U.S. patent application number 17/279638 was filed with the patent office on 2021-12-16 for conductive textiles.
This patent application is currently assigned to Chemische Fabrik Budenheim KG. The applicant listed for this patent is Chemische Fabrik Budenheim KG. Invention is credited to David ENGERS, Thomas FUTTERER, Tobias MOSS, Gideon RATH, Rudiger WISSEMBORSKI.
Application Number | 20210388532 17/279638 |
Document ID | / |
Family ID | 1000005867989 |
Filed Date | 2021-12-16 |
United States Patent
Application |
20210388532 |
Kind Code |
A1 |
ENGERS; David ; et
al. |
December 16, 2021 |
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.
Inventors: |
ENGERS; David; (Budenheim,
DE) ; FUTTERER; Thomas; (Ingelheim, DE) ;
MOSS; Tobias; (Darmstadt, DE) ; RATH; Gideon;
(Darmstadt, DE) ; WISSEMBORSKI; Rudiger;
(Neuruppin, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Chemische Fabrik Budenheim KG |
Budenheim |
|
DE |
|
|
Assignee: |
Chemische Fabrik Budenheim
KG
Budenheim
DE
|
Family ID: |
1000005867989 |
Appl. No.: |
17/279638 |
Filed: |
September 26, 2019 |
PCT Filed: |
September 26, 2019 |
PCT NO: |
PCT/EP2019/075991 |
371 Date: |
March 25, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D01F 2/08 20130101; D01F
1/10 20130101; D06M 10/005 20130101; D01F 1/09 20130101; D06M 10/06
20130101; D06M 11/83 20130101; D10B 2401/16 20130101 |
International
Class: |
D01F 1/09 20060101
D01F001/09; D01F 1/10 20060101 D01F001/10; D01F 2/08 20060101
D01F002/08; D06M 10/00 20060101 D06M010/00; D06M 10/06 20060101
D06M010/06; D06M 11/83 20060101 D06M011/83 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 2, 2018 |
DE |
10 2018 124 344.8 |
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
Bronsted acids and Lewis acids, wherein a Bronsted 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 Bronsted 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
SUBJECT-MATTER OF THE INVENTION
[0001] The present invention concerns a method of producing
electrically conductive metallic structures in or on textiles, the
use of selected metal phosphates as precursor compounds in such a
method and textiles produced in accordance with the method and
having electrically conductive metallic structures.
BACKGROUND OF THE INVENTION
[0002] The production of electrically conductive textiles or
electrically conductive structures in or on textiles is basically
known.
[0003] For example for producing conductive textiles electrically
conducting fibres or yarns like for example metal wires or
conductively impregnated or coated threads can be incorporated in
the textile manufacturing procedure. In that case the extent and
orientation of the conductive structures in the textile material is
determined inter alia by the manner of processing the fibres or
yarns to afford the textile material. In a woven material for
example the direction of conductivity will depend on whether the
incorporated conductive threads are incorporated in the form of
warp threads, weft threads or both. Corresponding considerations
apply to knitted fabrics, crocheted fabrics and so forth. The
implementation of conductivity in or on the textiles, in particular
the provision of given conductive structures like circuits,
antennae etc. is therefore severely restricted with that method. In
addition the conductive fibres or yarns to be incorporated
generally differ in respect of structure, strength and/or thickness
of the processed non-conductive fibres or yarns, which can require
suitably adapted processing machines like for example special
looms. In addition the incorporated conductive fibres or yarns,
besides conductivity, also influence other properties of the
textile material like for example its flexibility, haptic and
visual properties which can be unwanted or can also detrimentally
influence further processing of the textile material.
[0004] To circumvent some of the above-mentioned disadvantages, for
example to provide given conductive structures like circuits,
antennae etc. on textile material there are methods in which
conductive fibres or threads are sewn on to the textile material in
the desired structure. Alternatively conductive coatings of the
desired structure are applied to the textile material for example
in the form of hardening conductive lacquer or the like. Both
methods are laborious, work-intensive and often also poorly
scalable like for example in the case of large woven fabric areas
in the construction sector. Depending on the nature and extent of
the applied conductive structures they can detrimentally influence
further properties of the textile material like its flexibility,
haptic and visual properties and options for further processing of
the textile materials, and not infrequently the applied conductive
structures have inadequate mechanical resistance and adhesion on
the textile material.
[0005] Joohan Kim, JeongU Rho, Jong Hyeong Kim, Laser
solidification of conductive composites on a fabric surface,
Surface & Coating Technology 205 (2010) 1812-1819, describe a
further method of producing electrically conductive structures on
textile materials, in which a conductive paste is applied over a
large area to the textile material. Then, similarly as in the
production of conductor tracks using the so-called photoresist
method the paste is exposed by means of laser light along the
desired structure and in that way fixed or made resistant to a
subsequent washing step with which the non-exposed regions of the
paste are removed and the conducting structures remain behind. That
method however results in large amounts of waste in the form of the
washed-off paste which either has to be disposed of or processed in
an expensive and complicated procedure. A further disadvantage is
that the textile material, similarly as in the above-described
application of a conductive lacquer, is provided with the
conductive structures only on one side and at the surface.
[0006] US 2017/0204510 A1 describes a method of producing a
metal-coated non-woven fabric from a polymer material by
electrolytic coating with copper or nickel. In that case the entire
non-woven material is acted upon with a coating solution, with the
result that it is metalised throughout. The method does not allow
the application of desired conductive structures. In addition the
method is cost-intensive.
[0007] To produce specifically conductive structures on a
completely conductive textile material, as described hereinbefore,
methods are further known in which the material which is conductive
throughout is printed upon with an etch-resistant polymer mask and
protected thereby, in the regions in which the conductive
structures are to be retained. The conductive metal layer is then
removed by etching in the regions which are not protected by the
polymer mask. The polymer mask is then removed with an organic
solvent so that a conductive structure is produced on the woven
material. US 2018/0168032 describes an alternative method in which
the completely conductive textile material, in the regions in which
no conductivity is to be acquired, is printed upon with an etching
paste which removes the metallisation. Both methods are highly
laborious, cost-intensive and require the use of strongly corrosive
agents and disposal thereof.
[0008] EP 1 966 431 discloses a further method of producing
conductive structures on textiles including printing on the textile
material with a printing formulation containing a metal powder and
subsequent thermal treatment in which the metal is deposited. A
disadvantage here is once again the fact that the conductive
metallisation is applied to the textile material on one side.
[0009] US 2018/08017 describes a method of producing an
electrically conductive textile material in which the surface of
the textile material is firstly silanised and then modified with a
negatively charged polyelectrolyte. Metal particles are then
deposited in a current-free procedure. The method requires a large
number of process steps which are in part difficult to control.
[0010] Tariq Bashir, Mikael Skrifvars, Nils-Krister Persson,
Production of high conductive textile viscose yarns by chemical
vapor deposition technique: a route to continuous process, Polym.
Adv. Technol. 2011, 22 2214-2221, describe the production of
conductive textiles in which viscose fibres are coated by means of
chemical vapour deposition (CVD) with a conductive polymer and are
then processed to afford a textile material. The fibres obtained
exhibited high conductivity but the textile material is made
completely conductive with that method.
[0011] Liangbing Hu. Yi Cui, Energy and environmental
nanotechnology in conductive paper and textiles, Energy Environ.
Sci., 2012, 5, 6423-6435, describes the coating of textiles with
carbon nanotubes (CNTs). The conductive fibres produced in that way
exhibited good mechanical properties. However the high costs for
CNTs are a decisive factor, why that technology hitherto could not
gain acceptance.
OBJECT
[0012] The object of the present invention is to provide a method
which is improved over the state of the art of producing
electrically conductive metallic structures in or on textiles,
including highly complex structures which can be produced
individually for individual textiles, which is comparatively
simple, inexpensive, precise and resource-friendly and even with
ongoing and/or repeated loading of the textile material, for
example when washing, provides stable and long-lived conductive
structures which comparatively little impair the properties of the
textile material in terms of processing and/or use.
DESCRIPTION OF THE INVENTION
[0013] According to the invention that object is attained by a
method of producing electrically conductive metallic structures in
or on textiles, which has the following steps: [0014] (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, [0015] (b) producing a textile from the
fibre or yarn material, [0016] (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 [0017] (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.
[0018] In the first method step (a) of the method according to the
invention there is introduced into an initially not electrically
conductive fibre or yarn material at least one inorganic metal
phosphate compound which is referred to herein as the precursor
compound as it is selected from such compounds which are
activatable by means of laser light with the release of
metallisation seeds.
[0019] The inorganic metal phosphates, metal oxides or spinels used
according to the invention as the precursor compounds are
preferably temperature-resistant in such a way that even at
elevated temperatures as can occur for example in certain textile
production methods they remain stable, that is to say in this
connection that they are not already activated prior to the laser
treatment at the elevated temperatures and in that case already
undesirably form metallisation seeds distributed over the entire
textile material.
[0020] Optionally step (d) can advantageously be followed by a
post-treatment of the textile, in which an additional coating is
implemented to protect the metallised material. For example the
coating can be a covering comprising a suitable polymer
material.
[0021] Examples of metal oxides or spinels which are suitable
according to the invention of the general formula AB.sub.2O.sub.4,
wherein A and B are different metals, include copper-iron-spinel,
copper-chromium-spinel, magnesium-aluminium-oxide,
copper-chromium-manganese-oxide, copper-manganese-iron-oxide,
copper (I) oxide, copper (II) oxide, copper-chromium-oxide,
zinc-iron-oxide, cobalt-chromium-oxide, cobalt-aluminium-oxide,
magnesium-aluminium-oxide and mixtures thereof.
[0022] According to the invention preferred inorganic metal
phosphate compounds which are particularly suitable as precursor
compounds are selected from: [0023] copper hydroxide phosphate,
preferably copper hydroxide phosphate of the general formula
Cu.sub.2(OH)PO.sub.4, [0024] anhydrous iron (II) orthophosphate of
the general formula Fe.sub.3(PO.sub.4).sub.2 and [0025] 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,
[0026] 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.
[0027] Those compounds afford a large number of advantages over
many other metal compounds. They can be produced economically and
inexpensively, which has an advantageous effect on the production
costs of textiles with electrically conductive structures using the
method according to the invention. In addition they enjoy high
absorption in the near infra-red range (NIR) while they exhibit
only weak absorption in the visible range of electromagnetic
radiation. As a result the colour of the textile material is not
seriously affected at least in the regions in which no electrically
conductive structures are produced, while at the same time they can
be efficiently activated by means of laser light, in particular in
the NIR range. It is assumed that the high absorption capability of
those compounds according to the invention in the NIR range is
governed by their crystal structure. In that way a particularly
high yield in respect of the radiated laser light in relation to
the mass of precursor compound used is achieved. Those properties
make it possible to keep the amounts of those components used and
thus also the influences thereof on the material properties of the
textile material as low as possible.
[0028] There are various suitable possible ways of introducing the
non-conducting precursor compound into the fibre or yarn
material.
[0029] In an embodiment of the method according to the invention
the fibre or yarn material, during or after production thereof, is
acted upon with or is passed through a solution of the
non-conducting precursor compound which possibly contains further
components like for example a stabiliser or/or synergist which are
also described hereinafter. Preferably an aqueous solution is used.
Alternatively a solution in an organic or aqueously organic solvent
is used. The fibre or yarn material can be acted upon with the
solution by spraying, dipping or passing the fibre or yarn material
through a bath. In that case the fibre or yarn material is acted
upon or soaked with the solution either only in the region near the
surface or completely. The fibre or yarn material can then be
further processed either moist or after drying with complete or
partial removal of the solvent in the next method step.
[0030] In a preferred embodiment of the invention the at least one
non-conducting precursor compound and possibly additives used, for
example a stabiliser and/or synergist, as are described
hereinafter, is introduced into the fibre or yarn material by at
least one of those substances being suspended as a solid in a
spinning solution and then spun through nozzles.
[0031] The term "solution" of the non-conducting precursor compound
and possibly further components includes in accordance with the
present invention both true solutions and also suspensions and
dispersions of the constituents.
[0032] The operation of acting on the fibre or yarn material with
the precursor compound can also be effected directly in various
fibre spinning processes. Thus for example the precursor compound
can be homogenously distributed in powder form (suspended or
dispersed) in the wet spinning operation, for example in the
production of viscose fibres, or can be contained disolved in the
spinning solution, so that it is absorbed into the fibres in the
spinning process. In the melt spinning of polymer fibres the
precursor compound can be introduced into a polymer melt and thus
incorporated into the fibres in the melt spinning process. In the
case of electrospinning the precursor compound can be dispersed in
the polymer solution or polymer melt and also spun in the spinning
process in the electrical field.
[0033] If the precursor compounds are used in the form of solids,
for example in powder form in the spinning solution, it is
advantageous if the particle size is not greater than the diameter
of the spinning fibre. When using spinning nozzles a mean particle
size d50 of not more than 4 .mu.m is advantageous, in which case no
particles of sizes of more than 10 .mu.m should be involved in
order not to clog the nozzles. When using finer nozzles the mean
particle size and the maximum absolute particle size are to be
selected correspondingly smaller.
[0034] The term textiles in accordance with the present invention
denotes any kind of material which is produced by bringing together
and/or joining fibres or yarns, including non-woven fabrics. The
production of the textile from the fibre or yarn material in the
second method step (b) of the method according to the invention can
be effected using any method known in textile manufacture, for
example by weaving, knitting, laying, felting, needling, braiding,
tufting, spinning and so forth. Fibres and yarns include natural
and/or synthetic materials which can be treated and/or refined
prior to, during or after the production thereof mechanically
and/or chemically. The production of yarns is usually effected by
spinning crude fibres, for example vegetable fibres like cotton,
animal fibres like wool or synthetic fibres like viscose or
polyester.
[0035] Preferably in that respect only one fibre or yarn material
which in accordance with step (a) is subjected to the action of the
at least one non-conducting precursor compound is used.
Alternatively, depending on the respective situation of use and the
processing technology it is also possible for fibre or yarn
material to be jointly processed with and without a precursor
compound in the production of the textiles.
[0036] In step (c) of the method according to the invention the
laser is irradiated with laser light, with the release of
metallisation seeds, in the regions of the electrically conductive
structures to be generated. The suitable laser parameters depend on
various properties of the textile to be irradiated like textile
material, fibre thickness, concentration and nature of the at least
one precursor compound and further included components as well as
the desired result. The respectively suitable laser parameters can
therefore not be specified generally but are to be ascertained in
each case by simple tests by the man skilled in the art with
knowledge of the invention. The laser parameters to be taken into
consideration in that respect include the laser wavelength to be
applied, the laser power, the irradiation duration or scanning
speed and possibly pulse rate and pulse energy if pulsed laser
light is used.
[0037] Depending on the respective concentration and type of the at
least one precursor compound used and the further included
components such as a stabliser and synergist the desired
metallisation seeds for subsequent metallisation to provide the
conductive metal structures are formed when suitable laser
parameters are involved. If laser activation is excessively weak
then too few or no metallisation seeds are formed. If however the
laser irradiation is excessively strong the textile material can be
locally damaged.
[0038] The laser light provides that the at least one precursor
compound is locally activated, that is to say it is photochemically
converted so that metallisation seeds are formed for the subsequent
metal deposit. That reaction usually involves reduction of the
metal in the precursor compound.
[0039] The laser light for carrying out the method according to the
invention can be of a wavelength in the range of 200 nm to 12000
nm. A preferred wavelength is in the range of 700 nm to 1500 nm,
particularly preferably 850 nm to 1200 nm. Near infra-red lasers
like for example NdYAG lasers, IR diode lasers, VCSEL lasers and
Excimer lasers are preferred. The use of Excimer lasers as are
known from photolithography is suitable. Suitable Excimer lasers
are ArF-, KrF-, XeCl-, XeF-, and KrCl-lasers. The use of Excimer
lasers makes it possible to produce very sharp contours for the
structures. The use of a KrF Excimer laser with a wavelength of 248
nm is particularly advantageous, particularly if the fibre or yarn
material from which the textile material is produced is a
thermoplastic polymer material. The laser allows structuring
without substantial heating and at all events with minimum fusing
of the material in the operative area of the laser. In addition a
very high definition sharpness is achieved.
[0040] The use of Nd:YAG lasers as are known from medical
technology is also advantageous. Nd:YAG lasers using wavelengths of
1064 nm, 946 nm, 532 nm or 473 nm are particularly suitable, an
Nd:YAG laser using a wavelength of 1064 nm being particularly
preferred as in that way the laser radiation procedure can be
particularly delicately carried out and little charring or similar
degradation reactions of the textile material occur.
[0041] According to the invention VCSEL lasers (Vertical-Cavity
Surface-Emitting lasers) are also suitable. These involve
semiconductor lasers, specifically surface emitters, in which the
light is radiated perpendicularly to the plane of the semiconductor
chip in contrast to conventional edge emitters in which the light
issues at one or two sides of the chip. Advantages of such surface
emitters are on the one hand the low manufacturing costs and the
low power consumption. On the other hand the radiation profile,
with at the same time a lower level of output power, is better in
relation to edge emitters. The VCSEL is distinguished in that it is
available in single-mode form and the wavelength is tunable. That
makes it possible to specifically select the appropriate
wavelength, for example the wavelength at which the metal phosphate
compound used according to the invention presents the highest
absorption or at which disturbing effects in respect of laser
irradiation are kept particularly low. In that way it is possible
in accordance with the invention to achieve a highly precise laser
structuring result.
[0042] The production of the metallic conductive structures
requires in the last stage (d) metallisation which can be carried
out by means of electrical current or current-less (chemically
reductively or electrolytically or galvanically). In that case
metals are deposited on the activated structures (metallisation
seeds).
[0043] Current-less chemically reductive metallisation can
advantageously be effected in a wet-chemical process in a metal
bath, preferably in a copper, nickel, silver or gold bath,
particularly preferably in a copper bath. Suitable technologies and
methods for that purpose are known to the man skilled in that art.
Chemically reductive metallisation has the advantage over
electrolytic metallisation that in that method the semiconductors
which are often required and which serve as current bridges between
mutually insulated regions of the conductive structures are not
required and, unlike the situation with electrolytic metallisation,
do not have to be subsequently removed again in a further process
step.
[0044] After metal deposit the textile is desirably washed and
dried. In further steps coatings can also be applied for protection
purposes or for enhancing functionality.
[0045] The electrically conductive structures produced on textiles
according to the method of the invention can be for example
electrical circuits, sensors, heating elements or antenna
structures for the most widely varying applications. They can be
connected to further electronic components. Textiles with
electrically conductive structures thereon can also be used for
screening in relation to electromagnetic radiation. The possible
application options are multiple.
[0046] In an embodiment of the method according to the invention 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 Bronsted acids and Lewis acids, wherein a
Bronsted acid is defined as a proton-transmitting compound and a
Lewis acid is defined as a non-proton-transmitting
electron-deficient compound.
[0047] It was surprisingly found that the use of a stabiliser
according to the invention in combination with the at least one
precursor compound creates particularly desirable reaction
conditions for the production of electrically conducting structures
under the effect of a laser. It was further established that the
stabliser prevents or at least reduces unwanted degradation
reactions due to chemical and mechanical effects.
[0048] The term Bronsted acid in accordance with the present
invention indicates a compound which acts as a proton donor and can
transfer protons to a second reaction partner, the so-called
Bronsted base. In that respect the Bronsted acid is defined as that
compound whose pKs value is less than that of the reaction partner.
In the context according to the invention the pKs value of the
Bronstead acid is less than the pKs value of the water which is
14.
[0049] The term Lewis acid in accordance with the present invention
denotes a compound which acts as an electrophilic electron pair
acceptor and thus partially or completely acquires from a second
reaction partner, the so-called Lewis base, an electron pair, with
the formation of an adduct. The Lewis acids in accordance with the
present invention include compounds i) with an incomplete electron
octet, like: B(CH.sub.3).sub.3, BF.sub.3, AlCl.sub.3, FeCl.sub.2,
ii) metal cations as central atoms in chemical complexes, iii)
molecules with polarised multiple bonds, iv) halogenides with
unsaturated coordination like for example SiCl.sub.4 or PF.sub.5,
and v) other electron pair acceptors, for example condensed
phosphates.
[0050] According to the invention the at least one precursor
compound and the stabiliser can be introduced simultaneously or
successively into the fibre or yarn material during or after
production thereof.
[0051] The Bronsted acids and/or Lewis acids used as a stabiliser
according to the invention are desirably selected from such acids
which are temperature-resistant in such a way that in the
processing procedure they remain stable and do not degrade under
those and other conditions involved.
[0052] According to the invention Bronsted acids which are
preferred and suitable as the stabliser include 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.
[0053] Preferably 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. The aliphatic and aromatic carboxylic acids
and salts thereof are preferably selected from acetic acid, formic
acid, oxalic acid, phthalic acid, sulphonic acids, benzoic acid and
salts of the above-mentioned acids. Acids are advantageous which do
not deteriorate during introduction of the stabiliser into the
fibre or yarn material, do not attack same and influence the
material properties thereof not at all or only slightly.
[0054] According to the invention Lewis acids which are preferred
and suitable as the stabliser include sodium-aluminium-sulphate
(SOS), monocalciumphosphate-monohydrate (MCPM),
dicalciumphosphate-dihydrate (DCPD), sodium-aluminium-phosphate
(SALP), calcium-magnesium-aluminium-phosphate, calcium
polyphosphate, aluminium chloride, boron trifluoride, magnesium
polyphosphate, aluminium hydroxide, boric acid, alkyl borans,
aluminium alkyls, iron (II)-salts and mixtures of the
above-mentioned. Lewis acids have the advantage over Bronsted acids
that during the processing and structuring procedure they do not
separate off and liberate water which could result in foaming or
oxidation reactions on the part of the metal phosphate
compound.
[0055] In an embodiment of the invention the stabiliser includes a
combination of at least one Bronsted acid and at least one Lewis
acid. Such a combination has the advantage that the generally very
high stability of the diversely available Bronsted acids can very
easily provide advantageous conditions for the production of
electrically conducting structures and enhanced stability of the
precursor compound in the processing step. At the same time the use
of the at least one Lewis acid can provide that water which is
possibly liberated and which could adversely affect the result of
laser radiation can be caught.
[0056] In a further embodiment of the invention 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. Preferably the metal
atoms of the metal phosphates, metal oxides or mixtures thereof are
selected from the group consisting of Cu, Au, Ag, Pd, Pt, Fe, Zn,
Sn, Ti and Al. It was surprisingly found that the synergist
promotes the process of metal complex degradation and metal deposit
on the fibre or yarn material. Particularly preferred synergists
suitable according to the invention are selected from the group
consisting of copper phosphate, tricopper diphosphate, copper
pyrophosphate, tin phosphate, zinc phosphate, titanium oxide, zinc
oxide, tin oxide and iron oxide. The synergists used are desirably
so selected in respect of their temperature resistance that they
remain stable in the processing procedure and do not degrade in the
baths used for the metallisation operation.
[0057] Preferably the at least one non-conducting precursor
compound in the method according to the invention, 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
% or at least 0.1 wt % or at least 0.5 wt % and/or at most 15 wt %
or at most 10 wt % or at most 5 wt % or at most 2 wt % of the dry
fibre or yarn material.
[0058] An excessively small proportion involves excessively low
density of precursor compound, whereby poorly produced electrically
conductive structures can result whereas an excessively high
proportion of precursor compound can lead to impairment of the
material properties of the textile material.
[0059] Preferably the stabiliser in the method according to the
invention, 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 % or at least 0.1 wt % or at least
0.5 wt % and/or at most 15 wt % or at most 10 wt % or at most 5 wt
% or at most 2 wt % of the dry fibre or yarn material.
[0060] An excessively low proportion involves an excessively low
density of stabiliser, whereby the positive effect of the
stabiliser in relation to the formation of the electrically
conductive structures and the stability in the processing procedure
can be reduced whereas an excessively high proportion of stabilier
can lead to impairment of the material properties of the textile
material.
[0061] Preferably the synergist in the method according to the
invention, 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 % or at least 0.1 wt % or at least
0.5 wt % and/or at most 15 wt % or at most 10 wt % or at most 5 wt
% or at most 2 wt % of the dry fibre or yarn material.
[0062] An excessively low proportion involves an excessively low
density of synergist, whereby the positive effect of the synergist
in relation to the formation of the electrically conductive
structures and the stability in the processing procedure can be
reduced whereas an excessively high proportion of synergist can
lead to impairment of the material properties of the textile
material.
[0063] Suitable amounts and a suitable relationship of precursor
compound and optionally stabiliser and/or synergist can be
ascertained by simple tests by the man skilled in the art for a
given fibre or yarn material or textile material to be produced
therefrom, with knowledge of the invention.
[0064] Fibre or yarn material suitable according to the invention
for the production of textiles with electrically conductive
metallic structures according to the method according to the
invention include but are not limited to cotton, wool, flax, hemp,
viscose, polyamide, polyurethane, polyacrylonitrile, cellulose
acetate, polyesters like PET, PBT etc., polyolefins like PE, PP and
so forth and copolymers like elastane.
[0065] The invention further includes the use of at least one
inorganic metal phosphate compound selected from the group
consisting of: [0066] copper hydroxide phosphate, preferably copper
hydroxide phosphate of the general formula Cu.sub.2(OH)PO.sub.4,
[0067] anhydrous iron (II) orthophosphate of the general formula
Fe.sub.3(PO.sub.4).sub.2 and [0068] 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 a spinel of the general formula AB.sub.2O.sub.4 for
the production of electrically conductive metallic structures in or
on a textile.
[0069] Preferably the at least one inorganic precursor compound is
used in combination with a stabiliser and/or with a synergist as
are defined herein.
[0070] The invention also includes a textile which is or can be
produced in accordance with the method of the invention and having
electrically conductive metallic structures. A textile produced in
that way differs from known textiles with electrically conductive
metallic structures not only by the advantageous manufacturing
method according to the invention but also by virtue of the
resulting advantageous structural differences as are described
herein and which result in the advantages also described herein,
for example in regard to the particularly stable and durable
metallization.
[0071] The method according to the invention has many advantages
over the known methods in the state of the art. The production of
electrically conductive metallic structures on textiles is
substantially simplified by the method of the invention and can be
carried out at lower cost. Highly individual electrically
conductive metallic structures can be easily applied to individual
or a few textiles without the method of textile manufacture in
itself having to be reconfigured. It is sufficient in regard to the
textiles to suitably program the usually electronically controlled
irradiation operation with electromagnetic radiation, preferably
with laser light.
[0072] Structuring by means of laser irradiation makes it possible
to produce very precisely and quickly even complex electrically
conductive structures. It is possible to dispense with the use of
resist substances like for example polymer masks whereby it is
possible to save on additional chemicals and process steps to a
considerable degree. Complex etching and washing steps which are
difficult to handle are not required. The method according to the
invention is thus highly resource-sparing and does not require
laborious and expensive disposal or re-processing of
environmentally polluting chemicals. In the method according to the
invention the wastage rate is low in comparison with many other
known methods, whereby considerable costs can be saved.
[0073] A particular advantage of the method according to the
invention lies in particular in the stability of the electrically
conductive structures produced. It was found that the metallisation
created with the method according to the invention can be performed
in such a way that the fibres of the textile are metallised
completely and cohesively from all sides and a highly stable,
resistant and durable metallisation is achieved thereby. At the
same time the properties of the textile material are comparatively
little impaired in terms of processing and/or use.
[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
CuK.alpha.-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.2P.sub.2O.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.degree. 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.1.5Fe.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.degree. 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.degree. 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 .mu.m.
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.degree. 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.0.90Zn.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.degree. 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.0.75Zn.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.degree. 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.degree. 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.2O.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.degree. 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.TM. 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.TM. from BASF). The extrusion operation was
carried out at the upper end of the recommended temperature range
at 285.degree. 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.TM. from BASF) and a granulate was produced. The
extrusion operation was carried out at the upper end of the
recommended temperature range at 285.degree. 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 .mu.m/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 .mu.m (median value) and an exclusion value of
the maximum grain size of 10 .mu.m. 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 .mu.m 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 .mu.J while the
values in L2 were at 4 W and 40 .mu.J. In parameter set L3 the
laser power and the pulse energy were increased further to 8 W and
80 .mu.J. In addition the scanning speed was doubled to 1000 mm/s
and the longitudinal and transverse pitch were respectively
increased to 10 .mu.m.
[0157] A laser installation MicroLine 3D 160i from LPKF with a
focus diameter of 60 .mu.m 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 .mu.m/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.
* * * * *