WO2019042906A1 - Additif sensible au laser et additif pour matières plastiques à structuration directe par laser - Google Patents

Additif sensible au laser et additif pour matières plastiques à structuration directe par laser Download PDF

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Publication number
WO2019042906A1
WO2019042906A1 PCT/EP2018/072952 EP2018072952W WO2019042906A1 WO 2019042906 A1 WO2019042906 A1 WO 2019042906A1 EP 2018072952 W EP2018072952 W EP 2018072952W WO 2019042906 A1 WO2019042906 A1 WO 2019042906A1
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Prior art keywords
laser
additive
base body
pigments
lds
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PCT/EP2018/072952
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German (de)
English (en)
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Markus HEIDEBRECHT
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Merck Patent Gmbh
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Publication of WO2019042906A1 publication Critical patent/WO2019042906A1/fr

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    • 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
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • 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
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • 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
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the present invention relates to a laser additive for plastics and to an LDS-active additive for LDS plastics, and in particular to pigments based on an iron-modified phyllosilicate, their use as laser additive or LDS additive in polymer compositions suitable for the Production of a laser marking or for an LDS method are used, on a polymer composition containing such an additive, as well as on articles which are provided with a laser marking or articles with metallized conductor tracks, in which in each case a polymeric body of the article or a polymeric Coating on a base body contains a laser additive or an LDS additive of the type mentioned.
  • the marking of assets by laser beam is a common technology, which promises great advantages by applying durable and customizable markings on various surfaces containing plastic and can be carried out efficiently with comparatively little technological effort.
  • the plastic materials are added suitable additives that absorb the energy of the laser beam and thus either show a color change itself or cause the surrounding matrix to a color change.
  • a variety of different laser additives are commercially available that meet different technological requirements. Particularly desirable are, in particular, those additives which produce a readily visible color change in the plastic matrix under the action of lasers and which are readily available in terms of their starting materials and which are also inexpensive to produce, cost-effective and environmentally neutral as products.
  • Coatings of antimony-doped tin oxide which can optionally be combined with other metal oxide coatings on the sheet silicate substrates and lead to a very good laser activity of the resulting pigments, have proven to be a particularly effective coating.
  • tin oxide on the world market is increasingly limited and the use of heavy metals such as antimony is not allowed in every application and, moreover, is not free from environmental legislation
  • MIDs Molded Interconnect Devices
  • the LDS process (laser direct structuring method) developed by the company LPKF makes it possible to introduce circuit structures by means of a laser beam directly and individually adapted into a plastic base body or a plastic-containing coating on a base body and then to metallize.
  • the plastic base body or the plastic-containing In order to obtain metallizable circuit structures by laser beam, the plastic base body or the plastic-containing must be obtained.
  • LDS additive Coating a so-called LDS additive can be added. This must react to laser radiation and simultaneously prepare the subsequent metallization.
  • the LDS additive is generally metal compounds that are activated during processing with the laser beam on the surfaces machined by the laser in such a way that metal nuclei are released, which are the subsequent attachment of electrically conductive metals for the formation of electrical circuits to the activated Favor digits in the plastic. At the same time, these metal compounds react in a laser-active manner (usually laser-absorbing) and ensure that the plastic on the surfaces machined by the laser is ablated, so that a circuit structure is engraved in the plastic base body. At the points not activated by the laser in the plastic, the metal compounds remain unchanged.
  • the LDS additives may either be added to the plastic mass as a whole prior to deformation to the plastic base part or merely as a component in a separate plastic-containing layer, on the surface into which the circuit structure is to be cut by laser beam
  • Coating a lacquer layer, or the like may be present.
  • a microrough surface is also created within the circuit structure, which creates the prerequisite for the conductive metal, as a rule, to be Copper, during the subsequent metallization adherent to the plastic can anchor.
  • the metallization is then usually carried out in electroless copper baths, which can be followed by another application of nickel and gold layers, also in electroless baths.
  • nickel and gold layers also in electroless baths.
  • other metals such as tin, silver and palladium may also be applied, optionally in combination with, for example, gold.
  • the pre-structured plastic components are equipped with the individual electronic components.
  • the objective of the LDS method is to produce two- or three-dimensional electrically conductive switching structures on two- or three-dimensional plastic basic bodies or basic bodies with plastic-containing coating. It goes without saying that for this purpose, only the generated metallized switching structures may have an electrical conductivity, but not the plastic base body or the coating itself.
  • LDS additive organic heavy metal complexes were provided, which are in particular palladium-containing (EP 0 917 597 B1).
  • plastics are added as an LDS additive to inorganic metal compounds which are insoluble in the application medium and constitute inorganic metal compounds of metals of the d and f group of the periodic table with nonmetals. Preference is given to using copper compounds, in particular copper spinels.
  • Organic Pd complexes, or copper spinels also have a dark inherent color and also impart a dark color to plastics that contain them.
  • the copper compounds fertilize a partial degradation of the surrounding plastic molecules.
  • the degradation of the plastic base is undesirable.
  • WO 2012/126831 has proposed LDS-compatible plastics and a corresponding LDS process in which an LDS additive containing antimony-doped tin dioxide is added and in the ClELab color space has an L * value (brightness) of at least 45.
  • it is doped with antimony
  • Zinndioxid coated mica in amounts of 2 to 25 wt.%, Based on the total plastic composition used.
  • Modern plastics are often provided with fillers.
  • they are reinforced with optical fibers to set advantageous mechanical properties.
  • various laser additives or even LDS additives reduce the mechanical strength that is achieved by glass fibers, because they have such a high intrinsic hardness that the glass fibers in the polymer composition
  • thermoplastic resin composition for use in the LDS process has been proposed in which as LDS additive
  • antimony is subject to administrative restrictions in some countries because it fears environmental damage, the especially in the manufacture or recycling of the corresponding compounds or components containing them.
  • the object of the present invention is therefore a
  • a laser additive for plastics which is equally suitable as an LDS additive for LDS plastics and is free of antimony, tin and copper, used in glass fiber reinforced plastic compositions without mechanical impairment of the glass fibers
  • a good metallizability of the circuit structures obtainable in the LDS method as well as a good laser markability when using the widest possible range of laser parameters possible the starting materials are good and inexpensive available on the market and which can be produced in an economic process.
  • Another object of the present invention is to provide
  • An additional object of the present invention is to provide articles which have a laser marking or a circuit structure produced in the LDS method and have the above-mentioned properties.
  • the object of the present invention is achieved by pigments which have a base body of a modified phyllosilicate which contains alkali metal and / or alkaline earth metal ions in the unmodified state, the modification consisting in that at least part of the alkali metal and / or alkaline earth metal ions are replaced by iron in the oxidation state Fe (0) is replaced.
  • At least a portion of the alkali and / or alkaline earth ions are replaced by iron in the oxidation states Fe (0) and Fe (II).
  • the object of the invention is also achieved by the
  • pigments as laser additive or LDS additive (Laser direct structuring additive) in a polymeric composition.
  • the object of the present invention is also achieved by a polymeric composition
  • a polymeric composition comprising at least one polymeric plastic and a laser additive or LDS additive, wherein the laser additive or LDS additive contains pigments which have a base body of a modified sheet silicate, which in the unmodified Condition contains alkali and / or alkaline earth metal ions, wherein the
  • Modification consists in that at least part of the alkali and / or alkaline earth metal ions by iron in the oxidation state Fe (0) or in the
  • the object of the invention is achieved by an article with a laser marking consisting of a plastic base body or a plastic-containing coating having base body, wherein the plastic base body or the plastic-containing coating of the base body contains a laser additive containing pigments, which comprises a base body of a modified Have phyllosilicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, the modification is that at least a portion of the alkali and / or alkaline earth metal ions by iron in the oxidation state (0) or in the oxidation states Fe (0) and Fe (II) is replaced.
  • the object of the invention is likewise achieved by an article having a circuit structure produced in an LDS method, consisting of a plastic main body or a plastic-containing one
  • Coating having body and located on the surface of the body or the coating metallic conductor tracks, wherein the plastic body or the plastic-containing
  • Coating of the main body contains an LDS additive containing pigments, which is a base body of a modified sheet silicate which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein at least a part of the alkali and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0) or in the oxidation states Fe (0) and Fe (II).
  • LDS additive containing pigments which is a base body of a modified sheet silicate which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein at least a part of the alkali and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0) or in the oxidation states Fe (0) and Fe (II).
  • layer silicates have surprisingly been found according to the present invention, which are selectively modified.
  • the usual unmodified phyllosilicates show an extremely weak intrinsic laser activity, which, however, is not sufficient to be considered the only laser additive or LDS additive.
  • some phyllosilicates have a high ion exchange capacity.
  • the phyllosilicates from the group of smectites and vermiculites swell easily in aqueous suspension, so that the ions which are in the interlayers and / or on the phyllosilicate surface can be exchanged.
  • alkali metal and / or alkaline earth metal ions are suitable for use as the base body of the pigments according to the invention.
  • alkali metal and / or alkaline earth metal ions are to be understood as meaning, in particular, the ions of the alkali elements lithium and sodium and the ions of the alkaline earth elements magnesium and calcium.
  • Vermiculite and almost all members of the smectite group contain the said alkali and / or alkaline earth metal ions. Preference is given to
  • montmorillonite is due its very good availability and good swelling capacity, which leads to a high ion exchange efficiency, most preferred.
  • sheet silicates which are mixtures of various clay materials with a main constituent (> 50% by weight) of montmorillonite, for example bentonite or fuller's earth.
  • the phyllosilicates mentioned can be made from natural
  • Occurrences originate or be manufactured synthetically.
  • the good ion exchange capacity of the mentioned phyllosilicates is known and is already used for various purposes.
  • phyllosilicates are modified by incorporation of rare earth luminescent substances into the crystal structure.
  • the corresponding products can be used in bioanalytics or for security marking of objects.
  • Na-fluorohectorite can be modified by ion exchange by specific stable iron complex cations, namely trisbipyridine iron ( Il) cations ([Fe (bpy) 3] 2+ ).
  • the modified clay filler is proposed in admixture with polystyrene for delaying the inflammability of polystyrene. The preparation and use of reduced species of this species is not discussed.
  • modified sheet silicates in particular those sheet silicates which contain alkali metal and / or alkaline earth metal ions and have a good ion exchange activity, are well suited as laser additives or LDS additives in the form of pigments, if at least some of the alkali metal and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0).
  • Metallic iron can not be introduced directly into the layer structure of phyllosilicates.
  • the pigments according to the present invention are therefore particles of a sheet silicate containing alkali and / or alkaline earth metal ions and a good swelling on contact with solvents, in particular with water, suspended in water, and treated with a solution, the Fe (II) -containing ions of an organic iron complex, in particular [Fe (bpy) 3] 2+ ions, containing, after appropriate reaction time and at a suitable temperature, at least a portion of the alkali and / or alkaline earth metal ions in the layered silicate by divalent iron containing ions of the organic iron complex, in particular [Fe (bpy) 3] 2+ ions, is replaced. The resulting precipitate is washed, dried and ground and sieved if necessary. The reduction of Fe (II) to Fe (0) is then carried out under protective gas at a temperature in the range of 700 ° C to 1 100 ° C. The obtained
  • pigments may subsequently be ground again and / or screened in order to adjust the desired particle size.
  • the solution containing the [Fe (bpy) 3] 2+ ions may be a solution of a previously prepared [Fe (bpy) 3] Cl2 complex which is used in aqueous solution, or an aqueous / alcoholic solution of a - situ produced [Fe (bpy) 3] Cl2 complex.
  • the latter is prepared as is known from solutions of FeCl2 * 4H2O and 2,2'-bipyridine in water or alcohol by mixing.
  • the reaction time for the ion exchange is generally between 0.25 and 8 hours, preferably between 1 and 6 hours and takes place in a temperature range from 25 ° C to 150 ° C, preferably from 25 ° C to 80 ° C instead.
  • the precipitate is dried at a temperature in the range of 100 ° C to 130 ° C.
  • the reduction of Fe (II) to Fe (0) can, surprisingly, be carried out only under protective gas, for example in a nitrogen atmosphere, without the need for a proportion of reducing gas, for example when using forming gas (H2 / N2).
  • a reduction is with
  • Forming gas also suitable and can be carried out alternatively.
  • the reduction temperature is preferably set in the range of 750 ° C to 1050 ° C.
  • the duration of the reduction reaction is in the range of 40 to 200 minutes, in particular in the range of 60 to 120 minutes.
  • At least a portion of the alkali and / or alkaline earth ions in the phyllosilicate used is replaced in this way by atomic iron Fe (0).
  • the degree of replacement of the alkali and / or alkaline earth ions in the first reaction stage can be influenced by the reaction time and the reaction temperature. It is therefore not excluded that all
  • Iron complex to be replaced. During the subsequent reduction step, Fe (II) is reduced to Fe (0). However, it is not excluded here that at least part of the ions of the organic iron (II) complex are not reduced to metallic iron Fe (0) and therefore in addition to iron in the
  • Oxidation state Fe (0) also iron in the oxidation state Fe (II) in
  • the resulting product is present, which was introduced in advance via the organic iron complex in the layered silicate.
  • the organic complex component here, the pyridine component
  • at least parts of the organic complex component may be decomposed, so that atomic carbon e may be present in the resulting product.
  • the course of the ion exchange and the reduction reaction in the corresponding starting materials, intermediates and end products can be traced very well using the [Fe (bpy) 3] 2+ -lone-containing complexes based on the altered color position of the respective products.
  • sheet silicates the sheet silicates of the smectite group or vermiculite already described above are suitable, in particular the species beidellite, hectorite, montmorillonite, nontronite and saponite, all of which have good swelling behavior in aqueous suspension and contain alkali metal and / or alkaline earth metal ions, montmorillonite, Nontronite and saponite are particularly well available on the market and montmorillonite or mineral products containing montmorillonite as the main ingredient are the most preferred starting materials for the pigments according to the present invention.
  • the shape of the pigments according to the invention is not critical and may be platelet-shaped, rod-shaped, needle-shaped or regularly or irregularly granular.
  • platelet-shaped or acicular-shaped pigments are preferred, but in particular platelet-shaped
  • the pigments according to the invention have particle sizes in the range from 0.1 to 100 ⁇ m, preferably in the range from 1 to 50 ⁇ m, and in particular in the range from 1 to 25 ⁇ m. Particular preference is given to pigments having particle sizes in the range from 1 to 25 ⁇ , in which the dgs value is less than 15 ⁇ .
  • a dgs value of ⁇ 15 ⁇ means that 95 vol.% Of the particles of a pigment bed have a particle size of less than 15 ⁇ .
  • the corresponding dso value is ⁇ 10 ⁇ .
  • the specified particle sizes can be determined by conventional methods for particle size determination. Particularly preferred is a method for particle size determination according to the laser diffraction method, in which advantageously both the nominal particle size of the individual particles and their percentage particle size distribution can be determined.
  • a Malvern 3000 device from Malvern Instruments Ltd., UK is used under standard conditions of ISO / DIS 13320.
  • the pigments according to the invention consist of the base body, that is to say they consist of a modified phyllosilicate which contains alkali metal and / or alkaline earth metal ions in the unmodified state, the modification being that at least part of the alkali metal and / or alkaline earth metal ions replaced by iron in the oxidation state Fe (0).
  • the pigments are prepared as previously described.
  • Incorporation in the various application media behave as the unmodified original phyllosilicates, as the base material can generally be used with a good dispersing behavior and overall good incorporation properties in the application media.
  • the application medium requires a particular surface finish of the pigments and / or that the properties of the pigments according to the invention are to be changed or improved with regard to their coloring, their laser sensitivity or generally their incorporation properties into the corresponding medium, the novel pigments can be used Pigments on their surface also have a surface coating. This surface coating can be constructed as one or more layers and consist of inorganic and / or organic materials.
  • organic coatings containing fatty acids, silanes, siloxanes and the like alter the incorporation properties of the pigments into the application medium in the desired manner.
  • Inorganic coatings in particular of metal oxides such as, for example, SiO 2, Al 2 O 3, T 2 O 2, Fe 2 O 3, Fe 3 O 4 , SnO 2, ZrO 2, Cr 2 O 3, CuO, Ce 2 O 3, in some cases also in doped form, are suitable both for changing the color properties and for changing the surface properties or Change in the laser sensitivity of the pigments according to the invention.
  • the appropriate layer thicknesses of the Metal oxide-containing layers on the base body preferably do not exceed 100 nm, ie at 1 to 100 nm, in particular 1 to 50 nm.
  • the present invention also relates to the use of the pigments of the invention as a laser additive or as an LDS additive (laser direct structuring additive) in a polymeric composition.
  • the plastic bodies provided with the laser-absorbing additives should not have a large-area electrical conductivity. Therefore, specially developed additives are regularly used for the application in the LDS process. It is therefore possible with the present invention in a surprising manner to develop pigments which are suitable for both the one and the other method and with appropriate adjustment of the laser parameters when used for laser marking to the desired edge sharp marks with a consistently smooth surface of the lasered plastic-containing body, while in use for an LDS method and according to different laser parameters chosen the desired micro-rough surface structure is obtained and metal nuclei are released, which allow the subsequent metallization of the laser beam preformed conductive structure.
  • the pigments of the invention are in the respective polymeric
  • Composition as laser additive or as LDS additive in an amount of 0.1 to 30 wt .-%, preferably from 0.5 to 15 wt .-%, and in particular> 1 to 10 wt .-%, each based on the total weight the polymeric composition. They may also be used in mixtures with other laser additives known in the art or LDS additives in the particular polymeric composition. In the latter case, the proportion of the pigments according to the invention is reduced by the proportion of the other or the other laser additive or LDS additive. In sum, the proportion of laser additives or LDS additives is usually not more than the above-mentioned 30 wt .-%, based on the total weight of the respective polymeric composition. Preferably, the pigments according to the invention are used as the only laser additive or LDS additive in the respective polymeric compositions.
  • the polymeric composition contains, in addition to the pigments according to the invention, at least one polymeric plastic.
  • at least one polymeric plastic In principle, all types of plastic come into question, which usually already for the
  • the pigments of the invention can be used very well in plastic compositions containing glass fibers as a filler.
  • Plastics reinforced with glass fibers have a high mechanical stability and are therefore preferably used for modern plastics applications. If, however, these plastics are additionally mixed with particulate additives for other purposes, for example for the suitability for laser marking or for use in an LDS process, the effect of such additives often has the effect of mechanically destroying the glass fibers in the plastic, because the additives used have a high Mohs hardness, which significantly exceeds the Mohs hardness of the glass fibers.
  • the pigments according to the invention do not have this disadvantage because their base body has a Mohs hardness in the range of only 1 to 2 and the replacement of the alkali metal and / or alkaline earth metal ions by Fe (O) does not lead to a marked increase in these values. Therefore, the pigments of the invention are very suitable for use in glass fiber reinforced plastics.
  • the present invention is also a polymeric
  • Composition comprising at least one polymeric plastic and a laser additive or LDS additive, wherein the laser additive or LDS additive contains pigments which have a base body of a modified layered silicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein the modification therein There is at least a part of the alkali and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0) or in the oxidation states Fe (0) and Fe (II).
  • the polymeric composition may be both a thermoplastic polymeric composition and a thermosetting polymeric composition. Depending on the desired application of the polymeric materials and on a use for Laser marking or for the LDS process, either the thermoplastic or the thermosetting composition may be preferred in each case.
  • the polymeric compositions are composed to a predominant proportion (usually> 50 wt .-%) of thermoplastic or thermosetting plastics.
  • thermoplastics are amorphous and semi-crystalline thermoplastics in a wide range of materials, such as various polyamides (PA), polycarbonate (PC), polyphthalamide (PPA), polyphenylene oxide (PPO), polybutylene terephthalate (PBT), cycloolefin polymers (COP), polyaryl ethers - ketones, such as Polyetheretherketone (PEEK), liquid crystal polymers (LCP) or their copolymers or blends, such as acrylonitrile-butadiene-styrene / polycarbonate blend (PC / ABS) or PBT / PET. They are suitable by all well-known polymer manufacturers
  • thermosetting plastics in particular different polyurethanes ne, melamine resins, phenolic resins, polyesters and epoxy resins are suitable.
  • polysilicones of various compositions are suitable in principle as plastics in the polymeric composition.
  • the proportion of the pigments according to the invention in the polymeric composition according to the invention is 0.1 to 30 wt.%, Preferably 0.5 to 15 wt .-%, and in particular> 1 to 10 wt .-%, based on the Total weight of the polymeric composition, and is measured in detail depending on the current application for laser marking or in an LDS method. For the most
  • Applications range from percentages in the range of> 1 to 5 wt.%, based on the total weight of the polymeric composition, completely.
  • the pigments according to the invention are very particularly suitable as laser additive or LDS additive in glass fiber-reinforced plastics, as already explained above.
  • glass fibers it is possible to use all glass fibers customarily used in the production of polymeric plastic articles, regardless of their concrete material composition, size and shape.
  • the glass fibers, as well as the polymeric materials for the polymeric compositions, are commercially available from a variety of manufacturers. The material
  • composition, shape, size and amount of the glass fibers depends on the desired mechanical properties of the polymeric compositions and can be selected by the skilled person according to his general knowledge relevant thereto.
  • Composition can be effected for example by compounding, via masterbatches, pastes or by direct addition in the shaping processing step.
  • polymeric compositions containing the pigments according to the invention as laser additive or LDS additive may optionally additionally contain further fillers and / or colorants as well as stabilizers, auxiliaries and / or flame retardants.
  • Suitable further fillers are, for example, various natural or synthetic silicates, S1O2, talc, kaolin, mica, wollastonite, glass beads, carbon fibers or the like.
  • Suitable colorants are both organic dyes and inorganic or organic color pigments. They serve the coloring Change or the lightening of the polymer plastic compositions, which have a rather dark color due to the addition of the pigments of the invention as a laser additive or LDS additive depending on the percentage content.
  • white pigments ⁇ 2, ZnO, BaSO 4 and CaCO3 are mentioned here.
  • the amount and type of added fillers and / or colorants is limited only by the particular concrete material nature of the individual polymeric compositions, in particular the plastics used.
  • the pigments according to the invention have a high laser activity and can be advantageously used both for laser marking and in LDS processes.
  • bright, edge-sharp markings on a dark background result under the influence of the laser beam, with the surface of the lasered plastic body intact.
  • the use of the pigments according to the invention results in the desired microrough surfaces within the laser beam ablated and carbonized
  • Laser additive or LDS additive in plastic-containing polymer compositions also not to a degradation of the additives surrounding organic polymer molecules.
  • the pigments according to the invention are free of antimony, tin and copper and are especially suitable for suitable for use in glass fiber reinforced polymeric compositions.
  • the polymeric composition according to the invention is intended for use in a laser marking process or in an LDS process (laser direct structuring process) for producing metallized switching structures.
  • the plastic bodies used in each case consist of either two- or three-dimensional plastic base bodies or have coatings containing plastic on two- or three-dimensional basic bodies.
  • the polymeric composition can be provided with a permanent, edge-sharp laser marking by means of a laser marking process or, by adding the pigments according to the invention as LDS additive, good metallizability of the laser structures generated by laser beam structures, wherein the laser parameters can be selected in a wide range ,
  • the added LDS additive is free of antimony, tin and copper, so that no chemical influence due to degradation of the polymer matrix has to be feared. In addition, no mechanical impairment of glass fiber reinforced polymer masses takes place.
  • the present invention is also an article with laser marking, consisting of a Kunststoffsigkorper or a plastic-containing coating having basic body, wherein the Kunststoffgrinper or the plastic-containing coating of the base body contains a laser additive containing pigments having a base body of a modified sheet silicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein the modification consists in that at least part of the alkali and / or alkaline earth metal ions by iron in the oxidation state (0) or in the
  • Oxidation levels Fe (0) and Fe (II) is replaced.
  • the subject matter of the present invention is also an article with a circuit structure produced in an LDS method, consisting of a plastic main body or a plastic-containing one
  • Coating base body as well as located on the surface of the body or the coating metallic
  • alkaline earth ions wherein at least a portion of the alkali and / or alkaline earth metal ions by iron in the oxidation state Fe (0) or in the
  • Oxidation levels Fe (0) and Fe (II) is replaced.
  • Laser marking articles can be used in virtually all fields of technology in which permanent inscriptions on plastic-containing bodies, films or coatings are advantageous, for example as semi-finished or finished parts in the electrical, electronics and automotive industries, as marked or labeled cables , Cables, plugs, handles, switches, moldings, functional parts in the heating, ventilation or cooling, in packaging or labels, as consumables in the medical field, as animal ear tags or the like.
  • Articles with a circuit structure that is produced in the LDS process are used, for example, in telecommunications, in medical technology or in the automotive industry, where they are used, for example, as electronic components of mobile telephones, hearing aids, dental Instruments, car electronics and the like can be used.
  • the laser types and laser parameters for both the laser marking method and for the LDS method are known to those skilled in the art and can be selected from the usual used equipment and parameters are selected without special adjustments are needed.
  • the dried particles are ground in a ball mill to a particle size of ⁇ 40 ⁇ and then reduced at 800 ° C under nitrogen over a period of 60 to 120 minutes. There are black ones
  • Pigments which are optionally comminuted and sieved again.
  • the resulting particle size is ⁇ 40 ⁇ .
  • Nanoclay PGV composition and manufacturer see above
  • EXAMPLE 2 a A PVB-containing film produced as described above with a content of 5% by weight of the pigment according to Example 1 B is mixed with a 10W yttrium vanadate laser ( ⁇ : 1064 nm) with a test grid at different laser power and provided speed. Sharp-edged, clear, bright marks on black ground are obtained over almost the entire range tested.
  • PVB-containing films with the following ingredients are subjected in parallel to the same laser treatment:
  • test plates are processed with different laser power and frequency in the range of 3-16 W and 60-100 kHz in screened test fields by means of a 10W yttrium vanadate laser ( ⁇ : 1064 nm) so that a low material removal with simultaneous carbonation of the edited Surface is created.
  • a 10W yttrium vanadate laser ⁇ : 1064 nm
  • the metallization with copper in a commercially available reductive copper bath (MID Copper 100 XB, MacDermid).
  • MID Copper 100 XB commercially available reductive copper bath
  • shoulder bar type 1A, EN ISO 527-2, total length 170 mm, width at the ends 20 mm, width of the narrow parallel portion 10 mm, thickness 4 mm
  • the shoulder bars contain the LDS additive homogeneously and finely distributed and can be used for tensile tests according to DIN EN ISO 527-2.
  • Equal shoulder bars are used for notched impact testing by milling a 10 mm notch into the center of the parallel part. The introduction of the notch and the test is carried out according to DIN EN ISO 179-1. Comparative Examples 4b to 4d:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un additif sensible au laser pour matières plastiques ainsi qu'un additif de structuration directe par laser (LDS) pour des matières plastiques à structuration directe par laser, une composition polymère contenant un tel additif, ainsi qu'un article pourvu d'un marquage laser ou muni de pistes conductrices métallisées, un corps de base polymère dudit article ou un revêtement polymère sur un corps de base contenant un additif sensible au laser ou un additif de structuration directe par laser du type mentionné.
PCT/EP2018/072952 2017-08-29 2018-08-27 Additif sensible au laser et additif pour matières plastiques à structuration directe par laser WO2019042906A1 (fr)

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US11258184B2 (en) 2019-08-21 2022-02-22 Ticona Llc Antenna system including a polymer composition having a low dissipation factor
US11555113B2 (en) 2019-09-10 2023-01-17 Ticona Llc Liquid crystalline polymer composition
US11637365B2 (en) 2019-08-21 2023-04-25 Ticona Llc Polymer composition for use in an antenna system
US11646760B2 (en) 2019-09-23 2023-05-09 Ticona Llc RF filter for use at 5G frequencies
US11721888B2 (en) 2019-11-11 2023-08-08 Ticona Llc Antenna cover including a polymer composition having a low dielectric constant and dissipation factor
US11729908B2 (en) 2020-02-26 2023-08-15 Ticona Llc Circuit structure
US11728559B2 (en) 2021-02-18 2023-08-15 Ticona Llc Polymer composition for use in an antenna system
US11912817B2 (en) 2019-09-10 2024-02-27 Ticona Llc Polymer composition for laser direct structuring
US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11258184B2 (en) 2019-08-21 2022-02-22 Ticona Llc Antenna system including a polymer composition having a low dissipation factor
US11637365B2 (en) 2019-08-21 2023-04-25 Ticona Llc Polymer composition for use in an antenna system
US11705641B2 (en) 2019-08-21 2023-07-18 Ticoan Llc Antenna system including a polymer composition having a low dissipation factor
US11555113B2 (en) 2019-09-10 2023-01-17 Ticona Llc Liquid crystalline polymer composition
US11912817B2 (en) 2019-09-10 2024-02-27 Ticona Llc Polymer composition for laser direct structuring
US11646760B2 (en) 2019-09-23 2023-05-09 Ticona Llc RF filter for use at 5G frequencies
US11917753B2 (en) 2019-09-23 2024-02-27 Ticona Llc Circuit board for use at 5G frequencies
US11721888B2 (en) 2019-11-11 2023-08-08 Ticona Llc Antenna cover including a polymer composition having a low dielectric constant and dissipation factor
US11729908B2 (en) 2020-02-26 2023-08-15 Ticona Llc Circuit structure
US11728559B2 (en) 2021-02-18 2023-08-15 Ticona Llc Polymer composition for use in an antenna system

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