EP2995178A1 - Additif pour matières plastiques à structuration directe par laser - Google Patents

Additif pour matières plastiques à structuration directe par laser

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Publication number
EP2995178A1
EP2995178A1 EP14726515.1A EP14726515A EP2995178A1 EP 2995178 A1 EP2995178 A1 EP 2995178A1 EP 14726515 A EP14726515 A EP 14726515A EP 2995178 A1 EP2995178 A1 EP 2995178A1
Authority
EP
European Patent Office
Prior art keywords
lds
core
coating
use according
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14726515.1A
Other languages
German (de)
English (en)
Inventor
Helge Bettina Kniess
Ulrich Quittmann
Oliver Robert PIENING
Silvia Rosenberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2995178A1 publication Critical patent/EP2995178A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • 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
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0284—Details of three-dimensional rigid printed circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0141—Liquid crystal polymer [LCP]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0227—Insulating particles having an insulating coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09009—Substrate related
    • H05K2201/09118—Moulded substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam

Definitions

  • the present invention relates to an LDS-active additive for LDS plastics, and more particularly to the use of composite pigments consisting predominantly of titanium dioxide and of antimony-doped
  • Zinndtoxid as LDS additive in polymer compositions, which are used for an LDS process, on a polymer composition containing such an additive, and on an article with metallized interconnects, in which a polymeric body of the article or a polymeric coating on a base body contains an LDS additive of the type mentioned.
  • MIDs Molded Interconnect Devices
  • the LPDS-developed LDS process offers the decisive advantage that the circuit structures are cut directly into the plastic base part or the plastic-containing coating on the base part by a laser beam and then metallized can be.
  • LDS additive In order to be able to obtain metallizable circuit structures by laser beam, a so-called LDS additive must be added to the plastic base part or the plastic-containing coating. 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 laser-active (usually laser-absorbing) and cause the plastic on the surfaces machined by the laser to be ablated and carbonized, so that a circuit structure is engraved into the plastic base part.
  • the LDS additives can either be added to the plastic mass as a whole prior to deformation to the plastic base part or only as a component in a separate plastic-containing layer, a coating, a surface on which the circuit structure is to be cut by laser beam Lack Mrs, or the like, be present.
  • the objective of the LDS method is to produce three-dimensional electrically conductive switching structures on 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
  • plastics are added as an LDS additive to non-conductive inorganic metal compounds which are not soluble in the application medium and which are inorganic metal compounds of metals of the d and f groups of the periodic table with nonmetals.
  • Preference is given to using copper compounds, in particular copper spinels.
  • organic Pd complexes or copper spinels have the
  • EP 2 476 723 A1 has proposed tectoaluminosilicate (zeolites) as LDS additives for plastics.
  • LDS-compatible plastics and a corresponding LDS method are known, wherein an LDS additive is added, which contains antimony-doped tin dioxide and in the ClELab color space an L * value (brightness) of at least 45 has.
  • an LDS additive is added, which contains antimony-doped tin dioxide and in the ClELab color space an L * value (brightness) of at least 45 has.
  • mica coated with antimony-doped tin dioxide is used in amounts of from 2 to 25% by weight, based on the total plastic composition.
  • white color pigments can additionally be added for an even lighter coloring of the plastics material.
  • WO 2012/056416 also discloses a composition which contains 0.5 to 25% by weight of a metal oxide-coated filler, the latter preferably being antimony-doped tin dioxide-coated mica.
  • the LDS plastic compound has L * values of 40 to 85.
  • the plastic material can also be added to color pigments.
  • Antimony doped tin dioxide coated mica platelets are commonly used as an electrically conductive pigment in a variety of applications. used fertilizer, for example, where plastic masses are to be given antistatic properties. Pigments of the stated composition also serve as additives to plastics which are provided with laser markings because mica coated with antimony-doped tin dioxide absorbs conventional laser radiation and the stored heat penetrates into the pigment matrix surrounding the plastic matrix and blackens it.
  • the use of antimony-doped tin dioxide-coated mica as LDS additive in the corresponding LDS-suitable plastic materials can therefore also lead to the formation of conductive paths there, if a critical use concentration is exceeded.
  • conductive plastics are less suitable for use in the LDS process because they can significantly affect the electrical conductivity of the circuit structures deposited on the plastic base parts, and also the resulting MIDs for special high-frequency applications (RF applications) such as portable telephones with integrated antennas or electronic components for use in
  • the object of the present invention is thus to provide an LDS additive for LDS plastics which, by virtue of its light inherent coloration, enables the production of light LDS plastics which can easily be colored with small amounts of colorant admixtures in brightly colored colors the provided with it
  • Plastic dielectric or even so low electrically conductive properties imparts that this plastic is suitable for high frequency applications, which prevents the decomposition of the surrounding plastic matrix as far as possible and which also good metallization of the available in LDS circuit structures when using the widest possible bandwidth Laser parameters allows.
  • Another object of the present invention is to provide a polymeric composition which is suitable for the LDS process and has the properties described above.
  • An additional object of the present invention is to provide articles having a circuit structure produced by the LDS method and having the above-mentioned characteristics.
  • the object of the present invention is achieved by the use of composite pigments which contain at least 80% by weight, based on the total weight of the composite pigments, of titanium dioxide (TiO 2 ) and with Antimony doped tin dioxide ((Sb, Sn) 0 2 ) exist as LDS additive (laser direct structuring additive) in a polymeric composition.
  • the object of the present invention is also achieved by a polymeric composition containing at least one organic polymer plastic and an LDS additive, wherein the LDS additive is a composite pigment, which is at least 80 wt .-%, based on the total weight of Composite pigment, of titanium dioxide
  • the object of the invention is achieved by an article having a circuit structure produced in an LDS method, consisting of a polymer body of the article or a polymer
  • the polymeric body or the polymer-containing coating of the body contains an LDS additive which consists of Kompositpigmenten, which is at least 80 wt .-%, based on the overall
  • doped tin dioxide (Sb, Sn) O2) exist.
  • Composite pigments which largely consist of titanium dioxide (TiO 2 ) and antimony-doped tin dioxide ((Sb, Sn) O 2 ) are known per se, in particular in the form of pigments consisting of a titanium dioxide core and a coating present on the core consist of antimony-doped tin dioxide.
  • these pigments may also have a protective layer and / or an intermediate layer between core and (Sb, Sn) O 2 coating.
  • Pigments of this type in which the TiO 2 core can have various geometric shapes have long been used as antistatic agents in coatings and plastics. They themselves exhibit electrical conductivity and give the coating or plastics that contain them in sufficient concentration, also an electrical conductivity. To increase this electrical conductivity, in particular such pigments have been developed in recent years, in which the Ti0 2 core is needle-shaped.
  • composite pigments which consist of at least 80% by weight, based on the total weight of the composite pigments, of TiO 2 and antimony-doped tin dioxide are very well suited as LDS additives in a polymeric composition.
  • the present invention therefore relates to the use of said composite pigments as LDS additive in polymeric compositions for use in the LDS process.
  • the composite pigments used according to the invention have at least one core and a coating arranged on the core.
  • the coating can be composed of one or more individual layers.
  • the coating consists of a single, functional layer.
  • the coating between the core and the functional layer may have one or more intermediate layers and / or one or more on the surface of the functional layer
  • the composite pigments used according to the invention are composed exclusively of primary particles and thus monodisperse.
  • the embodiment in which the composite pigments used are agglomerates of two or more is more frequent and thus preferred Primary particles, each primary particle having a core and a coating disposed on the core.
  • both composite pigments whose primary particles have a layer structure of the order core / functional layer, a layer structure core / intermediate layer (s) / functional layer, a
  • Layer structure core / functional layer / protective layer (s) or a layer structure core / intermediate layer (s) / functional layer / protective layer (s) have to be used.
  • the core or the functional layer consists of TiO 2 or antimony-doped tin dioxide.
  • the composite pigments used according to the invention may have the following compositions:
  • the weight fraction of the sum of core and functional layer ie the sum of TiO 2 and antimony-doped tin dioxide, is in each case at least 80% by weight, preferably at least 90% by weight, and in particular 95-100% by weight. %, based on the total weight of the composite pigment. That is, in a particularly preferred embodiment of the present invention, the composite pigment used consist only of TiO 2 and (Sb, Sn) 0 2 or optionally only the smallest amounts of other ingredients are included.
  • the antimony-doped tin dioxide regardless of whether it is used as a core or as a functional layer in the coating of the primary particles, is a material in which the percentage by weight of antimony, relative to tin, between 2 and 35 wt .-%, preferably from 8 to 30 wt .-% and in particular from 10 to 20% by weight, based on the total weight of antimony and tin, is.
  • intermediate layers and / or protective layers consist predominantly of inorganic materials, if they are intermediate layers.
  • intermediate layers are metal oxides, in particular SiO 2 , SnO 2 , Al 2 O 3 , ZnO, CaO, ZrO 2 , Sb 2 O 3 , or mixtures thereof.
  • protective layers which can be present on the surface of the composite pigments used can be both inorganic and organic in nature. They are usually applied when the use of the composite pigments in the application medium, in this case the organic polymer plastic, is facilitated or made possible by a corresponding surface coating. But you can also be applied to make any desired color adjustments.
  • inorganic protective layers these are preferably ZrO 2, Ce 2 O 3, Cr 2 O3, CaO, SiO2, Al2O3, ZnO, TiO2, SnO2, antimony-doped SnO 2, Sb 2 O 3, or the corresponding oxide hydrates, as well as mixtures of two or more of these.
  • Organic protective layers are usually made of suitable
  • Organosilanes Organotitanates or Organozirkonaten.
  • suitable Substances are known to the person skilled in the art as agents for surface coating and subsequent coating of effect pigments.
  • the total weight fraction of intermediate and / or protective layer (s) is at most 20% by weight, preferably at most 10% by weight, and particularly preferably 0-5% by weight, based on the total weight of the composite pigment.
  • the composite pigment used as LDS additive consists only of one or more primary particles which are each composed of a core and a functional coating located on the core, ie a TiO 2 core and a (Sb, Sn ) O 2 coating or of a (Sb, Sn) O 2 core and a TiO 2 coating; but most preferred is the embodiment in which the composite pigment consists of primary particles (n) each consisting of a TiO 2 core and a (Sb, Sn) O 2 coating.
  • the composite pigment consists of primary particles (n) each consisting of a TiO 2 core and a (Sb, Sn) O 2 coating.
  • the composite pigment only up to 5% by weight, based on the total weight of the composite pigment, of foreign constituents which may be contained in interlayers and / or protective layers.
  • the core in the composite pigments used according to the invention may in itself have any conceivable form. However, it has proved to be advantageous, in particular with regard to the electrically conductive properties which lend the composite pigments used according to the invention as an LDS additive to the polymeric plastics provided therewith, if the core has an isotropic form in the composite pigments. These are shapes which are more or less ideal in all directions of the nucleus, viewed from an imaginary center, and are therefore the same, ie have no preferential direction. These include spherical and cube-shaped cores and cores that have irregular, compact granular forms, but also forms of regular or semi-regular polyhedra with n faces (Platonic and Archimedean bodies), where n ranges from 4 to 92.
  • spherical, cube-shaped or regular also apply here to core shapes that are not ideally spherical in the geometrical sense, ideally cube-shaped or ideally regular. Since the cores of the composite pigments are produced in technical processes, technological deviations from the ideal geometric shape, such as rounded edges or surfaces with slightly different size and shape in polyhedral bodies, are also included here.
  • the cores in the composite pigments used according to the invention have a particle size in the range from 0.001 to 10 ⁇ m, preferably from 0.001 to 5 ⁇ m and in particular from 0.01 to 3 ⁇ m.
  • TiO 2 particles are available on the market under the brand names KRONOS (KRONOS Worldwide, Inc.), HOMBITEC (Sachtleben) or Tipaque (Ishihara Corp.).
  • Antimony-doped tin dioxide particles may be obtained, for example, under the name Zelec (Milliken Chemical) or SN (Ishihara Corp.).
  • the primary particles of the composite pigments used according to the invention have a coating which has a layer thickness in the range from 1 to 500 nm, preferably in the range from 1 to 200 nm.
  • the coating contains, as already explained above, at least one functional layer which, depending on the material composition of the core, consists of TiO 2 or (Sb, Sn) O 2 .
  • Intermediate layer (s) or protective layers, if present, are also included in the coating.
  • the above said order of magnitude for the layer thickness of the coating applies both to the coating, which consists only of a functional layer as described above, as well as to the coating, which in addition to the functional layer still one or more intermediate layers and / or protective layers.
  • Particularly preferred is a
  • the proportion of the coating is 20 to 70 wt .-%, based on the total weight of a primary particle and also 20 to 70 wt .-%, based on the total weight of the Kompositpigmentes.
  • This information relates both to a coating which consists only of a functional layer as described above and to a coating which, in addition to the functional layer, also contains one or more intermediate layers and / or protective layers.
  • the core consists of ⁇ 2, the proportion of the coating which at least one functional layer of (Sb, Sn) 0 2 or consists of, more preferably in the range of 35 to 55 wt .-%, in particular in the range of 40 to 50 wt .-%, based on the total weight of a primary particle or on the total weight of the Kompositpigmentes.
  • the proportion of the coating which contains or consists of at least one functional layer of ⁇ 2 is particularly preferably in the range from 45 to 65% by weight, in particular in the range from 50 to 60 Wt .-%, based on the total weight of a primary particle or on the total weight of the composite pigment.
  • the particle size of the composite pigments used according to the invention is in the range from 0.1 to 20 ⁇ m, preferably from 0.1 to 10 ⁇ m and in particular from 0.1 to 5 ⁇ m. Particular preference is given to composite Pigments with particle sizes in the range of 0.1 to 1 pm with a D 90 - value in the range of 0.70 to 0.90 pm used.
  • All of the above 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, wherein advantageously both the nominal
  • Particle size of the individual particles and their percentage particle size distribution can be determined. All particle size determinations carried out in the present invention are determined according to the laser diffraction method with a Malvern 2000 instrument from Malvem Instruments Ltd., UK, according to standard conditions of ISO / DIS 3320. The layer thickness of the respective coating is determined numerically using SEM and / or TEM images.
  • the composite pigments used according to the invention are prepared by methods known per se.
  • the starting particles used as cores are provided with a coating which contains at least one functional layer in one of the abovementioned compositions, but preferably consists only of this functional layer. Since it is inorganic in each case
  • precursor materials for the metal oxides to be obtained are added in dissolved form to the aqueous suspension of the respective core materials and precipitated at appropriately adjusted pH on the cores, generally in the form of the metal oxide hydrates.
  • the metal oxide hydrates are treated by treatment with elevated Temperature converted into the corresponding oxides.
  • the coating of the cores with the optionally applied intermediate and / or protective layers can be carried out in the same way, as long as they are inorganic layers.
  • Organic post coats are also made by the methods commonly used in the art, in particular by directly contacting the surfaces of the composite particles with the corresponding organic materials in a suitable medium.
  • the composite pigments used according to the invention are prepared as follows:
  • Almost spherical TiO 2 particles of the desired size are mixed with demineralized water to form a suspension which is heated with stirring to a temperature in the range of 70 to 90 ° C.
  • an acid for example hydrochloric acid
  • the pH of the suspension is adjusted to a value in the range of 1.5 to 2.5.
  • a hydrochloric acid solution of tin-antimony chloride in the desired composition is added to the suspension while keeping the pH constant with a base, for example sodium hydroxide solution.
  • the pH is raised to a value of> 2.5 to 7.0 and stirred.
  • the product is filtered off, washed, dried and annealed in the temperature range of 500 ° C to 900 ° C for 0.5 to 2 hours.
  • the product can optionally be sieved.
  • a composite pigment of TiO 2 cores with a coating of (Sb, Sn) O 2 is obtained.
  • the coating of (Sb, Sn) O 2 core particles with TiO 2 can be carried out in an analogous process in aqueous suspension at a pH in the range from 1.5 to 2.5 with suitable titanium salts, for example with TiCl 4 .
  • the composite pigments described are in the respective polymeric composition 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 .-%, respectively based on the total weight of the polymeric composition. They may also be used in blends with other prior art known LDS additives in the LDS-enabled polymeric composition. In the latter case, the proportion of inventive LDS additive is reduced by the proportion of the other or the other LDS additive. In sum, the proportion of LDS additives is generally not more than the above-mentioned 30% by weight, based on the total weight of the LDS-compatible polymeric composition.
  • the polymeric composition is preferably a thermoplastic polymeric composition which is predominantly composed (generally> 50% by weight) of thermoplastics.
  • Suitable 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), liquid crystal polymers (LCP) or their copolymers or blends, such as acrylonitrile-butadiene-styrene / polycarbonate blend (PC / ABS) or PBT / PET. They are offered by all well-known polymer manufacturers in LDS-suitable qualities.
  • PA polyamides
  • PC polycarbonate
  • PPA polyphthalamide
  • PPO polyphenylene oxide
  • PBT polybutylene terephthalate
  • COP cycloolefin polymers
  • LCP liquid crystal polymers
  • PC / ABS acrylonitrile-butadiene-styrene / polycarbonate blend
  • PET PBT / PET
  • the polymeric compositions which contain the composite pigment used according to the invention as an LDS additive may optionally additionally contain fillers and / or colorants as well as stabilizers, auxiliaries and / or flame retardants.
  • Suitable fillers are, for example, various silicates, Si0 2 , talc, kaolin, mica, wollastonite, glass fibers, glass beads, carbon fibers or the like.
  • Suitable colorants are both organic dyes and inorganic or organic color pigments. Since the LDS plastic compositions provided with the LDS additives according to the invention are very light and thus readily dyeable, virtually all soluble dyes or insoluble color pigments suitable for plastics can be used.
  • the composite pigments used according to the invention which consist of at least 80% by weight, based on the total mass of the composite pigments, of TiO 2 and (Sb, Sn) O 2 , are very well suited as LDS additives and lead to the formation of electrical conduction paths in the polymer body or the polymer-containing coating on the base body of the article to be produced even in the thus added polymeric compositions for the LDS process at a conventional use concentration of 0.1 to 30 wt .-% although the composite pigments as such have a certain electrical conductivity. Furthermore, they have a bright, whitish-gray to bluish-gray intrinsic color, which does not give the stained plastics any disturbing dark intrinsic color.
  • the L * values (brightness values) measured in the ClELab * system are only the
  • Additives according to the invention in a concentration of 2 wt .-%, based on the plastic, containing plastics are greater than 65, measured with a Minolta CR-300. Therefore, the LDS-suitable Plastics containing the LDS additive according to the invention are colored with all the colored colorants as needed, without a large amount of colorants, the effectiveness of the LDS additive reduces or nullifies. At the same time, however, the LDS additives used according to the invention have a high laser activity and, in the case of laser action according to the LDS method, lead to the desired microrough surfaces within the laser structures ablated and carbonized conductive structures, so that a subsequent metallization in good quality is possible.
  • the LDS additive namely a composite pigment which has a TiO 2 core and a coating on the surface of the core which consists of antimony-doped tin dioxide or at least predominantly contains it
  • LDS additive a composite pigment which has a TiO 2 core and a coating on the surface of the core which consists of antimony-doped tin dioxide or at least predominantly contains it
  • the plastic compositions must have a relatively low relative permittivity ⁇ ' ⁇ (ratio of the permittivity, ie the permeability for electric fields, of the medium in comparison to Vacuum) and a low dielectric loss factor tan ⁇ (measure of the energy loss that causes the medium in the electric field) have.
  • Both characteristics are both frequency-dependent and temperature-dependent and should therefore be measured under the conditions of use under which the electronic components to be produced in the LDS process usually work. For high-frequency applications, therefore, measurement conditions at room temperature and at frequencies of at least 1 GHz come into question. When measured at frequencies equal to or greater than 1 GHz, the dielectric loss factor of the LDS-suitable compositions provided with the LDS additives should not exceed 0.01 if these polymeric compositions are to be suitable for HF applications.
  • the present invention also provides a polymeric composition which contains at least one organic polymer plastic and an LDS additive, wherein the LDS additive is a composite pigment which comprises at least 80% by weight, based on the total weight of the composite pigment, of titanium dioxide (Ti0 2 ) and with antimony-doped tin dioxide ((Sb, Sn) 0 2 ).
  • the polymeric composition contains the LDS additive in a proportion of 0.1 to 30 wt .-%, based on the total weight of the polymeric composition.
  • the novel polymeric composition is intended for use in an LDS process (laser direct structuring method) for producing metallized switching structures on three-dimensional plastic basic bodies or plastic-containing coatings bearing three-dimensional basic bodies. It has, without the use of colorants, such a light intrinsic coloration that they can be colored with conventional dyes and / or color pigments as needed, is very well suited for use in high-frequency applications and causes by the addition of the LDS additive according to the invention good metallization of the laser-generated line structures, the laser parameters can be selected in a wide range.
  • the subject matter of the present invention is also an article with a circuit structure produced in an LDS method, the article consisting of a polymer base body or a polymer-containing base body of the article and of metal conductor tracks which lie on the surface of the article
  • the basic body or the polymer-containing coating of the base body contains an LDS additive which consists of Kompositpi- elements which comprise at least 80 wt .-%, based on the total weight of the composite, of titanium dioxide (TiO 2 ) and antimony-doped tin dioxide (Sb, Sn) O.sub.2.
  • Such articles find use, for example, in the telecommunications, medical or automotive industries, where they are used, for example, as electronic components of mobile telephones, hearing aids, dental Instruments, car electronics and the like can be used ,
  • FIG. 1 shows the SEM image of an LDS additive according to the invention according to Example 1
  • the present invention will be explained below by means of examples, but not limited to these.
  • a hydrochloric tin-antimony chloride solution consisting of 264.5 g of a 50% SnCl 4 solution, 60.4 g of a 35% SbCl 3 solution and 440 g of a 10% hydrochloric acid is added slowly, wherein the pH of the suspension is kept constant by simultaneous slow addition of a 32% sodium hydroxide solution. After complete addition is still 5 min. stirred. The pH is then adjusted to a value of 3.0 by addition of 32% sodium hydroxide solution and a further 30 min. stirred.
  • the product is filtered off, washed, dried, at a temperature of 500-900 ° C for 30 min. annealed and screened through a 50 ⁇ sieve.
  • the composite pigment has a bright greenish-gray body color.
  • the ratio Sn.Sb in the coating is 85:15.
  • Measuring instrument of the brand Minolta CR-300 under standard conditions The average values from 5 different measurements are given.
  • mice Mica / (Sb, Sn) 0 2 Iriotec 8825 platelets 64 Comp.4
  • Example 1 balls. Primary part.
  • Example 51 and Iriotec® 8825 are products of Merck KGaA, the particle sizes in Table 1 with respect to the comparative examples are each rounded, in Example 2 according to the invention only 2.5% by weight of the additive are used).
  • LDS additive Cu spinel, material according to Comparative Example 4 and material according to Inventive Example 1 are incorporated into PC / ABS by means of an extruder and test plates are produced from the resulting compound on an injection molding machine.
  • the 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 using a 1064nm fiber laser so that a lower
  • the plating index (according to MacDermid) is given, which is calculated from the quotient of the built-up copper layer of the test material and the built-up
  • Copper layer of the reference material results.
  • Test plates such as those from Application Example 2 are measured with the difference that no laser processing and metallization takes place before the measurement.
  • the permittivity of the materials in different frequency ranges and with different methods is measured.
  • the measurements are carried out at room temperature.
  • an Agilent E4991A impedance analyzer is connected used with a test holder Agilent 16453.
  • the evaluation is carried out with the "Material Measurement Firmware" of the E4991A.
  • a high-quality resonator (cavity resonator in the TE11 mode) is used and the resonant characteristics of the empty resonator and the resonator loaded with the dielectric samples are measured using a network analyzer 'Rhode & Schwarz ZVA measured. The evaluation takes place after
  • the copper spinel commonly used as an LDS additive and the LDS additive according to the invention used according to Example 1 comparable, while coated with antimony doped tin dioxide mica flakes (Comparative Example 4) at frequencies> 1GHz both too high a relative permittivity and a much too high dielectric loss factor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un additif actif dans la structuration directe par laser pour des matières plastiques à structuration directe par laser, une composition polymère contenant un tel additif ainsi qu'un article muni de pistes conductrices métallisées, un corps de base dudit article ou un revêtement polymère situé sur le corps de base contenant un additif de structuration directe par laser du type mentionné.
EP14726515.1A 2013-05-07 2014-05-05 Additif pour matières plastiques à structuration directe par laser Withdrawn EP2995178A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013007750.8A DE102013007750A1 (de) 2013-05-07 2013-05-07 Additiv für LDS-Kunststoffe
PCT/EP2014/001183 WO2014180550A1 (fr) 2013-05-07 2014-05-05 Additif pour matières plastiques à structuration directe par laser

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EP2995178A1 true EP2995178A1 (fr) 2016-03-16

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JP (1) JP6423418B2 (fr)
KR (1) KR102171893B1 (fr)
CN (1) CN105230133B (fr)
DE (1) DE102013007750A1 (fr)
TW (1) TWI632205B (fr)
WO (1) WO2014180550A1 (fr)

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CN105230133A (zh) 2016-01-06
CN105230133B (zh) 2019-01-15
TWI632205B (zh) 2018-08-11
TW201510109A (zh) 2015-03-16
JP6423418B2 (ja) 2018-11-14
DE102013007750A1 (de) 2014-11-13
KR20160005742A (ko) 2016-01-15
JP2016520139A (ja) 2016-07-11
KR102171893B1 (ko) 2020-10-30
WO2014180550A1 (fr) 2014-11-13

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