METHOD FOR MANUFACTURING ELECTRICALLY CONDUCTIVE STRUCTURES ON A CARRIER MATERIAL

Abstract

A method for manufacturing electrically conductive structures, preferably conductive pathway structures using laser beams on a non-conductive carrier (LDS method), wherein a non-conductive carrier material is provided which contains at least one inorganic metal phosphate compound and at least one stabiliser finely distributed or dissolved therein, the carrier material is irradiated in regions by laser beams generating the electrically conductive structures in the irradiated regions.

Claims

1. A method for manufacturing electrically conductive structures comprising: providing a non-conductive carrier material which contains at least one inorganic metal phosphate compound and at least one stabiliser finely distributed or dissolved therein; and irradiating the carrier material in regions by of laser beams generating the electrically conductive structures in the irradiated regions, wherein the at least one inorganic metal phosphate compound is selected from the group, consisting of copper hydroxide phosphate of the general formula Cu.sub.2(OH)PO.sub.4, crystal water-free iron(II) orthophosphate of the general formula Fe.sub.3(PO.sub.4).sub.2 or crystal water-free iron(II) metal orthophosphate, iron(II) metal phosphonate, iron(II) metal pyrophosphate or iron(II) metal metaphosphate of the general formula Fe.sub.aMet.sub.b(PO.sub.c).sub.d, where a is a number from 1 to 5, b is a number from >0 to 5, c is a number from 2.5 to 5, d is a number from 0.5 to 3 and wherein Met represents one or more metals selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, the transition metals (d block), the metals and semimetals of the third, fourth and fifth main groups, and the lanthanoids or combinations of the above mentioned phosphates, and wherein the at least one stabiliser is selected from compounds of the group, consisting of Bronsted acids and Lewis acids, wherein a Bronsted acid is defined as a proton-transferring compound and a Lewis acid is defined as a non-proton-transferring electron-deficient compound.

2. The method according to claim 1, wherein the at least one stabiliser is or comprises a Bronsted acid, selected from oxoacids of phosphorous with phosphorous in the oxidation stage +V, +IV, +III, +II or +I, sulphuric acid, nitric acid, hydrofluoric acid, silicic acid, aliphatic and aromatic carboxylic acids and salts of the aforementioned acids.

3. The method according to claim 2, wherein the oxoacids of the phosphorous and their salts are selected from phosphoric acid, diphosphoric acid, polyphosphoric acids, hypodiphosphoric acid, phosphonic acid, diphosphonic acid, hypodiphosphonic acid, phosphinic acid and salts of the aforementioned acids and/or in that the aliphatic and aromatic carboxylic acids and their salts are selected from acetic acid, formic acid, oxalic acid, phthalic acid, sulfonic acids, benzoic acid and salts of the aforementioned acids.

4. The method according to claim 1, wherein the at least one stabiliser is or comprises a Lewis acid, selected from sodium aluminium sulphate (SAS), monocalcium phosphate monohydrate (MCPM), dicalcium phosphate dihydrate (DCPD), sodium aluminium phosphate (SALP), calcium magnesium aluminium phosphate, calcium polyphosphate, magnesium polyphosphate, aluminium hydroxide, boric acid, alkyl boranes, aluminium alkyls, iron(II) salts and mixtures of the foregoing.

5. The method according to claim 1, wherein metal is chemically reductively or electrolytically deposited on the electrically conductive structures generated by means of laser beams.

6. The method according to claim 1, wherein the non-conductive carrier material contains the at least one inorganic metal phosphate compound in a quantity of 0.01% by weight to 45% by weight in relation to the total mass of the composition made up of the sum of the mass of the non-conductive carrier material and the added material.

7. The method according to claim 1, wherein the non-conductive carrier material contains the at least one stabiliser in a quantity of 0.01% by weight to 25% by weight in relation to the total mass of the composition made up of the sum of the mass of the non-conductive carrier material and the added material.

8. The method according to claim 1, wherein the non-conductive carrier material also contains at least one synergist, which is selected from metal phosphates, metal oxides or mixtures thereof.

9. The method according to claim 8, wherein the non-conductive carrier material contains the at least one synergist in a quantity of 0.01% by weight to 15% by weight in relation to the total mass of the composition made up of the sum of the mass of the non-conductive carrier material and the added material.

10. The method according to claim 1, wherein the non-conductive carrier material is selected from the group consisting of thermoplastic polymers, thermosetting polymers, elastomers, glasses, ceramics, natural or synthetic varnishes, natural or synthetic resins, silicones or combinations or mixtures thereof.

11. The method according to claim 1, wherein the non-conductive carrier material is selected from the group consisting of polyvinyl butyral (PVB), polypropylene (PP), polyethylene (PE), polyamide (PA), polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene oxide, polyacetal, polymethacrylate, polyoxymethylene, polyvinyl acetal, polystyrene, acryl butadien styrene (ABS), acrylonitrile styrene acrylate (ASA), polycarbonate, polyethersulfone, polysulfonate, polytetrafluoroethylene, polyurea, formaldehyde resin, melamine resin, polyetherketone, polyvinyl chloride, polylactide, polysiloxane, phenol resin, epoxide resin, poly(imide), bismaleimide-triazine, thermoplastic polyurethane, copolymers and/or mixtures of the polymers mentioned above.

12. The method according to claim 1, wherein the laser beam has a wavelength in the region of 200 nm to 12000 nm.

13. A method comprising manufacturing electrically conductive structures with a combination of at least one inorganic metal phosphate compound and a stabiliser as they are defined in claim 1.

14. A carrier material with electrically conductive structures on a surface of the carrier material, wherein the carrier material contains at least one inorganic metal phosphate compound as defined in claim 1 and at least one stabiliser as well as possibly at least one synergist finely distributed therein.

Description

[0043] The invention will now be explained further based on exemplary embodiments as well as manufacturing examples for crystal water-free iron (II) orthophosphates of the general formula Fe.sub.3(PO.sub.4).sub.2 and crystal water-free iron(II) metal orthophosphate, iron(II) metal phosphonate, iron(II) metal pyrophosphate or iron (II) metal metaphosphate of the general formula Fe.sub.aMet.sub.b(PO.sub.c).sub.d, which are suitable according to the invention as metal phosphate compounds. The attached figures show X-ray diffraction diagrams of the metal phosphate compounds manufactured according to the manufacturing examples.

[0044] FIG. 1 shows the x-ray diffractogram of crystal water-free Fe.sub.2P.sub.2O.sub.7 manufactured in accordance with the invention in line with manufacturing example 1.

[0045] FIG. 2 shows the x-ray diffractogram of a phase mixture of crystal water-free Mg.sub.1.5Fe.sub.1.5(PO.sub.4).sub.2 and Fe.sub.3(PO.sub.4).sub.2 manufactured in accordance with the invention in line with manufacturing example 2.

[0046] FIG. 3 shows the x-ray diffractogram of crystal water-free Fe.sub.3(PO.sub.4).sub.2 manufactured in accordance with the invention in line with manufacturing example 3.

[0047] FIG. 4 shows the x-ray diffractogram of crystal water-free KFe(PO.sub.4) manufactured in accordance with the invention in line with manufacturing example 4.

[0048] FIG. 5 shows the x-ray diffractogram of crystal water-free KFe.sub.0.90Zn.sub.0.10(PO.sub.4) manufactured in accordance with the invention in line with manufacturing example 5.

[0049] FIG. 6 shows the x-ray diffractogram of crystal water-free KFe.sub.0.75Zn.sub.0.25(PO.sub.4) manufactured in accordance with the invention in line with manufacturing example 6.

[0050] FIG. 7 shows the x-ray diffractogram of crystal water-free KFe.sub.0.75Mn.sub.0.25(PO.sub.4) manufactured in accordance with the invention in line with manufacturing example 7.

[0051] FIG. 8 shows the x-ray diffractogram of crystal water-free BaFeP.sub.2O.sub.7 manufactured in accordance with the invention in line with manufacturing example 8.

EXAMPLES

[0052] X-Ray Diffractometry (XRD)

[0053] Of the products manufactured according to the examples below, x-ray diffraction measurements (XRD) are taken using a D8 Advance A25-type diffractometer (Bruker) and CuKoc radiation.

[0054] The products and their crystal structures were identified on the basis of corresponding reference diffractograms (Powder Diffraction Files; PDF) from the ICDD (International Centre for Diffraction Data), previously JCPDS (Joint Committee on Powder Diffraction Standards) database. If no PDF cards were available for the products manufactured, PDF cards for isotype compounds were used (=compounds of the same structural type).

[0055] Elementary Analysis

[0056] Elementary analyses were carried out by means of x-ray fluorescence analysis (XRF) using an Axios FAST spectrometer (PANalytical) in order to determine and confirm the stoichiometries of the products manufactured.

[0057] Manufacturing Example 1Crystal Water-Free Fe.sub.2P.sub.2O.sub.7

[0058] A suspension of

[0059] i) 35.5 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0060] ii) 16.5 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0061] iii) 26.5 kg 75% phosphoric acid [H.sub.3PO.sub.4] and solvent 220 kg water

[0062] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 4 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 700 C. An almost colourless to slightly pink product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 1. The product was identified using PDF card 01-072-1516.

[0063] Manufacturing Example 2Phase Mixture of Crystal Water-Free Mg.sub.1.5Fe.sub.1.5(PO.sub.4).sub.2 and Fe.sub.3(PO.sub.4).sub.2

[0064] A suspension of

[0065] i) 8.45 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0066] ii) 7.95 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0067] iii) 19.6 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O],

[0068] iv) 8.43 kg magnesium carbonate [MgCO.sub.3] and solvent 160 kg water

[0069] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 3 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 750 C. An almost colourless product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 2. The product was identified using the PDF cards as a phase mixture of a main phase Mg.sub.1.5Fe.sub.1.5(PO.sub.4).sub.2 (PDF card 01-071-6793) and a subsidiary phase Fe.sub.3(PO.sub.4).sub.2 (PDF card 00-49-1087).

[0070] Manufacturing Example 3Crystal Water-Free Fe.sub.3(PO.sub.4).sub.2

[0071] A suspension of

[0072] i) 21.75 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0073] ii) 12.15 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0074] iii) 10.3 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O] and solvent: 140 kg water

[0075] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 90 minutes in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 750 C. An almost colourless product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 3. The product crystallises in the graftonite structure and was identified using PDF card 00-49-1087. The product was ground such that 50% by weight of the product had a particle size of less than 3 m. The particle size distribution of the ground product is shown in FIG. 9.

[0076] Manufacturing Example 4Manufacture of Crystal Water-Free KFe(PO.sub.4)

[0077] A suspension of

[0078] i) 11.80 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0079] ii) 10.70 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0080] iii) 24.8 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O]

[0081] IV) 29.8 kg 50% lye [KOH]

[0082] V) 1.0 kg 75% phosphoric acid [H.sub.3PO.sub.4] and solvent: 110 kg water

[0083] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 3 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 650 C. A pale light green product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 4. The product was identified using PDF card 01-076-4615.

[0084] Manufacturing Example 5Crystal Water-Free KFe.sub.0.90Zn.sub.0.10(PO.sub.4)

[0085] A suspension of

[0086] i) 10.60 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0087] ii) 9.65 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0088] iii) 22.30 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O]

[0089] IV) 2.15 kg zinc oxide [ZnO]

[0090] IV) 29.8 kg 5% lye [KOH]

[0091] V) 4.15 kg 75% phosphoric acid [H.sub.3PO.sub.4] and

[0092] solvent: 120 kg water

[0093] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 2 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 600 C. A light grey product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 5. The product is a new structure type which appears to be closely linked to the KFe(PO.sub.4) structure according to PDF card 01-076-4615.

[0094] Manufacturing Example 6Crystal Water-Free KFe.sub.0.75Zn.sub.0.25(PO.sub.4)

[0095] A suspension of

[0096] i) 8.85 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0097] ii) 8.05 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0098] iii) 18.60 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O]

[0099] IV) 5.40 kg zinc oxide [ZnO]

[0100] IV) 29.8 kg 50% potash lye [KOH]

[0101] V) 9.30 kg 75% phosphoric acid [H.sub.3PO.sub.4] and solvent: 120 kg water

[0102] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 2 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 600 C. A light grey product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 6. The product is not known from the literature. It crystallises in an isotype manner to form KZn(PO.sub.4) according to PDF card 01-081-1034.

[0103] Manufacturing Example 7Crystal Water-Free KFe.sub.0.75Mn.sub.0.25(PO.sub.4)

[0104] A suspension of

[0105] i) 8.85 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0106] ii) 8.05 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0107] iii) 18.60 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O]

[0108] IV) 8.85 kg manganese carbonate hydrate [MnCO.sub.3 H.sub.2O]

[0109] IV) 29.8 kg 50% lye [KOH]

[0110] V) 9.30 kg 75% phosphoric acid [H.sub.3PO.sub.4] and solvent: 140 kg water

[0111] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 2 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 600 C. A light grey product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 7. The product is not known from the literature. It crystallises in an isotype manner to KFe(PO.sub.4) according to PDF card 01-076-4615.

[0112] Manufacturing Example 8Crystal Water-Free BaFeP.sub.2O.sub.7

[0113] A suspension of

[0114] i) 8.70 kg iron(III) oxide-hydroxide [FeO(OH) or Fe.sub.2O.sub.3 1H.sub.2O],

[0115] ii) 8.20 kg 98% phosphonic acid [H.sub.3PO.sub.3],

[0116] iii) 19.05 kg iron(III) phosphate dihydrate [FePO.sub.4 2H.sub.2O]

[0117] IV) 63.09 kg barium hydroxide octahydrate [Ba(OH).sub.2 8H.sub.2O]

[0118] V) 26.15 kg 75% phosphoric acid [H.sub.3PO.sub.4] and

[0119] solvent: 250 kg water

[0120] was spray granulated. The granulate obtained in this way was temperature treated in a rotary kiln for an average residence time of 4 h in a forming gas atmosphere (5% by volume H.sub.2 in N.sub.2) at 800 C. A light grey product is obtained. The x-ray diffractogram (XRD) of the product is shown in FIG. 8. The product crystallises in an isotype manner to form BaCoP.sub.2O.sub.7 according to PDF card 01-084-1833.

[0121] The following examples explain the method according to the invention.

Example 1

[0122] 1 kg of copper hydroxide phosphate was put with 100 g titanium dioxide in a reactor with water and stirred for 1 h. The preparation obtained was filtered and dried at approx. 120 C. up to a water content of max. 0.5% by weight. The powder obtained was dry mixed with 1% by weight disodium dihydrogen phosphate, Na.sub.2H.sub.2P.sub.2O.sub.7. Five percent by weight of the mixture was worked into a PC/ABS copolymer by Sabic (LNPTMCOLORCOMPTM Compound NX05467) using an extruder (ZSK18-type by Coperion GmbH). The plastic was then processed with the aid of an injection moulding machine to form approx. 2 mm thick plates. The plates were irradiated with an Nd:YAG laser (Trumpf) with a wavelength of 1064 nm and structures were generated. Uniform metal separation (metal nuclei) took place which was suitable as conductive pathways or precursors of conductive pathways.

Example 2

[0123] Iron(II) magnesium phosphate of the formula Fe.sub.2Mg(PO.sub.4).sub.2 was dry mixed with 1% by weight disodium dihydrogen phosphate, Na.sub.2H.sub.2P.sub.2O.sub.7. Five percent by weight of the mixture was worked into a polyamide 6.6 (Ultramid by BASF) using an extruder (ZSK18-type by Coperion GmbH) and a granulate manufactured. The granulate was then further processed to form plates of 3 cm4 cm3 mm. The plates were irradiated with an Nd:YAG laser (Trumpf) with a wavelength of 1064 nm and electrically conductive structures were generated.

Example 3 (Comparison)

[0124] Three percent by weight copper hydroxide phosphate was worked into a polyamide 6.6 (Ultramid by BASF) using an extruder (ZSK18-type by Coperion GmbH). The extrusion was carried out at the upper end of the recommended temperature range at 285 C. In this case, there was undesired discolouration of the plastic. The initially slightly greenish compound changed its colour to brown.

[0125] In addition, a slight, but undesired separation of metallic copper on the shaft of the extruder was found.

Example 4

[0126] Four percent by weight copper hydroxide phosphate and 2 percent by weight sodium aluminium sulphate (SAS) were worked into a polyamide 6.6 (Ultramid by BASF) using an extruder (ZSK18-type by Coperion GmbH) and a granulate manufactured. The extrusion was carried out at the upper end of the recommended temperature range at 285 C. The granulate was then further processed to form plates of 3 cm4 cm3 mm. There was no undesired discolouration in the plastic and no deposition of metallic copper on the shaft of the extruder. The plates were irradiated with an Nd:YAG laser (Trumpf) with a wavelength of 1064 nm and structures were generated. Uniform formation of conductive structures took place which were suitable as conductive pathways or precursors of conductive pathways.

Example 5

[0127] Forty percent by weight iron(II) orthophosphate Fe.sub.3(PO.sub.4).sub.2 and 1 percent by weight sodium aluminium sulphate (SAS) were worked into an LDPE (Lupolen 1800 S by LyondellBasell) using an extruder (ZSK18-type by Coperion GmbH) and a granulate manufactured. The granulate was then further processed to form plates of 3 cm4 cm3 mm. There was a slight green colouration in the plastic, but no deposition on the shaft of the extruder. The plates were irradiated with an Nd:YAG laser (Trumpf) with a wavelength of 1064 nm and structures were generated. Uniform formation of conductive structures took place which were suitable as conducting pathways or precursors of conducting pathways.