EP3157991A1

EP3157991A1 - Additive for lds plastics

Info

Publication number: EP3157991A1
Application number: EP15727557.9A
Authority: EP
Inventors: Helge Bettina Kniess; Ulrich Quittmann; Silvia Rosenberger
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2014-06-23
Filing date: 2015-06-01
Publication date: 2017-04-26
Also published as: WO2015197157A1; US20170137611A1; US9982113B2; KR20170021326A; CN106471872A; TW201612225A; DE102014008963A1; JP2017531046A

Abstract

The present invention relates to an LDS-active additive for LDS plastics, to a polymer composition containing such an additive, and to an article having metalized conductive tracks, a polymeric base of the article or a polymeric coating on a base containing an LDS additive of said type.

Description

Additive for LDS plastics

The present invention relates to an LDS-active additive for LDS plastics, and more particularly to the use of pigments containing doped tin dioxide doped with non-metallic elements as an LDS additive in polymer compositions used for an LDS process be a polymer composition containing such an additive, as well as 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.

Three-dimensional plastic components that carry circuits, so-called MIDs (Molded Interconnect Devices) have been established on the market for years and have contributed significantly to enabling state-of-the-art technologies in many applications, such as in telecommunications, automotive or medical technology. Likewise, they make a significant contribution to the miniaturization and complexity of the individual electronic components in such applications.

There are various methods for producing three-dimensional MIDs, by means of which the basic components made of plastic or plastic-containing coating obtained, for example, by means of 2-component injection molding or hot stamping, are provided with the necessary switching structures. As a rule, this requires product-specific special tools that are expensive to purchase and inflexible in use.

In contrast, the LPDS-developed LDS process (laser direct structuring method) 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. For the production of the plastic base parts simpler methods, such as the 1-component injection molding process are suitable and the cutting of the circuit structures can also be controlled three-dimensionally.

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. At the points in the plastic which are not activated by the laser, the metal compounds remain unchanged. 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 Lackschicht, or the like, be present.

When working with the laser beam, in addition to the future circuit structure, which contains metal nuclei, a micro-rough surface within the circuit structure, which creates the condition that the conductive metal, as a rule, is

Copper, during the subsequent metallization adherent to the plastic can anchor. The metallization is then usually in electroless copper baths, which can be followed by another order of nickel and gold layers, also in electroless baths. However, it is also possible to apply other metals such as tin, silver and palladium, if appropriate in combination with, for example, gold. Subsequently, the thus pre-structured plastic components are equipped with the individual electronic components.

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

Coating itself. As additives in the past, therefore, additives have generally been proposed in the past which themselves do not have electrical conductivity and do not impart such to the base material. Originally, non-conductive organic heavy metal complexes were provided as LDS additive, which are especially palladium-containing

(EP 0 917 597 B1).

In EP 1 274 288 B1, 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. However, organic Pd complexes or copper spinels have the

Disadvantage that they themselves have a dark inherent color and give plastics that contain them, also a dark color. Furthermore in particular, the copper compounds cause a partial degradation of the surrounding plastic molecules. Especially for MIDs that are to be used in telecommunications, however, there is an increased demand for plastics which have a light inherent color, so that they can be colored with all the desired colored shades without the addition of color pigments are made with such a large mass fraction must be such that the effectiveness of the LDS additives is disturbed or weakened. In addition, the degradation of the plastic base is undesirable.

In order to make plastics with a light inherent color accessible to the LDS method, WO 2012/126831 has therefore proposed LDS-compatible plastics and a corresponding LDS method, in which an LDS additive containing antimony-doped tin dioxide is added and an L * value in the ClELab color space

(Brightness) of at least 45. Preferably, antimony doped tin dioxide coated mica is used in amounts of from 2 to 25

% By weight, based on the total weight of the plastic. Of

Furthermore, white color pigments can additionally be added for even brighter coloring of the plastic compound.

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.

Although the addition of LDS additives containing antimony-doped tin dioxide leads to bright, readily-dyeable plastics that can be directly provided with metal line structures by LDS processes, the use of antimony as a dopant in some countries administrative constraints because of the fear of damage to the environment that could occur, in particular, in the manufacture or recycling of the corresponding joints or components containing them. The same restrictions apply country-specifically in part to compounds containing other heavy metals.

There was therefore still a need for plastics which are suitable for the LDS process and have a light inherent color. In particular, there has been a demand for suitable antimony-free LDS additives for plastics, which are preferably additionally suitable for HF, wherein the LDS additives should preferably have the least possible amount of various heavy metals. Of course, all other requirements for an LDS additive must be met, namely the activability by laser radiation, the release of metal nuclei by the laser bombardment and the formation of a microrough surface by the laser beam as the basis for the subsequent metallization.

The object of the present invention is therefore to provide an antimony-free LDS additive for LDS plastics which, due to its light inherent coloration, enables the production of light LDS plastics which can easily be colored with small amounts of colorant admixtures in multicolored colors, which imparts dielectric or only so little electrically conductive properties to the plastic provided therewith, that this plastic is suitable for high-frequency applications, which prevents the decomposition of the surrounding plastic matrix as far as possible and which, moreover, ensures good metallizability of the circuit structures obtainable in the LDS method when using the widest possible range of laser parameters. In addition, the LDS additive in addition to tin should contain no further heavy metal. 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 pigments containing doped tin dioxide as LDS additive (laser direct structuring additive) in a polymeric composition, wherein the doping consists of one or more non-metallic elements.

Furthermore, 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 contains pigments containing doped tin dioxide, wherein the doping consists of one or more non-metallic elements ,

In addition, the object of the invention is achieved by an article having a circuit structure produced in an LDS method, consisting of a plastic base body or a plastic-containing coating having base body as well as on the surface of the base body or the coating metal conductor tracks, wherein the plastic base body or the plastic-containing coating of the base body contains an LDS additive containing pigments containing doped tin dioxide, wherein the doping consists of one or more non-metallic elements.

Pigments containing or consisting of tin oxide doped with non-metallic elements are known per se. They have an electric Conductivity and also give the coatings or plastics that contain them in sufficient concentration, an electrical conductivity. Therefore, they are commonly used as antistatic agents in coatings and plastics. However, they are equally for the

Formation of electrically conductive layers in displays and solar cells suitable, for example, as a replacement for the high-priced ITO (indium-doped tin oxide).

Surprisingly, however, it has now been found that pigments containing a tin dioxide doped with non-metallic elements are very well suited as an LDS additive in a polymeric composition.

The present invention therefore relates to the use of said pigments as LDS additive in polymeric compositions for use in the LDS process.

As non-metallic elements for doping the tin dioxide, the elements fluorine, iodine, bromine, chlorine, boron, nitrogen or phosphorus are most suitable according to the invention, either alone or in combination of at least two of these. The elements are preferably used alone or in the combinations fluorine / nitrogen or fluorine / phosphorus. Particularly preferred is a doping with fluorine as the only doping element. The LDS additive pigments used according to the invention, which contain the tin dioxide doped with the non-metallic elements, can be of different composition.

In a first, simplest embodiment, the LDS additive pigments used according to the invention consist of the tin dioxide doped with non-metallic elements. In this embodiment, the pigments may be used both as the primary particles of the moon-dispersed type and in the form of Agglomerates are present. They have particle sizes in the range of 0.001 to 100 μηι, preferably in the range of 0.01 to 50 pm and in particular in the range of 0.1 to 30 μιη, based on primary particles. According to the invention, agglomerates generally have particle sizes in the range from 1 to 100 μm, preferably from 5 to 50 μm, and in particular from> 5 to 30 μm.

The corresponding particle sizes are selected according to the main requirements of the respective application. Thus, smaller particle sizes in the range of up to 5 pm are particularly suitable when highly transparent, almost colorless particles are desired, which can impart the desired color neutrality to the feed medium, whereas particle sizes of greater than about 5 pm increasingly lead to a greater roughness with lead to the laser machined surfaces and thus to a better adhesion of the subsequently applied, electrically conductive metal layer (plating index), but with a slight loss in the brightness of the plastics go along.

With respect to the particle shape, the above-described pigments are not limited. They may, for example, be spherical, oval, rod-shaped, platelet-shaped or in the form of regular or irregular polygons (granules). Preference is given to round shapes, with "spherical" and "oval" of course not the exact geometric definition, but the technically achievable form.

Pigments of the type described above are known and commercially available. They can, for example, according to the DE 4006044 A1,

EP 627385 A1 or JP 5181322 B are produced.

In a second embodiment, the LDS additive pigments used according to the invention consist of a substrate and one on the Substrate located coating. The coating preferably completely or at least partially envelops the substrate.

In this embodiment, this is with non-metallic

Elements doped tin dioxide preferably in the coating.

Suitable substrates for the last-mentioned variant of the second embodiment are both silicate materials and, preferably, known white pigments. Suitable silicate materials are, for example, talc, kaolin, natural or synthetic mica, feldspar, wollastonite, natural or synthetic silicon dioxide or else various barite. Of these, mica and silica are particularly preferred. Zinc sulfide and titanium dioxide, which may be present in the anatase as well as, preferably, in the rutile modification, as well as various potassium titanates (K 2 O 6 T 1 O 2, K 2 O 8 T 1 O 2) are used in particular as white pigments.

For the use according to the invention as LDS additive, the abovementioned substrates have a coating which contains doped tin dioxide which is doped with non-metallic elements. In this case, the coating can be formed in one or more layers. If it is multi-layered, at least one of the coating layers must consist of the doped tin dioxide. As a rule, this coating layer will be the layer formed on the surface of the pigment, while one or more intermediate layers may be present between the substrate and the doped tin dioxide-containing coating layer. Preferably, the

Coating on the substrate formed in one layer and consists of the doped tin dioxide.

As a rule, the coating has a geometric thickness in the range from 1 to 300 nm, in particular from 10 to 200 nm. Pigments of this type are also known and commercially available. They can be, for example, described in DE 4237355 A1, DE 10051872 C2, EP 1647997 A1, EP 567868 A1 and JP 5071621 B.

Produce process.

Due to the comparatively high percentage by weight of the substrates very bright LDS additives can be obtained in this way, which lead to a very bright color in the plastics provided with it. At the same time, the proportion of the doped tin dioxide layer which is at least 10% by weight, preferably 20 to 70% by weight, based on the weight of the total pigment, is sufficient to produce the necessary sensitivity for the laser radiation in the plastics and subsequent metallization to allow the laser-defined structures.

The inventively used LDS additive pigments of the second embodiment have particle sizes in the range of 2 to 100 μητι, in particular of> 5 to 50 μιτι, preferably from 6 to 30 pm on. The outer shape of the pigments is determined by the shape of the substrates used. These can be formed isotropically (without preferential direction) or anisotropically (with preferred direction) and are usually in the form of spheres, oval bodies, rods, platelets or as granules, as already described above for the carrier-soluble pigments. All previously 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. Preferred is a device of the type

Malvern 2000 from Malvern Instruments Ltd., UK, used under standard conditions of ISO / DIS 13320. The non-metallic element-doped tin dioxide, whether used in pure form or as a coating on a substrate, is a material in which the molar percentage of doping elements, relative to tin, is from 1 to 20 moles -%, preferably from 1 to 15 mol%, based on the total molar mass of doping elements and tin, is. In the case of doping with a plurality of said non-metallic elements, for example of fluorine in combination with nitrogen or phosphorus (F / N or F / P doping), the total molar fraction of all doping elements is likewise in the abovementioned range. In the case of an F / N or F / P doping, the fluorine content in each case is significantly higher than the proportion of nitrogen or phosphorus.

The described, with non-metallic elements doped tin dioxide pigments 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 .-%, each based on the total weight of the polymeric composition. They can also be used in mixtures with other LDS additives known from the prior art in the LDS-compatible 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 usually not more than the above-mentioned 30 wt .-%, based on the total weight of the LDS-capable polymeric composition. Preferably, the pigments containing non-metallic elements doped with tin dioxide are used as the only LDS additive in the LDS suitable polymeric compositions. Particularly when using tin dioxide doped with fluorine as the sole doping element, the resulting pigment, when used as an LDS additive, has a particularly high selective sensitivity (absorption capacity) to IR radiation with which many laser devices operate. Therefore, in fluorine-doped tin dioxide-containing pigments, the concentration of these LDS additives in the polymeric composition tends to be reduced (> 1 to 5 wt .-%), which at the same time leads to a very light color of the plastic composition with good plating behavior. The polymeric composition can be either a thermoplastic or a thermosetting polymeric composition. Depending on the desired application of the polymeric LDS-suitable materials, either the thermoplastic or the thermosetting composition may be preferred in each case.

In this case, both the corresponding thermoplastic and the thermosetting polymeric composition to a predominant proportion (usually> 50 wt .-%) of thermoplastic or thermosetting plastics see composite.

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.

As thermosetting plastics in particular different polyurethanes, melamine resins, phenolic resins, polyesters and epoxy resins are suitable.

The incorporation of the LDS additives described in the invention into the polymeric composition can be carried out, for example, by compounding, via masterbatches, pastes or by direct addition in the shaping processing step. In addition, the polymeric compositions containing the doped pigments used according to the invention as LDS additive may optionally contain additional fillers and / or colorants and stabilizers, auxiliaries and / or flame retardants.

Suitable fillers are, for example, various silicates, S1O2, 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 used according to the invention are very light and thus readily dyeable, virtually all soluble dyes suitable for plastics or insoluble color pigments can be used. As examples, only the especially frequently used white pigments ΤΊΟ2, ZnO, BaSÜ4 and CaCO3 should be mentioned here. The amount and type of added fillers and / or colorants is limited only by the particular concrete material properties of the individual LDS-suitable compositions, in particular the plastics used.

It has surprisingly been found that the doped pigments used according to the invention, which contain at least 10% by weight, based on the total mass of the pigments, of tin dioxide doped with non-metallic elements, in particular of F, I, Br, Cl, B, N and / or P doped tin dioxide exist, are very suitable as LDS additives and also in the offset therewith polymer compositions for the LDS process at a conventional use concentration of 0.1 to 30 wt .-% not for the formation of electrical Guide paths in the polymeric body or the polymer-containing coating on the body of the article to be produced, although the pigments as such have their own electrical conductivity. Therefore, those with the T EP2015 / 001105

- 14 - inventively used LDS additive provided polymers

Compositions also suitable for high frequency applications. Since the LDS additives according to the invention selectively react (absorb) selectively on laser beams in the IR range (infrared wavelength range of light with wavelengths greater than 780 nm), their mass fraction in the polymeric composition can be located in the lower range of the stated proportions or in return the laser energy is lowered. Furthermore, they have a light, whitish-gray to pale gray intrinsic color, which gives the staggered art fabrics no disturbing dark intrinsic color. Therefore, the LDS-suitable plastics containing the LDS additive according to the invention can be 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 carbon structures ablated and carbonized by the laser beam, so that a subsequent

Metallization in good quality is possible. In this case, an excellent metallization is possible under best conditions as well as, very surprisingly, a very good metallability with a wide range of different laser settings. Thus, for the LDS method, the conditions that are most suitable for the laser action which are actually present can be selected in each case without any quality dips being to be expected in the subsequent metallization. In addition, their use as LDS additive in plastic-containing polymer compositions also does not lead to a degradation of the organic polymer molecules surrounding the composite pigments. In addition, they are free of antimony and, except tin, other heavy metals (provided that all metals are considered to be heavy metals whose density is> 5g / cm ³ ). The present invention also provides a polymeric composition containing at least one organic polymeric plastic and an LDS additive, wherein the LDS additive contains pigments containing doped tin dioxide, and wherein the doping consists of one or more non-metallic elements. In this case, the non-metallic elements are preferably selected from fluorine, iodine, bromine, chlorine, boron, nitrogen and phosphorus, either individually or in a mixture of at least two of these. Particular preference is given to using a fluorine-doped tin dioxide (FTO). The doped with non-metallic elements tin dioxide can be in particulate form directly as

Pigment are used or else present as part of a pigment, which is composed of a substrate and a coating. In this case, the doped tin dioxide is usually in the coating on the substrate; Preferably, the coating is wholly or partially composed of the doped tin dioxide. The polymeric composition of the invention contains the LDS additive in a proportion of 0.1 to 30 wt .-%, preferably from 0.5 to 15 wt .-%, and in particular> 1 to 10 wt .-%, based on the total weight the polymeric composition.

Details regarding the material composition of the LDS additive, the polymer materials used and any auxiliary substances and additives such as fillers, colorants and the like have been described above. This is referred to here.

The polymeric composition according to the invention is intended for use in an LDS process (laser direct structuring method) for producing metallized switching structures on three-dimensional plastic base bodies or plastic-containing coatings bearing three-dimensional basic bodies. It is, without the use of colorants, so bright a color on their own that it can be colored with conventional dyes and / or color pigments as needed, is 01105

- 16 - well suited for use in high-frequency applications and causes by the addition of the LDS additive according to the invention a good

Metallisierbarkeit the laser-generated line structures, the laser parameters can be selected in a wide range. In this case, the added LDS additive is free of antimony and contains no tin other metal components.

The present invention is also an article with a circuit structure produced in an LDS method, wherein the article consists of a polymeric base body or a polymer-containing coating having base body of the article and metallic interconnects, which on the surface of the body or are on the surface of the polymer-containing coating of the base body, wherein the polymeric base body or the polymer-containing coating of the base body contains an LDS additive containing pigments containing tin oxide doped with non-metallic elements. The non-metallic elements used are preferably fluorine, iodine, bromine, chlorine, boron, nitrogen and / or phosphorus. Such articles, in particular articles made of organic thermoplastic or thermosetting plastics, are used, for example, in telecommunications, medical technology or in the automotive industry, where they are used, for example, as electronic components of mobile phones, hearing aids, dental

Instruments, car electronics and the like can be used. Fig. 1: shows the absorption curve of a plastic plate with a

Content of 0.1% by weight FTO

The present invention will be explained below by means of examples, but not limited to these. Example 1 :

A) Preparation of a pigment with FTO (F.SnO 2) layer on a TiO 2 support material:

The preparation of the pigment is carried out according to Example 1

DE 4237355 A1:

156.7 g of stannous fluoride are dissolved in 31 parts of water. 80 g of titanium dioxide particles (particle size 100-300 nm) are added to this solution with vigorous stirring. The dispersion is at 85 to 90 ° C

heated. At a pH of 3.5 to 4.5, a solution of 260.5 g of tin tetrachloride in 943 ml of ethanol is added dropwise. During the addition, the pH is kept constant by simultaneous addition of 5% ammonia solution. After completion of the SnCU addition, the temperature is kept constant for one hour and then filtered. The filter cake is washed several times with water. After the product has dried, it is annealed at 500 ° C. The annealing time is 10 minutes.

B) Preparation of a pigment from FTO

The preparation of the pigment is carried out according to Example 2

DE 4006044 A1:

In a mortar mill, 250 g of stannous oxide, 14.75 g of stannous chloride and 14.75 g of stannous fluoride are intimately mixed by grinding for 10 minutes. The mixture of substances thus obtained is calcined in a corundum shell at 300 ° C. for 1 hour. After cooling, the resulting light gray, electrically conductive, doped tin oxide is ground again for 10 minutes in a mortar mill, Application as LDS additive:

By means of a co-rotating twin-screw extruder, 5% by weight of the LDS additive prepared in accordance with procedure B) is incorporated into PC / ABS (Xantar C CM 406, Mitsubishi Engineering Plastics). The extrudate is strand granulated and then dried at 100 ° C for 4 hours. Thereafter, test plates of dimensions 60 × 90 × 1.5 mm are injection-molded 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 by means of a 1064nm fiber laser, so that a low material removal occurs with simultaneous carbonation of the machined surface. Subsequently, the metallization is carried out with copper in a commercially available reductive copper bath (MID Copper 100 B1, MacDermid). The metallization properties are judged by the structure of the copper layer on the substrate. The plating index (according to MacDermid) is given, which results from the quotient of the built-up copper layer of the test material and the built-up copper layer of the reference material. As reference material are test plates made of PBT with a share of 5 wt .-% copper spinel (reference).

Comparative Example 1

Analogously to Example 1, 5% by weight of a pigment is incorporated as an LDS additive into the PC / ABS test plates, the pigment having an antimony-doped tin dioxide layer on a mica substrate. The pigment is a product of Merck KGaA, which is commercially available under the name Iriotec® 8825. EP2015 / 001105

- 19 -

Laser adjustment plating index

Cu Spinel Comp.ex.1 Ex.

(Reference)

3W / 60 kHz 0.41 0.00 0.00

4W / 60kHz 0.56 0.00 0.00

5W / 60 kHz 0.65 0.00 0.00

6W / 60 kHz 0, 71 0.00 0, 15

8W / 60 Hz 0.69 0, 15 0.65

4W / 80 kHz 0.65 0.00 0.00

6W / 80 kHz 0.83 0.00 0.00

8W / 80 kHz 0, 76 0.00 0.36

10W / 80kHz 0, 73 0.00 1.02

12W / 80 kHz 0, 70 0, 16 0.93

14W / 80 kHz 0.63 0.54 0.81

6W / 100 Hz 0.88 0.00 0.01

8W / 100 kHz 0, 79 0.00 0, 18

10W / 100Hz 0, 70 0.00 0.86

12W / 100 kHz 0.68 0.00 0.93

14W / 100 kHz 0, 72 0.34 0.85

16W / 100 kHz 0.67 0, 75 0, 83

The experiments show that the fluorine-doped tin dioxide used according to the invention as an LDS additive exhibits significantly better values in terms of metallizability both in the width of the laser parameters and in terms of the nominal values of the plating index than the antimony-doped tin dioxide-coated mica flakes according to Comparative Example 1, in the peak values with the Cu spinel (reference)

is comparable and shows very good metallization especially at higher laser power.

Claims

claims

1. Use of pigments containing doped tin dioxide as LDS additive (laser direct structuring additive) in a polymeric composition, characterized in that the doping consists of one or more non-metallic elements.

2. Use according to claim 1, characterized in that the doping of one or more of the elements fluorine, iodine, bromine, chlorine, boron, phosphorus and nitrogen is selected.

3. Use according to claim 1 or 2, characterized in that the tin dioxide is doped with fluorine.

4. Use according to claims 1 to 3, characterized

in that the pigments consist of the doped tin dioxide or contain it in an amount of at least 10% by weight, based on the weight of the total pigment.

5. Use according to claim 4, characterized in that the pigments each consist of a substrate and one located thereon

Coating exist and the doped tin dioxide in the

Coating is included.

6. Use according to claim 5, characterized in that the substrate has an isotropic or anisotropic form.

7. Use according to one or more of claims 5 and 6, characterized in that the substrate consists of a silicate material, zinc sulfide, titanium dioxide or potassium titanate and has a coating containing doped tin dioxide.

8. Use according to one or more of claims 1 to 7, characterized in that the doped tin dioxide a percentage molar proportion of doping elements of 1 to 20 mol%, based on the total molar mass of tin and doping element (s) having.

9. Use according to one or more of claims 1 to 8, characterized in that the pigments have a particle size in the range of 0.001 to 100 pm.

10. Use according to one or more of claims 1 to 9, characterized in that the pigments in the polymeric

Composition in a proportion in the range of 0.1 to 30% by weight, based on the total weight of the polymeric

Composition, present.

11. Use according to one or more of claims 1 to 10, characterized in that the polymeric composition contains in addition to the LDS additive at least one organic polymeric plastic and optionally fillers and / or colorants.

12. Use according to one or more of claims 1 to 11, characterized in that the doped tin dioxide is present in a mixture with other conventional LDS additives in the polymeric composition.

13. A polymeric composition containing at least one organic polymeric plastic and an LDS additive, the LDS additive containing pigments containing doped tin dioxide, the dopant being one or more non-metallic elements.

14. A polymeric composition according to claim 13, characterized

characterized in that the LDS additive in a proportion of 0.1 to 30

Wt .-%, based on the total weight of the polymeric composition, is contained in the polymeric composition.

Polymer composition according to claim 3 or 14, characterized in that the polymeric composition is a thermoplastic or thermosetting material.

16. Article having a circuit structure produced in an LDS method, consisting of a plastic base body or a plastic-containing coating having base body and located on the surface of the base body or the coating metallic interconnects, wherein the plastic base body or the plastic-containing coating of the base body an LDS additive containing pigments containing doped tin dioxide, wherein the doping consists of one or more non-metallic elements.