Molecular ink with improved thermal stability

Information

  • Patent Grant
  • 11472980
  • Patent Number
    11,472,980
  • Date Filed
    Thursday, February 8, 2018
    6 years ago
  • Date Issued
    Tuesday, October 18, 2022
    2 years ago
Abstract
A molecular ink contains a silver carboxylate (e.g. silver neodecanoate), a solvent (e.g. terpineol) and a polymeric binder comprising a polyester, polyimide, polyether imide or any mixture thereof having functional groups that render the polymeric binder compatible with the solvent. Such an ink may have good thermal stability with higher silver carboxylate content.
Description
FIELD

This application relates to inks, particularly to printable molecular inks.


BACKGROUND

The mechanical properties of nanoparticle inks are typically poor. Further, the thickness of the traces can be decreased to improve the mechanical properties, but the traces derived from thinner layers of nanoparticle have lower volume resistivity values. It has been previously demonstrated that molecular inks produced with ethyl cellulose binders can have significantly enhanced mechanical properties (International Patent Publication WO 2015/192248 published Dec. 23, 2015). However, when the traces printed from this formulation are subjected to high temperatures (>230° C.) for extended periods of time (>20 minutes), mechanical failure can result (i.e. resistance change following flex or crease testing becomes greater than 10%). Such a failure could be problematic when the ink is used in multilayer processes, because the traces produced from the molecular ink printed as a first layer will have to be processed for up to 20-30 minutes at temperatures exceeding 220° C. as multiple layers are constructed in the device. Further, the narrowest traces (measured 3-5 mil linewidths) tend to sinter more quickly than the wider traces (measured 7-20 mil traces). As such, it can be difficult to fine tune processing conditions to allow for all of the traces, regardless of line width or thickness, to process under identical conditions.


With respect to such a molecular ink, decreasing sintering temperature and increasing sintering time can improve the mechanical properties of the resulting traces. However, resistivity of the traces sintered at temperatures below 200° C. can be up to 1.3 times higher than when sintered at higher temperatures (>230° C.).


Therefore, a need remains for an ink formulation that has improved thermal stability permitting sintering at high temperatures e.g. (>230° C.) and/or for longer periods of time (e.g. >20 minutes) of time while producing narrow conductive lines (e.g. <100 μm or about 4 mil) with good mechanical properties (e.g. less than 10% change in resistance following flexing and creasing according to ASTM F1683-02) and low resistivity (e.g. <5 mΩ/□/mil).


SUMMARY

A molecular silver ink with the ability to increase the loading of silver salt to 80% by weight (32% by weight silver) or more has been formulated that enables the production of traces with extraordinary thermal stability.


In one aspect, there is provided a molecular ink comprising: a silver carboxylate; a solvent; and, a polymeric binder comprising a hydroxyl- and/or carboxyl-terminated polyester.


In another aspect, there is provided a molecular ink comprising: a silver carboxylate in an amount that provides a silver loading in the ink of about 24 wt % or more, based on total weight of the ink; a solvent; and, a polymeric binder comprising a polyester, polyimide, polyether imide or any mixture thereof having functional groups that render the polymeric binder compatible with solvent.


In another aspect, there is provided a process for producing a conductive silver trace on a substrate, the process comprising depositing the molecular ink onto a substrate to form a non-conductive trace of the ink on the substrate, and sintering the non-conductive trace of the ink on the substrate to form the conductive silver trace.


In another aspect, there is provided a substrate comprising a conductive silver trace produced by a process as described above.


In another aspect, there is provided an electronic device comprising a substrate having a conductive silver trace produced by a process as described above.


Further features will be described or will become apparent in the course of the following detailed description. It should be understood that each feature described herein may be utilized in any combination with any one or more of the other described features, and that each feature does not necessarily rely on the presence of another feature except where evident to one of skill in the art.





BRIEF DESCRIPTION OF THE DRAWINGS

For clearer understanding, preferred embodiments will now be described in detail by way of example, with reference to the accompanying drawings, in which:



FIG. 1 depicts a graph the viscosity of the molecular ink (Ink I1) where the viscosity decreases from about 180000 to about 31000 cP as the shear stress increases from 735 to 4335 Pa (filled circles) and returns to about 130000 cP as the shear stress returns to 530 Pa (hollow diamonds).



FIG. 2A and FIG. 2B depict a three dimensional profilometer image (FIG. 2A) and cross section analysis (FIG. 2B) of a trace screen-printed from a molecular ink of the present invention, which has been dried but not sintered. Note that the linewidths and line spacing of the printed trace are about 64±6 μm and about 34±1 μm, respectively.



FIG. 3A and FIG. 3B depict a three dimensional profilometer image (FIG. 3A) and cross section analysis (FIG. 3B) of a trace screen-printed from a molecular ink of the present invention, which has been dried and sintered. Note that the linewidths and line spacing of the printed trace are about 70±5 μm and about 28±1 μm, respectively.



FIG. 4 depicts a graph of the sheet resistivity (mΩ/□/mil) as a function of sintering temperature (° C.) for a silver neodecanoate (AgND) ink of the present invention (Ink I1) compared another AgND ink having a different formulation (Ink C1).



FIG. 5 depicts a plot of the sheet resistivity (mΩ/□/mil) vs. sintering temperature (° C.) for 4.6, 8.4 and 22.8 mil traces (measured linewidths) produced from Ink I1.



FIG. 6A depicts photographs showing results of a crease test on traces produced from Ink C1 following heating at 240° C. for 30 minutes.



FIG. 6B depicts photographs showing results of a crease test on traces produced from Ink I1 following heating at 240° C. for 30 minutes.



FIG. 7A depicts photographs showing results of an adhesion test using scotch tape on traces produced from Ink C1 following heating at 240° C. for 30 minutes.



FIG. 7B depicts photographs showing results of an adhesion test using scotch tape on traces produced from Ink I1 following heating at 240° C. for 30 minutes.





DETAILED DESCRIPTION

Silver carboxylates comprise a silver ion and an organic group containing a carboxylic acid moiety. The carboxylate preferably comprises from 1 to 20 carbon atoms, more preferably from 6 to 15 carbon atoms, even more preferably from 8 to 12 carbon atoms, for example 10 carbon atoms. The carboxylate is preferably an alkanoate. The silver carboxylate is preferably a silver salt of an alkanoic acid. Some non-limiting examples of preferred silver carboxylates are silver ethylhexanoate, silver neodecanoate, silver benzoate, silver phenylacetate, silver isobutyrylacetate, silver benzoylacetate, silver oxalate, silver pivalate and derivatives thereof and any mixtures thereof. Silver neodecanoate is particularly preferred. One or more than one silver carboxylate may be in the ink. The silver carboxylate is preferably dispersed in the ink. Preferably, the ink does not contain flakes or other particles of metallic silver material.


The silver carboxylate is preferably present in the ink in an amount to provide a silver loading of about 19 wt % or more in the ink, based on total weight of the ink. More preferably, the silver carboxylate provides a silver loading of about 23 wt % or more, or about 24 wt % or more, or about 25 wt % or more, or about 27 wt % or more, or about 31 wt % or more, or about 32 wt % or more. When the silver carboxylate is silver neodecanoate, the silver neodecanoate may be preferably present in the ink in an amount of about 50 wt % or more, based on total weight of the ink, or about 60 wt % or more, or about 65 wt % or more, or about 70 wt % of more, or about 80 wt % or more.


The solvent is preferably compatible with one or both of the silver salt or polymeric binder. The solvent is preferably compatible with both the silver salt and polymeric binder. The silver salt and/or polymeric binder are preferably dispersible, for example soluble, in the solvent. The solvent is preferably an organic solvent, more preferably a non-aromatic organic solvent. Non-aromatic organic solvents include, for example, terpenes (e.g. terpene alcohols), glycol ethers (e.g. dipropylene glycol methyl ether), alcohols (e.g. methylcyclohexanols, octanols, heptanols), carbitols (e.g. 2-(2-ethoxyethoxy)ethanol) or any mixture thereof. The solvent preferably comprises a terpene, more preferably a terpene alcohol. Terpene alcohols may comprise monoterpene alcohols, sesquiterpene alcohols and the like. Monoterpene alcohols, for example terpineols, geraniol, etc., are preferred. Terpineols, for example α-terpineol, β-terpineol, γ-terpineol, and terpinen-4-ol are particularly preferred. Especially preferred is α-terpineol. The solvent may be present in the ink in any suitable amount, preferably in a range of about 1 wt % to about 50 wt %, based on total weight of the ink. More preferably, the amount is in a range of about 5 wt % to about 50 wt %, or about 10 wt % to about 40 wt %.


The polymeric binder may comprise a polyester, polyimide, polyether imide or any mixture thereof having functional groups that render the polymeric binder compatible with the solvent. Preferably, the polymeric binder is dispersible, for example soluble, in the solvent. Thus, a mixture of the polymeric binder in the solvent does not lead to significant phase separation. Functional groups that render the polymeric binder compatible with the solvent are preferably polar groups capable of participating in hydrogen bonding, for example one or more of hydroxyl, carboxyl, amino and sulfonyl groups. Preferably, the polymeric binder comprises terminal hydroxyl and/or carboxyl groups. The polymeric binder preferably comprises a polyester having functional groups that render the polyester compatible with the solvent. More preferably, the polymeric binder comprises a hydroxyl- and/or carboxyl-terminated polyester.


The polymeric binder may be present in the ink in any suitable amount, preferably in a range of about 0.1 wt % to about 5 wt %, based on total weight of the ink. More preferably, the amount is in a range of about 0.5 wt % to about 3 wt %, or about 1 wt % to about 2 wt %.


The ink with the polymeric binder enables uniform processing of narrow traces even following heating at high temperature for a long time, for example at temperatures greater than about 230° C. for at least about one hour. Further, the polymeric binder advantageously is not required to be a rheology modifier in the ink. Viscosity of the ink may be controlled by adjusting the amount of silver salt in the ink. The polymeric binder may therefore be used in lower concentration, while permitting the use of more silver salt, and therefore higher silver loading, without unduly affecting the viscosity. These properties make the ink particularly well suited for screen printing, where the application of shear stress significantly decreases the viscosity of the paste, as shown in FIG. 1. In addition, the weight ratio of silver loading to polymeric binder may be as high as 10:1 or more, or even 15:1 or more, or even 20:1 or more. The increase in silver carboxylate concentration coupled with the decrease in binder concentration leads to the production of sintered silver traces having lower resistivity values than previously demonstrated (e.g. <5 mΩ/□/mil), and the ability to print narrow features.


The described molecular ink enables the production of traces with extraordinary thermal stability, specifically, with respect to the ability to survive flex and crease testing following exposure to high temperatures for long periods of time. Preferably, the ink traces can survive flex and crease testing following exposure to temperatures greater than about 230° C. for time periods of at least about one hour. Traces produced from the molecular ink may have mechanical stability when exposed to temperatures from about 180-300° C.


In one embodiment, the molecular ink consists of a silver carboxylate, a solvent, and a polymeric binder comprising a hydroxyl- and/or carboxyl-terminated polyester. In another embodiment, the molecular ink consists of a silver carboxylate in an amount that provides a silver loading in the ink of about 24 wt % or more, based on total weight of the ink, a solvent; and a polymeric binder comprising a polyester, polyimide, polyether imide or any mixture thereof having functional groups that render the polymeric binder compatible with solvent.


The ink may be deposited on a substrate by any suitable method to form a non-conductive trace of the ink on the substrate. The ink is particularly suited for printing, for example, screen printing, inkjet printing, flexography printing, gravure printing, off-set printing, stamp printing, airbrushing, aerosol printing, typesetting, or any other method. The ink is uniquely optimizable for a variety of different printing techniques.


After deposition on the substrate, drying and decomposing the silver carboxylate within the non-conductive trace forms a conductive trace. Drying and decomposition may be accomplished by any suitable technique, where the techniques and conditions are guided by the type of substrate on which the traces are deposited and the type of silver carboxylate in the ink. For example, drying the ink and decomposing the silver carboxylate may be accomplished by heating (thermal, IR, microwave, etc.) and/or intense-pulsed light-based photonic sintering.


In one technique, heating the substrate dries and sinters the trace to form the conductive trace. Sintering decomposes the silver carboxylate to form conductive particles (for example nanoparticles) of the silver. It is an advantage that heating may be performed at a relatively high temperature range for longer periods of time without compromising mechanical properties of the conductive traces formed from the ink, which is particularly advantageous in applications where multiple layers of the ink must be deposited and processed, and in applications involving thermoforming of substrates.


Heating may be performed at a temperature of about 150° C. or higher, or 165° C. or higher, or 175° C. or higher, or 180° C. or higher, or 185° C. or higher, or 200° C. or higher, or 220° C. or higher, or 230° C. or higher, or 240° C. or higher while producing relatively highly conductive silver traces that have good mechanical properties. In one embodiment, the temperature is in a range of about 200° C. to about 250° C.


Heating is preferably performed for a time in a range of about 1-180 minutes, for example 5-120 minutes, or 5-60 minutes. Heating is performed at a sufficient balance between temperature and time to sinter the trace on the substrate to form a conductive trace. Improved thermal stability of the ink permits heating for longer periods of time, for example up to 1 hour or more. The type of heating apparatus also factors into the temperature and time required for sintering. Sintering may be performed with the substrate under an oxidizing atmosphere (e.g. air) or an inert atmosphere (e.g. nitrogen and/or argon gas).


In another technique, a photonic sintering system may feature a high intensity lamp (e.g. a pulsed xenon lamp) that delivers a broadband spectrum of light. The lamp may deliver about 5-27 J/cm2 in energy to the traces. Pulse widths are preferably in a range of about 0.58-1.5 ms. Driving voltages are preferably in a range of about 1.6-3.0 kV. Photonic sintering may be performed under ambient conditions (e.g. in air). Photonic sintering is especially suited for polyethylene terephthalate and polyimide substrates.


A conductive trace formed by drying and sintering the ink on the substrate may be of any desired thickness and width. It is an advantage that the ink may be dried and sintered to form a conductive trace that is relatively thin and/or narrow, while maintaining relatively high conductivity (i.e. relatively low resistivity). The ink is well suited in applications where functional traces with linewidths ranging from about 50 μm to about 1000 μm are used in the same circuit. However, conductive traces may have width and/or thicknesses lower than 50 μm, enabling miniaturization of electronic circuits. In one embodiment, the ink enables uniform processing of traces with measured linewidths of about 3.5-23.0 mils with volume resistivity values ranging from 1.5-2.0 mΩ/□/mil capable of passing ASTM F1683-02 flex and crease testing, even following heating at 230° C. for up to one hour.


The substrate may be any suitable surface, especially printable surface. Suitable surfaces may include, for example polyethylene terephthalate (PET) (e.g. Melinex™), polyolefin (e.g. silica-filled polyolefin (Teslin™)), polydimethylsiloxane (PDMS), polystyrene, acrylonitrile/butadiene/styrene, polycarbonate, polyimide (e.g. Kapton™), thermoplastic polyurethane (TPU), silicone membranes, wool, silk, cotton, flax, jute, modal, bamboo, nylon, polyester, acrylic, aramid, spandex, polylactide, paper, glass, coated glass (e.g. ITO-coated glass), metal, dielectric coatings, among others.


The deposited conductive trace on the substrate may be incorporated into an electronic device, for example electrical circuits, conductive bus bars (e.g. for photovoltaic cells), sensors (e.g. touch sensors, wearable sensors), antennae (e.g. RFID antennae), thin film transistors, diodes, smart packaging (e.g. smart drug packaging), conformable inserts in equipment and/or vehicles, and multilayer circuits and MIM devices including low pass filters, frequency selective surfaces, transistors and antenna on conformable surfaces that can withstand high temperatures. The ink enables miniaturization of such electronic devices.


EXAMPLES
Example 1: Silver Neodecanoate Inks

Silver neodecanoate (AgND)-based inks were formulated as described in Table 1. Ink I1 was formulated in accordance with the present invention and Ink C1 is a comparative example of another formulation of AgND-based ink. The inks were prepared by combining all components and mixing in a plenary mixer until the solutions were homogenous. One of two polymeric binders was added in the inks: Rokrapol™ 7005 (a polyester) or ethyl cellulose 46 cP.













TABLE 1







Ink Component
Ink I1
Ink C1




















silver neodecanoate (wt %)
60
52.1



Rokrapol ™ 7075 (wt %)
1.6
/



ethylcellulose 46 cp (wt %)
/
4.2



terpineol (wt %)
38.4
/



octanol (wt %)
/
12.0



diethylbenzene (wt %)
/
35.9










The inks were screen printed onto 8.5×11″ sheets of Kapton™ HPP-ST using a screen with a mesh count of 400 (stainless steel screen with a 19 μm thread diameter and 45 μm mesh opening). As shown in FIGS. 2A and 2B (for printed and dried traces) and 3A and 3B (for printed, dried and sintered traces), Ink I1 is capable of producing traces with linewidths/line spacings of 64±6/34±1 μm for the dried traces and 70±5/28±1 μm for the dried and sintered traces, respectively. Screen printed lines 10 cm in length and nominal widths of 2-20 mil were also produced. These printed traces were thermally sintered in air at reflow temperatures (T) varying from ˜140° C. to 240° C. using the heating programs described in Table 2. The temperatures quoted are those measured by a thermocouple attached to the Kapton™ substrate.














TABLE 2







Zone
Front
Rear
Time, sec





















Pre-heat 1
100° C.
100° C.
300



Pre-heat 2
150° C.
150° C.
300



Soak
160° C.
160° C.
300



Reflow
T
T
3600



Cool
 60° C.
 60° C.
300










The electrical properties of the traces were characterized by measuring the resistance across the 10 cm long traces with an ohm meter. The widths and thickness of the sintered traces were measured using an optical profilometer (Cyber Technologies 3D Surface Profiler). The trace widths can be used to determine the number of squares in each 10-cm long trace, and subsequently used to calculate the sheet resistance. Using the thickness measurements, the sheet resistance values for the traces were calculated. The electrical properties of the sintered traces are provided in Table 3.


It is evident from FIG. 4 that sintering about 21 mil traces produced from Ink C1 for 60 minutes can produce traces with lower sheet resistivity values in comparison to Ink I1 up to about 180° C. However, at temperatures higher than about 180° C. the traces produced from Ink C1 plateau with sheet resistivity values of about 5 mΩ/□/mil, whereas those produced from Ink I1 continue to decrease to about 1.5 mΩ/□/mil.


The sheet resistivity of the Ink I1 vs. sintering temperature was also determined for ink traces having linewidths in a range of 4.6-22.8 mil. The sintering temperatures ranged from 180° C. to 240° C. (substrate temperature) and the sintering times were 50 minutes. FIG. 5 illustrates the results. It is evident from FIG. 5 that the ink can provide very narrow conductive traces having very low sheet resistivity even when sintered at a temperature as high as 240° C. (see the 4.6 mil line in particular), and that for all linewidths, the resistivity of the sintered traces drops as the sintering temperature increases. The data illustrate the excellent thermal stability of Ink I1. At increasingly higher temperatures (>230° C.) for times greater than 20 minutes, the narrowest traces (linewidths less than about 3-4 mil), Ink C1 typically produces nonconductive traces.


Table 3 shows physical data (nominal and measured line widths and trace thicknesses) and electrical properties (sheet resistances and resistivity values) for 100 mm (100,000 μm) long screen printed traces having nominal linewidths from 2-20 mil produced from Ink I1 by sintering at 240° C. (substrate temperature) for 50 minutes in a batch reflow oven. It is evident from Table 3 that conductive traces produced by sintering Ink I1 at a relatively high temperature for a relatively long time have consistently very low resistivity over a wide range of linewidths, once again illustrating the excellent thermal stability of Ink I1.
















TABLE 3





Nominal









line

Line



Line


width

width
Line width


thickness


(mil)
Ω
(mil)
(μm)
# of □
mΩ/□
(μm)
mΩ/□/mil






















20
18.8 ± 1.0
23.1 ± 0.9
586.0 ± 24.0
172 ± 8 
110 ± 12
0.54 ± 0.07
1.7 ± 0.2


15
25.0 ± 0.3
18.0 ± 0.2
456.7 ± 6.0 
221 ± 2 
113 ± 23
0.48 ± 0.06
2.1 ± 0.4


10
39.2 ± 2.4
12.9 ± 0.3
326.7 ± 8.6 
307 ± 3 
128 ± 28
0.39 ± 0.08
1.9 ± 0.4


5
85.2 ± 2.7
 8.0 ± 1.2
202.3 ± 30.8
497 ± 12
172 ± 28
0.32 ± 0.08
2.4 ± 0.4


3
157.6 ± 2.1 
 5.5 ± 1.5
147.4 ± 37.4
685 ± 15
350 ± 28
0.20 ± 0.08
2.3 ± 0.4


2
263.2 ± 1.9 
 4.6 ± 1.4
117.8 ± 35.9
852 ± 14
309 ± 11
0.19 ± 0.05
2.4 ± 0.1









Bend a crease testing in accordance with ASTM F1683-09 was performed on traces produced by sintering Ink I1 at 240-245° C. for 50 minutes. The results are shown in Table 4. It is evident from Table 4 that resistance does not increase by more than 5% following any of the tests.
















TABLE 4










% change






% change

in




in
% change in
resistance
% change in




resistance
resistance
following
resistance



Line
following
following
crease
following
# of



width
bend test,
bend test,
test,
crease test,
lines



(mil)
tensile
compressive
tensile
compressive
tested






















Avg.
23.1
1.0
2.6
0.5
4.9
35


SD
0.9
1.7
2.6
1.9
3.2


Avg.
18
0.9
2.8
0.7
4.0
35


SD
0.2
1.6
2.5
1.2
2.5


Avg.
12.9
2.2
3.1
0.5
3.3
35


SD
0.3
1.5
2.9
1.1
2.8


Avg.
8
2.4
3.3
1.1
2.6
34


SD
1.2
1.4
1.8
1.3
1.8


Avg.
5.8
3.5
4.5
1.0
2.1
20


SD
1.5
2.0
2.4
0.6
0.7


Avg.
4.6
1.1
2.2
0.9
1.1
5


SD
1.4
0.3
0.4
0.2
0.2





Avg. = Average;


SD = standard deviation






Crease testing in accordance with ASTM F1683-09 was performed on traces produced by sintering Ink C1 and Ink I1 at 240° C. for 30 minutes. FIG. 6A are photographs showing the results for Ink C1 and FIG. 6B are photographs showing the results for Ink I1. Photographs (ii) and (iii) in each of FIG. 6A and FIG. 6B are magnified views of respective photograph (i). As best seen in the magnified views (ii) and (iii) for FIG. 6A and FIG. 6B, the traces containing cellulose-based polymers are cracked/broken (FIG. 6A(ii) and FIG. 6A(iii), whereas the traces containing Rokrapol™ 7075 remain unaffected by creasing (FIG. 6B(ii) and FIG. 6B(iii).


Adhesion tests were performed using scotch tape on traces produced by sintering Ink C1 and Ink I1 at 240° C. for 30 minutes. FIG. 7A are photographs showing the results for Ink C1 and FIG. 7B are photographs showing the results for Ink I1. Photograph (i) in each of FIG. 7A and FIG. 7B show the traces with the scotch tape applied. Photograph (ii) in each of FIG. 7A and FIG. 7B show the traces after the scotch tape has been removed. As seen in FIG. 7A(ii), a significant amount of the trace is removed when cellulose-based polymer (Ink C1) is used to produce the trace. In contrast, as seen in FIG. 7B(ii), no detectable amount of the trace is removed when Rokrapol™ 7050 (Ink I1) is used to produce the trace.


The novel features will become apparent to those of skill in the art upon examination of the description. It should be understood, however, that the scope of the claims should not be limited by the embodiments, but should be given the broadest interpretation consistent with the wording of the claims and the specification as a whole.

Claims
  • 1. A molecular ink comprising: a silver carboxylate; a solvent comprising a terpineol; and, a polymeric binder comprising a hydroxyl-and/or carboxyl-terminated polyester wherein the silver carboxylate comprises silver neodecanoate and is in the ink in an amount that provides a silver loading in the ink of about 24 wt % or more, based on total weight of the ink, the ink having a viscosity in a range of 31,000 cp to 180,000 cp and the ink providing a conductive trace on a substrate that exhibits less than 10% change in resistance following flexing and creasing in accordance with ASTM F1683-09 following exposure to temperatures greater than 230° C., wherein the ink is a shear thinning paste at room temperature.
  • 2. The ink according to claim 1, wherein the silver neodecanoate is present in the ink in an amount of about 60 wt % or more, based on total weight of the ink.
  • 3. The ink according to claim 1, wherein the silver neodecanoate is present in the ink in an amount of about 80 wt % or more, based on total weight of the ink.
  • 4. The ink according to claim 1, wherein the polymeric binder is present in an amount of about 0.5 wt % to about 3 wt %, based on total weight of the ink.
  • 5. The ink according to claim 1, wherein the solvent comprises a-terpineol.
  • 6. The ink according to claim 1, wherein the solvent is in the ink in an amount in a range of about 1 wt % to about 50 wt %, based on total weight of the ink.
  • 7. The ink according to claim 1, wherein the solvent is in the ink in an amount in a range of about 10 wt % to about 40 wt %, based on total weight of the ink.
  • 8. The ink according to claim 1, wherein the hydroxyl- and/or carboxyl-terminated polyester is a carboxyl-terminated polyester.
  • 9. The ink according to claim 8, wherein the carboxyl-terminated polyester is present in an amount of about 1 wt % to about 2 wt %, based on total weight of the ink.
  • 10. The ink according to claim 8, wherein the carboxyl-terminated polyester comprises Rokrapol™ 7075.
  • 11. The ink according to claim 1, wherein the ink is a homogeneous solution during mixing in a plenary mixer.
  • 12. A process for producing a conductive silver trace on a substrate, the process comprising depositing an ink as defined in claim 1 onto a substrate to form a non-conductive trace of the ink on the substrate, and sintering the non-conductive trace of the ink on the substrate to form the conductive silver trace.
  • 13. The process according to claim 12, wherein the sintering is performed at a temperature of about 180° C. or higher.
  • 14. The process according to claim 12, wherein the sintering is performed for a time in a range of about 1 minute to 180 minutes.
  • 15. The process according to claim 12, wherein the substrate comprises polyethylene terephthalate, polyolefin, polydimethylsiloxane, polystyrene, acrylonitrile/butadiene/styrene, polycarbonate, polyimide, thermoplastic polyurethane, a silicone membrane, wool, silk, cotton, flax, jute, modal, bamboo, nylon, polyester, acrylic, aramid, spandex, polylactide, paper, glass, metal or a dielectric coating.
  • 16. The process according to claim 12, wherein the depositing comprises printing.
  • 17. The process according to claim 16, wherein the printing comprises screen printing.
Cross-reference to Related Applications

This application is a National Entry of International Application PCT/IB2018/050789 filed Feb. 8, 2019, and claims the benefit of U.S. Provisional Application USSN 62/456,300 filed Feb. 8, 2017.

PCT Information
Filing Document Filing Date Country Kind
PCT/IB2018/050789 2/8/2018 WO
Publishing Document Publishing Date Country Kind
WO2018/146617 8/16/2018 WO A
US Referenced Citations (82)
Number Name Date Kind
3228897 Nellessen et al. Jan 1966 A
3702259 Nielsen Nov 1972 A
3729339 Kiel Apr 1973 A
3989644 Bolon et al. Nov 1976 A
4088801 Bolon et al. May 1978 A
4099376 Japs Jul 1978 A
4180407 Gibson et al. Dec 1979 A
4248921 Steigerwald et al. Feb 1981 A
4396666 Ernsberger Aug 1983 A
4487811 Eichelberger et al. Dec 1984 A
4552690 Nobuyuki et al. Nov 1985 A
4687597 Siuta Aug 1987 A
4775594 Desjarlais Oct 1988 A
4857111 Haubennestel et al. Aug 1989 A
5045236 Tsunaga et al. Sep 1991 A
5074978 Debroy Dec 1991 A
5248451 Tsunaga et al. Sep 1993 A
5306590 Felder Apr 1994 A
5900327 Pei et al. May 1999 A
5960251 Brusic et al. Sep 1999 A
5980622 Byers Nov 1999 A
5989700 Krivopal Nov 1999 A
6036889 Kydd Mar 2000 A
6048389 Price et al. Apr 2000 A
6090890 Murakami et al. Jul 2000 A
6521032 Lehmann et al. Feb 2003 B1
6663799 Kokubo et al. Dec 2003 B2
6770122 Thompson Aug 2004 B2
7115218 Kydd et al. Oct 2006 B2
7141104 De Voeght et al. Nov 2006 B2
7211205 Conaghan et al. May 2007 B2
7473307 Song et al. Jan 2009 B2
7566357 Zhao Jul 2009 B2
7629017 Kodas et al. Dec 2009 B2
7683107 Yang Mar 2010 B2
7691664 Kodas et al. Apr 2010 B2
7731812 Wang et al. Jun 2010 B2
7960037 Liu et al. Jun 2011 B2
7976737 Heo et al. Jul 2011 B2
8043535 Kamikoriyama et al. Oct 2011 B2
8262894 Xu et al. Sep 2012 B2
8282860 Chung et al. Oct 2012 B2
8339040 Bruton et al. Dec 2012 B2
8597397 Kunze et al. Dec 2013 B2
8945328 Longinotti-Buitoni et al. Feb 2015 B2
8948839 Longinotti-Buitoni et al. Feb 2015 B1
9028599 Abe May 2015 B2
9145503 Yu et al. Sep 2015 B2
9187657 Yano et al. Nov 2015 B2
9198288 Wu et al. Nov 2015 B2
9283618 Wu et al. Mar 2016 B2
9460824 Liu et al. Oct 2016 B2
20030180451 Kodas et al. Sep 2003 A1
20050070629 Roberts Mar 2005 A1
20060118768 Liu et al. Jun 2006 A1
20070078215 Yoon et al. Apr 2007 A1
20070125989 Kodas et al. Jun 2007 A1
20070154644 Hwang et al. Jul 2007 A1
20080093422 Kodas et al. Apr 2008 A1
20080108218 Kodas et al. May 2008 A1
20080178761 Tomotake et al. Jul 2008 A1
20090267060 Forrest et al. Oct 2009 A1
20110111138 McCullough et al. May 2011 A1
20120104330 Choi et al. May 2012 A1
20130121872 Matsumoto May 2013 A1
20130156971 McCullough et al. Jun 2013 A1
20130161573 Torardi et al. Jun 2013 A1
20130277096 Seong et al. Oct 2013 A1
20140124713 Majumdar et al. May 2014 A1
20140178601 Wei et al. Jun 2014 A1
20140034901 Abe Nov 2014 A1
20140349017 Abe Nov 2014 A1
20140349025 Hui et al. Nov 2014 A1
20150004325 Walker et al. Jan 2015 A1
20150056426 Grouchko et al. Feb 2015 A1
20150132476 Wu May 2015 A1
20150231740 Grabey et al. Aug 2015 A1
20150257279 Shahbazi et al. Sep 2015 A1
20150298248 Walker et al. Oct 2015 A1
20150299489 Walker Oct 2015 A1
20160081189 Shimoda et al. Mar 2016 A1
20160095547 Wang et al. Apr 2016 A1
Foreign Referenced Citations (62)
Number Date Country
2017808 Dec 1990 CA
1071182 Apr 1993 CN
101271929 Sep 2008 CN
101519356 Sep 2009 CN
102270514 Dec 2011 CN
102618033 Aug 2012 CN
102863845 Jan 2013 CN
103084581 May 2013 CN
104263082 Jan 2015 CN
104479463 Apr 2015 CN
106147405 Nov 2016 CN
0335237 Oct 1989 EP
2871260 May 2015 EP
1443099 Jul 1976 GB
S61136978 Jun 1986 JP
63278983 Nov 1988 JP
H10279868 Oct 1998 JP
2000136333 May 2000 JP
2004162110 Jun 2004 JP
2005537386 Dec 2005 JP
2006519291 Aug 2006 JP
2008013466 Jan 2008 JP
2008031104 Feb 2008 JP
2008531810 Aug 2008 JP
2009212182 Sep 2009 JP
2009256218 Nov 2009 JP
20100018696 Jan 2010 JP
2012234803 Nov 2012 JP
2014148732 Aug 2014 JP
2014182913 Sep 2014 JP
2015187259 Oct 2015 JP
2011-0002022 Jan 2011 KR
20120132424 Dec 2012 KR
101350507 Jan 2014 KR
20150045605 Apr 2015 KR
20150077676 Jul 2015 KR
20150082133 Jul 2015 KR
20150085332 Jul 2015 KR
201406991 Feb 2014 TW
201435925 Sep 2014 TW
201437299 Oct 2014 TW
03032084 Apr 2003 WO
2003095701 Nov 2003 WO
200416261 Sep 2004 WO
2006093398 Sep 2006 WO
2009036921 Mar 2009 WO
2009126918 Oct 2009 WO
2010036397 Apr 2010 WO
2010128107 Nov 2010 WO
2012014933 Feb 2012 WO
2012135551 Oct 2012 WO
2012144610 Oct 2012 WO
2013036519 Mar 2013 WO
2013073331 May 2013 WO
2013073349 May 2013 WO
2013096664 Jun 2013 WO
2013128449 Sep 2013 WO
2015024115 Feb 2015 WO
2015160938 Oct 2015 WO
2015183679 Dec 2015 WO
2015192248 Dec 2015 WO
2016012753 Jan 2016 WO
Non-Patent Literature Citations (81)
Entry
Stay D, et al. Macromolecules. 2013, 46, 4361-4369.
Suran S, et al. Thin Solid Films. 2016, 607, 36-42.
Szeremeta J, et al. Optical Materials. 2011, 33, 1372-1376.
Tsai C-Y, et al. Nanoscale Research Letters. 2015, 10, 357 (7 pages).
Vaseem M, et al. ACS Appl. Mater. Interfaces. 2016, 8, 177-186.
Walker SB, et al. J. Am. Chem.Soc. 2012, 134, 1419-1421.
Wang H, et al. small. 2015, 11(1), 126-133.
Yabuki A, et al. Thin Solid Films. 2011, 519, 6530-6533.
Kabuki A, et al. Materials Research Bulletin. 2012, 47, 4107-4111.
Yabuki A, et al. Synthesis of copper conductive film by low-temperature thermal decomposition of coppereaminediol complexes under an air atmosphere. Materials Chemistry and Physics. 2014, http://dx.doi.org/10.1016/j.matchemphys.2014.07.047, 1e6.
Yim C, et al. ACS Appl. Mater. Interfaces. 2016, 8, 22369-22373.
Yong Y, et al. Scientific Reports. 7, 45150, DOI: 10.1038/srep45150, 9 pages.
Zhai D, et al. Colloids and Surfaces A: Physicochem. Eng. Aspects. 2013, 424, 1-9.
Zhu X, et al. Langmuir. 2012, 28, 14461-14469.
Stranks SD, et al. Adv. Mater. 2013, 25, 4365-4371.
Search Report dated Nov. 9, 2020 on European application 18750597.9.
Araki T, et al. Langmuir. 2013, 29, 11192-11197.
Bjornholm, T et al. J. Am. Chem. Soc. 1998, 120, 7643-7644.
Chen W, et al. Journal of Electronic Materials. 2015, 44(7), 2479-2487.
Choi T-H, et al. Journal of Materials Chemistry. 2012, 22, 3624.
Chung W-H, et al. Thin Solid Films. 2015, 580, 61-70.
Curtis C, et al. NCPV Program Review Meeting Conference Paper (Lakewood Colorado). Metallizations by Direct-Write Inkjet Printing. NREL/CP-520-31020, 2001, 6 pages.
Dang Z-M, et al. Journal of Applied Polymer Science. 2012, 126, 815-821.
Dearden AL, et a. Macromol. Rapid Commun. 2005, 26, 315-318.
De Boer B, et al. Macromolecules. 2002, 35, 6883-6892.
Deore B, et al. Conference Poster. New Conductors for Advanced User Interfaces, Circuits and Devices. Canadian Society for Chemistry. 2015.
Ding J, et al. Nanoscale. 2014, 6, 2328-2339.
Dong Y, et al. Thin Solid Films. 2015, 589, 381-387.
Farraj Y, et al. Chem. Commun., 2015, 51, 1587-1590.
Gu L, et al. Applied Mechanics and Materials Online. 2013, 469, 51-54.
Henkel's Printed Electronic Inks. Product Brochure F_LR615251. 2015.
Hokita Y, et al. ACS Appl. Mater. Interfaces. 2015, 7, 19382-19389.
Hu Y, et al. 15th International Conference on Electronic Packaging Technology. 2014, 1565-1567.
Hwang J, et al. Bull. Korean Chem. Soc. 2014, 35(1), 147-150.
International Preliminary Report on Patentability for PCT/IB2018/050788 dated Jul. 24, 2018.
International Preliminary Report on Patentability for PCT/IB2018/050789 dated Jul. 23, 2018.
International Preliminary Report on Patentability for PCT/IB2018/050790 dated Jul. 17, 2018.
International Preliminary Report on Patentability for PCT/IB2018/050791 dated Jul. 25, 2018.
International Search Report for PCT/IB2018/050788 dated Jul. 24, 2018.
International Search Report for PCT/IB2018/050789 dated Jul. 23, 2018.
International Search Report for PCT/IB2018/050790 dated Jul. 17, 2018.
International Search Report for PCT/IB2018/050791 dated Jul. 25, 2018.
Jahn SF, et al. Thin Solid Films. 2010, 518, 3218-3222.
Kamyshny A, et al. The Open Applied Physics Journal. 2011, 4, 19-36.
Kawaguchi Y, et al. Journal of Coating Science and Technology. 2016, 3(2), 56-61.
Kim SJ, et al. Thin Solid Films. 2012, 520, 2731-2734.
Kim I, et al. RSC Advances. 2013, 3, 15169-15177 (with ESI).
Lee B, et al. Current Applied Physics. 2009, 9, e157-e160.
Li Y, et al. J Mater Sci: Mater Electron. 2016, 27, 11432-11438.
Li W, et al. J. Mater. Chem. C. 2016, 4, 8802-8808.
Lin H-C, et al. Microelectronic Engineering. 2009, 86, 2316-2319.
Lyons AM, et al. Abstract of J. Phys. Chem. 1991, 95(3), 1098-1105.
Malenfant PRL, et al. NRC Printable Electronics. Presentation at IDTechEx (Santa Clara 2013).
Nie X, et al. Applied Surface Science. 2012, 261, 554-560.
Pacioni NL, et al. Silver Nanoparticle Applications, Engineering Materials. (Springer International Publishing Switzerland 2015, E.I. Alarcon et al. (eds.), DOI 10.1007/978-3-319-11262-6_2) pp. 13-46.
Paquet C, et al. New Conductors for Advanced User Interfaces, Circuits and Devices. Poster Presentation at CPEIA 2015.
Park K-H, et al. J. Am. Chem. Soc. 2005, 127(26), 9330-9331.
Pham LQ, et al. Journal of Colloid and Interface Science. 2012, 365, 103-109.
Polzinger B, et al. 2011 11th IEEE International Conference on Nanotechnology. (Portland Marriott. Aug. 15-18, 2011, Portland, Oregon, USA) pp. 201-204.
Rajan K, et al. Nanotechnology, Science and Applications. 2016, 9, 1-13.
Rao RVK, et al. RSC Adv. 2015, 5, 77760-77790.
Sakamoto M, et al. Journal of Photochemistry and Photobiology C: Photochemistry Reviews. 2009, 10, 33-56.
Schulz DL, et al. Electrochemical and Solid-State Letters. 2001, 4(8), C58-C61.
Shen L, et al. Journal of Electronic Materials. 2015, 44(2), 720-724.
Shin D-Y, et al. J. Mater. Chem. 2012, 22, 11755-11764.
Shin D-H, et al. ACS Appl. Mater. Interfaces. 2014, 6, 3312-3319.
First Examination Report dated Mar. 30, 2021 on Indian application 201927032221.
First Office Action dated Dec. 2, 2021 on Japanese Patent Application 2019-563709.
First Examination Report dated Sep. 27, 2021 on Chinese Patent Application 2018800160488.
First Examination Report dated Sep. 15, 2021 on Taiwan Patent Application 107104323.
Office action dated Mar. 16, 2022 on European application 18750597.9.
Office action dated Apr. 21, 2022 on Chinese application 2018800160488.
Choi Y-H, et al. Langmuir 2015, 31, 8101-8110.
Greer JR, et al. J. Appl. Phys. 101, 103529 (2007).
Jahn SF, et al. Chem. Mater. 2010, 22, 3067-3071.
Kim J-H, et al. Adv. Mater. Interfaces 2015, 2, 1500283.
Kim K-S, et al. Journal of Nanoscience and Nanotechnology. (2011) vol. 11, 1493-1498.
Kim K-S, et al. Journal of Nanoscience and Nanotechnology. (2012) vol. 12, 5769-5773.
Moon YJ, et al. Journal of Electronic Materials. (2015) vol. 44, No. 4, 1192-1199.
Office action dated Jul. 12, 2022 on Japanese patent application 2019-563709.
Office action dated Aug. 19, 2022 on Korean application 10-2019-7026320.
Related Publications (1)
Number Date Country
20200010706 A1 Jan 2020 US
Provisional Applications (1)
Number Date Country
62456300 Feb 2017 US