KR20160005742A - Additive for lds plastics - Google Patents

Abstract

The present invention relates to an LDS-active additive for LDS plastics, a polymer composition containing such additive, and a metallized conductor track containing the LDS additive of the type, an article having a polymeric coating on the polymeric base or base of the article will be.

Description

Additives for LDS Plastics {ADDITIVE FOR LDS PLASTICS}

The present invention relates to the use of LDS-active additives for LDS plastics, and in particular composite pigments consisting mainly of titanium dioxide and antimony-doped tin dioxide as LDS additives in polymer compositions used in LDS processes, And a polymeric basic body of the article or a polymeric coating on a basic body having a metallized conductor track comprising an LDS additive of this type.

Three-dimensional plastic parts with circuits, so called MIDs (molded interconnection elements), have been recognized in the market for many years and have been recognized for their many applications, for example in the field of telecommunications, automotive construction or medical technology. Which is a crucial factor. At the same time, this has contributed significantly to the miniaturization and complexity of the individual electronic components in the workpiece.

There are various manufacturing methods of three-dimensional MIDs, whereby basic parts with plastics or plastic-containing coatings obtained, for example, by two-component injection molding or hot embossing, / RTI > In general, this requires a special product-specific mold, which is expensive to purchase and inflexible in use.

In contrast, the LDS process (laser direct structuring process) developed by LPKF is a process whereby the circuit structure is directly and individually adapted by a laser beam to a plastic base coating on a plastic base or base, It can be cut with water and then metallized.

A simpler process, for example a one-component injection-molding process, is suitable for the production of plastic bases, and the cutting of the circuit structure can also be three-dimensionally controlled.

So-called LDS additives must be added to the plastic base or the plastic-containing coating in order to be able to obtain a circuit structure that can be metallized by a laser beam. These additives must react to laser radiation and be ready for subsequent metallization at the same time. The LDS additive is generally a metal compound that is activated during processing by the laser beam in the laser-processing region in such a way that the metal nuclei favor the subsequent deposition of an electrically conductive metal for the formation of an electrical circuit at the point of activation of the plastic . At the same time, these metal compounds react in a laser-actuated (generally laser-absorptive) manner and ensure that the plastic is removed and carbonized in the laser-treated area so that the circuit structure is engraved on the plastic base. The metal compound remains unchanged at the point of the plastic that is not activated by the laser. The LDS additive may be added to the plastic material as a whole before shaping to produce the plastic base, or alternatively only the circuit structure may be cut by a laser beam as a component into a separate plastic-containing layer, coating, It can exist only on the surface.

In processing by a laser beam in addition to the future circuit structure containing metal nuclei, a microrough surface also occurs in the circuit structure, which can fix itself to the plastic with strong adhesion during subsequent metallization It is a requirement for conductive metals, generally copper.

The metallization is generally carried out subsequently in a current-free copper bath, here followed by the further application of a nickel and gold layer in a no-current bath. However, other metals such as tin, silver and palladium may also optionally be applied with, for example, gold. In this way, the pre-structured plastic parts are then fitted with individual electronic components.

The purpose of the LDS process consists in creating a three-dimensional electrically conductive circuit structure on a basic body having a three-dimensional plastic basic body or a plastic-containing coating. Needless to say, for this purpose, only the resulting metallization circuit structure may have electrical conductivity, and the plastic base body or coating itself is not. Thus, the LDS additives proposed in the past are generally additives that do not themselves have electrical conductivity and do not impart electrical conductivity to the base material.

Originally, nonconductive organic heavy metal complexes containing, in particular, palladium (EP 0 917 597 B1) were intended as LDS additives.

In EP 1 274 288 B1, a nonconductive inorganic metal compound which is insoluble in the application medium and is an inorganic metal compound of the metals d and f of the periodic table and of the nonmetal group is added to the plastic as an LDS additive. Copper compounds, especially copper spinel, are preferably used.

However, organic Pd complexes or also copper spinels have the advantage that they have a dark intrinsic color itself and also give a dark color on the plastic containing it. Copper compounds also affect the partial deterioration of the surrounding plastic material, in particular. However, an increase in the number of plastics that can be painted in any desired hue without the need to add colored pigments at a large weight ratio, especially where the MIDs used in telecommunications have light intrinsic colors and in which the efficacy of the LDS additive is adversely affected or weakened There is a demand. Further, deterioration of the plastic base is not preferable.

EP 2 476 723 A1 accordingly proposes tetoalumimosilicate (zeolite) as an LDS additive for plastics in order to produce plastics with a light inherent color usable for LDS processes.

WO 2012/126831 discloses a corresponding LDS process which comprises plastic and antimony doped tin dioxide suitable for LDS and adds an LDS additive with an L ^* value (emission) of 45 or more in the CIELab color space. The mica coated with antimony-doped tin dioxide is preferably used in an amount of from 2 to 25% by weight based on the total plastic material. In addition, white colored pigments may also be added for uniform, lighter coloring of the plastic material.

WO 2012/056416 also discloses a composition comprising from 0.5 to 25% by weight of a metal oxide-coated filler, wherein the latter is preferably mica coated with antimony-doped tin dioxide. The LDS plastic material has an L ^* value of 40 to 85. Color pigments can also be added to plastic materials as well.

Mica flakes coated with antimony-doped tin dioxide are generally used as electroconductive pigments in a wide variety of applications where, for example, plastic materials are provided with antistatic properties. The pigments of the composition also serve as additive for plastics provided with laser engraving, in which the mica coated with antimony-doped tin dioxide absorbs ordinary laser radiation and the stored heat passes through the plastic material surrounding the pigment and makes it black . The use of mica coated with antimony-doped tin dioxide as an LDS additive in corresponding plastic materials suitable for LDS can thus also yield the formation of a conduction path if the critical use concentration is exceeded. Conductive plastics, however, are less suitable for use in LDS processes, which can significantly impair the electrical conductivity of circuit structures applied to plastic bases and that the resulting MIDs require rigid requirements for their dielectric properties, (HF applications), integrated antennas, or electronic devices for use in WLAN systems.

In order to obtain plastics with a sufficiently good dielectric value in polymeric materials which are suitable for LDS processes and in which electronic components suitable for HF can be obtained, for example in US 8,309,640 B2, having a dielectric constant of at least 25 measured at 900 MHz It has been proposed to add a ceramic filler to the thermoplastic material in addition to the appropriate LDS additive. However, since the LDS additive used here is already the common copper compound mentioned above, such LDS-compliant plastics are dark-colored in black, however, even though they have good dielectric values.

There is therefore still a need for plastics that are suitable for LDS processes and have light intrinsic colors and which have sufficiently high dielectric constants in polymeric materials that they can be used in high frequency applications. In particular, there has been a demand for LDS additives suitable for plastics. Naturally, all other requirements of the LDS additive, namely the ability to be activated by laser radiation, the formation of micro-rough surfaces by the laser beam as the basis for the glass and subsequent metallization of the metal nucleus by laser impact must be satisfied here.

It is therefore an object of the present invention to enable the production of a light LDS plastic which can be easily colored using a small amount of a chromatic colorant mixture through its light intrinsic color and to provide a dielectric or only a slight electrical conductivity to the provided plastic (Such plastics are suitable for high frequency applications), where possible, to prevent deterioration of the surrounding plastic matrix, and also to enable the use of the best possible metallization of the circuit structures available in the LDS process And an LDS additive for LDS plastics which enables harmony.

It is a further object of the present invention to provide a polymeric composition suitable for LDS processes and having the properties described above.

It is a further object of the present invention to provide an article having a circuit structure fabricated in an LDS process and having the above-mentioned characteristics.

It is an object of the present invention to provide a pigment composition comprising 80% or more by weight of titanium dioxide (TiO ₂ ) and antimony-doped tin dioxide ((Sb, Sn) O ₂ ). ≪ / RTI >

An object of the present invention can also be achieved by a polymeric composition comprising at least one organic polymeric plastic and the LDS additive, wherein the LDS additive is more than 80% by weight of titanium, based on the total weight of the composite pigment dioxide (TiO _2), and antimony -Doped tin dioxide ((Sb, Sn) O ₂ ).

It is also an object of the present invention to provide a circuit structure made by an LDS process, which comprises a basic body of an article having a polymeric basic body or a polymer-containing coating of the article and a metallic conductor track disposed on the surface of the basic body achieved by a product, wherein the polymeric base body, or the polymer of the main body-containing coating is more than 80% by weight of titanium, based on the total weight of the composite pigment dioxide (TiO _2), and antimony-doped tin dioxide ((Sb, Sn ) O < ₂ >).

Composite pigments consisting essentially of titanium dioxide (TiO ₂ ) and antimony-doped tin dioxide ((Sb, Sn) O ₂ ) are used as such, in particular coatings present in the titanium dioxide core and core, antimony-doped tin dioxide In the form of pigments. Such pigments may optionally also have a layer and / or a protective layer between the core and the (Sb, Sn) O ₂ coating. This type of pigment, in which the TiO ₂ core can have a variety of geometric shapes, has long been used as an antistatic agent in coatings and plastics. It has electrical conductivity itself and confer electrical conductivity to plastics or coatings which also contain them in a sufficient concentration. In order to increase such electrical conductivity, pigments in which the TiO ₂ core is needle-shaped are particularly developed recently.

However, surprisingly, based on the total weight of the composite pigment 80% by weight or more of TiO _2, and antimony-doped tin dioxide comprising the composite pigment has been found now is very suitable as the LDS additive in the polymeric composition.

The present invention therefore relates to the use of said composite pigment as an LDS additive in a polymeric composition for use in an LDS process.

The composite pigments used according to the invention have at least one core and a coating arranged in the core. The coating may be composed of one or more individual layers.

In the simplest case, the coating consists of a single, functional layer. The coating may also have one or more interlayers between the core and the functional layer and / or may also have one or more protective layers on the surface of the functional layer.

When the single composite pigment particle consists solely of a single core and a coating disposed on the core, the composite pigment used according to the invention is exclusively composed of primary particles and thus monodisperse. However, a more frequent and thus preferred embodiment is where the composite pigment used is an agglomerate of two or more primary particles, wherein each primary particle has a core and a coating arranged on the core.

In accordance with the present invention, the primary particles can be selected from the group consisting of a layer structure of the ordered core / functional layer, a layer structure of the core / interlayer (s) / functional layer, a layer structure of the core / functional layer / All functional pigments having a layered structure of the functional layer / protective layer (s) can be used. According to the invention, the core or functional layer consists of TiO ₂ or antimony-doped tin dioxide.

Since the core and functional layer in one and the same composite pigment or primary particle are not naturally made of the same material, the composite pigment used according to the invention can have the following composition:

TiO ₂ core / (Sb, Sn) O ₂ layer,

TiO ₂ core / interlayer (s) / (Sb, Sn) O ₂ layer,

TiO ₂ core / (Sb, Sn) O ₂ layer / protective layer (s),

TiO ₂ core / interlayer (s) / (Sb, Sn) O ₂ layer / protective layer (s)

(Sb, Sn) O ₂ core / TiO ₂ layer,

(Sb, Sn) O ₂ core / interlayer (s) / TiO ₂ layer,

(Sb, Sn) O ₂ core / TiO ₂ layer / protective layer (s),

(Sb, Sn) O ₂ core / interlayer (s) / TiO ₂ layer / protective layer (s).

The ratio of the total of the core and the functional layer, namely the total weight of TiO ₂ and antimony-doped tin dioxide, is in each case at least 80% by weight, preferably at least 90% by weight, 95 to 100% by weight. This means that the composite pigment used in a particularly preferred embodiment of the invention consists solely of TiO ₂ and (Sb, Sn) O ₂ or optionally only very small amounts of other components.

Antimony-doped tin dioxide, whether it is used as a core in a coating of primary particles or as a functional layer, has a percentage ratio by weight of antimony to tin of 2 To 35% by weight, preferably from 8 to 30% by weight, in particular from 10 to 20% by weight.

When a layer and / or a protective layer is present, it is predominantly made of an inorganic material in the case of interlayers. A preferred gancheung are metal oxides, in particular _{SiO 2, SnO 2, Al 2} O 3, ZnO, CaO, ZrO 2, Sb is ₂ O _3, or mixtures thereof.

The protective layer which may be present on the surface of the composite pigment used may, by contrast, be inorganic or organic in nature. This applies in general when the use of a composite pigment, i. E. An organic polymeric plastic, here in the application medium is simplified or even at least by a corresponding surface coating. However, it can also be applied to perform any desired color fidelity. For the inorganic protective layer, which preferably _{ZrO 2, Ce 2 O 3,} Cr 2 O 3, CaO, SiO 2, Al 2 O 3, ZnO, TiO 2, SnO 2, antimony-doped SnO _2, Sb ₂ O ₃ , or a corresponding oxide hydrate, and a mixture of two or more thereof.

The organic protective layer generally comprises a suitable organosilane, organotitanate or organozirconate. Suitable components are known to those skilled in the art as agents for surface coating and subsequent coating of effective pigments.

The total proportion by weight of the interlayer (s) and / or protective layer (s) is here not more than 20% by weight, preferably not more than 10% by weight, particularly preferably 0-5% by weight % to be.

In a preferred embodiment of the present invention, the composite pigment used as an LDS additive consists of only one or more primary particles, which in each case contains a functional coating disposed on the core and core, namely TiO ₂ core and (Sb, Sn) O ₂ coating or (Sb, Sn) O ₂ core and a TiO ₂ coating; Most preferred, however, is that the composite pigment is in each case composed of primary particles (s) consisting of TiO ₂ core and (Sb, Sn) O ₂ coating. Optionally, no more than 5% by weight of a foreign constituent, based on the total weight of the composite pigment, is present in the interlayer and / or protective layer.

In the composite pigments used according to the invention, the core may itself be of any possible shape. However, this has proved to be advantageous in relation to the electrical conductivity properties imparted to the polymeric plastics provided therewith, in particular that the composite pigments used according to the invention as LDS additives have a core isotropic shape in the composite pigment. This is a shape that is almost ideally the same in all directions of the core from the viewpoint of the virtual center point, i.e., does not have a preferred orientation. This includes spherical and rectangular parallelepiped cores and cores with irregular, compressed granular shapes, as well as regular or semi regular polygons (Plato and Archimedes bodies) with n faces where n is in the range of 4 to 92.

It is needless to say that the term spherical, rectangular, or regular polygon is also applied to a core shape that is not an ideal spherical shape, an ideal rectangular shape, or an ideal regular polygonal shape in the geometric sense. Since the core of the composite pigment is produced in an industrial process, the geometry is also included here in the case of technically derived deviations from the ideal geometry, for example in the case of surfaces and polyhedra with finished edges or slightly different sizes.

In the composite pigments used according to the invention, the core has a particle size in the range from 0.001 to 10 μm, preferably from 0.001 to 5 μm, in particular from 0.01 to 3 μm.

It consists of TiO ₂ or (Sb, Sn) O ₂ , which is available on the order of magnitude shown. Thus, for example TiO ₂ particles are available under the trade names KRONOS (KRONOS Worldwide, Inc.), HOMBITEC (Sachtleben) or Tipaque (Ishihara Corp.). Antimony-doped tin dioxide particles may be purchased, for example, under the name Zelec (Milliken Chemical) or SN (Ishihara Corp.).

At the surface of the core having the above indicated sizes and material compositions, the primary particles of the composite pigments used according to the invention have a thin coating with a layer thickness in the range from 1 to 500 nm, preferably from 1 to 200 nm.

The coating comprises at least one functional layer consisting of TiO ₂ or (Sb, Sn) O ₂ according to the material composition of the core as already indicated above. The interlayer (s) or protective layer (s), if present, are likewise included in the coating. The magnitude of the aforementioned extent with regard to the layer thickness of the coating is applied here only to the coating comprising the functional layer described above and also to the coating having at least one interlayer and / or protective layer in addition to the functional layer. In particular, a layer-thickness in the range of 1 to 100 nm is preferred for coatings consisting only of (Sb, Sn) O ₂ functional layers.

The proportion of the coating is from 20 to 70% by weight, based on the total weight of the primary particles, and also from 20 to 70% by weight, based on the total weight of the composite pigment. Such data relate only to coatings comprising the functional layers described above, as well as to coatings comprising, in addition to the functional layer, also at least one interlayer and / or a protective layer.

When the core is composed of TiO ₂ , the proportion of coatings comprising or consisting of one or more functional layers of (Sb, Sn) O ₂ is particularly preferably in the range of from 35 to 60% by weight, based on the total weight of the primary particles or on the total weight of the composite pigment 55% by weight, especially 40 to 50% by weight.

When the core is composed of (Sb, Sn) O ₂ , the proportion of coatings comprising or consisting of one or more of the functional layers of TiO ₂ is particularly preferably in the range of from 45 to 60%, based on the total weight of the composite pigment or on the total weight of the primary pigment 65% by weight, especially 50 to 60% by weight.

The particle size of the composite pigment used according to the present invention is in the range of 0.1 to 20 mu m, preferably 0.1 to 10 mu m, particularly 0.1 to 5 mu m. In particular, the use of the composite pigment having a particle size of 0.1 to 1 ㎛ range having a D ₉₀ value in the range 0.70 to 0.90 ㎛ preferred.

All particle sizes shown above can be measured using conventional methods for particle size measurement. Particularly preferred is a method for particle size measurement by a laser diffraction method, wherein the nominal particle size of the individual particles and also their percentage particle size distribution can be advantageously measured. All particle size measurements performed in the present invention are measured by laser diffraction methods using a Malvern 2000 instrument from Malvern Instruments Ltd., UK under standard conditions of ISO / DIS 13320.

The layer thickness of each coating is measured numerically from SEM and / or TEM images.

The composite pigments used in accordance with the invention are prepared by known processes themselves. Here, the starting particles used as cores are provided with a coating comprising one or more functional layers in one of the compositions shown above, but preferably consisting solely of such a functional layer. Since the starting material is an inorganic in each case, the coating of the core with the functional layer is preferably carried out in an aqueous suspension by subsequent conversion to a metal oxide with precipitation of the respective metal oxide or metal oxide hydrate. The precursor material of the metal oxide to be obtained, typically a dissolved salt of the metal salt, is added to the aqueous suspension of the respective core material and precipitated on the core, generally in the form of a metal oxide hydrate at a roughly set pH. The metal oxide hydrate is then converted to the corresponding oxide by treatment at elevated temperature. The coating of the core optionally with the interlayer and / or protective layer to be applied can be carried out in the same way in the case of an inorganic layer. The organic after-coating is likewise carried out by conventional methods in the prior art, in particular by bringing the surface of the composite particles into contact with the corresponding organic material in a suitable medium.

The composite pigments used according to the invention are prepared as follows with reference to the example of a TiO ₂ core provided with a functional coating of antimony-doped tin dioxide:

TiO ₂ particles of a size of substantially spherical desired degree is calculated and the suspension is mixed with minerals and can ride, which is heated to a temperature in the range of 70 to 90 ℃ with stirring. The pH of the suspension is adjusted to a value in the range of 1.5 to 2.5 using an acid, such as hydrochloric acid. The tin antimony chloride solution in the hydrochloric acid solution of the desired composition is added to the suspension and the pH constant is maintained using a base, for example, a sodium hydroxide solution. When the addition is completed, the pH is raised to a value of more than 2.5 to 7.0, and stirring is continued. The product is filtered, washed, dried and calcined at a temperature ranging from 500 ° C to 900 ° C for 0.5 to 2 hours. The product can then optionally be sieved. A composite pigment comprising a TiO ₂ core having a coating of (Sb, Sn) O ₂ is obtained.

By TiO ₂ (Sb, Sn) is suitable titanium salt coatings of O ₂ core particles, for example, be carried out in a similar process in an aqueous suspension at a pH of 1.5 to 2.5 range using TiCl _4.

The described complex pigments are present in each polymeric composition in each case as an LDS additive in an amount of from 0.1 to 30% by weight, preferably from 0.5 to 15% by weight, in particular from 1 to 10% by weight, based on the total weight of the polymeric composition do. It can also be used in polymeric compositions suitable for LDS in admixture with other LDS additives known from the prior art. In the latter case, the proportion of the LDS additive according to the invention is reduced in proportion to the other LDS additive (s). In general, the proportion of the LDS additive is generally less than or equal to 30% by weight based on the total weight of the polymeric composition suitable for LDS.

The polymeric composition is preferably a thermoplastic polymeric composition consisting of a predominant proportion (generally greater than 50% by weight) of thermoplastic.

Suitable thermoplastic resins include, but are not limited to, amorphous and semi-crystalline thermoplastic resins such as various polyamides (PA), polycarbonates (PC), polyphthalamides (PPA), polyphenylene oxides Such as acrylonitrile-butadiene-styrene / polycarbonate blend (PC / ABS) or PBT (polybutylene terephthalate), or copolymers or blends thereof, such as ethylene terephthalate (PBT), cycloolefin polymer / PET. It is commercially available in a quality suitable for LDS from all well known polymer manufacturers.

In addition, the polymeric compositions comprising the composite pigments used according to the invention as LDS additives may optionally further comprise fillers and / or colorants and stabilizers, adjuvants and / or flame retardants.

Suitable fillers are, for example, various silicates, SiO _2, talc, kaolin, mica, wollastonite, glass fibers, glass beads, and carbon fiber.

Suitable colorants are organic dyes and also inorganic or organic colored pigments. The LDS plastic composition provided with the LDS additive according to the present invention is very light and can easily be colored accordingly, so virtually any soluble dye or insoluble colored pigment suitable for plastics can be used. Examples which may be mentioned here are only the white pigments TiO ₂ , ZnO, BaSO ₄ and CaCO ₃ , which are particularly frequently used. The amount and type of filler and / or colorant added is limited here only by the particular composition properties of the individual compositions suitable for LDS, in particular of the plastics used.

Surprisingly, the composite pigments used according to the invention consisting of at least 80% by weight, based on the total weight of the composite pigments, of TiO ₂ and (Sb, Sn) O ₂ are very suitable as LDS additives and even if they contain from 0.1 to 30% In polymeric compositions for LDS processes added at typical use concentrations, even though such a composite pigment has certain electrical conductivity, it may be desirable to provide the polymeric-containing coating or polymeric basic body on a basic body of the article to be produced It does not produce the formation of an electrically conductive path. It also has a pale white-gray to bluish-gray inherent color that does not impart disturbing dark intrinsic color to the plastic to which they are added. The L ^* value (emission value) measured in the CIELab * system of plastics containing additives according to the invention at a concentration of only 2 wt.% Based on plastic is greater than 65 as measured using Minolta CR-300. The LDS-compliant plastics comprising the LDS additives according to the invention can thus be colored with all of the chromic agents without the use of large amounts of colorants which, if necessary, reduce or eliminate the efficacy of the LDS additive. However, at the same time, the LDS additive used in accordance with the present invention has high laser activity and, when applied to a laser in an LDS process, is removed by the laser beam and produces the desired microfine surface within the carbonized conduction structure, . Under the best conditions, excellent metallization is only very surprisingly possible with very good metallizability due to the wide band width of the various laser settings. The conditions for the most suitable laser action in the actual environment can thus be selected for the LDS process in each case and there is no expected reduction in quality in the case of subsequent metallization. A particularly preferred implementation of the LDS additive used the invention, that is, TiO ₂ core and a core of antimony disposed on the surface or composed of a doped tin dioxide, at least when the composite pigment having a coating comprising the same predominantly, composite pigment Does not occur when used as an LDS additive in plastic-containing polymeric compositions.

However, it is particularly surprising that, as already mentioned above, LDS-compliant compositions comprising the LDS additive used according to the invention and which do not otherwise contain further electrically conductive components are used in the high frequency range (HF range, 1-20 GHz) It is a fact that the condition for using is satisfied. To achieve this, the plastic composition should have a relatively low relative dielectric constant epsilon _r (ratio of dielectric constant of the medium compared to vacuum) and a low dielectric loss factor tan delta (the measurement of the energy loss caused by the electric field in the medium). Both parameters are frequency- and also temperature-dependent and must therefore be measured under the conditions of use produced by the LDS process in which the electronic components are generally operated. For high frequency applications, suitable measurement conditions are therefore at frequencies above 1 GHz and at room temperature. The dielectric loss factor of an LDS-compliant composition provided with an LDS additive, measured at frequencies above 1 GHz, should be below 0.01 when such polymeric composition is suitable for HF applications. Polymeric compositions, especially thermoplastic compositions, comprising LDS additives used in accordance with the invention in the amounts mentioned above and not having additional electrically conductive components satisfy the above conditions.

The invention also relates to a polymeric composition comprising at least one organic polymeric plastic and the LDS additive, wherein the LDS additive is more than 80% by weight of titanium, based on the total weight of the composite pigment dioxide (TiO _2), and antimony-doped tin Dioxide ((Sb, Sn) O ₂ ). The polymeric composition herein comprises LDS additive in a proportion of from 0.1 to 30% by weight, based on the total weight of the polymeric composition.

Details of the composition of the LDS additive, the polymeric material used and optional adjuvants and additives present, such as fillers, colorants and the like, have already been described above. A reference to this is made here.

The polymeric compositions according to the present invention are intended for use in an LDS process (laser direct structuring process) for the fabrication of metallized circuit structures on a three dimensional basic body or a three dimensional basic body with a plastic-containing coating. It has a light intrinsic coloration which can be colored as required using conventional dyes and / or colored pigments without the use of colorants, is well suited for use in high frequency applications, and can be obtained through the addition of LDS additives according to the invention It affects the good metallization of the conduction structure produced by the laser beam, where the laser parameters can be selected in a broad spectrum.

The invention also relates to an article having a circuit structure fabricated by an LDS process wherein the article comprises a metallic conductor track disposed on a surface of a primary body and a primary body of the article having a polymer- It made and in which the polymeric base body or the polymer of the basic body as-containing coating is more than 80% by weight of titanium, based on the total weight of the composite pigment dioxide (TiO _2), and antimony-doped tin dioxide ((Sb, Sn) O ₂ ). ≪ / RTI > Such articles, especially articles containing organic plastics, are used, for example, in telecommunications, medical technology or automotive construction, where they are used as electronic components, for example mobile phones, hearing aids, dental devices,

1 shows an SEM photograph of an LDS additive according to the present invention according to Example 1. Fig.

The invention will be described below with reference to an embodiment, but it is not limited thereto.

Example 1:

Preparation of composite pigments:

Realistic spherical TiO ₂ particles (Kronos 2900, manufactured by KRONOS Inc, Inc.) having an average particle size in the range of 100-300 nm (measured by laser diffraction method using a measuring device from Malvern Ltd., UK, Malvern 2000 under standard conditions) 100 g) is heated to 75 DEG C with stirring in 2 l of demineralized water. The pH of the suspension is adjusted to a value of 2.0 using 10% hydrochloric acid. A solution of tin antimony chloride in hydrochloric acid consisting of 264.5 g of 50% SnCl ₄ solution, 60.4 g of 35% SbCl ₃ solution and 440 g of 10% hydrochloric acid was then slowly weighed and the pH of the suspension was adjusted to 32% sodium hydroxide solution Is slowly added at the same time and kept constant. When the addition is complete, the mixture is stirred for an additional 15 minutes. The pH is then adjusted to a value of 3.0 by the addition of a 32% sodium hydroxide solution, and the mixture is stirred for an additional 30 minutes.

The product is filtered, washed, dried, calcined at a temperature of 500-900 ° C for 30 minutes, and sieved through a 50 μm sieve.

A composite pigment comprising TiO ₂ and (Sb, Sn) O ₂ having a particle size in the range of 0.1 to 1.7 μm with a D ₅₀ value of 0.18 μm and a D ₉₀ value of 0.74 μm is obtained. The composite pigment has a light green-gray mass tone. The Sn: Sb ratio in the coating is 85:15.

Use case 1:

Minolta Co., Ltd. Measurement of luminescence values corresponding to L * in a CIELab * system, measured using a Minolta CR-300 measuring device from the company:

5% by weight of the LDS additive is incorporated into the PC / ABS (Xantar C CM 406, Mitsubishi Engineering Plastics) by a co-rotating twin screw extruder. The extrudate is a pelletized strand and then dried at 100 ° C. A test plate having dimensions of 60 x 90 x 1.5 mm is then injection-molded in an injection-molding machine.

In the CIELab system, the emission value L * is measured using a Minolta CR-300 measuring device under standard conditions. The average value of the five different measurements is shown in each case.

The following values are measured:

Table 1:

(Minatec® 51 and Iriotec® 8825 are products from Merck KGaA; with respect to the comparative examples, the particle sizes in Table 1 are rounded in each case and only 2.5% by weight of additives are used in Example 2 according to the invention)

It can be seen from Table 1 that the composite pigment used according to the invention has a significantly higher luminescence value in the polymeric plastic matrix than granules comprising antimony-doped tin dioxide. The luminescence values compared to the mica coated with antimony-doped tin dioxide were slightly better in the examples according to the invention than in the comparative example at half and the same concentration of the LDS additive.

Use Case 2:

Identification of Metallization Properties:

Similar to use example 1, 5 wt% of the LDS additive (Cu spinel, the material according to comparative example 4 and the material according to example 1 of the present invention) is in each case incorporated into the PC / ABS by means of an extruder, Is produced from the compound produced in the injection-molding machine. The test plates were irradiated with 1064 nm at different laser intensities and frequencies ranging from 3-16 W and 60-100 kHw in the test field on the grid in such a way that some material ablation occurred with the simultaneous carbonization of the treatment area It is treated by fiber laser. Metallization by copper is then carried out in commercially available reducing copper baths (MID Copper 100 B1, MacDermid). The metallization properties are approached with reference to the structure of the copper layer on the substrate. A plating index (according to MacDermid) is shown, which is obtained from the quotient of the built-up copper layer of the test material and the built-up copper layer of the reference material. The reference material used is a PBT test plate with a proportion of copper spinel of 5% by weight.

The experiment shows that the LDS additive used according to the invention is significantly better than the mica flakes according to Comparative Example 4 coated with antimony-doped tin dioxide for the degree of metallization both in the range of laser parameters and also for the nominal value of the plating index Values and shows very good metallization values at peak values comparable to Cu spinel, especially at relatively high laser powers.

Use Case 3:

Material measurement for HF conformity:

Test plates, such as those from Example 2, are measured with the difference that the laser treatment and metallization is not performed before the measurement.

The permittivity of a material is measured in various frequency ranges and using various methods. The measurement is carried out at room temperature. For measurements at frequencies ranging from 1 MHz to 1 GHz, an Agilent E4991A impedance analyzer is used with the Agilent 16453 test holder. Evaluation is performed using the "Mate-trial Measurement Firmware" of E4991A.

For measurements at 2.69 GHz and 3.9 GHz, a high quality resonator (cavity resonator in TE111 mode) is used, and the resonance characteristics of resonators containing empty resonator and dielectric samples are measured using a Rhode & Schwarz ZVA network analyzer. The evaluation is described in S. Zinal and G. Boeck, "Complex Permittivity Measurements Using TE11p Modes in Circular Cylindrical Cavities," IEEE Trans. Microwave Theory Tech., Vol. 53, pp. 1870-1874, June 2005.

The following measurements are obtained for a frequency of 1 GHz:

ε '_r tanδ

Example 1: 3.04 0.00373

Cu Spinel: 2.91 0.00411

Compound Example 4: 2.98 0.00488

The following measurements are obtained for a frequency of 2.69 GHz:

ε '_r tanδ

Example 1: 2.861 0.0048

Cu Spinel: 2.759 0.00496

Compound Example 4: 4.029 0.0216

The following measurements were obtained for a frequency of 3.9 GHz:

ε '_r tanδ

Example 1: 2.892 0.005

Cu Spinel: 2.736 0.0047

Compound Example 4: 4.072 0.0253

As the measurements show, copper spinel is generally used as an LDS additive and the LDS additive according to example 1 used in accordance with the present invention is comparable in suitability in the high frequency range, while mite flakes coated with antimony-doped tin dioxide (Comparative Example 4) has both an excessively high relative permittivity and a significantly excessively high dielectric loss factor at frequencies above 1 GHz.

Claims (16)

(TiO ₂ ) and antimony-doped tin dioxide ((Sb, Sn) O ₂ ) based on the total weight of the composite pigment as LDS additive (laser direct structured additive) in the polymeric composition. Uses of pigments. The use according to claim 1, wherein the composite pigment has at least one core and a coating arranged on the core. 3. Use according to claim 1 or 2, characterized in that the core has an isotropic shape. 4. The method according to any one of claims 1 to 3, characterized in that the core is in the form of a sphere, a rectangular parallelepiped, a regular polygonal or semi regular polygonal with n faces (where n ranges from 4 to 92) Purpose. 5. Use according to any one of claims 1 to 4, characterized in that the core is made of TiO ₂ and has a coating comprising (Sb, Sn) O ₂ . Any one of claims 1 to A method according to any one of claim 4, wherein the core is made of a (Sb, Sn) O ₂ for use characterized in that it has a coating containing TiO _2. 7. Use according to any one of claims 1 to 6, characterized in that the proportion of the coating is from 20 to 70% by weight, based on the total weight of the composite pigment. 8. Use according to any one of claims 1 to 7, characterized in that the core has a particle size in the range of 0.001 to 10 mu m. 9. Use according to any of the claims 1 to 8, characterized in that the coating has a layer thickness in the range of 1 to 500 nm. 10. A process according to any one of claims 1 to 9, wherein the composite pigment comprises one or two or more primary particles, each primary particle having a core and a coating arranged on the core Uses as a feature. 11. Use according to any one of the preceding claims, characterized in that the composite pigments each have a particle size in the range of 0.1 to 20 mu m. 12. Use according to any one of claims 1 to 11, characterized in that the composite pigment is present in the polymeric composition in a proportion ranging from 0.1 to 30% by weight, based on the total weight of the polymeric composition. 13. Use according to any of the claims 1 to 12, characterized in that the polymeric composition comprises at least one organic polymeric plastic and optionally a filler and / or a colorant in addition to the LDS additive. LDS additive is more than 80% by weight of titanium dioxide based on the total weight of the composite pigment (TiO _2), and antimony-doped tin dioxide _{((Sb, Sn) O 2} ) of composite pigment is at least one organic polymeric plastic and LDS consisting of A polymeric composition comprising an additive. 15. The polymeric composition of claim 14 wherein the LDS additive is present in the polymeric composition in a ratio of from 0.1 to 30 weight percent based on the total weight of the polymeric composition. An article having a circuit structure made by an LDS process consisting of a plastic base body or a base body having a plastic-containing coating and a metal conductor track disposed on the surface of the base body, wherein the plastic base body or the plastic body- An article comprising an LDS additive wherein the water comprises a composite pigment consisting of at least 80% by weight, based on the total weight of the composite pigment, of titanium dioxide (TiO ₂ ) and antimony-doped tin dioxide ((Sb, Sn) O ₂ ).

Images