Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/10—Encapsulated ingredients
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0001—Post-treatment of organic pigments or dyes
  • C09B67/0004—Coated particulate pigments or dyes
  • C09B67/0008—Coated particulate pigments or dyes with organic coatings
  • C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
  • C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
  • C09C1/3638—Agglomeration, granulation, pelleting
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/44—Carbon
  • C09C1/48—Carbon black
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/44—Carbon
  • C09C1/48—Carbon black
  • C09C1/50—Furnace black ; Preparation thereof
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/30—Particle morphology extending in three dimensions
  • C01P2004/32—Spheres
• • 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
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • 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

Definitions

• the present invention relates to microspheres, a process for their preparation, and their use, preferably as a laser-absorbing additive.
• Laser beams and therefore the interaction with the material, depends on the chemical structure of the composition and on the laser wavelength used. It is often necessary to add suitable additives such as absorbents to make plastics laser writable.
• the successful absorbent should have a very pale inherent color and / or be used only in very small quantities. It is known from the prior art that the contrast agent antimony trioxide meets such criteria as described in US Pat. No. 4,816,374, US Pat. No. 6,214,917 B1, WO 01/0719 and WO 2009/003976. However, antimony trioxide is toxic and suspected to be carcinogenic, and therefore, antimony-free laser marking additives are desired.
• Antimony oxide or antimony oxide-free laser marking additives are known from the literature. For example, in US 2007/02924
• antimony-free laser marking additives are not suitable for all types of plastic.
• Plastic compounds show the additives a strong
• the object of the present invention is therefore to find a heavy metal-free laser additive which does not have the abovementioned disadvantages and at the same time is physiologically harmless.
• the laser additive should continue to be a high contrast labeling when exposed to Allow laser light and have a significantly improved contrast at both low and at high labeling speeds of the laser compared to the laser additives from the prior art.
• Microspheres which serve as laser absorbents and are based on core-shell particles are known, for example, from WO 2004/050766 A1, WO 2004/050767 A1 and WO 2009/003976 A1.
• the present invention thus microspheres
• Polyolefinmatrix characterized in that the core elemental carbon, at least one metal oxide and / or at least one
• Metal titanate and at least one non-olefinic polymer and the shell contains at least one compatibilizer.
• Color formers in the core and the polymer of the shell can serve the light colored microspheres as laser absorbents with improved laser marking performance in terms of contrast and speed compared to the known laser additives used commercially available and described in the literature.
• the improved performance results in lower dosage in the final product, thereby achieving a cost reduction.
• the lower dosage of the laser additive according to the invention in the end product (polymer matrix) means that the properties, such as the mechanical properties, of the polymer to be inscribed are not or only insignificantly influenced. Since the absorbent mixture of carbon and metal oxide and / or metal titanate physiological
• the laser light absorbent used may be made of such materials
• Metal oxides and metal titanates can be produced, which can absorb laser light of a certain wavelength.
• metal oxides and metal titanates can be produced, which can absorb laser light of a certain wavelength.
• Nd YAG or Nd: YVO 4 lasers (1064 nm, 532 nm, 355 nm, 266 nm) and excimer lasers wavelengths: F 2 (157 nm), ArF (193 nm), KrCl (222 nm), KrF (248 nm), XeCl (308 nm) and XeF (351 nm), Fayb fiber lasers, diode lasers and diode array lasers.
• Nd: YAG lasers, Nd: YV0 4 lasers and C0 2 lasers are used because these types operate at a wavelength that is particularly suitable for inducing a thermal process for marking purposes.
• Suitable examples of the laser light absorber are one or more metal oxides, preferably selected from the group Ti0 2 , Zr0 2 , ⁇ 2 ⁇ , ZnO, Al 2 O 3 , in particular TiO 2 , and / or one or more metal titanates selected from the group calcium titanate, barium titanate , Magnesium titanate, in particular barium titanate.
• Particularly preferred as the absorbent is a mixture of
• the laser light absorber is a mixture of elemental carbon and titania or elemental carbon and barium titanate.
• the weight ratio of elemental carbon to metal oxide and / or metal titanate is preferably 0.001: 99.999% to
• the elemental carbon is preferably used in the form of carbon black or as a black pigment.
• the carbon preferably has average primary particle sizes of 1 to 100 nm, in particular 10 to 50 nm.
• the microspheres preferably contain 10-90 wt.%, More preferably 20-80 wt.% And most preferably 25-75 wt.% Of absorbent based on the microsphere as such (i.e., not dispersed in the polyolefin matrix). Most preferably, the microspheres contain a mixture of carbon and titanium dioxide or a mixture of carbon and barium titanate, preferably in amounts of 20-80% by weight. When the microspheres are dispersed in the polyolefin matrix, the amount of absorbent is preferably 12.5-25% based on the total formulation, i. The microspheres dispersed in the polyolefin matrix according to claim 1.
• the mixture of carbon and metal oxide and / or metal titanate is preferably in the form of agglomerates or spherical spheres.
• the absorbent ie the mixture of carbon and metal oxide / titanate, is present in the microsphere, for example in the form of spherical beads.
• the particle size of the absorbent is determined by the requirement that the absorbent must be miscible into the polymer in the core. A person skilled in the art is aware of that this miscibility is determined by the total surface area of a given amount by weight of the absorbent, and that those skilled in the art can readily determine the lower limit of particle size of the absorbent to be incorporated, knowing the desired size of the microspheres and the desired amount of absorbent to be mixed.
• Elemental carbon is commercially available, for example from the company. Evonik under the trade name Printex ® 90, or by the company. Cabot under the trade name Monarch 1300th
• Suitable metal oxides are commercially available, for. Kronos 2900 from Kronos or HOMBITEC RM 30F from Sachtleben.
• Suitable metal titanates are, for example, BaTiO 3 , MgTiO 3 , CaTiO 3 , eg calcium titanate 99% of ABCR GmbH & Co. KG (d 50 max 3.5 pm) Calcium titanium oxide 99 +% of Alfa Aesar, barium titanate 99.9 % nano from ABCR GmbH & Co. KG (about 400 nm, BET 2.3-2.7 m 2 / g).
• the absorbent used preferably has an average particle size in the range from 0.1 to 10 ⁇ m, in particular from 0.13 to 4 ⁇ m, and very particularly preferably in the range from 0.5 to 3.5 ⁇ m.
• the preferably used absorption medium TiO 2 preferably has an average particle size in the range of 0.13-4 ⁇ m and very particularly preferably in the range of 0.15-3 ⁇ m.
• the core of the microspheres contains at least one non-olefinic polymer, which is preferably a thermoplastic polymer.
• thermoplastic polymers are preferably selected from the following group:
• PC polycarbonates
• polyesters are polybutylene terephthalate (PBT) or polyethylene terephthalate (PET).
• styrenics is styrene-acrylonitrile.
• the core contains PBT, PPO / PS, PET or polycarbonate (PC) or mixtures thereof as a color former.
• the core of the microspheres consists of
• the adhesion of the polymer of the core to the mixture of carbon and metal oxide and / or metal titanate is usually higher than that
• a chemical reaction between the absorbent and the polymer in the core should be avoided. Such chemical reactions could cause decomposition of the absorbent and / or the polymer causing undesirable by-products, discoloration and poor mechanical and labeling properties.
• the core is embedded in a shell containing a compatibilizer.
• the compatibilizer is usually u.a. responsible for forming the microspheres during manufacture using (reactive) extrusion.
• the compatibilizer improves due to its
• the compatibilizer is preferably a thermoplastic polymer.
• Preferred thermoplastic polymers contain either functional groups, such as. Carboxylic acid groups, alkoxysilane groups, alcohol groups or graft or block copolymers having chain segments which are only partially compatible with the core, e.g. Styrene-ethylene / butylene-styrene (SEBS) block copolymers.
• SEBS Styrene-ethylene / butylene-styrene
• thermoplastic polymer In a particularly preferred
• the compatibilizer is a grafted thermoplastic polymer or a block copolymer.
• the grafted thermoplastic polymer or a block copolymer.
• thermoplastic polymer a grafted polyolefin or a styrene-ethylene / butylene-styrene block copolymer.
• Polyolefin polymers are, for example, homopolymers and copolymers of one or more olefin monomers which can be grafted with an ethylenically unsaturated, functionalized compound.
• suitable polyolefin polymers are ethylene and propylene homo- and copolymers.
• suitable ethylene polymers are all
• the amount of comonomer is usually 0-50% by weight, preferably 5-35% by weight, based on the weight of the total composition.
• Such polyethylenes are for.
• High density polyethylene high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density linear polyethylene (Linear very low-density polyethylene (VL (L) DPE)) and metallocene polyethylene (m-PE).
• Suitable polyethylenes preferably have a density of 860-970 kg / m 3 , measured at 23 ° C according to ISO 1183.
• suitable propylene polymers are homopolymers of propylene and copolymers of propylene with ethylene, in which the proportion of ethylene is at most 30 wt. -%, and preferably at most 25 wt .-% is.
• Suitable ethylenically unsaturated, functionalized compounds are the unsaturated carboxylic acids as well as esters, anhydrides and metal or non-metal salts thereof.
• the ethylenic unsaturation in the compound is conjugated to a carbonyl group.
• examples are acrylic, methacrylic, maleic, fumaric, itaconic, crotonic, methyl crotonic and cinnamic acid, as well as esters, anhydrides and possible salts thereof.
• maleic anhydride is preferred.
• Suitable, ethylenically unsaturated, functionalized compounds having at least one epoxy ring are, for example, glycidyl esters of unsaturated carboxylic acids, glycidyl ethers of unsaturated alcohols and of alkylphenols, and vinyl and allyl esters of epoxycarboxylic acids.
• Glycidyl methacrylate is particularly suitable.
• Suitable, ethylenically unsaturated, functionalized compounds having at least one amine functionality are amine compounds having at least one ethylenically unsaturated group, for example allylamine, propenyl, butenyl, pentenyl and hexenylamine, amine ethers, for example, isopropenylphenylethylamine ether.
• the amine group and the unsaturated function should be in such an arrangement with each other that they do not affect the grafting reaction to an undesirable degree.
• the amines may be unsubstituted, but may also be substituted, for example, with alkyl and aryl groups, halo groups, ether groups and thioether groups.
• suitable, ethylenically unsaturated, functionalized compounds having at least one alcohol functionality are all compounds having a hydroxyl group, which may optionally be etherified or esterified, and an ethylenically unsaturated compound, for example allyl and vinyl ethers of alcohols, such as ethyl alcohol and higher, branched and unbranched Alkyl alcohols and allyl and vinyl esters of alcohol-substituted acids, preferably carboxylic acids and C3-C8 alkenyl alcohols.
• the alcohols may be substituted with, for example, alkyl and aryl groups, halogen groups, ether groups and thioether groups which do not affect the grafting reaction to an undesirable degree.
• the amount of the ethylenically unsaturated functionalized compound in the graft-functionalized polyolefin polymer is preferably in a range of 0.05 to 1 mg eq. per gram of polyolefin polymer.
• the compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.
• the amount of compatibilizer with respect to the polymer in the core of the microspheres is, for example, in the range of 0.1-10% by weight and is preferably 1-5% by weight.
• Both the polymer in the core and in the shell are preferably thermoplastic polymers independently of each other, since this facilitates the incorporation of the absorbent (s) into the polymer in the core or the microspheres into a polymer matrix, eg, a plastic mass suitable for laser writing. If the polymer in the core and the compatibilizer in the shell contain functional groups, these may be functional
• the present invention further relates to the use of the microsphere as a laser inscription additive.
• the activity of the microsugar appears to be based on the transmission of energy absorbed by the laser light to the polymer in the nucleus. The polymer may decompose due to this heat release, causing the
• the absorbents are present in the microsugar, for example in the form of particles.
• the particle size of the absorbents is determined by the requirement that the absorbents must be mixable into the polymer in the core. It is known to one skilled in the art that this miscibility is determined by the total surface area of a particular weight amount of absorbent and that one skilled in the art can readily determine the lower limit particle size of the absorbents to be incorporated if the desired size of the microsphere and the desired amount of absorbent to be mixed are known.
• the core-shell particles are dispersed in a carrier polymer, which in the present invention is a polyolefin.
• This polyolefin matrix preferably contains no functional groups.
• the polyolefin is preferably a polyethylene or a polypropylene.
• the polyolefin matrix is selected from the group consisting of linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), low density polyethylene (LDPE), or metallocene polyethylene (m-PE) and most preferably an LLDPE.
• LLDPE linear low density polyethylene
• VLDPE very low density polyethylene
• LDPE low density polyethylene
• m-PE metallocene polyethylene
• the carrier polymer the same polymers as those listed for the compatibilizer may be considered. albeit in its unfunctionalized form.
• the amount of carrier polymer is preferably in the range of 20-60% by weight of the total polymer (ie, the entire formulation) of core, shell, and
• microspheres of the present invention according to the present application
• polyolefin carrier polymer
• wt .-% carrier polymer
• the polymer in the core, in the shell and in particular the carrier polymer may additionally contain one or more additives, e.g. Pigments, colorants and / or dyes or a mixture thereof.
• additives e.g. Pigments, colorants and / or dyes or a mixture thereof.
• microspheres according to the invention preferably have an average diameter in the range from 0.5 to 10 gm and particularly preferably in the range from 0.5 to 5 ⁇ m with respect to their size.
• the microspheres of the present invention are incorporated into a polymer matrix, e.g. a plastic compound, incorporated. It is possible to also select the polymer matrix to be marked as the carrier polymer for the microspheres.
• the present invention also relates to a process for the preparation of the microspheres of the invention.
• the microspheres are prepared by extrusion or reactive extrusion.
• the absorbent is off
• Carbon and metal oxide or metal titanate produced is preferably done by the elemental carbon, for example carbon black with one or more metal oxides and / or one or more
• Metal titanates are mixed, preferably in a Rhönrad.
• the usually resulting agglomerates, usually in the form of spherical balls, are then screened to a suitable particle size and subsequently mixed with the core-forming polymer in the melt.
• the ratio between the amount of the core-forming polymer and the amount of absorbent is preferably in the range of 90-10% by weight: 25-75% by weight.
• the mixture is off Absorbent and polymer melt mixed with the compatibilizer. This blending preferably takes place above the melting point of both polymer and compatibilizer, preferably in the presence of an amount of unfunctionalized carrier polymer.
• Suitable carrier polymers are, in particular, those mentioned above for the compatibilizer but in their unfunctionalized form. This carrier polymer need not be the same as the compatibilizer. The presence of an unfunctionalized carrier polymer insures adequate melt processability of the overall mixture so that the desired homogeneous distribution of the microspheres is obtained.
• the microspheres according to the invention are mixed into a polymer matrix.
• the polymer matrix containing the microspheres according to the invention shows, compared to the laser-markable polymers or
• the present invention therefore also relates to a laser writable composition containing a polymer matrix and the microspheres of the invention.
• plastics such as plastics, binders, resins, etc. can be used for laser marking and laser welding application.
• Suitable plastics are, for example
• thermosets such as Polyethylene (PE), polypropylene (PP), polyamide (PA), polyester, polyether, polyphenylene ether, polyacrylate, polyurethane (PU), polyoxymethylene (POM), polymethacrylate,
• PMMA Polymethyl methacrylate
• PVAC polyvinyl acetate
• PS polystyrene
• ABS acrylonitrile butadiene styrene
• ASA acrylonitrile styrene acrylate
• ABS grafted polymer polybutylene terephthalate (PBT)
• PET Polyethylene terephthalate
• PVC polyvinyl chloride
• PVDC Polyvinylidene chloride
• PVDF polyvinylidene fluoride
• PTFE Polytetrafluoroethylene
• PC Polycarbonate
• PC Polyethersulfone
• Polyetherketone Thermoplastic Polyurethane
• TPU Thermoplastic Polyurethane
• TPE Thermoplastic Elastomers
• EP epoxy resin
• SI silicone resin
• UP unsaturated polyester resin
• PF phenol-formaldehyde resin
• UF urea-formaldehyde resin
• MF melamine resin
• copolymers thereof and / or mixtures thereof The polymer may also be a copolymer or block copolymer, etc.
• the polymer matrix to be marked can furthermore also
• Examples of preferred polymers are all PE and PP types known to those skilled in the art, in particular ultrahigh molecular weight polyethylene
• UHMWPE UltraMWPE
• Solpor TM styrenics, including ABS, styrene-acrylonitrile (SAN) and polymethyl (meth) acrylate, polyurethane, polyesters, including PET and PBT, polyoxymethylene (POM),
• Polyvinyl chloride PVC
• PE polyethylene
• PP polypropylene
• PA polyamide
• PU polyurethane
• thermoplastic vulcanizates such as Santoprene TM and SARLINK ®
• thermoplastic elastomers such as Hytrel ® and Arnitel ®
• silicone rubbers such as for example Cenusil ® and Geniomer ®.
• the laser writable composition according to the present invention may also contain other additives, for example, known to enhance certain properties of the polymer matrix or impart further properties thereto.
• suitable additives include i.a. reinforcing materials such as glass fibers and carbon fibers, nanofillers such as clays, including wollastonite, mica, pigments, dyes, colorants, fillers such as calcium carbonate, talc, processing aids, stabilizers, antioxidants, plasticizers, tougheners, flame retardants, mold release agents,
• Foaming agent etc.
• the amount of absorbent in the polymer matrix can be of very small amounts, such as. From 0.05% to 5% by weight, based on the total composition.
• the microspheres according to the invention are generally used in amounts such that no or only little influence on the contrast of the laser inscription result is observed upon irradiation of the polymer composition to be inscribed. The following are typical ranges for concentrations of
• Laser marking indicated. For a laser marking are usually 0.2 to 5 wt .-%, preferably 0.2 to 2 wt .-% of
• microspheres (complete formulation including carrier polymer) based on the polymer matrix used.
• the laser writable composition of the present invention can be prepared by simply incorporating the microspheres of the present invention into the molten polymer matrix, such as the like. a plastic mass, are mixed.
• the plastic pellets can optionally with
• Adhesion promoters organic, polymer-compatible solvents, stabilizers, dispersants and / or surfactants are treated, which are stable at operating temperatures.
• Plastic pellets are usually produced by the
• Plastic pellets are placed in a suitable mixer, these are wetted with any additives and then the microspheres are added and installed.
• the plastic is generally pigmented by means of a color concentrate (color granules) or a compound.
• the resulting mixture can then be processed directly in an extruder or an injection molding machine.
• the formed during processing molded parts have a very homogeneous absorbent distribution.
• the polymer composition to be inscribed is generally inscribed or welded as follows by means of suitable laser irradiation.
• the labeling method by laser is such that the sample is brought into the beam path of a pulsed laser beam, preferably a Nd.YAG laser or Nd: YV0 4 laser.
• the label can also be used with a C0 2 laser, z. B. using a mask technique.
• the desired results can also be achieved with other common types of lasers whose wavelengths are within the range of high absorption of those used
• Irradiation time (or number of pulses in the case of a pulsed laser) and determined by the laser emitted power and by the polymer matrix used.
• the power of the laser used depends on the specific application and can be readily determined by one skilled in the art.
• the laser used generally has a wavelength in a range of 157 nm to 10.6 pm, preferably in a range of 532 nm to 10.6 pm.
• Examples that can be mentioned are a CO 2 laser (10.6 pm) and a Nd: YAG laser (1064 nm, 532 nm or 355 nm) and a pulsed UV laser.
• Excimer lasers have the following wavelengths: F2 excimer laser: 157 nm, ArF excimer laser: 193 nm, KrCl excimer laser: 222 nm, KrF excimer laser: 248 nm, XeCl excimer laser: 308 nm, XeF excimer laser: 351 nm and frequency multiplied Nd: YAG laser: wavelength of 355 nm (frequency tripled) or 265 nm (frequency quadrupled). Particularly preferred is the use of Nd.YAG lasers (1064 or 532 nm) and C0 2 lasers.
• the energy densities of the lasers used are generally within a range of 0.3 mJ / cm 2 to 50 J / cm 2 , preferably from 0.3 mJ / cm 2 to 10 J / cm 2 .
• the pulse frequency is generally within a range of 1 to 150 kHz.
• Corresponding lasers which can be used in the process according to the invention are commercially available. Labeling with the laser is preferably carried out by introducing the object into the beam path of a C0 2 laser (10.6 ⁇ ) or a pulsed laser, preferably an Nd: YAG laser.
• Laser welding is performed by introducing the sample into the beam path of a continuous wave laser, preferably an Nd.YAG or diode laser.
• the wavelengths are preferably between 808 and 1100 nm. Since most polymers are more or less permeable at these wavelengths, the absorption property is achieved by the addition of the microspheres of the invention.
• Welding using other common laser types is also possible if they operate at a wavelength at which the absorbent in the microspheres used has a high absorption. Welding is determined by the irradiation time and the irradiation power of the laser as well as the plastic system used. The performance of the lasers used will vary with the particular application and can be readily determined by one skilled in the art for a particular case.
• the polymer compositions containing the microspheres as laser marking additive according to the invention can be used in any area in which conventional printing processes have hitherto been used for marking or marking plastics. Almost every plastic article can be obtained in a laser-markable or laser-inscribable form. Any article consisting of a polymer matrix, such as plastic, can be provided with functional data, bar codes, logos, graphics, images and identification codes. In addition, they can be applied
• Single-layer and multi-layer films, bottles, caps, and closures including, but not limited to, bottle caps, safety caps, and synthetic corks.
• moldings made from the inventively doped plastics can be used in the electrical, electronic and motor vehicle industries.
• With the aid of laser light it is possible to produce identification marks or marking marks even in places where access is difficult, for example on cables, wires, decorative strips or functional parts in the heating, ventilation and cooling sector or on switches, plugs, levers or handles, which consist of the inventive plastic.
• the polymer system according to the invention can also be used for packaging in the food and beverage sector or in the toy sector.
• the labels on the packaging are smudge and scratch resistant, resistant to downstream sterilization processes and can be used in a hygienically clean way during the labeling process.
• Full label motifs can be permanently applied to packaging of reusable systems.
• laser marking Another important application of laser marking is the marking of plastics for the production of individual identification marks for animals known as cattle ear tags or ear tags only.
• the information specific to the animal is stored via a bar code system. If necessary, they can be retrieved using a scanner.
• the label must be extremely durable, as some marks remain on the animals for many years.
• Laser welding with the microspheres according to the invention can be carried out in all areas in which conventional joining methods are used and in which it has hitherto not been possible to use the
• the welding process for laser-permeable plastics thus represents an alternative to conventional joining methods, for example high-frequency welding, vibration welding, ultrasonic welding, hot-air welding or adhesion of plastic parts.
• compositions of LMAC and CCC are listed in Table 1 and 1, 1, respectively.
• the mixture of Ti0 2 (Kronos 2900) and carbon black (Printex ® 90, Evonik) is pre-mixed on a tumbling mixer and then sieved through a 2.5 mm sieve.
• the mixture of barium titanate (ABCR) and carbon black (Printex ® 90, Evonik) is premixed in a tumble mixer.
• a series of diluted laser marking concentrates LMDC 01-LMDC 05 are prepared The composition of the LMDC is shown in Table 3 listed. The screw speed is 200 revolutions per minute and the throughput 10 kg / h. For the diluted concentrates LMDC 01 - LMDC 05 the temperature in zone 1 is 220 ° C and in zone 10 220 ° C.
• Laser marking products were produced using a twin-screw extruder (Leistritz Mikro 27).
• the composition of the LMP is shown in Table 4.
• the screw speed is 200 revolutions per minute and the throughput 10 kg / h.
• the temperature in zone 1 is 220 ° C and in zone 10 220 ° C.
• Table 4 Composition of laser marking products (LMP)
• LMSA Laser marking samples
• the composition of LMSA is listed in Tables 5a, 5b and 5c.
• the temperature in zone 1 is set to 220 ° C for all samples.
• the temperature in zone 2 is
• the laser marking ratings are performed with a 11 Watts Trumpf VMc5 diode-pumped IR laser system. So-called evaluation matrices are coined. In such matrices, the
• the evaluation matrices indicate which contrast can be obtained at a particular labeling speed by varying the laser parameters.
• An evaluation of the laser marking performance in terms of contrast and labeling speed, indicated with + and - in one Range from excellent (+++++) to poor (-) is listed in Table 6.

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