WO2019042906A1

WO2019042906A1 - Laser additive and additive for lds plastics

Info

Publication number: WO2019042906A1
Application number: PCT/EP2018/072952
Authority: WO
Inventors: Markus HEIDEBRECHT
Original assignee: Merck Patent Gmbh
Priority date: 2017-08-29
Filing date: 2018-08-27
Publication date: 2019-03-07

Abstract

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

Description

Laser additive and additive for LDS plastics

The present invention relates to a laser additive for plastics and to an LDS-active additive for LDS plastics, and in particular to pigments based on an iron-modified phyllosilicate, their use as laser additive or LDS additive in polymer compositions suitable for the Production of a laser marking or for an LDS method are used, on a polymer composition containing such an additive, as well as on articles which are provided with a laser marking or articles with metallized conductor tracks, in which in each case a polymeric body of the article or a polymeric Coating on a base body contains a laser additive or an LDS additive of the type mentioned. In nearly all branches of industry, the marking of assets by laser beam is a common technology, which promises great advantages by applying durable and customizable markings on various surfaces containing plastic and can be carried out efficiently with comparatively little technological effort. Since not all plastics per se are laser markable, the plastic materials are added suitable additives that absorb the energy of the laser beam and thus either show a color change itself or cause the surrounding matrix to a color change. A variety of different laser additives are commercially available that meet different technological requirements. Particularly desirable are, in particular, those additives which produce a readily visible color change in the plastic matrix under the action of lasers and which are readily available in terms of their starting materials and which are also inexpensive to produce, cost-effective and environmentally neutral as products.

Very readily available and inexpensive worldwide are phyllosilicates such as mica, talc, kaolin, sericite and the like. In untreated Form, when used as a particle, they show weak to very weak laser activity, ie they are able to absorb the energy of the laser beam and partly release it to the surrounding plastic matrix. However, the markings in the plastic matrix that are obtainable in this way are neither sufficient in their intensity nor in their edge sharpness to consider using this layered silicate as the sole laser additive. Therefore, attempts have not been made in the past to provide layered silicate particles with one or more coatings, in particular metal oxides or doped metal oxides, in order to increase their laser activity. Coatings of antimony-doped tin oxide, which can optionally be combined with other metal oxide coatings on the sheet silicate substrates and lead to a very good laser activity of the resulting pigments, have proven to be a particularly effective coating. However, the availability of tin oxide on the world market is increasingly limited and the use of heavy metals such as antimony is not allowed in every application and, moreover, is not free from environmental legislation

Concerns. Therefore, there continues to be a need for laser additives which, with good availability, have high laser sensitivity without having the disadvantages described.

Also, three-dimensional plastic components that carry circuits, so-called MIDs (Molded Interconnect Devices) have been established on the market for years and contributed significantly to enabling state-of-the-art technologies in many applications, for example 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. The LDS process (laser direct structuring method) developed by the company LPKF makes it possible to introduce circuit structures by means of a laser beam directly and individually adapted into a plastic base body or a plastic-containing coating on a base body and then to metallize.

In order to obtain metallizable circuit structures by laser beam, the plastic base body or the plastic-containing must

Coating a so-called LDS additive can be added. This must react to laser radiation and simultaneously prepare the subsequent metallization. The LDS additive is generally metal compounds that are activated during processing with the laser beam on the surfaces machined by the laser in such a way that metal nuclei are released, which are the subsequent attachment of electrically conductive metals for the formation of electrical circuits to the activated Favor digits in the plastic. At the same time, these metal compounds react in a laser-active manner (usually laser-absorbing) and ensure that the plastic on the surfaces machined by the laser is ablated, so that a circuit structure is engraved in the plastic base body. At the points not activated by the laser in the plastic, the metal compounds remain unchanged. The LDS additives may either be added to the plastic mass as a whole prior to deformation to the plastic base part or merely as a component in a separate plastic-containing layer, on the surface into which the circuit structure is to be cut by laser beam

Coating, a lacquer layer, or the like may be present.

During laser beam processing, in addition to the future circuit structure, which contains metal nuclei, a microrough surface is also created within the circuit structure, which creates the prerequisite for the conductive metal, as a rule, to be Copper, during the subsequent metallization adherent to the plastic can anchor.

The metallization is then usually carried out in electroless copper baths, which can be followed by another application of nickel and gold layers, also in electroless baths. However, other metals such as tin, silver and palladium may also be applied, optionally in combination with, for example, gold. Subsequently, the pre-structured plastic components are equipped with the individual electronic components.

The objective of the LDS method is to produce two- or three-dimensional electrically conductive switching structures on two- or three-dimensional plastic basic bodies or basic bodies with plastic-containing coating. It goes without saying that for this purpose, only the generated metallized switching structures may have an electrical conductivity, but not the plastic base body or the coating itself. Originally LDS additive organic heavy metal complexes were provided, which are in particular palladium-containing (EP 0 917 597 B1).

In EP 1 274 288 B1, plastics are added as an LDS additive to inorganic metal compounds which are insoluble in the application medium and constitute inorganic metal compounds of metals of the d and f group of the periodic table with nonmetals. Preference is given to using copper compounds, in particular copper spinels.

Organic Pd complexes, or copper spinels, also have a dark inherent color and also impart a dark color to plastics that contain them. In addition, in particular, the copper compounds fertilize a partial degradation of the surrounding plastic molecules. Of course, the degradation of the plastic base is undesirable. In order to make plastics with a light inherent color available for the LDS process, WO 2012/126831 has proposed LDS-compatible plastics and a corresponding LDS process in which an LDS additive containing antimony-doped tin dioxide is added and in the ClELab color space has an L ^* value (brightness) of at least 45. Preferably, it is doped with antimony

Zinndioxid coated mica in amounts of 2 to 25 wt.%, Based on the total plastic composition used.

Modern plastics are often provided with fillers. In particular, they are reinforced with optical fibers to set advantageous mechanical properties. However, it has been found that various laser additives or even LDS additives reduce the mechanical strength that is achieved by glass fibers, because they have such a high intrinsic hardness that the glass fibers in the polymer composition

damaged or even destroyed. For this reason, in EP 2

676 799 A1, a thermoplastic resin composition for use in the LDS process has been proposed in which as LDS additive

Materials containing at least one element selected from copper, antimony and tin, and having a Mohs hardness which is at least 1, 5 lower than the Mohs hardness of the added inorganic fibers, which are usually glass fibers.

However, the addition of copper-containing compounds can lead to a degradation of the plastic matrix, as already described above.

The use of antimony is subject to administrative restrictions in some countries because it fears environmental damage, the especially in the manufacture or recycling of the corresponding compounds or components containing them.

The same restrictions apply country-specifically in part to compounds containing other heavy metals.

Although there is no fear of environmental damage from the use of tin, its availability on the world market is falling, as previously mentioned with regard to laser additives, because natural supplies are limited and recycling products can not be used everywhere. There is therefore still a need for laser additives with good

Availability and laser sensitivity as well as LDS additives, all

Meet the requirements for good metallizability and high mechanical strength of the plastic compositions provided therewith when used in the LDS process and at the same time are not subject to any restrictions with regard to the availability of the raw materials or administrative application restrictions. Of course, all requirements for laser additives or LDS additives must be complied with, namely the ability to be activated by laser radiation and the generation of edge-sharp, highly visible marks in laser additives but also the release of metal germinate by the laser bombardment and the formation of a microrough surface by the laser beam Basis for the subsequent metallization of LDS additives. At the same time there is a need for additives for plastics, which can be used both as laser additives and as LDS additives, since such an equally good suitability for both applications is not automatically given.

The object of the present invention is therefore a

To provide a laser additive for plastics, which is equally suitable as an LDS additive for LDS plastics and is free of antimony, tin and copper, used in glass fiber reinforced plastic compositions without mechanical impairment of the glass fibers In addition, a good metallizability of the circuit structures obtainable in the LDS method as well as a good laser markability when using the widest possible range of laser parameters possible, the starting materials are good and inexpensive available on the market and which can be produced in an economic process.

Another object of the present invention is to provide

Use of such laser additives and LDS additives

to propose and provide polymeric compositions which are suitable for laser marking or for use in an LDS process and have the properties described above. An additional object of the present invention is to provide articles which have a laser marking or a circuit structure produced in the LDS method and have the above-mentioned properties. The object of the present invention is achieved by pigments which have a base body of a modified phyllosilicate which contains alkali metal and / or alkaline earth metal ions in the unmodified state, the modification consisting in that at least part of the alkali metal and / or alkaline earth metal ions are replaced by iron in the oxidation state Fe (0) is replaced.

In a preferred embodiment, at least a portion of the alkali and / or alkaline earth ions are replaced by iron in the oxidation states Fe (0) and Fe (II). The object of the invention is also achieved by the

Use of said pigments as laser additive or LDS additive (Laser direct structuring additive) in a polymeric composition.

Furthermore, the object of the present invention is also achieved by a polymeric composition comprising at least one polymeric plastic and a laser additive or LDS additive, wherein the laser additive or LDS additive contains pigments which have a base body of a modified sheet silicate, which in the unmodified Condition contains alkali and / or alkaline earth metal ions, wherein the

Modification consists in that at least part of the alkali and / or alkaline earth metal ions by iron in the oxidation state Fe (0) or in the

Oxidtionsstufen Fe (0) and Fe (II) is replaced.

In addition, the object of the invention is achieved by an article with a laser marking consisting of a plastic base body or a plastic-containing coating having base body, wherein the plastic base body or the plastic-containing coating of the base body contains a laser additive containing pigments, which comprises a base body of a modified Have phyllosilicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, the modification is that at least a portion of the alkali and / or alkaline earth metal ions by iron in the oxidation state (0) or in the oxidation states Fe (0) and Fe (II) is replaced. The object of the invention is likewise achieved by an article having a circuit structure produced in an LDS method, consisting of a plastic main body or a plastic-containing one

Coating having body and located on the surface of the body or the coating metallic conductor tracks, wherein the plastic body or the plastic-containing

Coating of the main body contains an LDS additive containing pigments, which is a base body of a modified sheet silicate which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein at least a part of the alkali and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0) or in the oxidation states Fe (0) and Fe (II).

As particularly suitable for laser additives or LDS additives, layer silicates have surprisingly been found according to the present invention, which are selectively modified. As already mentioned above, the usual unmodified phyllosilicates show an extremely weak intrinsic laser activity, which, however, is not sufficient to be considered the only laser additive or LDS additive. However, some phyllosilicates have a high ion exchange capacity. In particular, the phyllosilicates from the group of smectites and vermiculites swell easily in aqueous suspension, so that the ions which are in the interlayers and / or on the phyllosilicate surface can be exchanged.

Therefore, phyllosilicates which have alkali metal and / or alkaline earth metal ions in their crystal lattice, in particular phyllosilicates from the group of smectites and vermiculite which have alkali metal and / or alkaline earth metal ions in their crystal lattice, are suitable for use as the base body of the pigments according to the invention. According to the present invention, alkali metal and / or alkaline earth metal ions are to be understood as meaning, in particular, the ions of the alkali elements lithium and sodium and the ions of the alkaline earth elements magnesium and calcium.

Vermiculite and almost all members of the smectite group contain the said alkali and / or alkaline earth metal ions. Preference is given to

Phyllosilicates beidellite, hectorite, montmorillonite, nontronite and saponite, montmorillonite, nontronite and saponite being the most frequently occurring members of the smectite group and are therefore used with particular preference. In particular, montmorillonite is due its very good availability and good swelling capacity, which leads to a high ion exchange efficiency, most preferred. It is also particularly preferred to use sheet silicates which are mixtures of various clay materials with a main constituent (> 50% by weight) of montmorillonite, for example bentonite or fuller's earth. The phyllosilicates mentioned can be made from natural

Occurrences originate or be manufactured synthetically.

The good ion exchange capacity of the mentioned phyllosilicates is known and is already used for various purposes.

Thus, according to US Pat. No. 5,866,645, various polymers are introduced into the interstices of the crystal lattices of phyllosilicates, in particular of hectorite, and the correspondingly obtained products are proposed for use as reinforcing fillers or rheology control agents in organic polymers.

According to DE 10 2009 024 673 A1, phyllosilicates are modified by incorporation of rare earth luminescent substances into the crystal structure. The corresponding products can be used in bioanalytics or for security marking of objects.

It is known from J. Hausner et al., Polymer Degradation and Stability 128 (2016) 141-148, Elsevier Ltd., 2016, that Na-fluorohectorite can be modified by ion exchange by specific stable iron complex cations, namely trisbipyridine iron ( Il) cations ([Fe (bpy) 3] ²⁺ ). The modified clay filler is proposed in admixture with polystyrene for delaying the inflammability of polystyrene. The preparation and use of reduced species of this species is not discussed. It has now surprisingly been found that modified sheet silicates, in particular those sheet silicates which contain alkali metal and / or alkaline earth metal ions and have a good ion exchange activity, are well suited as laser additives or LDS additives in the form of pigments, if at least some of the alkali metal and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0).

Metallic iron can not be introduced directly into the layer structure of phyllosilicates.

For the preparation of the pigments according to the present invention are therefore particles of a sheet silicate containing alkali and / or alkaline earth metal ions and a good swelling on contact with solvents, in particular with water, suspended in water, and treated with a solution, the Fe (II) -containing ions of an organic iron complex, in particular [Fe (bpy) 3] ²⁺ ions, containing, after appropriate reaction time and at a suitable temperature, at least a portion of the alkali and / or alkaline earth metal ions in the layered silicate by divalent iron containing ions of the organic iron complex, in particular [Fe (bpy) 3] ²⁺ ions, is replaced. The resulting precipitate is washed, dried and ground and sieved if necessary. The reduction of Fe (II) to Fe (0) is then carried out under protective gas at a temperature in the range of 700 ° C to 1 100 ° C. The obtained

If appropriate, pigments may subsequently be ground again and / or screened in order to adjust the desired particle size.

The solution containing the [Fe (bpy) 3] ²⁺ ions may be a solution of a previously prepared [Fe (bpy) 3] Cl2 complex which is used in aqueous solution, or an aqueous / alcoholic solution of a - situ produced [Fe (bpy) 3] Cl2 complex. The latter is prepared as is known from solutions of FeCl2 ^* 4H2O and 2,2'-bipyridine in water or alcohol by mixing. The reaction time for the ion exchange is generally between 0.25 and 8 hours, preferably between 1 and 6 hours and takes place in a temperature range from 25 ° C to 150 ° C, preferably from 25 ° C to 80 ° C instead. The precipitate is dried at a temperature in the range of 100 ° C to 130 ° C.

The reduction of Fe (II) to Fe (0) can, surprisingly, be carried out only under protective gas, for example in a nitrogen atmosphere, without the need for a proportion of reducing gas, for example when using forming gas (H2 / N2). However, a reduction is with

Forming gas also suitable and can be carried out alternatively. The reduction temperature is preferably set in the range of 750 ° C to 1050 ° C. The duration of the reduction reaction is in the range of 40 to 200 minutes, in particular in the range of 60 to 120 minutes.

At least a portion of the alkali and / or alkaline earth ions in the phyllosilicate used is replaced in this way by atomic iron Fe (0). The degree of replacement of the alkali and / or alkaline earth ions in the first reaction stage can be influenced by the reaction time and the reaction temperature. It is therefore not excluded that all

Alkali metal and / or alkaline earth metal ions in the phyllosilicate used during the first reaction stage by Fe (II) -containing ions of the organic

Iron complex to be replaced. During the subsequent reduction step, Fe (II) is reduced to Fe (0). However, it is not excluded here that at least part of the ions of the organic iron (II) complex are not reduced to metallic iron Fe (0) and therefore in addition to iron in the

Oxidation state Fe (0) also iron in the oxidation state Fe (II) in

resulting product is present, which was introduced in advance via the organic iron complex in the layered silicate. In addition, at least parts of the organic complex component (here, the pyridine component) may be decomposed, so that atomic carbon e may be present in the resulting product. The course of the ion exchange and the reduction reaction in the corresponding starting materials, intermediates and end products can be traced very well using the [Fe (bpy) 3] ²⁺ -lone-containing complexes based on the altered color position of the respective products.

Whilst the layer silicate particles used as starting materials are light products with virtually no inherent color (whitish-gray), this is the organic iron complex containing

Intermediate deep red and the present after the reduction process end product almost black. As sheet silicates, the sheet silicates of the smectite group or vermiculite already described above are suitable, in particular the species beidellite, hectorite, montmorillonite, nontronite and saponite, all of which have good swelling behavior in aqueous suspension and contain alkali metal and / or alkaline earth metal ions, montmorillonite, Nontronite and saponite are particularly well available on the market and montmorillonite or mineral products containing montmorillonite as the main ingredient are the most preferred starting materials for the pigments according to the present invention. In principle, the shape of the pigments according to the invention is not critical and may be platelet-shaped, rod-shaped, needle-shaped or regularly or irregularly granular. However, because of the original presence of the unmodified phyllosilicates in needle form or in a layer structure which readily changes into a platelet form during comminution, platelet-shaped or acicular-shaped pigments are preferred, but in particular platelet-shaped

Pigments. The pigments according to the invention have particle sizes in the range from 0.1 to 100 μm, preferably in the range from 1 to 50 μm, and in particular in the range from 1 to 25 μm. Particular preference is given to pigments having particle sizes in the range from 1 to 25 μιτι, in which the dgs value is less than 15 μιτι. A dgs value of <15 μιτι means that 95 vol.% Of the particles of a pigment bed have a particle size of less than 15 μιτι. Preferably, the corresponding dso value is <10 μιτι.

The specified particle sizes can be determined by conventional methods for particle size determination. Particularly preferred is a method for particle size determination according to the laser diffraction method, in which advantageously both the nominal particle size of the individual particles and their percentage particle size distribution can be determined. Preferably, a Malvern 3000 device from Malvern Instruments Ltd., UK is used under standard conditions of ISO / DIS 13320. In a first embodiment, the pigments according to the invention consist of the base body, that is to say they consist of a modified phyllosilicate which contains alkali metal and / or alkaline earth metal ions in the unmodified state, the modification being that at least part of the alkali metal and / or alkaline earth metal ions replaced by iron in the oxidation state Fe (0). The pigments are prepared as previously described.

Since these pigments, their coarse structure and their main components correspond to those of the unmodified phyllosilicates, in the

Incorporation in the various application media behave as the unmodified original phyllosilicates, as the base material can generally be used with a good dispersing behavior and overall good incorporation properties in the application media. If, however, the application medium requires a particular surface finish of the pigments and / or that the properties of the pigments according to the invention are to be changed or improved with regard to their coloring, their laser sensitivity or generally their incorporation properties into the corresponding medium, the novel pigments can be used Pigments on their surface also have a surface coating. This surface coating can be constructed as one or more layers and consist of inorganic and / or organic materials. Thus, organic coatings containing fatty acids, silanes, siloxanes and the like, for example, alter the incorporation properties of the pigments into the application medium in the desired manner. Inorganic coatings, in particular of metal oxides such as, for example, SiO 2, Al 2 O 3, T 2 O 2, Fe ₂ O 3, Fe 3 O ₄ , SnO 2, ZrO 2, Cr 2 O 3, CuO, Ce 2 O 3, in some cases also in doped form, are suitable both for changing the color properties and for changing the surface properties or Change in the laser sensitivity of the pigments according to the invention. However, with these metal oxides some metal ions are again introduced into the pigments according to the invention, which are attributable to the heavy metals or for other reasons (SnO 2) should be avoided according to the present object of the invention. Therefore, the additional use of said metal oxides advantages and disadvantages are well balanced against each other. If an application is considered, the appropriate layer thicknesses of the Metal oxide-containing layers on the base body preferably do not exceed 100 nm, ie at 1 to 100 nm, in particular 1 to 50 nm.

The present invention also relates to the use of the pigments of the invention as a laser additive or as an LDS additive (laser direct structuring additive) in a polymeric composition.

The usual laser marking of plastics differs significantly from the laser processing of plastics in the LDS process. In conventional laser marking, a laser-absorbing additive takes the

Energy of the laser beam on and gives it to the surrounding plastic matrix, so that the latter either foamed or carbonized, which causes the desired laser marking. In this case, the surface of the plastic body, if no ablation of the surface is desired to remain undamaged and the mark are generated only in the interior of the plastic body below the surface. The energy required for the process of the laser beam is adjusted accordingly.

In the generation of switching structures by means of a laser beam in the LDS method, however, the future switching structure using the

Engraved laser beam into the surface of the corresponding body and at the same time a rough surface structure and metal nuclei are generated, which allow the subsequent attachment of pure metals in the metal bath (plating). The generation of such surface structures must be possible over a wide range of laser parameters and the corresponding subsequent metallization sufficiently strong to

Lead structure for microelectronics in question at all.

In addition, the plastic bodies provided with the laser-absorbing additives should not have a large-area electrical conductivity. Therefore, specially developed additives are regularly used for the application in the LDS process. It is therefore possible with the present invention in a surprising manner to develop pigments which are suitable for both the one and the other method and with appropriate adjustment of the laser parameters when used for laser marking to the desired edge sharp marks with a consistently smooth surface of the lasered plastic-containing body, while in use for an LDS method and according to different laser parameters chosen the desired micro-rough surface structure is obtained and metal nuclei are released, which allow the subsequent metallization of the laser beam preformed conductive structure.

The pigments of the invention are in the respective polymeric

Composition as laser additive or as LDS additive in an amount of 0.1 to 30 wt .-%, preferably from 0.5 to 15 wt .-%, and in particular> 1 to 10 wt .-%, each based on the total weight the polymeric composition. They may also be used in mixtures with other laser additives known in the art or LDS additives in the particular polymeric composition. In the latter case, the proportion of the pigments according to the invention is reduced by the proportion of the other or the other laser additive or LDS additive. In sum, the proportion of laser additives or LDS additives is usually not more than the above-mentioned 30 wt .-%, based on the total weight of the respective polymeric composition. Preferably, the pigments according to the invention are used as the only laser additive or LDS additive in the respective polymeric compositions.

The polymeric composition contains, in addition to the pigments according to the invention, at least one polymeric plastic. In principle, all types of plastic come into question, which usually already for the

Use in a laser marking method or in an LDS method are provided. In addition, it has also been found that the pigments of the invention can be used very well in plastic compositions containing glass fibers as a filler. Plastics reinforced with glass fibers have a high mechanical stability and are therefore preferably used for modern plastics applications. If, however, these plastics are additionally mixed with particulate additives for other purposes, for example for the suitability for laser marking or for use in an LDS process, the effect of such additives often has the effect of mechanically destroying the glass fibers in the plastic, because the additives used have a high Mohs hardness, which significantly exceeds the Mohs hardness of the glass fibers. The pigments according to the invention do not have this disadvantage because their base body has a Mohs hardness in the range of only 1 to 2 and the replacement of the alkali metal and / or alkaline earth metal ions by Fe (O) does not lead to a marked increase in these values. Therefore, the pigments of the invention are very suitable for use in glass fiber reinforced plastics.

The present invention is also a polymeric

Composition comprising at least one polymeric plastic and a laser additive or LDS additive, wherein the laser additive or LDS additive contains pigments which have a base body of a modified layered silicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein the modification therein There is at least a part of the alkali and / or alkaline earth ions is replaced by iron in the oxidation state Fe (0) or in the oxidation states Fe (0) and Fe (II).

The polymeric composition may be both a thermoplastic polymeric composition and a thermosetting polymeric composition. Depending on the desired application of the polymeric materials and on a use for Laser marking or for the LDS process, either the thermoplastic or the thermosetting composition may be preferred in each case. The polymeric compositions are composed to a predominant proportion (usually> 50 wt .-%) of thermoplastic or thermosetting plastics.

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), polyaryl ethers - ketones, such as Polyetheretherketone (PEEK), liquid crystal polymers (LCP) or their copolymers or blends, such as acrylonitrile-butadiene-styrene / polycarbonate blend (PC / ABS) or PBT / PET. They are suitable by all well-known polymer manufacturers

Qualities offered.

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

Also polysilicones of various compositions are suitable in principle as plastics in the polymeric composition. As already described above, the proportion of the pigments according to the invention in the polymeric composition according to the invention is 0.1 to 30 wt.%, Preferably 0.5 to 15 wt .-%, and in particular> 1 to 10 wt .-%, based on the Total weight of the polymeric composition, and is measured in detail depending on the current application for laser marking or in an LDS method. For the most

Applications range from percentages in the range of> 1 to 5 wt.%, based on the total weight of the polymeric composition, completely.

However, the pigments according to the invention are very particularly suitable as laser additive or LDS additive in glass fiber-reinforced plastics, as already explained above. As glass fibers, it is possible to use all glass fibers customarily used in the production of polymeric plastic articles, regardless of their concrete material composition, size and shape. The glass fibers, as well as the polymeric materials for the polymeric compositions, are commercially available from a variety of manufacturers. The material

The composition, shape, size and amount of the glass fibers depends on the desired mechanical properties of the polymeric compositions and can be selected by the skilled person according to his general knowledge relevant thereto.

The incorporation of the pigments according to the invention into the polymers

Composition can be effected for example by compounding, via masterbatches, pastes or by direct addition in the shaping processing step.

In addition, the polymeric compositions containing the pigments according to the invention as laser additive or LDS additive may optionally additionally contain further fillers and / or colorants as well as stabilizers, auxiliaries and / or flame retardants.

Suitable further fillers are, for example, various natural or synthetic silicates, S1O2, talc, kaolin, mica, wollastonite, glass beads, carbon fibers or the like. Suitable colorants are both organic dyes and inorganic or organic color pigments. They serve the coloring Change or the lightening of the polymer plastic compositions, which have a rather dark color due to the addition of the pigments of the invention as a laser additive or LDS additive depending on the percentage content. As examples, only the most commonly used white pigments ΤΊΟ2, ZnO, BaSO ₄ and CaCO3 are mentioned here. The amount and type of added fillers and / or colorants is limited only by the particular concrete material nature of the individual polymeric compositions, in particular the plastics used.

The pigments according to the invention have a high laser activity and can be advantageously used both for laser marking and in LDS processes. When used in laser marking, bright, edge-sharp markings on a dark background result under the influence of the laser beam, with the surface of the lasered plastic body intact. When laser action according to the LDS method and the laser parameters adapted thereto, the use of the pigments according to the invention results in the desired microrough surfaces within the laser beam ablated and carbonized

Conductor structures, so that a subsequent metallization in good quality is possible. In this case, a very good metallizability is possible with a wide range of different laser settings. Thus, for the LDS method, the most suitable conditions for the laser action that are most suitable for the actual circumstances can be selected without the subsequent metallization

Quality losses would be expected.

In addition, the use of the pigments according to the invention as

Laser additive or LDS additive in plastic-containing polymer compositions also not to a degradation of the additives surrounding organic polymer molecules. In addition, the pigments according to the invention are free of antimony, tin and copper and are especially suitable for suitable for use in glass fiber reinforced polymeric compositions.

The polymeric composition according to the invention is intended for use in a laser marking process or in an LDS process (laser direct structuring process) for producing metallized switching structures. The plastic bodies used in each case consist of either two- or three-dimensional plastic base bodies or have coatings containing plastic on two- or three-dimensional basic bodies. Depending on requirements, the polymeric composition can be provided with a permanent, edge-sharp laser marking by means of a laser marking process or, by adding the pigments according to the invention as LDS additive, good metallizability of the laser structures generated by laser beam structures, wherein the laser parameters can be selected in a wide range , The added LDS additive is free of antimony, tin and copper, so that no chemical influence due to degradation of the polymer matrix has to be feared. In addition, no mechanical impairment of glass fiber reinforced polymer masses takes place.

The present invention is also an article with laser marking, consisting of a Kunststoffgrundkorper or a plastic-containing coating having basic body, wherein the Kunststoffgrundkorper or the plastic-containing coating of the base body contains a laser additive containing pigments having a base body of a modified sheet silicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein the modification consists in that at least part of the alkali and / or alkaline earth metal ions by iron in the oxidation state (0) or in the

Oxidation levels Fe (0) and Fe (II) is replaced. In addition, the subject matter of the present invention is also an article with a circuit structure produced in an LDS method, consisting of a plastic main body or a plastic-containing one

Coating base body as well as located on the surface of the body or the coating metallic

Conductor tracks, wherein the plastic base body or the plastic-containing coating of the base body contains an LDS additive containing pigments which have a base body of a modified sheet silicate, which in the unmodified state alkali and / or

Contains alkaline earth ions, wherein at least a portion of the alkali and / or alkaline earth metal ions by iron in the oxidation state Fe (0) or in the

Oxidation levels Fe (0) and Fe (II) is replaced.

Laser marking articles can be used in virtually all fields of technology in which permanent inscriptions on plastic-containing bodies, films or coatings are advantageous, for example as semi-finished or finished parts in the electrical, electronics and automotive industries, as marked or labeled cables , Cables, plugs, handles, switches, moldings, functional parts in the heating, ventilation or cooling, in packaging or labels, as consumables in the medical field, as animal ear tags or the like.

Articles with a circuit structure that is produced in the LDS process, in particular articles made of organic thermoplastic or thermosetting plastics, are used, for example, in telecommunications, in medical technology or in the automotive industry, where they are used, for example, as electronic components of mobile telephones, hearing aids, dental Instruments, car electronics and the like can be used. The laser types and laser parameters for both the laser marking method and for the LDS method are known to those skilled in the art and can be selected from the usual used equipment and parameters are selected without special adjustments are needed.

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

Example 1 :

Preparation of the pigment of the invention A) 21, 2 g of FeCl ₂ ^* 4H ₂ 0 is dissolved in water and mixed with 50 g of ethanol dissolved in 2,2 'bipyridine in a crystallization sounds. The

Deposition of deep red [Fe (bpy) 3] Cl2 crystals occurs within several days at room temperature. 43.14 g of the [Fe (bpy) 3] Cl2 complex are dissolved in water and slowly added dropwise to a suspension of 75 g Nanoclay PGV (hydrophilic bentonite, product of Nanocor, particle size <25 μm) in water. With stirring at 70 ° C over a period of about 5 hours, the ion exchange of alkali and / or alkaline earth ions in bentonite takes place. The resulting red particles are sucked off, the solid with

Washed water and acetone and dried at 1 10 ° C. The dried particles are ground in a ball mill to a particle size of <40 μιτι and then reduced at 800 ° C under nitrogen over a period of 60 to 120 minutes. There are black ones

Pigments, which are optionally comminuted and sieved again. The resulting particle size is <40 μιτι.

B) 150 g Nanoclay PGV (composition and manufacturer see above) are suspended in water and at 60 ° C with a mixture of 28.81 g FeCl ₂ ^* 4H ₂ 0 in water and 67.94 g of 2,2 'bipyridine in ethanol added. The suspension is stirred for a further 1 hour at 50.degree. In this period, the ion exchange of alkali and / or alkaline earth ions in bentonite takes place.

The workup of the resulting red particles is carried out as described under A).

The advantage of the method described in variant B) lies in the shortened production time.

Example 2:

Application as laser additive

Preparation of the test specimen:

60 g of a PVB (Movital B 20H, Kuraray) are dissolved in ethanol at reflux at a temperature of 92 ° C. 4.25 g of the resulting solution are mixed with 0.5 g of triethylene glycol monobutyl ether and 0.25 of the pigment according to Example 1 B and mixed at 2800 rpm for 2 min. The paint obtained in this way is applied to a triacetate support film with a 500 μm doctor blade and dried overnight at room temperature. Subsequently, the lacquer layer is removed from the carrier film. EXAMPLE 2 a: A PVB-containing film produced as described above with a content of 5% by weight of the pigment according to Example 1 B is mixed with a 10W yttrium vanadate laser (λ: 1064 nm) with a test grid at different laser power and provided speed. Sharp-edged, clear, bright marks on black ground are obtained over almost the entire range tested.

Comparative Examples 2a to 2e:

For comparison, PVB-containing films with the following ingredients are subjected in parallel to the same laser treatment:

2b: 5% by weight of [Fe (bpy) 3] Cl2 ^ red film, no laser marking; 2c: 5 wt.% Nanociay PGV ^ bright film, very weak in places

Bad quality mark;

2d: 5% by weight physical mixture of [Fe (bpy) 3] Cl2 and Nanociay PGV in the ratio 1: 1 ^ red film, low reddish marking in a few test fields;

2e: 5% by weight of the ion-exchanged Nanociay PGV from Example 1 B before the reduction red film, a few reddish

Markings in Individual Test Fields From Example 2a, in comparison with Comparative Examples 2b to 2e, it can be clearly seen that only the reduced species according to the present invention produces the desired laser marking.

Example 3:

Application as LDS additive:

By means of a co-rotating twin-screw extruder (Prism Eurolab, Thermo Scientific) 5 wt .-% of the LDS additive (pigment according to Example 1 B) in PC / ABS (Xantar C CM 406, Mitsubishi Engineering Plastics) incorporated. The metering of the previously ground polymer and the LDS additive takes place as a premix via the main hopper. The extruder has a screw diameter of 16 mm and an L / D ratio of 32. The extrudate is strand granulated and then dried at 100 ° C for 4 hours. Thereafter, test plates measuring 60 × 90 × 1.5 mm are injection-molded on an injection molding machine (Arburg Allrounder 320 M). The test plates contain the LDS additive homogeneously and finely distributed.

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 10W yttrium vanadate laser (λ: 1064 nm) so that a low material removal with simultaneous carbonation of the edited Surface is created. Subsequently, the metallization with copper in a commercially available reductive copper bath (MID Copper 100 XB, MacDermid). The metallization properties are based on the structure of the

Copper layer on the substrate assessed.

It will get a good, uniform metallization over almost the entire test grid.

Example 4:

Mechanical strength of the samples

4a: Using a co-rotating twin-screw extruder (Prism Eurolab, Thermo Scientific), 5% by weight of the LDS additive (pigment according to Example 1 B) are incorporated in PA6-GF30 (Durethan BG30X, Lanxess, 30% glass fibers / glass beads). The metering of the previously ground polymer and the LDS additive takes place as a premix via the main hopper. The extruder has a screw diameter of 16 mm and a L / D ratio of 32. The extrudate is strand granulated and then dried at 70 ° C for 24 hours. Thereafter, standard bodies (shoulder bar, type 1A, EN ISO 527-2, total length 170 mm, width at the ends 20 mm, width of the narrow parallel portion 10 mm, thickness 4 mm) are injection-molded on an injection molding machine. The shoulder bars contain the LDS additive homogeneously and finely distributed and can be used for tensile tests according to DIN EN ISO 527-2. Equal shoulder bars are used for notched impact testing by milling a 10 mm notch into the center of the parallel part. The introduction of the notch and the test is carried out according to DIN EN ISO 179-1. Comparative Examples 4b to 4d:

5% by weight of a copper spinel are incorporated as an LDS additive in PA6-GF30 analogously to Example 4a, and shoulder rods are produced therefrom (FIG. 4d). As further comparative samples serve zero samples of the PA6-GF30 polymer in the following form:

Comparison 4b: Polymer without LDS additive, without extrusion, in

Delivery condition

Comparison 4c: Polymer without LDS additive, extruded

The specimens are examined for their mechanical strength. The results are shown in Table 1. The following parameters are checked:

Type of test Standard Unit Test condition

Tensile modulus DIN EN ISO 527-2 / 1A MPa 1 mm / min

Breaking stress DIN EN ISO 527-2 / 1A MPa 5 mm / min

Elongation at break DIN EN ISO 527-2 / 1A% 5 mm / min Charpy

Notched impact strength DIN EN ISO-179-1 / 1 eA kJ / m ² 23 ° C

Results of the test: Table 2

Comparison 4b Comparison 4c Compare example 4d Ex.4a

Pull-E module 6100 5600 5600 5800

Breaking stress 106 75 70 89

Elongation at break 2.7 1, 6 1, 5 2.3 Charpy

Notched Toughness 4 3.4 2.8 3.5

The results show that with the use of the pigment used according to the invention as an LDS additive in glass fiber reinforced plastics in terms of mechanical strength both a higher fracture stress and Charpy notched impact strength can be achieved compared to the use of copper spinel. With regard to the train E modulus is Example according to the invention comparable to the values that can be achieved with the extruded, unpigmented polymer.

When using copper spinel (Comparative Example 4d) as LDS additive, however, as expected, a significant drop in stress at break and notched impact strength compared to Comparison 4c is observed, which is due to the damage and thus reduction of the glass fiber.

Claims

claims

Pigments which have a base body of a modified sheet silicate which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein the modification consists in that at least a part of the alkali and / or alkaline earth ions replaced by iron in the oxidation state Fe (0) is.

Pigments according to claim 1, characterized in that at least a part of the alkali and / or alkaline earth ions is replaced by iron in the oxidation states Fe (0) and Fe (II).

Pigments according to Claim 1 or 2, characterized in that the base body is a modified sheet silicate from the group of smectites.

Pigments according to claim 3, characterized in that the base body is a modified montmorillonite or a modified bentonite.

Pigments according to one or more of claims 1 to 4, characterized in that the base body additionally contains carbon.

Pigments according to one or more of claims 1 to 5, characterized in that they have a platelet or needle shape

respectively.

Pigments according to one or more of claims 1 to 6, characterized in that they have a particle size in the range of 0.1 to 100 μιτι each.

Pigments according to one or more of claims 1 to 7, characterized in that they consist of the base body.

9. Pigments according to one or more of claims 1 to 7, characterized in that they have a surface coating on the base body.

10. Pigments according to one or more of claims 1 to 9, characterized in that the iron in the oxidation state Fe (0) by exchange of alkali and / or alkaline earth ions against an organic Fe (II) complex and a subsequent reduction of Fe (II) is introduced to Fe (0) in the base body.

0

1 1 .Verwendung of pigments according to one or more of

Claims 1 to 10 as a laser additive or LDS additive (laser direct structuring additive) in a polymeric composition.

12. Use according to claim 1 1, characterized in that the pigments in the polymeric composition in a proportion in the range of 0.1 to 30 wt .-%, based on the total weight of the polymeric composition, are present.

13. Use according to claim 1 1 or 12, characterized in that 0

in that the polymeric composition contains at least one polymeric plastic in addition to the laser additive or LDS additive.

14. Use according to one or more of claims 1 1 to 13, characterized in that the polymeric composition contains 5 glass fibers as filler.

15. Use according to one or more of claims 11 to 14, characterized in that the pigment is present in admixture with other customary laser additives or LDS additives in the polymeric composition.

16. A polymeric composition containing at least one polymeric plastic and a laser additive or LDS additive, wherein the laser additive or LDS additive contains pigments which have a base body made of a modified phyllosilicate, which in the non-modified state, alkali metal and / or alkaline earth metal ions contains, where the

Modification consists in that at least part of the alkali and / or alkaline earth metal ions is replaced by iron in the oxidation state Fe (0) or in the oxidation states Fe (0) and Fe (II).

^ Q

17. A polymeric composition according to claim 15, characterized

in that the laser additive or LDS additive is contained in the polymeric composition in a proportion of 0.1 to 30% by weight, based on the total weight of the polymeric composition.

15

18. A polymeric composition according to claim 15 or 16, wherein

Glass fibers are included as a filler.

19. Polymeric composition according to one or more of

Claims 15 to 17, characterized in that it is in the

20 polymeric composition is a thermoplastic material, a thermosetting material or a polysilicon.

20. Article with laser marking, consisting of a Kunststoffgrundkorper or having a plastic-containing coating

25 basic body, wherein the Kunststoffgrundkorper or the plastic-containing

Coating of the base body contains a laser additive which contains pigments which have a base body of a modified sheet silicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein the modification consists in

2Q that at least a portion of the alkali and / or alkaline earth metal ions by

Iron in the oxidation state (0) or in the oxidation states Fe (0) and Fe (II) is replaced. Article having a circuit structure produced in an LDS method, consisting of a plastic base body or a base body containing a plastic-containing coating, and metal traces located on the surface of the base body or coating, the plastic base body or the plastic-containing coating of the base body being an LDS additive contains, which contains pigments, which have a base body of a modified sheet silicate, which contains in the unmodified state alkali and / or alkaline earth metal ions, wherein at least a portion of the alkali and / or alkaline earth metal ions by iron in the

Oxidation stage Fe (0) or in the oxidation states Fe (0) and Fe (II) is replaced.