Plastic molding compound and use thereof

Abstract

A method for producing a laser-structurable component, wherein an extruded single- or multilayer molded part with at least one laser-structurable layer that forms an exposed surface of the molded part is applied onto the surface of a non-laser-structurable support element. Alternatively, the at least one laser-structurable layer may be back-molded with a non-laser-structurable thermoplastic support element so that at least one laser-structurable layer of the molded part forms at least one part of the surface of the laser-structurable component. The extruded single- or multilayer molded part is deep-drawn into the component. In the process, the laser-structurable layer of the molded part consists of a thermoplastic molding compound consisting of: (A) 30-99.9 wt. % of a thermoplastic consisting of polyamide; (B) 0.1-10 wt. % of an LDS additive; and (C) 0-60 wt. % of an additive material which is different from (A) and (B).

Claims

1. A process for producing a laser-structurable component, wherein an extruded, single-layer or multilayer molding in the form of a laser-structurable foil with a thickness in the range of 10-100 micrometers that forms an exposed surface of the molding is in mold-coated with a non-laser-structurable thermoplastic carrier element, so that at least one laser-structurable foil forms at least one part of the surface of the laser-structurable component, with or without having already formed conductor tracks, the laser-structurable foil of the molding consisting substantially over its entire area of a thermoplastic molding composition consisting of: (A) 30-99.9 wt % of thermoplastic consisting of polyamide (A1), wherein (A1) consists of: an amorphous semiaromatic polyamide (A1_3); a cycloaliphatic amorphous polyamide (A1_4); or a mixture of an aliphatic polyamide (A1_1) and at least one of a semiaromatic, semicrystalline polyamide (A1_2) or an amorphous semiaromatic polyamide (A1_3) or an cycloaliphatic amorphous polyamide (A1_4); or of a mixture of said polyamide (A1) and another thermoplastic (A2), the fraction of polyamide (A1) being at least 70 wt %, based on the sum of (A1) and (A2); (B) 0.1-10 wt % of LDS additive; and (C) 0-25 wt % of adjuvants different from (A) and (B), composed of compatibilizers or impact modifiers and/or additives (C4), wherein said additives (C4) are selected from the group consisting of: adhesion promoters, halogen-containing flame retardants, halogen-free flame retardants, stabilizers, aging inhibitors, antioxidants, antiozonants, light stabilizers, UV stabilizers, UV absorbers, UV blockers, inorganic heat stabilizers, organic heat stabilizers, conductivity additives, carbon black, optical brighteners, processing assistants, nucleating agents, crystallization accelerators, crystallization retarders, flow assistants, lubricants, mold release agents, plasticizers, organic pigments, organic dyes, marker substances, and mixtures thereof; the sum of (A)-(C) making 100 wt %.

2. The process as claimed in claim 1, wherein the at least one laser-structurable foil of the molding is designed without having already formed conductor tracks.

3. The process as claimed in claim 1, wherein the molding is introduced as a foil in a mold and is coated by the carrier element in the mold.

4. The process as claimed in claim 1, wherein the carrier element contains polyamide.

5. The process as claimed in claim 1, wherein the cycloaliphatic amorphous polyamide (A1_4) is constructed from: a) 60 to 100 mol %, of at least one aliphatic and/or aromatic dicarboxylic acid having 6 to 14 carbon atoms, and also 0 to 40 mol %, of at least one cycloaliphatic dicarboxylic acid having 8 to 20 carbon atoms, based on the total amount of the dicarboxylic acids; b) 50 to 100 mol %, of at least one cycloaliphatic diamine selected from PACM, MACM, EACM, TMDC, BAC and IPD, and also 0 to 50 mol %, of at least one aliphatic diamine, having 4-18 carbon atoms, based on the total amount of diamines, and also optionally; and c) aminocarboxylic acids and/or lactams each having 6 to 12 carbon atoms.

6. The process as claimed in claim 1, wherein the polyamide (A1) consists of 20-100 wt %, of amorphous cycloaliphatic polyamide (A1_4) and of 0-80 wt %, of aliphatic polyamide (A1_1) and/or semicrystalline, semiaromatic polyamide (A1_2).

7. The process as claimed in claim 1, wherein conductor tracks are formed on the component in one of the following operating steps on the component, by laser direct structuring and subsequent electroless deposition, and also, optionally, electrical and/or electronic components are subsequently incorporated.

8. The process as claimed in claim 1, wherein the molding is a foil formed by the laser-structurable layer alone, or having one or more carrier layers which are different from the laser-structurable layer and on which one or more carrier layers a laser structurable layer is disposed on one or both sides, forming the surface.

9. The process as claimed in claim 1, wherein the molding is a foil, having a thickness in the range of 40-100 micrometers, and the foil being formed by the laser-structurable layer alone, or having one or more carrier layers which are different from the laser-structurable layer and on which one or more carrier layers a laser structurable layer is disposed on one or both sides, forming the surface.

10. The process as claimed in claim 1, wherein the carrier element and/or, the molding consist of a mixture of a polyamide (A1) and another thermoplastic (A2), the fraction of polyamide (A1) being at least 70 wt % based on the sum of (A1) and (A2), wherein the amount of component (A1_1), based on the sum of the components (A1_1), (A1_2), (A1_3) and (A1_4), is in the range from 40 to 95 wt %, and/or wherein component (A1_1) is selected from the group consisting of the following: polyamide PA610, PA106, PA1010, PA1012, PA1212, PA11, PA12, or mixtures or copolyamides thereof; and/or wherein component (A1_2) is selected from the group consisting of the following: PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/6, PA 6T/6I, PA 6T/6116, PA 6T/66, 6T/610, 6T/612, PA 6T/10T, PA 6T/10I, PA 9T, PA 10T, PA 12T, PA 10T/10I, PA10T/106, PA10T/12, PA10T/11, PA 6T/9T, PA 6T/12T, PA 6T/10T/6I, PA 6T/6116, PA 6T/61112, and also mixtures or copolyamides thereof; and/or wherein component (A1_3) is selected from the group consisting of the following: 6I/6T, 10I/10T, 12/6T, MXD6/MXDI, and also mixtures or copolyamides thereof; and/or wherein component (A1_4) is selected from the group consisting of the following: polyamide PA MACM12, PA MACMI/12, PA MACMT/MACMI/12, MACM9, MACM10, MACM14, MACM16, MACM18, PACM12, PACM14, PACM16, PACM18, MACM12/PACM12, MACM14/PACM14, MACM16/PACM16, MACM18/PACM18, PACM9 18, 6I/6T/MACMI/MACMT/12, 6I/MACMI/MACMT, 6I/PACMI/PACMT, 6I/6T/MACMI, MACMI/MACM36, 12/PACMI or 12/MACMT, 6I/PACMT, 6/IPDT, BACI/BACT, MACM12/BAC12, 10I/10T/BACI/BACT, or mixtures or copolyamides thereof.

11. The process as claimed in claim 1, wherein the fraction of amorphous cycloaliphatic polyamide (A1_4) is in the range of 20-100 wt % and the fraction of aliphatic polyamide (A1_1) is in the range of 0-80 wt %.

12. The process as claimed in claim 1, wherein the cycloaliphatic amorphous polyamide (A1_4) is constructed from a) 80 to 100 mol %, of at least one aliphatic and/or aromatic dicarboxylic acid having 6-12 carbon atoms, and also 0 to 20 mol %, of at least one cycloaliphatic dicarboxylic acid having 8 to 20 carbon atoms, based on the total amount of the dicarboxylic acids; b) 85 to 100 mol % of at least one cycloaliphatic diamine, having 6 to 20 carbon atoms, selected from PACM, MACM, EACM, TMDC, BAC and IPD, and also 0-15 mol % of at least one aliphatic diamine, having 6 to 12 carbon atoms, based on the total amount of diamines, and also optionally; c) aminocarboxylic acids and/or lactams each having 6 to 12 carbon atoms.

13. The process as claimed in claim 1, wherein the polyamide (A1) consists of 35-80 wt % of amorphous cycloaliphatic polyamide (A1_4) and of 20-65 wt % of at least one of an aliphatic polyamide (A1_1).

Description

(1) Preferred embodiments of the invention are described below with reference to the drawings, which serve merely for elucidation and should not be interpreted restrictively.

(2) The FIGURE shows the parameters of the laser structuring.

DESCRIPTION OF PREFERRED EMBODIMENTS

(3) The invention is to be described hereinafter using specific working examples (B), and compared with the less highly performing systems of the prior art (VB). The working examples specified below serve to support the invention and to demonstrate the differences relative to the prior art, but they are not intended to limit the general subject matter of the invention, as it is defined in the claims.

Examples B1 to B11 and Comparative Examples VB1-VB3

(4) The components specified in Tables 2a, 2b and 3 are compounded in a twin-screw extruder from Werner and Pfleiderer having a screw diameter of 25 mm, with specified processing parameters (see Table 1); the polyamide pellets along with the adjuvants are metered into the intake zone, while the glass fibers optionally used are metered into the polymer melt via a side feeder 3 barrel units ahead of the die. The compounded formulations were taken off in the form of an extruded strand, from a die having a diameter of 3 mm, and were pelletized after water cooling. After pelletizing and drying at 110 C. for 24 hours, the properties of the pellets were measured and the test specimens were produced.

(5) TABLE-US-00001 TABLE 1 Conditions for compounding, injection molding and foil extrusion for the examples and comparative example VB1, Processing Parameter Unit B1-B11, VB3 VB2 Compounding Barrel temperatures C. 250-260 260-280 Screw speed rpm 200 200 Throughput kg/h 15 15 Injection Barrel temperatures C. 265-280 265-280 molding Mold temperature C. 80 130 Melt temperature 280 275 Foil Barrel temperature C. 220-265 260-275 extrusion Melt temperature C. 250-260 265-275 Screw speed r/min 60 60 Takeoff rate m/min 5.8 5.8 Takeoff roll C. 60-62 70-72 temperature
Processing:

(6) The compounded formulations were injected on an Arburg Allrounder 320-210-750 injection-molding machine to give specimens at defined barrel temperatures for zones 1 to 4 and at a defined mold temperature (see Table 1). The molding produced by injection molding in the form of a plate for comparative example VB3 and example B11 had a thickness of 2 mm; the thickness of the ISO test specimens was 4 mm.

(7) In example B11, the foil B7 (thickness 100 m) for the individual test specimens was cut to an exact fit and placed against the inner wall of the mold cavity, bearing against it over its full area. The foil was then in-mold-coated under the conditions specified in table 1 with the molding composition specified in table 3.

(8) The foils were produced on a single-screw extruder for examples B1 to B11 and VB1 or on a Dr. Collin GmbH E 30 flat-film coextrusion unit (e.g. VB2) having one (two) 30 mm 3-zone screw(s). The foils were produced using a slot die/multilayer die. The dimensions of the foil were 200 mm width or 250 mm and 100 m thickness. The foils were wound up using a chill roll and cut to the required length. The further production parameters can be seen in table 1.

(9) TABLE-US-00002 TABLE 2a Composition and properties of examples B1-B7 Unit B1 B2 B3 B4 B5 B6 B7 Composition PA1010 moderate % wt 85.8 76.3 76.3 viscosity PA1010 high % wt 76.3 viscosity PA6I/6T % wt 9.5 19 95.3 PA10I/10T % wt 19 19 PA12 % wt 57.3 PAMACM12 % wt 38 95.3 Nucleation % wt 0.2 0.2 0.2 0.2 0.2 0.2 0.2 LDS additive % wt 4 4 4 4 4 4 4 Irganox 1098 % wt 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Properties Modulus of MPa 2100 2200 2000 2000 1500 2900 1600 elasticity in tension Tensile MPa 56 61 59 61 59 90 62 strength Elongation at % 35 40 140 50 230 10 120 break Impact strength kJ/m.sup.2 no no no no no 50 no 23 C. break break break break break break Notched impact kJ/m.sup.2 8 5 5 6 7 9 9 strength 23 C. Planarity of foil after foil + + + + + + + production after laser 0 0 0 0 + + + structuring after 0 0 + + metallization Detachment of no no no no no no no the metal layer on 10-fold roll-up (d = 10 mm) Metallizability % 86 100 100 100 100 94 100 (proportion of metalized fields)

(10) TABLE-US-00003 TABLE 2b Composition and properties of examples B8-B10 and VB1, VB2 Unit B8 B9 B10 VB1 VB2 Composition PA1010 high % wt 50 viscosity PA12 % wt 35.5 45.5 PA MACM12 % wt 45.5 60 PA MACMI/12 % wt 50 PET % wt 75 PA6I/6T % wt 20 Aluminum % wt 1 oxide LDS additive % wt 4 4 4 4 Irganox 1098 % wt 0.5 0.5 0.5 Properties Modulus of MPa 2000 1550 2000 3400 elasticity in tension Tensile MPa 60 60 65 90 strength Elongation at % 180 190 160 15 break Impact strength kJ/m.sup.2 no no no no 23 C. break break break break Notched impact kJ/m.sup.2 7 10 8 4 strength 23 C. Planarity of foil after foil + + + + + production after laser + + + 0 0 structuring after + + + metallization Detachment of no no no no Detachment the metal layer at the on 10-fold edges roll-up (d = 10 mm) Metallizability % 100 100 100 75 63 (proportion of metalized fields)

(11) In comparative example VB2 a 3-layer foil with the layer sequence ABA, layer A being a 5 to 10 m layer of VB1 and the middle layer B being an 80 to 90 m layer of PET (with no additions), was subjected to the laser structuring and subsequent electroless metallization, without the foil having been drawn and heat-set beforehand. The foil, which was smooth after extrusion, underwent warping during laser irradiation and became highly corrugated.

(12) TABLE-US-00004 TABLE 3 Composition and properties of examples B11 and VB3 B11 VB3 Moldings Moldings produced by produced by in-mold- injection coating of Unit molding foil B7 Composition of injection molding or in-mold-coated thermoplastic PA1010 wt % 36.6 36.6 PA6I/6T wt % 9.1 9.1 Glass fibers wt % 50 54 LDS additive wt % 4 0 Irganox 1098 wt % 0.3 0.3 Properties Modulus of elasticity MPa 12900 14500 in tension Tensile strength MPa 139 187 Elongation at break % 2.0 2.8 Impact strength 23 C. kJ/m.sup.2 50 95 Notched impact kJ/m.sup.2 9 20 strength 23 C. Metallizability % 100 100 (proportion of metalized fields) Amount of LDS wt % 4.0 0.2 additive relative to molding (60 60 2 mm plate)*.sup.) *.sup.)The plate in B11 has dimensions of 60 60 2 mm, with a surface formed by foil B7 (thickness 0.1 mm).
Materials:

(13) TABLE-US-00005 PA 6I/6T (70:30) Amorphous, semiaromatic polyamide based on terephthalic acid, isophthalic acid and 1,6- hexanediamine, with a glass transition temperature of 125 C. and a solution viscosity of 1.54. PA 10I/10T (60:40) Amorphous, semiaromatic polyamide based on 1,10-decanediamine, isophthalic acid and terephthalic acid, with a glass transition temperature of 101 C. and a solution viscosity of 1.59. PA 1010 Semicrystalline, aliphatic polyamide based on 1,10-decanediamine and sebacic acid, having a melting point of 200 C. and a solution viscosity of 1.78 (medium viscosity) or 2.06 (high viscosity). PA 12 Semicrystalline, aliphatic polyamide based on laurolactam, having a melting point of 178 C. and a solution viscosity of 1.96. MACM12 Amorphous polyamide based on MACM and DDDS, Tg = 156 C., rel = 1.82, Hm < 4 J/g, LT = 93%. MACMI/12 Amorphous polyamide based on MACM, isophthalic acid and lactam 12; Tg = 155 C., rel = 1.86, Hm < 4 J/g Glass fibers Chopped glass fibers CSG3PA-820 of E glass, with a length of 3 mm, a principal cross-sectional axis of 28 m, a secondary cross-sectional axis of 7 m and an axial ratio of 4 (noncircular cross section) from NITTO BOSEKI, Japan LDS additive Shepherd Black 30C965 (The Shepherd Color Company), copper chromite (CuCr.sub.2O.sub.4), average particle size 0.6 m. Nucleation Brggolen P22, Brggermann Chemical PET Polyethylene terephthalate having a standard viscosity SV (dichloroacetic acid) of 800 Aluminum oxide Aerosil 90, Evonik
Measurements:

(14) The measurements were carried out according to the following standards on the following test specimens. The modulus of elasticity in tension was determined in accordance with ISO 527 at a tensioning speed of 1 mm/min, the yield stress, breaking strength and elongation at break in accordance with ISO 527 with a tensioning speed of 50 mm/min (unreinforced versions) or with a tensioning speed of 5 mm/min (reinforced versions) at a temperature of 23 C., the specimen used being an ISO tensile rod, standard: ISO/CD 3167, type A1, 17020/104 mm.

(15) Impact strength and Charpy notched impact strength were measured according to ISO 179 on the ISO test rod, standard: ISO/CD 3167, type B1, 80104 mm at 23 C. temperature.

(16) The thermal characteristics (melting temperature (Tm), enthalpy of fusion (Hm), glass transition temperature (Tg)) were determined on the pellets in accordance with ISO standard 11357-11-2. Differential scanning calorimetry (DSC) was carried out with 20 C./min heating rate. For the glass transition temperature (Tg), the temperature for the middle stage or for the point of inflection is reported.

(17) The relative viscosity (rel) was measured in accordance with DIN EN ISO 307 on 0.5 wt % strength solutions in m-cresol at 20 C. Pellets are the sample used.

(18) Laser Structuring:

(19) To assess the metallization performance, injection moldings in VB3 and B11 (plate 60602 mm or, for example B11, the in-mold-coated foil B7 in the same dimensions 60602 mm) and also foil sections with dimensions of 60600.1 mm for examples B1 to B10 were structured using an Nd:YAG laser and afterward subjected to electroless metallization in a copperizing bath. For the laser structuring, 32 adjacent regions measuring 44 mm were irradiated on the surface of the molding. Laser structuring took place using a Trumpf TruMark Station 5000 laser at a wavelength of 1064 nm. The rate was varied in the range from 300 to 7200 mm/s, the pulse frequency in the range of 10-80 kHz, and the hatch (pulse overlap) in the range from 0.03 to 0.09 mm (see the FIGURE). Following the laser structuring, the moldings are subjected to a cleaning operation in order to remove the residues from the laser process. In this procedure, the moldings passed through successively ultrasound baths containing surfactant and deionized water. After cleaning, the moldings are metalized in succession in reductive copperizing baths (MID Copper 100 XB Strike and MID Copper 100 XB Build, MacDermid) at 55 to 65 C. The residence time here is 20 min in the strike bath and 1-3 h in the build bath. The rate of copper deposition (thickness of the copper layer) in the MID Copper 100 XB Build bath on the laser-irradiated areas averages 3 to 5 m/h.

(20) Metallizability:

(21) The metallizability was calculated as the ratio of metalized fields to the total number of fields, and reported as a percentage fraction. In total 32 fields having different parameters per sample plate, as shown in the FIGURE, are structured with the laser and then metalized as described above. Metalized fields are only the fields metalized uniformly and completely in the procedure described above.

(22) In all MID technologies, chemically reductive copper deposition is the key initial metallizing operation, and determines the quality of the layer as a whole. It is therefore completely sufficient for the quality of the primary metal layer to be assessed. In order to arrive at the completed MID part, building on the first copper layer (primary layer), generally nickel and then a final layer of immersion gold are deposited. Of course other metal layers as well, such as further layers of copper, palladium, tin or silver, may also be applied to the primary layer.

(23) Planarity:

(24) The foils are assessed for their planarity by inspection, using foil sections with dimensions of 60600.1 mm or 1501500.1 mm, as used for the laser structuring, with assessment taking place in each case after foil production, after laser structuring, and after metallization. Foil planarity is characterized as follows:

(25) +: foil lies flat on a smooth surface and at no point in the foil plane has visible elevations or depressions; in other words, the foil is flat.

(26) o: foil does not lie flat on a smooth surface and in the foil plane clearly has a number of elevations or depressions which occupy a multiple of the foil thickness; overall or in the region treated with the laser, the foil is corrugated.

(27) : foil is severely corrugated or has clear three-dimensional deformation.

(28) Summary of Results:

(29) The compositions listed for B1 to B10 (tables 2a and b) can be readily processed by extrusion to give smooth, speck-free foils having a thickness of 100 micrometers. The mechanical properties determined on ISO specimens show that for these molding compositions, elongation at break and impact strength are high and breaking strength is good. The foils can all be structured and metalized to good or very good effect, without the thin foils becoming damaged. It was also found that the metal layer applied electrolessly to the foils possesses very good adhesion to the foil material. Accordingly, the metalized foils can be rolled up multiply to give a roll having a diameter (d) of less than or equal to 10 mm without any observation of detachment or visible damage to the metal layer. The foils in experiments B5, B7 and B8-B10 retain their planarity, moreover, after laser structuring and metallization, whereas other foils, especially those of VB1 and VB2, undergo warping as early as during laser structuring, or at the latest during metallization, becoming corrugated and so completely losing their flat form.

(30) Table 3 contains the comparison between an injection molding containing the LDS additive throughout (VB3) and a molding of the same size produced by in-mold-coating of the foil B7 (example B11), which contains the LDS additive in a thin surface micrometers thick. The layer formed from the in-mold-coated plastic is free from LDS additives. The in-mold-coated foil adheres very well and over the full area to the in-mold-coated plastic, making the foil layer impossible to detach without destruction. The molding produced by in-mold-coating has significantly better mechanical properties. Thus for inventive example B11, with a higher modulus of elasticity, the breaking strength is 35%, the elongation at break is 40%, the impact strength is 90%, and the notched impact strength is more than 100% higher than for VB3, and with equally good metallizability on the part of the molding. A further advantage of B11 is the much lower level of LDS additive required for the production of laser-structurable moldings of this kind. Overall, based on the molding, much less LDS additive is necessary for B11, specifically just 1/20 of the LDS additive amount for VB3 in order to achieve equally good metallizability on the part of the molding.