_active Application Discontinuation
- 1996-06-13 CA CA002225717A patent/CA2225717A1/en not_active Abandoned
- 1996-06-13 EP EP96922802A patent/EP0835185A1/en not_active Withdrawn
- 1996-06-13 WO PCT/EP1996/002551 patent/WO1997001446A1/en not_active Application Discontinuation
- 1996-06-13 JP JP9504126A patent/JPH11508202A/en active Pending
- 1996-06-25 TW TW085107582A patent/TW404963B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0345522A2 (en) * | 1988-06-04 | 1989-12-13 | Bayer Ag | Flame-retardant, impact-resistant polycarbonate moulding compositions |
EP0572178A1 (en) * | 1992-05-29 | 1993-12-01 | Ge Plastics Japan Limited | Resin compositions for laser marking |
EP0708147A1 (en) * | 1994-10-21 | 1996-04-24 | Japan Synthetic Rubber Co., Ltd. | Laser marking resin composition |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100413859B1 (en) * | 1995-08-25 | 2004-03-30 | 테사 악티엔게젤샤프트 | How labels are used to label rubber parts, especially tires |
WO2000006644A1 (en) * | 1998-07-27 | 2000-02-10 | Daicel Chemical Industries, Ltd. | Resin composition capable of laser marking, marking method, and marked molded article |
US6586518B1 (en) | 1998-07-27 | 2003-07-01 | Daicel Chemical Industries, Ltd. | Resin composition capable of laser marking method, and marked molded article |
US8833663B2 (en) | 2002-04-09 | 2014-09-16 | L-1 Secure Credentialing, Inc. | Image processing techniques for printing identification cards and documents |
WO2004050767A1 (en) * | 2002-12-04 | 2004-06-17 | Dsm Ip Assets B.V. | Laser writable composition |
CN1312224C (en) * | 2002-12-04 | 2007-04-25 | 帝斯曼知识产权资产管理有限公司 | Laser writable composition |
US7674845B2 (en) | 2002-12-04 | 2010-03-09 | Van Duijnhoven Franciscus G H | Laser writable composition |
CN103059557A (en) * | 2011-10-20 | 2013-04-24 | 合肥杰事杰新材料股份有限公司 | PA/ABS alloy with laser identification function, and preparation method thereof |
CN112218921A (en) * | 2018-05-25 | 2021-01-12 | 赢创运营有限公司 | Laser markable material comprising a polyamide component and carbon black |
Also Published As
Publication number | Publication date |
---|---|
CA2225717A1 (en) | 1997-01-16 |
JPH11508202A (en) | 1999-07-21 |
EP0835185A1 (en) | 1998-04-15 |
DE19523086A1 (en) | 1997-01-02 |
KR19990028386A (en) | 1999-04-15 |
TW404963B (en) | 2000-09-11 |
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