WO2002083567A2 - Additive for yag laser marking - Google Patents
Additive for yag laser marking Download PDFInfo
- Publication number
- WO2002083567A2 WO2002083567A2 PCT/US2002/010408 US0210408W WO02083567A2 WO 2002083567 A2 WO2002083567 A2 WO 2002083567A2 US 0210408 W US0210408 W US 0210408W WO 02083567 A2 WO02083567 A2 WO 02083567A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- laser marking
- laser
- marking additive
- article
- additive
- Prior art date
Links
- 239000000654 additive Substances 0.000 title claims abstract description 41
- 238000010330 laser marking Methods 0.000 title claims abstract description 41
- 230000000996 additive effect Effects 0.000 title claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 39
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 20
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 13
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 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 15
- 239000000047 product Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 7
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910017835 Sb—Sn Inorganic materials 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/004—Oxides; Hydroxides; Oxyacids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/20—Powder free flowing behaviour
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Definitions
- a number of printing techniques for applying markings to articles are well known. These are generally surface printing methods which means that the identification mark realized can become unreadable through mechanical damage, abrasion, chemical influences, and the like. Such printing is particularly difficult to apply to curved or textured surfaces and the special tooling costs required add to the overall cost of the product.
- the desirability of marking articles through the use of a laser system is well known. Lasers have been developed so that the beam impinged on the article to be marked can be highly focused to provide fine lines in the form of letters and/or numbers of the desired size, as well as images. Lasers permit the marking to be on the surface of the article or beneath the surface.
- a subsurface mark can for example, contribute to anti-counterfeiting efforts.
- Laser marking whether surface or subsurface, can also be used, for example, for electronically scanning and control purposes during production.
- a number of laser beam processes in which an identification mark is burned into the surface of an article part are known.
- the resulting rough surface usually has to be coated with a transparent lacquer on account of the danger of contamination and the unpleasant feel that results. This can become a very involved operation in the case of mass produced parts and adds to the cost of the product.
- U.S. 4,822,973 discloses a system in which the laser beam passes through the surface of a first plastic material in order to be absorbed in a layer of a second plastic material.
- This system requires a special configuration of materials of construction in the part to be marked.
- Other systems incorporate a quantity of carbon black, coated mica or a highly absorbing green pigment, all of which absorb energy from the laser beam to produce a visible mark.
- these materials have a degree of color which is sufficient to be visible prior to application of the laser beam and that can be unsightly or interfere with the distinctness of the mark after the laser beam has been applied.
- the additives tend to be specific to the wavelength emitted by the laser.
- materials initially developed for use in conjunction with carbon dioxide lasers tend not to work particularly well (or even at all) with the increasingly popular yttrium aluminum garnet (YAG) lasers which require a material which absorbs at 1064 nm.
- YAG yttrium aluminum garnet
- surrounding area when exposed to YAG laser energy but prior thereto does not impart an appreciable color to the surrounding area or cause a significant change in the performance of the material in which it has been added.
- This invention relates to a YAG laser marking additive and its use.
- the YAG laser marking additive of the present invention is a calcined powder of co-precipitated mixed oxides of tin and antimony.
- the powder absorbs YAG laser energy and converts it into heat, carbonization of the surrounding material occurs and results in the formation of a black or dark mark that contrasts to the remainder of the surrounding area. Because of the particle size of the powder and its efficiency, the powder does not impart an appreciable amount of color to the object in which it is incorporated. It also does not cause excess foaming so that the mark achieved is smoother in texture.
- a laser marking additive that is adapted for use in conjunction with a YAG laser.
- the additive is a calcined powder of co-precipitated mixed oxides of tin and antimony in which the antimony concentration is greater at the surface of the co-precipitate particles than in the interior of the particles.
- the powder is principally tin oxide and only a small amount of antimony oxide that is expressed as Sb 2 O 3 .
- Sb 2 O 3 level can be up to about 17 %.
- the amount of antimony oxide is about 1 to 5 % of the tin oxide.
- Any procedure which causes the co-precipitate to form preferably at low pH can be employed.
- One procedure which can be used involves forming a solution from salts or oxides of tin and antimony and then adjusting the
- the identity of the oxide or salt is not critical and any material can be selected as long as both the tin and antimony reagents can be dissolved in the same solvent.
- aqueous acidic solutions can be prepared using the oxides, sulfates, fluorides, chlorides, bromides and iodides of the metals, as well as salts of organic acids which are soluble.
- Tin chloride and antimony oxide are both readily available commercially and these are presently preferred. It is also presently preferred to dissolve these materials in water, with the assistance of a mineral acid if needed or helpful.
- the mixed oxides can be made to precipitate from such a solution by changing the pH to an appropriate level. Any convenient base can be used to adjust the pH but sodium hydroxide is presently preferred because of its availability.
- the pH during precipitation is preferably low and by that is meant the pH is less than about 2.6 and more preferably about 1.6 to 2.1.
- the resulting precipitate can be recovered from the solution by any convenient means such as filtering or centrifuging and, if desired, washed.
- the resulting precipitate is thereafter calcined at an appropriate temperature, for example, at least about 550 °C and preferably at least about 650°C, and which usually does not exceed about 750°C.
- the calcination time is usually at least about 0.5 hour and preferably at least about 1 hour but usually less than about 2 hours.
- the resulting calcined material is usually a particulate but can, and usually is, thereafter ground or milled to a desired size. It is desirable that the particles have an average size in the range of about 0.1-10 ⁇ m, and more preferably, about 0.5-1 ⁇ m, when measured by light scattering.
- the calcination of the co-precipitated material results in a mixed metal oxide containing tin in the +4 oxidation state and antimony in the +3 oxidation state. If the antimony is not present, the material does not effectively function
- 00481607 1 as a YAG laser marking additive.
- the process described above also results in a tin oxide particle which has been surface-enriched with antimony but whether there is an minimum degree of enrichment necessary to achieve good results has not yet been ascertained.
- the surface enrichment was analyzed by XPS (X-ray photoelectron spectroscopy) which has a depth of penetration of about 100
- the surface antimony concentration was at least 15 % higher than the antimony concentration as a whole. Whether insufficient surface enrichment has occurred is readily apparent since the material exhibits a beige color and does not effectively operate as a YAG laser marking additive. When sufficient surface enrichment has occurred, the calcined product exhibits a dark to light grey or pale green color depending on the total antimony concentration of the particle. Because of this characteristic, it is not necessary to undertake the time and expense of actually measuring local concentrations of antimony in the particles. Instead, the appearance of the calcined powder can be used to determine if the desired powder has been achieved.
- the calcined product does exhibit a dark to light grey or pale green color, it is also highly efficient as a YAG laser marking additive. That efficiency allows only a small quantity of the powder to be added to the material to be marked and achieve the desired marking attributes. The small quantity permits the gray or pale green color contributed by the marking additive to become well dispersed and diffused into the color which is otherwise exhibited by the object.
- the marking additive loading is about 0.01-5 % of the total weight of the article to be marked, and preferably about 0.05-0.1 %.
- the laser marking additive of the present invention is incorporated into any material which is transparent to YAG laser irradiation by any convenient
- Dispersing the marking additive within the object is also assisted by the small particle size.
- the material to be marked can be an organic object such as a plastic or polymeric article.
- Typical polymers include, but are not limited to, polyolefins such as polyethylene, polypropylene, polybutadiene and the like; (mefh)acrylic polymers such as polyethyl acrylate and polymethyl methacrylate and the like; polyesters such as polyethylene terephthalate and polybutylene terephthalate and the like; polyvinyl chloride; polyvinylidene chloride; polyacrylonitrile; epoxy resins; and polyurethanes.
- the polymer can also be a copolymer or block copolymer, etc. Conventional additives may be present.
- the material of which the object is composed is limited only by the necessity of being transparent to
- the resulting antimony-tin solution was added to 500 ml of water that was being maintained at 75 °C and a pH of 1.6.
- the solution was added at a rate of 4.5 g/minute with 35% sodium hydroxide being used to maintain the pH at 1.6.
- the reaction mixture was filtered to obtain an orange-yellow filter cake. This was calcined for 2 hours at 650 °C to obtain a medium grey colored free- flowing powder that was then milled to 0.5 ⁇ m particle size.
- a charge of 0.1 wt% of the calcined powder of co-precipitated mixed oxides of tin and antimony of Example 1 plus 0.5% TiO 2 was added to polypropylene and dispersed therein and injection molded into a flat plaque.
- YAG laser beam was imposed on the resulting plaque using a current of 14 amps, a pulse frequency of 6 kHz, a scan velocity of 300 mm/sec. and an aperture of 0.05. It was found that distinct lines having a width of about 0.1 mm could be achieved. This was a result of the laser marking additive absorbing the YAG laser energy and converting it to heat so as to carbonize the surrounding polymeric material, thereby making a black or dark mark which was in contrast to the surrounding area.
- a flask with 500 ml of water was initially heated to 75°C and the pH was adjusted to 1.6.
- 578 g of 78.1% SnCl 4 -5H 2 O solution was added at 4.5 g/min, while NaOH was added as needed to hold pH at 1.6.
- the slurry was filtered and the particles were washed 4 times with 500 ml portions of water.
- the filtercake was dried for 1 hr at 120°C and then calcined for 30 min at 650°C. The calcined product had an off white color.
- Example 2 The marking procedure in Example 2 was used except that 0.01 wt% of the calcined powder of Example 3 and 0.2% TiO 2 were substituted for the powder of Example 1 and 0.5% TiO 2 . Only a faint mark was produced when only tin oxide was used without the antimony doping.
- the Sb 2 O 3 used in these experiments was marked as is using the process of Example 4 by substituting powdered Sb 2 O 3 for the tin oxide powder. A negligible mark was produced when only antimony oxide was used without being doped into the tin oxide.
- Example 7 Marking of Example 6 Product
- Example 4 The marking procedure in Example 4 was used except only 0.02 wt% of the calcined powder of Example 6 was used instead of the tin oxide powder. A distinctive mark was obtained.
- Example 6 The procedure in Example 6 was repeated but only 3.83 g of antimony oxide were used. The resulting powder had a pale green color.
- Example 4 The marking procedure in Example 4 was used except only 0.06 wt%> of the calcined powder of Example 8 was used in place of the tin oxide powder. A distinctive mark was obtained.
- Example 11 Alternate Preparation The procedure in Example 10 was repeated with the only change being that the addition rate was 3g/min. The resulting powder was yellow-green in color.
- Example 10 The procedure in Example 10 was repeated with the following changes.
- the pH was 2.6 and the calcination temperature was 550°C.
- the resulting powder was pale green in color.
- Example 12 The procedure in Example 12 was also repeated changing the calcination temperature to 750°C and also resulted in a powder with a pale green color.
- Example 14 Alternate Preparation The procedure in Example 10 was repeated with the following changes.
- the initial reaction temperature was 45°C, the pH was 2.6, and the addition rate was 6 g/min.
- the resulting powder was pale yellow green in color.
- Example 10 The procedure in Example 10 was repeated using only 1.96 g of Sb 2 O 3 . The resulting powder was light greenish yellow in color.
- Example 10 The procedure in Example 10 was repeated using only 0.97 g of Sb 2 O 3 .
- the resulting powder was pale yellow green in color.
- Examples 17-23 - Marking with Examples 10-16 Products The marking procedure of Example 4 was repeated with each of the products of examples 10 through 16, where the loading was at 0.1 wt%>. In each instance, a distinctive mark was obtained. The appearance of each unmarked plaque is listed in the table below and compared to a plaque with only TiO 2 .
- Example 4 The marking procedure of Example 4 was repeated with the products of Example 10 except that the following plastics were substituted for the polypropylene. In each instance, a distinctive mark was obtained.
- Example 10 was repeated except that the pH was held at 7 during the coprecipitation.
- the resulting product had an off-white color.
- Example 17 Marking in accordance with Example 17 was done using the calcined powder of Example 26. A negligible mark was produced.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02721658A EP1377522B1 (en) | 2001-04-12 | 2002-04-01 | Additive for yag laser marking |
AU2002252578A AU2002252578A1 (en) | 2001-04-12 | 2002-04-01 | Additive for yag laser marking |
DE60236855T DE60236855D1 (en) | 2001-04-12 | 2002-04-01 | ADDITIVE FOR YAG LASER MARKING |
JP2002581329A JP4493071B2 (en) | 2001-04-12 | 2002-04-01 | Additive for YAG laser marking |
AT02721658T ATE472513T1 (en) | 2001-04-12 | 2002-04-01 | ADDITIVE FOR YAG LASER MARKING |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/833,355 US6693657B2 (en) | 2001-04-12 | 2001-04-12 | Additive for YAG laser marking |
US09/833,355 | 2001-04-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002083567A2 true WO2002083567A2 (en) | 2002-10-24 |
WO2002083567A3 WO2002083567A3 (en) | 2003-02-20 |
Family
ID=25264191
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/010408 WO2002083567A2 (en) | 2001-04-12 | 2002-04-01 | Additive for yag laser marking |
Country Status (10)
Country | Link |
---|---|
US (1) | US6693657B2 (en) |
EP (1) | EP1377522B1 (en) |
JP (1) | JP4493071B2 (en) |
CN (2) | CN1240619C (en) |
AT (1) | ATE472513T1 (en) |
AU (1) | AU2002252578A1 (en) |
DE (1) | DE60236855D1 (en) |
ES (1) | ES2345765T3 (en) |
TW (1) | TW542764B (en) |
WO (1) | WO2002083567A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005047009A1 (en) * | 2003-11-07 | 2005-05-26 | Engelhard Corporation | Nanometer size antimony tin oxide (ato) particles comprising laser marking additive |
US7169471B1 (en) | 2003-02-06 | 2007-01-30 | Emd Chemicals, Inc. | Laser-marking additive |
WO2011124920A1 (en) | 2010-04-08 | 2011-10-13 | De La Rue International Limited | Security articles comprising security features and methods of manufacture thereof |
US10344145B2 (en) | 2014-11-05 | 2019-07-09 | Merck Patent Gmbh | Laser-markable and laser-weldable polymeric materials |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10136479A1 (en) * | 2001-07-27 | 2003-02-06 | Merck Patent Gmbh | Colored labeling and marking of plastics and paints |
EP1800885B1 (en) | 2004-09-03 | 2010-08-11 | Toyo Ink Mfg. Co., Ltd. | Recording material and method of recording |
US7479195B2 (en) * | 2004-10-26 | 2009-01-20 | Freudenberg Vliesstoffe Kg | Method of forming multi-colored composite by pinsonic embossing |
US20070098900A1 (en) * | 2004-11-05 | 2007-05-03 | Fuji Hunt Photographic Chemicals, Inc. | Media providing non-contacting formation of high contrast marks and method of using same, composition for forming a laser-markable coating, a laser-markable material and process of forming a marking |
DE102006045495A1 (en) * | 2006-09-27 | 2008-04-03 | Mitsubishi Polyester Film Gmbh | Laser markable film |
DE102006062269A1 (en) * | 2006-12-22 | 2008-06-26 | Eckart Gmbh & Co. Kg | Use of spherical metal particle, that is free of antimony and/or antimony containing compounds, as laser marking or laser-weldable agent in plastics |
CN101678692B (en) * | 2007-05-09 | 2012-07-11 | 阿克泰加Ds有限公司 | Use of spherical metal particles as laser marking additives for sealing, closure or coating materials or paints comprising polymer, and also laser-markable sealing, closure or coating material or lase |
KR101530725B1 (en) * | 2007-06-29 | 2015-06-22 | 메르크 파텐트 게엠베하 | Microsphere comprising a polymer core, a shell and an absorber |
EP2065165B1 (en) | 2007-11-30 | 2009-11-04 | Eckart GmbH | Utilisation of a mixture of spherical metal particles and metal flakes as laser markability or laser weldability means and laser markable and/or laser weldable plastic |
US20100092700A1 (en) * | 2008-10-15 | 2010-04-15 | James Carroll | Heavy metal-free laser marking pigment |
EP2179857A1 (en) | 2008-10-23 | 2010-04-28 | Bayer MaterialScience AG | ID cards with blocked laser engraving writeability |
EP2181858A1 (en) * | 2008-11-04 | 2010-05-05 | Agfa-Gevaert N.V. | Security document and methods of producing it |
WO2010075357A1 (en) | 2008-12-22 | 2010-07-01 | 3M Innovative Properties Company | Internally patterned multilayer optical films using spatially selective birefringence reduction |
EP2199100A1 (en) * | 2008-12-22 | 2010-06-23 | Agfa-Gevaert N.V. | Security laminates for security documents. |
EP2218579A1 (en) | 2009-02-13 | 2010-08-18 | Bayer MaterialScience AG | Improved method for manufacturing a laminated multi-layer film |
EP2332738B1 (en) | 2009-12-10 | 2012-07-04 | Agfa-Gevaert | Security document with security feature on edge |
EP2335937B1 (en) | 2009-12-18 | 2013-02-20 | Agfa-Gevaert | Laser markable security film |
EP2335938B1 (en) | 2009-12-18 | 2013-02-20 | Agfa-Gevaert | Laser markable security film |
WO2012004295A1 (en) | 2010-07-08 | 2012-01-12 | Bayer Materialscience Ag | Security and/or value document containing an electroluminescent arrangement |
EP2441589A1 (en) | 2010-10-14 | 2012-04-18 | Bayer Material Science AG | Safety document and/or document of value containing an electromechanical converter |
EP2455228A1 (en) | 2010-11-18 | 2012-05-23 | Bayer Material Science AG | Safety document and/or document of value containing an electromechanical converter |
AU2011250831A1 (en) | 2010-12-03 | 2012-06-21 | Bayer Intellectual Property Gmbh | Security and/or valuable documents with a top layer with a scratch-resistant finish |
US20130168133A1 (en) † | 2011-03-18 | 2013-07-04 | Mitsubishi Chemical Europe Gmbh | Process for producing a circuit carrier |
CN103131184A (en) * | 2011-11-23 | 2013-06-05 | 合肥杰事杰新材料股份有限公司 | Polyphenylene sulfide composite material and preparation method thereof |
DE102011088564A1 (en) * | 2011-12-14 | 2013-06-20 | Robert Bosch Gmbh | Method for producing a labeled battery cell housing |
JP2015511894A (en) | 2012-01-19 | 2015-04-23 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH | Plastic film for printing by dye diffusion thermal transfer printing |
WO2013107777A1 (en) | 2012-01-19 | 2013-07-25 | Bayer Intellectual Property Gmbh | Plastic film for printing by dye diffusion thermal transfer printing |
EP2864128A1 (en) | 2012-06-21 | 2015-04-29 | 3M Innovative Properties Company | A static dissipating laser engravable film |
CN107815713B (en) | 2012-06-22 | 2020-11-17 | 苹果公司 | White appearance anodized film and forming method thereof |
US9493876B2 (en) | 2012-09-14 | 2016-11-15 | Apple Inc. | Changing colors of materials |
DE102013100252A1 (en) | 2013-01-11 | 2014-07-17 | Kuraray Europe Gmbh | Use of a mixture comprising a polyvinyl acetal and a laser absorber as laser marking agent for laser-markable polymers e.g. polyethylene, polypropylene, polyesters, polyamide, polyurethane or polybutylene |
CN103450654B (en) * | 2013-09-04 | 2016-03-30 | 上海锦湖日丽塑料有限公司 | A kind of can the resin and preparation method thereof of laser direct forming |
US9181629B2 (en) | 2013-10-30 | 2015-11-10 | Apple Inc. | Methods for producing white appearing metal oxide films by positioning reflective particles prior to or during anodizing processes |
US9839974B2 (en) | 2013-11-13 | 2017-12-12 | Apple Inc. | Forming white metal oxide films by oxide structure modification or subsurface cracking |
WO2015153979A1 (en) | 2014-04-03 | 2015-10-08 | 3M Innovative Properties Company | Apertured film and method of making the same |
DE102014008186A1 (en) | 2014-06-10 | 2015-12-31 | Merck Patent Gmbh | Laser-markable and laser-weldable polymeric materials |
FR3022183B1 (en) | 2014-06-13 | 2016-07-29 | Fasver | PROCESS FOR MANUFACTURING A LASER-MARKED, SAFETY MARKING MULTILAYER DATA MEDIUM |
EP3209261B1 (en) | 2014-10-22 | 2019-04-10 | 3M Innovative Properties Company | Printed components and methods for making the same |
DE102014018586A1 (en) | 2014-12-17 | 2016-06-23 | Merck Patent Gmbh | Laser-markable and laser-weldable polymeric materials |
DE102015009854A1 (en) | 2015-08-04 | 2017-02-09 | Merck Patent Gmbh | Laser-markable polymers and coatings |
CN107849290B (en) | 2015-07-28 | 2021-05-28 | 默克专利股份有限公司 | Laser markable polymers and coatings |
WO2018095834A1 (en) | 2016-11-22 | 2018-05-31 | Merck Patent Gmbh | Additive for laser-markable and laser-weldable polymer materials |
DE102017212099A1 (en) | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additive mixtures for plastics, laser-markable polymer compositions containing them and their use |
WO2019219557A1 (en) | 2018-05-16 | 2019-11-21 | Merck Patent Gmbh | Laser additive and its use in polymer materials |
CN112961484B (en) * | 2021-05-14 | 2021-07-20 | 苏州奥美材料科技有限公司 | Laser etching agent, laser etching polycarbonate, and preparation method and application thereof |
WO2024068509A1 (en) | 2022-09-27 | 2024-04-04 | Basf Se | Thermoplastic moulding compositions having an improved colour stability-1 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4822973A (en) | 1984-03-30 | 1989-04-18 | Bayer Aktiengesellschaft | Composite plastic with laser altered internal material properties |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6050813A (en) * | 1983-08-31 | 1985-03-20 | 触媒化成工業株式会社 | Conductive material for transmitting light |
US4753863A (en) * | 1985-02-01 | 1988-06-28 | Motorola Inc. | Laser markable molding compound |
JPH0797465B2 (en) | 1985-03-28 | 1995-10-18 | 株式会社東芝 | Puffer type gas breaker |
JPS61286224A (en) | 1985-06-12 | 1986-12-16 | Ishihara Sangyo Kaisha Ltd | Production of electroconductive fine powder |
JPH01224230A (en) * | 1988-03-03 | 1989-09-07 | Sanyo Shikiso Kk | Porous coarse granule of tin oxide having solid solution of antimony oxide |
DE3842330A1 (en) | 1988-12-16 | 1990-06-21 | Merck Patent Gmbh | CONDUCTIVE LABEL-SHAPED PIGMENTS |
JPH05279039A (en) | 1992-03-27 | 1993-10-26 | Mitsubishi Materials Corp | Production of tin oxide fine powder |
AU4537193A (en) * | 1992-06-29 | 1994-01-24 | E.I. Du Pont De Nemours And Company | Electroconductive material and process |
DE4415802A1 (en) * | 1994-05-05 | 1995-11-09 | Merck Patent Gmbh | Laser-markable plastics |
JP3444655B2 (en) * | 1994-06-14 | 2003-09-08 | 三井金属鉱業株式会社 | Composite conductive powder and conductive film |
US5582963A (en) * | 1994-10-28 | 1996-12-10 | Fuji Photo Film Co., Ltd. | Process for preparation of silver halide photographic material having emulsion layer and antistatic backing layer |
US5484694A (en) * | 1994-11-21 | 1996-01-16 | Eastman Kodak Company | Imaging element comprising an electrically-conductive layer containing antimony-doped tin oxide particles |
DE19522397A1 (en) | 1995-06-23 | 1997-01-02 | Merck Patent Gmbh | Laser-markable plastics |
US5705328A (en) * | 1995-08-30 | 1998-01-06 | Konica Corporation | Silver halide photographic light-sensitive material |
-
2001
- 2001-04-12 US US09/833,355 patent/US6693657B2/en not_active Expired - Fee Related
-
2002
- 2002-04-01 AU AU2002252578A patent/AU2002252578A1/en not_active Abandoned
- 2002-04-01 AT AT02721658T patent/ATE472513T1/en not_active IP Right Cessation
- 2002-04-01 EP EP02721658A patent/EP1377522B1/en not_active Expired - Lifetime
- 2002-04-01 DE DE60236855T patent/DE60236855D1/en not_active Expired - Lifetime
- 2002-04-01 WO PCT/US2002/010408 patent/WO2002083567A2/en active Application Filing
- 2002-04-01 CN CN02809475.1A patent/CN1240619C/en not_active Expired - Fee Related
- 2002-04-01 JP JP2002581329A patent/JP4493071B2/en not_active Expired - Fee Related
- 2002-04-01 ES ES02721658T patent/ES2345765T3/en not_active Expired - Lifetime
- 2002-04-01 CN CNB2005101276984A patent/CN100368303C/en not_active Expired - Fee Related
- 2002-04-08 TW TW091106998A patent/TW542764B/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4822973A (en) | 1984-03-30 | 1989-04-18 | Bayer Aktiengesellschaft | Composite plastic with laser altered internal material properties |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7169471B1 (en) | 2003-02-06 | 2007-01-30 | Emd Chemicals, Inc. | Laser-marking additive |
WO2005047009A1 (en) * | 2003-11-07 | 2005-05-26 | Engelhard Corporation | Nanometer size antimony tin oxide (ato) particles comprising laser marking additive |
US7187396B2 (en) | 2003-11-07 | 2007-03-06 | Engelhard Corporation | Low visibility laser marking additive |
JP2007512215A (en) * | 2003-11-07 | 2007-05-17 | エンゲルハード・コーポレーシヨン | Additives for marking with lasers with low visibility (additives for marking with lasers comprising nano-sized antimony-tin oxide (ATO) particles) |
JP4783736B2 (en) * | 2003-11-07 | 2011-09-28 | バスフ・カタリスツ・エルエルシー | Additives for marking with lasers with low visibility (additives for marking with lasers comprising nano-sized antimony-tin oxide (ATO) particles) |
WO2011124920A1 (en) | 2010-04-08 | 2011-10-13 | De La Rue International Limited | Security articles comprising security features and methods of manufacture thereof |
US10344145B2 (en) | 2014-11-05 | 2019-07-09 | Merck Patent Gmbh | Laser-markable and laser-weldable polymeric materials |
Also Published As
Publication number | Publication date |
---|---|
CN100368303C (en) | 2008-02-13 |
ATE472513T1 (en) | 2010-07-15 |
WO2002083567A3 (en) | 2003-02-20 |
JP2004535310A (en) | 2004-11-25 |
US6693657B2 (en) | 2004-02-17 |
CN1507415A (en) | 2004-06-23 |
ES2345765T3 (en) | 2010-10-01 |
AU2002252578A1 (en) | 2002-10-28 |
US20020171732A1 (en) | 2002-11-21 |
CN1240619C (en) | 2006-02-08 |
EP1377522B1 (en) | 2010-06-30 |
TW542764B (en) | 2003-07-21 |
DE60236855D1 (en) | 2010-08-12 |
JP4493071B2 (en) | 2010-06-30 |
CN1827530A (en) | 2006-09-06 |
EP1377522A2 (en) | 2004-01-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6693657B2 (en) | Additive for YAG laser marking | |
US20120010345A1 (en) | Pigment for laser marking | |
US6706785B1 (en) | Methods and compositions related to laser sensitive pigments for laser marking of plastics | |
US20100092700A1 (en) | Heavy metal-free laser marking pigment | |
TWI770084B (en) | Additive for laser-markable and laser-weldable polymer materials | |
US10066075B2 (en) | Pigments based on bismuth compounds | |
JP5028213B2 (en) | Additive for laser marking | |
CN112119128B (en) | Laser additives and their use in polymeric materials | |
JP3549347B2 (en) | Ytterbium oxide spherical fine particles for infrared absorbing material and method for producing the same | |
TW201118137A (en) | Pigment for laser marking | |
JPH09156234A (en) | Thermal reversible recording medium, thermal reversible recording and printing matter and data recording method | |
MXPA01003789A (en) | Koh neutralized metatitanic acid mixture and complex inorganic pigments containing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002581329 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002721658 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 028094751 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2002721658 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |