WO2006065611A1 - Utilisation d'oxydes de bismuth pour des marquages au laser dans des composes en polyurethanne thermoplastique - Google Patents
Utilisation d'oxydes de bismuth pour des marquages au laser dans des composes en polyurethanne thermoplastique Download PDFInfo
- Publication number
- WO2006065611A1 WO2006065611A1 PCT/US2005/044383 US2005044383W WO2006065611A1 WO 2006065611 A1 WO2006065611 A1 WO 2006065611A1 US 2005044383 W US2005044383 W US 2005044383W WO 2006065611 A1 WO2006065611 A1 WO 2006065611A1
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- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic
- compound
- laser
- bismuth
- article
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 32
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 32
- 238000010330 laser marking Methods 0.000 title abstract description 8
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 title description 3
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 15
- 230000005855 radiation Effects 0.000 claims abstract description 13
- 239000003086 colorant Substances 0.000 claims abstract description 11
- 239000003605 opacifier Substances 0.000 claims abstract description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 244000144972 livestock Species 0.000 claims abstract description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 20
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001429 visible spectrum Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- -1 bismuth oxide halide Chemical class 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229940073609 bismuth oxychloride Drugs 0.000 description 4
- 241000283690 Bos taurus Species 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910014235 MyOz Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K11/00—Marking of animals
- A01K11/001—Ear-tags
- A01K11/004—Ear-tags with electronic identification means, e.g. transponders
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K11/00—Marking of animals
- A01K11/001—Ear-tags
-
- 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
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Definitions
- thermoplastic polyurethane (TPU) compounds that contain bismuth oxide to assist in laser marking of the TPU compounds.
- Laser marking is a well known and important means for quickly and cleanly inscribing plastic surfaces with identification marks, such as date codes, batch codes, bar codes or part numbers, functional marks, such as computer keyboard characters, and decorative marks, such as company logos.
- the most common laser marks are either a dark mark oh a lighter colored background or a light mark on a dark colored background.
- a light, dark or colored laser mark on a thermoplastic material may be produced by several different mechanisms or combination of mechanisms, depending on the resin and additives employed, the nature of any colored pigments, and the laser energy characteristics.
- a dark marking has also been achieved by the use of additives that are colorless in the visible light spectrum but which change into a visible dark or black product when irradiated by laser light just outside the visible range, such as by a Nd:YAG (Neodymium doped Yttrium Aluminum Garnet) laser (wavelength 1064 nm) or an excimer laser (wavelength 308 nm or 351 nm).
- Nd:YAG Neodymium doped Yttrium Aluminum Garnet
- excimer laser wavelength 308 nm or 351 nm
- U.S. Pat. No. 4,816,374 discloses the use of antimony oxide as a laser radiation opacifier substance in a polyurethane plastic material to satisfy French standard (number NF-T-54006) for abrasion in order to make and use ear tags for livestock animals.
- U.S. Pat. No. 6,214,917 discloses thermoplastic polyurethanes as laser-markable plastics.
- the TPU's contain pigments having a coating of tin dioxide thereon, which coating is doped with
- antimony 0.5-20% by weight of antimony, arsenic, bismuth, copper, gallium, germanium, or a corresponding oxide thereof.
- U.S. Pat. No. 6,503,316 disclose a laser markable pigment and a laser markable compound containing that pigment, wherein the pigment is of the formula Bi x M y O z , where M is at least one metal selected from Zn, Ti, Fe, Cu, Al, Zr, P, Sn, Sr, Si, Y, Nb, La, Ta, Pr, Ca, Mg,
- x is from 0.3 to about 70
- y is from about 0.05 to about
- the laser markable compounds comprise Bi and at least one additional metal.
- thermoplastic compound comprising: (a) thermoplastic polyurethane; (b) a laser radiation opacifier substance; and (c) optionally visible-spectrum colorant, wherein the laser radiation opacifier substance comprises bismuth oxide.
- thermoplastic article made from the thermoplastic compound described above.
- Another aspect of the present invention is the use of bismuth oxide as a laser radiation opacifier substance.
- thermoplastic compound An advantage of the use of bismuth oxide in the thermoplastic compound is good opacifying power.
- Another advantage of using bismuth oxide is the easy dispersion of that chemical into TPU compounds.
- bismuth oxide or “bismuth oxides” means bismuth trioxide (Bi 2 O 3 ), bismuth pentoxide (Bi 2 O 5 ), and any other oxide of bismuth known to exist.
- bismuth oxide or “bismuth oxides” does not include any bismuth oxide halide, such as bismuth oxychloride (BiOCl). or a bismuth metal oxide, such as Bi x M y O z where M is a metal.
- TPU Thermoplastic polyurethane
- TPU is available from a number of commercial sources including Merquinsa
- TPU compounds can contain a variety of optional additives to improve handling, processing, stability, durability, color, and the like. Any of these TPU compounds are suitable for use in the present invention.
- TPU is desired because it is a soft and flexible material particularly suited for identification tags for domestic livestock, etc.
- thermoplastic polymer that is suitable for blending with TPU is useful in the present invention also for making a laser markable compound and article therefrom.
- Non-limiting examples of other polymers include polymers of ethylenically unsaturated monomers, such as polyethylene, polypropylene, polybutylenes, polystyrenes, poly (-methyl styrene), polyvinyl chloride, polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyacrylonitrile and the like; copolymers of ethylenically unsaturated monomers such as copolymers of ethylene and propylene, ethylene and styrene, and polyvinyl acetate, styrene and maleic anhydride; styrene and methyl methacrylate; styrene and ethyl acrylate; styrene and acrylonitrile; methyl methacrylate and ethyl acrylate and the like; and polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, and poly
- thermosetting materials useful in this invention include synthetic butyl rubbers, synthetic isoprene rubbers, silicone RTV (room temperature vulcanizing) rubbers, styrene butadiene rubber, ethylene-propylene- diene rubber, acrylonitrile-styrene butatiene rubber and the like; saturated and unsaturated polyesters including alkyds and other polyesters; nylons and other polyamides; polyesteramides and polyurethanes; chlorinated polyethers, epoxy polymers, cellulose esters such as cellulose acetate butyrate, and the like.
- the laser radiation opacifying substance need only comprise bismuth oxide, although it is within the scope of the invention to combine bismuth oxide with another laser radiation opacifying substance, such as BiOCl. It is preferable to use bismuth oxide alone.
- Bismuth trioxide is often used as a replacement for lead oxides in food contacting articles. Thus, it is well understood by those skilled in the art that bismuth trioxide is considered benign for contact with mammals.
- Bismuth trioxide is commercially available in major chemical- producing nations. For example, bismuth oxide is commercially available in France at the Pharmacie Centrale de France and in the United States of America at Pechiney Chemicals Division of Stamford, CT. BiOCl is also available commercially from these sources.
- Optional Additives are commercially available in major chemical- producing nations. For example, bismuth oxide is commercially available in France at the Pharmacie Centrale de France and in the United States of America at Pechiney Chemicals Division of Stamford, CT. BiOCl is also available commercially from these sources.
- the compound of the present invention can optionally include colorants (pigments, dyes, or both) to provide a specific color, against with the laser-marking can be contrasted for easy reading of the information thereon.
- colorants pigments, dyes, or both
- the use of titanium dioxide (or any other metallic pigment that doesn't contain any Bismuth) for improving color of the TPU compound should not be considered a bismuth metal oxide, as disclosed in U.S. Pat. No. 6,503,316 (Sakoske et al.).
- the titanium dioxide is a separate chemical discrete from the bismuth oxide also dispersed in the TPU.
- colorants are often delivered in the form of colorant concentrates for dilution or "letdown" into the compound at the mixer or extruder.
- Colorant concentrates are commercially available from PolyOne Corporation in North America, Europe, and Asia. (www.polyone.com)
- Non-limiting examples of pigment colors are red, orange, yellow, and green in the lighter hues so that the dark image of laser marked information can be seen in considerable contrast.
- Table 1 shows the acceptable, desirable, and preferred concentrations of the TPU (alone or with other thermoplastic or thermosetting polymers), non-metallic bismuth compound(s), and optional pigment(s).
- the compound of the present invention can be mixed using any conventional mixing equipment, including without limitation high speed mixers and extruders.
- a twin-screw extruder is used at melt-mixing temperatures and speeds to provide excellent dispersion of the non-metallic bismuth compound and optional colorant therein. More preferably, after the polymer is melted, the bismuth oxide and additives are added via a side feeder.
- Mixing temperatures can range from about 180°C to about
- 26O 0 C and preferably from about 200°C to about 220°C.
- Mixing speeds can range from about 50 to about 1000, and preferably from about 150 to about 300550 revolutions per minute.
- the ingredients can be fully premixed using a low/high speed mixer operating at about 25°C temperature and about 500rpm mixing speed.
- the extruded product can be formed into pellets for subsequent molding or extrusion operations.
- TPU compounds of the present invention are particularly suitable for laser marking where durability is important.
- cattle identification tags are exposed to all of the environmental elements that the cattle endure, as well as conditions created by the cattle such as rubbing against trees, posts, etc.
- Agriculture regulations, such as French Standard No. NF-T- 54006 must be satisfied in order for laser markable identification ear tags can be used in an agricultural environment in France.
- Laser marking of the TPU compounds of the present invention can use any of the lasers reported in U.S. Pat. No. 6,503,316 (Sakoske et al.), such as neodymium: yttrium aluminum garnet (Nd:YAG) lasers, carbon dioxide (CO 2 ) lasers, diode lasers, excimer lasers and the like.
- neodymium: yttrium aluminum garnet (Nd:YAG) lasers carbon dioxide (CO 2 ) lasers
- diode lasers diode lasers
- excimer lasers excimer lasers and the like.
- typical YAG lasers emit light in the near-infrared spectrum at wavelengths of 1064 nm.
- Such lasers typically have continuous power outputs of from about 1 to about 50 watts, and can be operated in a pulsed mode at typical peak powers of from about 1 watt to about 45 kilowatts.
- pulsed mode operation frequencies of from about 1 to about 64,000 pulses/second may be used.
- CO 2 lasers emit light in the far-infrared region of the spectrum, with intensity spikes at wavelengths of 9.8 and 10.6 microns.
- Such CO 2 lasers typically operate at a continuous output power of from about 1 to about 40 watts.
- the size of the laser spot that impinges the substrate is typically greater than 0.1 micron in diameter, preferably from about 40 to about 500 microns, and more preferably from about 50 to about 125 microns.
- the speed at which the laser beam travels across the surface of the substrate preferably ranges from 0 to about 254 cm/second, more preferably from about 5 to 50 cm/second for most thicknesses and compositions.
- the laser beam may be projected with a seam overlap of 0 to 100 percent, preferably from about 10 to about 90 percent for many applications.
- the laser parameters are controlled in order to provide sufficient localized heating of the bismuth-containing compound, while avoiding unwanted damage to the substrate.
- the laser beam the movement of which can be controlled by a computer, may be used to create discrete symbols or designs or, alternatively, may be serially indexed across the surface of the substrate to create multiple symbols or designs at the same time.
- a word may be created by separately making each letter of the word with the laser, or by rastering the laser across the entire word to form all of the letters at the same time.
- a single laser beam may be used for marking in accordance with the present invention. Alternatively, two or more laser beams may be used.
- the surface of the substrate may be exposed to any desired type of atmosphere.
- the atmosphere may comprise air at atmospheric, sub-atmospheric or super-atmospheric pressures.
- the atmosphere may comprise an inert gas such as nitrogen, argon or carbon dioxide, an oxidizing atmosphere such as air or oxygen, a reducing atmosphere such as hydrogen or carbon monoxide, or a vacuum. Oxidizing or reducing gases can be used in a combination with inert gases.
- Table 2 shows the ingredients and sources for the ingredients used to exemplify the invention.
- Examples 1-2 were made via an extruder, with the TPU being fed into the input hopper and bismuth oxide (Example 1) and the bismuth oxide and colorant concentrate were fed into a side hopper of a Werner & Pfleiderer_ZSK twin screw extruder having a 25mm diameter and a LengthiDistance ratio of 30.
- the extruder was operated at a temperature of between 200 and 22O 0 C in the mixing zones and at a rotation of about 500 revolutions per minute.
- the fully mixed compound was extruded after cooling of strands in a water bath through a pelletizer and made into pellets of approximately 2 mm diameter.
- a plaque from each of the Examples was exposed to a Nd: YAG laser at 1064 nm wavelength (made by TRUMPF located in Roissy en France (95) FRANCE) using the following parameters: 2000 to 32,000 pulses/second; 10 to 120 cm per second; 1.7kW power; 60 ⁇ m dot size; and 0-10% percent seam overlap.
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Abstract
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US63583304P | 2004-12-14 | 2004-12-14 | |
US60/635,833 | 2004-12-14 |
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WO2006065611A1 true WO2006065611A1 (fr) | 2006-06-22 |
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PCT/US2005/044383 WO2006065611A1 (fr) | 2004-12-14 | 2005-12-09 | Utilisation d'oxydes de bismuth pour des marquages au laser dans des composes en polyurethanne thermoplastique |
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Cited By (10)
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WO2011083100A1 (fr) | 2010-01-05 | 2011-07-14 | Basf Se | Polyuréthane transparent apte à l'impression laser |
US8790769B2 (en) | 2010-01-05 | 2014-07-29 | Basf Se | Transparent, laser-inscribable polyurethane |
WO2014188828A1 (fr) * | 2013-05-20 | 2014-11-27 | 東罐マテリアル・テクノロジー株式会社 | Additif à base d'oxyde de bismuth pour un marquage laser |
WO2015051868A1 (fr) | 2013-10-11 | 2015-04-16 | Merck Patent Gmbh | Pigments à base de composés de bismuth |
WO2015106788A1 (fr) | 2014-01-16 | 2015-07-23 | Merck Patent Gmbh | Pigments à base de composés de bismuth |
EP3363649A1 (fr) * | 2017-02-20 | 2018-08-22 | Clariant Plastics & Coatings Ltd | Composition sans antimoine pour le marquage au laser de composés thermoplastiques |
RU2772273C2 (ru) * | 2017-02-20 | 2022-05-18 | Клариант Плэстикс Энд Коутингз Лтд | Свободная от сурьмы композиция для лазерной маркировки термопластических соединений |
EP4063444A1 (fr) * | 2021-03-23 | 2022-09-28 | Covestro Deutschland AG | Tpu utilisant du cuivre en tant qu'absorbeur ir et processus d'impression 3d utilisant un tel tpu |
WO2022200258A1 (fr) * | 2021-03-23 | 2022-09-29 | Covestro Deutschland Ag | Tpu renfermant du cuivre en tant qu'absorbeur d'ir et procédé d'impression 3d employant un polymère thermoplastique contenant du cuivre |
CN116332636A (zh) * | 2023-03-29 | 2023-06-27 | 常州大学 | 一种碳掺杂氧化铋粉末注射成型专用料及其激光辐照烧结制备氧化铋陶瓷的方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2011083100A1 (fr) | 2010-01-05 | 2011-07-14 | Basf Se | Polyuréthane transparent apte à l'impression laser |
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US9637651B2 (en) | 2013-05-20 | 2017-05-02 | Tokan Material Technology Co., Ltd. | Bismuth oxide-based addictive for laser marking |
WO2015051868A1 (fr) | 2013-10-11 | 2015-04-16 | Merck Patent Gmbh | Pigments à base de composés de bismuth |
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DE102014000359A1 (de) | 2014-01-16 | 2015-07-30 | Merck Patent Gmbh | Pigmente |
WO2018150033A1 (fr) * | 2017-02-20 | 2018-08-23 | Clariant Plastics & Coatings Ltd | Composition exempte d'antimoine pour marquage laser de composés thermoplastiques |
EP3363649A1 (fr) * | 2017-02-20 | 2018-08-22 | Clariant Plastics & Coatings Ltd | Composition sans antimoine pour le marquage au laser de composés thermoplastiques |
CN110337463A (zh) * | 2017-02-20 | 2019-10-15 | 科莱恩塑料和涂料有限公司 | 用于激光标记热塑性配混物的无锑组合物 |
RU2772273C2 (ru) * | 2017-02-20 | 2022-05-18 | Клариант Плэстикс Энд Коутингз Лтд | Свободная от сурьмы композиция для лазерной маркировки термопластических соединений |
CN110337463B (zh) * | 2017-02-20 | 2022-07-01 | 科莱恩塑料和涂料有限公司 | 用于激光标记热塑性配混物的无锑组合物 |
US11780255B2 (en) | 2017-02-20 | 2023-10-10 | Clariant Plastics & Coatings Ltd | Antimony free composition for laser marking thermoplastic compounds |
EP4063444A1 (fr) * | 2021-03-23 | 2022-09-28 | Covestro Deutschland AG | Tpu utilisant du cuivre en tant qu'absorbeur ir et processus d'impression 3d utilisant un tel tpu |
WO2022200258A1 (fr) * | 2021-03-23 | 2022-09-29 | Covestro Deutschland Ag | Tpu renfermant du cuivre en tant qu'absorbeur d'ir et procédé d'impression 3d employant un polymère thermoplastique contenant du cuivre |
CN116332636A (zh) * | 2023-03-29 | 2023-06-27 | 常州大学 | 一种碳掺杂氧化铋粉末注射成型专用料及其激光辐照烧结制备氧化铋陶瓷的方法 |
CN116332636B (zh) * | 2023-03-29 | 2024-04-02 | 常州大学 | 一种碳掺杂氧化铋粉末注射成型专用料及其激光辐照烧结制备氧化铋陶瓷的方法 |
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