CONDUCTIVE TEXTILES

Abstract

A method of producing electrically conductive metallic structures in or on textiles, which has the following steps: (a) introducing at least one non-conducting precursor compound into a fibre or yarn material during or after the production thereof, wherein the at least one precursor compound is an inorganic metal phosphate compounds, a metal oxide or a spinel of the general formula AB.sub.2O.sub.4, (b) producing a textile from the fibre or yarn material, (c) irradiating the textile with electromagnetic radiation, preferably with laser light in the regions of the electrically conductive structures to be produced, with the release of metallisation seeds, and (d) electrical or non-electrical treatment of the textile with deposit of metals at the metallisation seeds with the production of conductive structures in the textile.

Claims

1. A method of producing electrically conductive metallic structures in or on textiles, which has the following steps: (a) introducing at least one non-conducting precursor compound into a fibre or yarn material during or after the production thereof, wherein the at least one precursor compound is an inorganic metal phosphate compound, a metal oxide or a spinel of the general formula AB.sub.2O.sub.4, (b) producing a textile from the fibre or yarn material, (c) irradiating the textile with electromagnetic radiation, preferably with laser light in the regions of the electrically conductive structures to be produced, with the release of metallisation seeds, and (d) electrical or non-electrical treatment of the textile with deposit of metal at the metallisation seeds with the production of conductive structures in the textile.

2. The method according to claim 1, wherein the at least one inorganic metal phosphate compound is selected from the group consisting of: copper hydroxide phosphate; anhydrous iron (II) orthophosphate of the general formula Fe.sub.3(PO.sub.4).sub.2; and anhydrous 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, wherein a is a number of 1 to 5, b is a number of >0 to 5, c is a number of 2.5 to 5, d is a number of 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 metalloids of the third, fourth and fifth main groups, and the lanthanoids, or combinations of the above-mentioned phosphates.

3. The method according to claim 1, wherein in addition to the at least one precursor compound at least one stabiliser is introduced into the fibre or yarn material during or after production thereof, which is selected from compounds of the group consisting of Brönsted acids and Lewis acids, wherein a Brönsted acid is defined as a proton-transmitting compound and a Lewis acid is defined as a non-proton-transmitting electron-deficient compound.

4. The method according to claim 1, wherein the at least one stabiliser is or includes a Brönsted acid selected from oxyacids of phosphorus with phosphorus 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 above-mentioned acids.

5. The method according to claim 4, wherein the oxyacids of phosphorus and salts thereof are selected from phosphoric acid, diphosphoric acid, polyphosphoric acids, hypodiphosphoric acid, phosphonic acid, diphosphonic acid, hypodiphosphonic acid, phosphinic acid and salts of the above-mentioned acids and/or the aliphatic and aromatic carboxylic acids and salts thereof are selected from acetic acid, formic acid, oxalic acid, phthalic acid, sulphonic acids, benzoic acid and salts of the above-mentioned acids.

6. The method according to claim 1, wherein the at least one stabiliser is or includes a Lewis acid selected from sodium-aluminium-sulphate (SOS), monocalciumphosphate-monohydrate (MCPM), dicalciumphosphate-dihydrate (DCPD), sodium-aluminium-phosphate (SALP), calcium-magnesium-aluminium-phosphate, calcium polyphosphate, magnesium polyphosphate, aluminium hydroxide, boric acid, alkyl borans, aluminium alkyls, iron (II)-salts and mixtures of the above-mentioned.

7. The method according to claim 1, wherein in addition at least one synergist is introduced into the fibre or yarn material during or after manufacture thereof, which is selected from metal phosphates, metal oxides or mixtures thereof.

8. The method according to claim 1, wherein the at least one non-conducting precursor compound and the optionally used stabiliser and/or the optionally used synergist are introduced into the fibre or yarn material by the fibre or yarn material during or after production thereof being acted upon with a solution thereof or passed through same, wherein the solution is an aqueous solution or a solution in an organic or aqueously organic solvent.

9. The method according to claim 1, wherein the at least one non-conducting precursor compound, with respect to the solid of the precursor compound, is introduced into the fibre or yarn material in an amount which corresponds to at least 0.01 wt % at most 15 wt % of the dry fibre or yarn material.

10. The method according to claim 2, wherein the at least one stabiliser, with respect to the solid of the stabiliser, is introduced into the fibre or yarn material in an amount which corresponds to at least 0.01 wt % and at most 15 wt % of the dry fibre or yarn material.

11. The method according to claim 7, wherein the at least one synergist, with respect to the solid of the synergist, is introduced into the fibre or yarn material in an amount which corresponds to at least 0.01 wt % and at most 15 wt % of the dry fibre or yarn material.

12. The method according to claim 1, wherein the laser light used for irradiating the textile has a wavelength in the range of 200 nm to 12000 nm.

13. The method according to claim 1, wherein the fibre or yarn material is selected from the group consisting of cotton, wool, flax, hemp, viscose, polyamide, polyurethane, polyacrylonitrile, cellulose acetate, polyesters, polyolefins, and copolymers of the above-mentioned.

14. A method comprising adding in or on a textile at least one inorganic metal phosphate compound selected from the group consisting of: copper hydroxide phosphate, anhydrous iron (II) orthophosphate of the general formula Fe.sub.3(PO.sub.4).sub.2 and anhydrous 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, wherein a is a number of 1 to 5, b is a number of >0 to 5, c is a number of 2.5 to 5, d is a number of 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), in particular Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Mn, Cu, Zn, Co, Ni, Ag, Au, the metals and metalloids of the third, fourth and fifth main groups, in particular B, Al, Ga, In, Si, Sn, Sb, Bi and the lanthanoids, or combinations of the above-mentioned phosphates; or a metal oxide or spinel of the general formula AB.sub.2O.sub.4.

15. The method according to claim 14, wherein the at least one inorganic metal phosphate compound or the metal oxide or spinel of the general formula AB.sub.2O.sub.4 is added in combination with a stabiliser and/or with a synergist.

16. (canceled)

17. A textile having electrically conductive metallic structures which is or can be produced according to claim 1.

Description

[0074] The invention will now be further described by means of embodiments by way of example and examples of manufacture for anhydrous iron (II) orthophosphate of the general formula Fe.sub.3(PO.sub.4).sub.2 and anhydrous 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 precursor compounds. The attached Figures show X-ray diffraction diagrams of the metal-phosphate compounds produced in accordance with the production examples.

[0075] FIG. 1 shows the X-ray diffraction diagram of anhydrous Fe.sub.2P.sub.2O.sub.7 produced in accordance with the invention according to production example 1,

[0076] FIG. 2 shows the X-ray diffraction diagram of a phase mixture of anhydrous Mg.sub.1.5Fe.sub.1.5(PO.sub.4).sub.2 and Fe.sub.3(PO.sub.4).sub.2 produced in accordance with the invention according to production example 2,

[0077] FIG. 3 shows the X-ray diffraction diagram of anhydrous Fe.sub.3(PO.sub.4).sub.2 produced according to the invention in accordance with production example 3,

[0078] FIG. 4 shows the X-ray diffraction diagram of anhydrous KFe.sub.3(PO.sub.4) produced according to the invention in accordance with production example 4,

[0079] FIG. 5 shows the X-ray diffraction diagram of anhydrous KFe.sub.0.90Zn.sub.0.10(PO.sub.4) produced according to the invention in accordance with production example 5,

[0080] FIG. 6 shows the X-ray diffraction diagram of anhydrous KFe.sub.0.75Zn.sub.0.25(PO.sub.4) produced according to the invention in accordance with production example 6,

[0081] FIG. 7 shows the X-ray diffraction diagram of anhydrous KFe.sub.0.75Mn.sub.0.25(PO.sub.4) produced according to the invention in accordance with production example 7,

[0082] FIG. 8 shows the X-ray diffraction diagram of anhydrous BaFeP.sub.2O.sub.7 produced according to the invention in accordance with production example 8, and

[0083] FIG. 9 shows conductive metallic structures produced in accordance with example 5 on viscose textile.

EXAMPLES

X-Ray Diffractometry (XRD)

[0084] Taking the products produced in accordance with the examples hereinafter X-ray diffraction measurements were carried out on a diffractometer of the type D8 Advance A25 (Bruker) using CuKα-radiation.

[0085] The products and their crystal structures were identified on the basis of suitable reference diffraction diagrams (Powder Diffraction Files; PDF-cards) of the database of the ICDD (International Centre for Diffraction Data), formerly JCPDS (Joint Committee on Powder Diffraction Standards). Insofar as no PDF cards were available for the products manufactured PDF-cards of isotype compounds (=compounds of the same structure type) were used.

Elementary Analysis

[0086] To ascertain and confirm the stoichiometries of the products manufactured elementary analyses were carried out by means of X-ray fluorescence analysis (XRF) using the Axios FAST spectrometer (from PANalytical).

Production Example 1

Anhydrous Fe.SUB.2.P.SUB.2.O.SUB.7

[0087] A suspension comprising

[0088] i) 35.5 kg of iron (II) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0089] ii) 16.5 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0090] iii) 26.5 kg of 75% phosphoric acid [H.sub.3PO.sub.4] and

[0091] LM: 220 kg of water

[0092] was sprayed granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 4 h in a formine gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 700° C. The result obtained is an almost colourless to pink-coloured product. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 1. The product was identified on the basis of the PDF-card 01-072-1516.

Production Example 2

Phase Mixture of Anhydrous Mg.SUB.1.5.Fe.SUB.1.5.(PO.SUB.4.).SUB.2 .and Fe.SUB.3.(PO.SUB.4.).SUB.2

[0093] A suspension comprising

[0094] i) 8.45 kg of iron (II) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0095] ii) 7.95 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0096] iii) 19.6 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O],

[0097] iv) 8.43 kg of magnesium carbonate [MgCO.sub.3] and

[0098] LM: 160 kg of water

[0099] was spray granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 3 h in a forming gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 750° C. An almost colourless product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 2. The product was defined on the basis of the PDF-cards as a phase mixture comprising a main phase Mg.sub.1.5Fe.sub.1.5(PO.sub.4).sub.2 (PDF-card 01-071-6793) and a secondary phase Fe.sub.3(PO.sub.4).sub.2 (PDF-card 00-49-1087).

Production Example 3

Anhydrous Fe.SUB.3.(PO.SUB.4.).SUB.2

[0100] A suspension comprising

[0101] i) 21.75 kg of iron (II) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0102] ii) 12.15 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0103] iii) 10.3 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O] and

[0104] LM: 140 kg of water

[0105] was spray granulated. The granulate obtained in that way was temperature treated in a rotary furnace for a mean residence time of 90 minutes in a forming gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 750° C. An almost colourless product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 3. The product crystalises in the graftonite structure and was defined on the basis of the PDF-card 00-49-1087. The product was ground in such a way that 50 wt % of the product was of a particle size of less than 3 μm.

Production Example 4

Production of Anhydrous KFe(PO.SUB.4.)

[0106] A suspension comprising

[0107] i) 11.80 kg of iron (III) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0108] ii) 10.70 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0109] iii) 24.8 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O],

[0110] iv) 29.8 kg of 50% potash [KOH]

[0111] v) 1.0 kg of 75% phosphoric acid [H.sub.3PO.sub.4] and

[0112] LM: 110 kg of water

[0113] was spray granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 3 h in a forming gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 650° C. A pale light green product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 4. The product was identified on the basis of the PDF-card 01-076-4615).

Production Example 5

Anhydrous KFe.SUB.0.90.Zn.SUB.0.10.(PO.SUB.4.)

[0114] A suspension comprising

[0115] i) 10.60 kg of iron (III) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0116] ii) 9.65 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0117] iii) 22.30 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O],

[0118] iv) 2.15 kg of zinc oxide [ZnO]

[0119] v) 29.8 kg of 50% potash [KOH]

[0120] vi) 4.15 kg of 75% phosphoric acid [H.sub.3PO.sub.4] and

[0121] LM: 120 kg of water

[0122] was spray granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 2 h in a forming gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 600° C. A light grey product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 5. The product involves a new structure type which seems to be closely related to the KFe(PO.sub.4) structure in accordance with PDF-card 01-076-4615.

Production Example 6

Anhydrous KFe.SUB.0.75.Zn.SUB.0.25.(PO.SUB.4.)

[0123] A suspension comprising

[0124] i) 8.85 kg of iron (III) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0125] ii) 8.05 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0126] iii) 18.60 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O],

[0127] iv) 5.40 kg of zinc oxide [ZnO]

[0128] v) 29.8 kg of 50% potash [KOH]

[0129] vi) 9.30 kg of 75% phosphoric acid [H.sub.3PO.sub.4] and

[0130] LM: 120 kg of water

[0131] was spray granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 2 h in a forming gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 600° C. A light grey product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 6. The product is not known from the literature. It crystalises isotypically to KZn(PO.sub.4) in accordance with PDF-card 01-081-1034.

Production Example 7

Anhydrous KFe.SUB.0.25.(PO.SUB.4.)

[0132] A suspension comprising

[0133] i) 8.85 kg of iron (III) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0134] ii) 8.05 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0135] iii) 18.60 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O],

[0136] iv) 8.85 kg of manganese carbonate-hydrate [MnCO.sub.3H.sub.2O]

[0137] v) 29.8 kg of 50% potash [KOH]

[0138] vi) 9.30 kg of 75% phosphoric acid [H.sub.3PO.sub.4] and

[0139] LM: 140 kg of water

[0140] was spray granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 2 h in a forming gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 600° C. A light grey product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 7. The product is not known from the literature. It crystalises isotypically to KFe(PO.sub.4) in accordance with PDF-card 01-076-4615.

Production Example 8

Anhydrous BaFeP.SUB.2.O.SUB.7

[0141] A suspension comprising

[0142] i) 8.70 kg of iron (III) oxide hydroxide [FeO(OH) or Fe.sub.2O.sub.31H.sub.2O],

[0143] ii) 8.20 kg of 98% phosphonic acid [H.sub.3PO.sub.3],

[0144] iii) 19.05 kg of iron (III)-phosphate-dihydrate [FePO.sub.42H.sub.2O],

[0145] iv) 63.09 kg of barium hydroxide-octahydrate [Ba(OH).sub.28H.sub.2O]

[0146] v) 26.15 kg of 75% phosphoric acid [H.sub.3PO.sub.4] and

[0147] LM: 250 kg of water

[0148] was spray granulated. The granulate obtained in that way was temperature-treated in a rotary furnace for a mean residence time of 4 h in a formin gas atmosphere (5 vol-% H.sub.2 in N.sub.2) at 800° C. A light grey product was obtained. The X-ray diffraction diagram (XRD) of the product is shown in FIG. 8. The product crystalises isotypically to BaCoP.sub.2O.sub.7 in accordance with PDF-card 01-084-1833.

[0149] The following Examples explain the method according to the invention.

Example 1

[0150] Iron (II) magnesium phosphate of the formula Fe.sub.2Mg(PO.sub.4).sub.2 was dry mixed with 1 wt % of disodium dihydrogen phosphate, Na.sub.2H.sub.2P.sub.2O.sub.7. 5 wt % of the mixture was incorporated by means of an extruder (type ZSK 18 from Coperion GmbH) into a polyamide 6,6 (Ultramid™ from BASF) and a granulate was produced. The granulate could be processed to give fibres by means of melt spinning.

Example 2

Comparative

[0151] 3 wt % of copper hydroxide phosphate was incorporated by means of an extruder (type ZSK 18 from Coperion GmbH) into a polyamide 6,6 (Ultramid™ from BASF). The extrusion operation was carried out at the upper end of the recommended temperature range at 285° C. Unwanted discolouration of the plastic occurred. The initially light greenish compound changed its colour to brown. In addition a slight but unwanted deposit of metallic copper on the shaft of the extruder was found.

Example 3

[0152] 4 wt % of copper hydroxide phosphate and 2 wt % of sodium-aluminium-sulphate (SAS) was incorporated by means of an extruder (type ZSK 18 from Coperion GmbH) into a polyamide 6,6 (Ultramid™ from BASF) and a granulate was produced. The extrusion operation was carried out at the upper end of the recommended temperature range at 285° C. No unwanted discolouration of the plastic occurred and there was no deposit of metallic copper on the shaft of the extruder. It was possible to produce polyamide fibres by way of the melt spinning method.

Example 4

[0153] Polyamide fibres produced in Examples 1 and 3 were used to produce textiles by weaving. They were activated by means of laser light of a wavelength of 1064 mm with different laser parameters. For first investigations relating to the metallisation the textile patterns were processed over 120 min in the chemical copper electrolyte at a copper deposit rate of 3-5 μm/h.

Example 5

Production of Electrically Conductive Metallic Structures on a Viscose Textile

[0154] In a first step viscose fibres were produced in an industrial viscose spinning process known to the man skilled in the art. Copper hydroxide phosphate (Cu.sub.2(OH)PO.sub.4; Fabulase 361, Chemische Fabrik Budenheim KG) was added as the precursor compound to the spinning solution. The precursor compound was of a grain size of 3.4 μm (median value) and an exclusion value of the maximum grain size of 10 μm. The viscose fibre obtained had a fineness in accordance with ISO 1144 and DIN 60905 of 1.7 dtex. The loading of the viscose fibre with the precursor compound copper hydroxide phosphate was 3 wt % with respect to the weight of the dry viscose fibre.

[0155] In a next processing step non-wovens (spun non-wovens) were produced from the viscose fibres produced, using the so-called spunlace method. In that case respective mixtures of fibres with and without loading with precursor compound were used in defined ratios. Non-woven consisting only of non-loaded fibres was produced as a reference. The non-wovens respectively were of a weight in relation to surface area of 100 g/m.sup.2.

TABLE-US-00001 TABLE 1 Textiles produced (non-wovens): Textile pattern # Cu.sub.2(OH)PO.sub.4 loaded fibre [%] Non-loaded fibre [%] 1 (Ref.) — 100%  2 20% 80% 3 80% 20% 4 100%  —

[0156] Structures were produced on the textile pattern #4 by means of laser irradiation with different laser parameters. The pulse rate was constant at 100 kHz. The laser power, pulse energy, scanning speed, longitudinal pitch and transverse pitch were varied. “Longitudinal pitch” denotes the spacing between two points of the laser irradiation in the longitudinal direction of a linear structure. “Transverse pitch” denotes the spacing between two points of the laser irradiation transversely to the longitudinal direction of a linear structure. By way of example 3 parameter sets are explained in greater detail. With the parameter sets L1 and L2 the scanning speed at 500 mm/s as well as the longitudinal and transverse pitch at 5 μm were kept constant while the laser power and pulse energy were varied. In the case of L1 the values of laser power and pulse energy were at 2 W and 20 μJ while the values in L2 were at 4 W and 40 μJ. In parameter set L3 the laser power and the pulse energy were increased further to 8 W and 80 μJ. In addition the scanning speed was doubled to 1000 mm/s and the longitudinal and transverse pitch were respectively increased to 10 μm.

[0157] A laser installation MicroLine 3D 160i from LPKF with a focus diameter of 60 μm and a wavelength of 1064 nm was used for laser structuring. After laser irradiation the textile patterns were cleaned by a wet chemical procedure.

[0158] The textile patterns were firstly visually assessed after laser irradiation but prior to metallisation. Here the structuring with adequate energy input could already be well observed but an excessively high energy input resulted in partial destruction of the textile.

[0159] For metallisation the textile patterns were processed over 120 min in the chemical copper electrolyte with a copper deposit rate of 3-5 μm/h.

[0160] Good Cu deposit could be observed over wide ranges of the laser parameter sets used, as is shown in FIG. 9 reproducing the modified viscose textile after laser structuring and metallisation (laser parameter set L1 at the left, laser parameter set L2 at the middle and laser parameter set L3 at the right). In general laser parameter sets involving greater longitudinal and transverse pitches like for example parameter set L3 severed the textile to a lesser degree.

[0161] In addition it was possible to observe that no closed metal layer was formed by virtue of the condition of the substrate in the investigations. Rather the individual textile fibres were coated in the laser-structured regions upon processing in the Cu electrolyte. Electrical accelerated tests on metallised regions gave electrical conductivity of the structures.