POLYMER LAYERS BY REACTIVE PRINTING

Abstract

The invention relates to a process of manufacturing a composite comprising a layer of a polyimide and a substrate, comprising at least these steps: i. Providing a first composition comprising an acid compound; and a second composition comprising a diamine compound; ii. Forming a first layer on the substrate, and iii. Forming a second layer on the first layer, wherein if the first layer is formed by applying the first composition, the second layer is formed by applying the second composition, and vice versa; wherein the first and the second layer overlap at least in part thereby forming a pattern on the substrate; iv. Conducting a thermal treatment on the pattern wherein the polyimide layer is formed. The invention further relates to such a composite, a kit comprising a first composition comprising an acid compound and a second composition comprising a diamine compound as well as a use of the kit.

Claims

1-15. (canceled)

16. A process of manufacturing a composite comprising at least a layer of polyimide and a substrate wherein the process comprises at least these steps: i. providing a first composition comprising at least an acid compound and a first organic carrier; and a second composition comprising at least a diamine compound and a second organic carrier; ii. forming a first layer on the substrate, wherein the first or the second composition can be applied; iii. forming a second layer on the first layer, wherein if the first layer is formed by applying the first composition, the second layer is formed by applying the second composition, wherein if the first layer is formed using the second composition, the second layer is formed by applying the first composition; wherein the first and the second layer overlap at least in part thereby forming a pattern on the substrate; iv. conducting a thermal treatment on the pattern wherein the polyimide layer is formed.

17. The process of claim 16, wherein at least one of the forming steps ii. and iii. comprises inkjet printing.

18. The process of claim 16, wherein the first composition comprises an amount of acid compound in the range from 1 to 25 wt. %, based on the total amount of the first composition.

19. The process of claim 16, wherein the second composition comprises an amount of diamine compound in the range from 1 to 25 wt. %, based on the total amount of the second composition.

20. The process of claim 16, wherein the first or the second, or both organic carriers comprise at least an dipolar aprotic solvent.

21. The process of claim 20, wherein the dipolar aprotic solvent is selected from the group consisting of: Dimethylsulfoxide (DMSO), N-Methyl-2-pyrrolidone (NMP), N,N-Dimethylformamide (DMF), N,N-Dimethylacetamide (DMAc), N,N,N′,N′-Tetramethylurea (TMU), Tetrahydrofurane and Acetonitril.

22. The process of claim 16, wherein the thermal treatment is conducted at a temperature in the range from 200 to 400° C.

23. The process of claim 16, wherein a thermal pretreatment is conducted on the pattern.

24. The process of claim 16, wherein at least one of the following features applies: a) the at least one diamine compound is selected from the group consisting of I. aliphatic diamines, such as Hexamethylenediamine (HMDA); II. aromatic diamines, such as 4,4′-(9-Fluorenylidene)dianiline (FDA), p-Phenylenediamine (PPDA), m-Phenylenediamine (MPDA), m-Xylylenediamine, p-Xylylenediamine, 2,2′-Bis(trifluoromethyl)benzidine (TFMB); III. ether diamines, such as 2,2-Bis[4(4-aminophenoxy)phenyl] propane (BAPP), 2,2-Bis[4-(4-aminophenoxy) phenyl]hexafluoropropane, 4,4′-Oxydianiline (ODA), 4,4′-Bis(4-aminophenoxy)biphenyl; IV. sulfonyl diamines, such as 3,3′-Sulfonyldianiline; V. mixed, aliphatic-aromatic diamines, such as 4,4′-((Cyclohexane-1,1-diylbis(4,1-phenylene))bis(oxy))dianiline, 4,4′-(((4-Methylcyclohexane-1,1-diyl)bis(4,1-phenylene))bis(oxy))dianiline, Bis[4(4-aminobenzyl)phenyl] methane, 1,1-Bis[4-(4-aminobenzyl)phenyl] cyclohexane, 3,3′-Methylenedianiline, 4,4′-Methylenedianiline; or VI. a combination of two or more of the compounds of same or different kind, according to the groups I., II., III., IV. and V.; b) the at least one acid compound is a polycarboxylic acid or a polycarboxylic anhydride, preferably selected from the group consisting of i. aromatic tricarboxylic polyacids and anhydrides, such as 3,4,4′-(Benzophenone)tricarboxylic anhydride (BTDA), trimellitic acid, trimellitic anhydride, phenylether tricarboxylic acid anhydride; ii. aromatic tetracarboxylic polyacids and anhydrides, such as 3,3′-4,4′-(Benzophenone)tetracarboxylic anhydride (BTDA), 4,4′-(Hexafluoroisopropylidene)diphthalic anhydride (6-FDA), Pyromellitic dianhydride (PMDA), 4,4′-Oxydiphtalic anhydride (ODPA), 3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-Diphenylsulfonetetracarboxylic dianhydride (DSDA), Hydroquinone diphthalic anhydride (HQDA), 4,4′-(4,4′-lsopropylidendiphenoxy) bis(phthalic anhydride); iii. aliphatic tetracarboxylic polyacids and anhydrides, such as Cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), 3,3′,4,4′-Bicyclohexyl tetracarboxylic dianhydride; iv. mixed, aliphatic-aromatic polyacids and anhydrides, such as Ethylene glycol bis(4-trimellitate anhydride); or v. a combination of two or more of the compounds of same or different kind, according to the groups i., ii., iii. and iv.; c) the substrate is selected from the group consisting of polyamide, polyimide, polyaramid, polytetrafluoroethylene, glass, metal, ceramics, Polyethyleneimine (PEI), Polyether ether ketone (PEEK); or a combination of two or more of these features.

25. The process of claim 16, wherein the polyimide layer has at least one of these features: i) a thickness of at least 20 nm; ii) a weight average molecular weight in the range from 5,000 to 1,000,000 g/mol; iii) an ultimate tensile strength of 5 MPa or more, for example of 10 MPa or more, or 20 MPa or more, each determined according to ASTM D-882-91; iv) or a combination of two or more features according to i) to iii).

26. A kit comprising a first and a second composition, wherein the first composition comprises an acid compound and a first organic carrier; and the second composition comprises a diamine compound and a second organic carrier.

27. The kit of claim 26, wherein the amount of the acid compound in the first composition is in the range of from 1 to 25 wt. %, the wt. % with respect to the total weight of the first composition; and the amount of the diamine compound in the second composition is in the range of from 1 to 25 wt. %, the wt. % with respect to the total weight of the second composition.

28. A composite comprising a layer of polyimide and a substrate obtainable by a process according to claim 16.

29. The composite of claim 28, wherein the layer has at least one of these features: i) a thickness of at least 20 nm; ii) a weight average molecular weight in the range from 5,000 to 1,000,000 g/mol; iii) an ultimate tensile strength of 5 MPa or more, for example of 10 MPa or more, or 20 MPa or more, each determined according to ASTM D-882-91.

30. A use of a kit comprising a first and a second composition, each comprising an organic carrier, to manufacture a polyimide layer having a pattern, wherein the first composition comprises at least an acid compound and the second composition comprises at least a diamine compound.

Description

SUMMARY OF THE FIGURES

[0158] The invention is now further elucidated with reference to the figures. The figures and figure descriptions are exemplary and are not to be considered as limiting the scope of the invention. The figures and descriptions focus on the features of the process relating to the invention and are not intended to be a comprehensive description of already established processes. The skilled person is aware of the technical details required to implement parts of the process which fall outside the focus of the invention, such as standard processes for distillation, phase separation and drying.

[0159] FIG. 1 shows the process of manufacture according to the first aspect.

[0160] FIG. 2 shows a kit, as in the second aspect.

[0161] FIG. 3 shows a composite, side view, as in the third aspect.

[0162] FIG. 4 shows a top view of a first (or second) composition printed with an inkjet.

[0163] FIG. 5 shows a top view of a superimposed first (straight) and second (dashed) composition, which overlap in part.

[0164] FIG. 6 shows another top view of a superimposed first (straight) and second (dashed) composition which overlap in part.

DESCRIPTION OF THE FIGURES

[0165] FIG. 1 shows a process according to the first aspect which is a process of manufacturing a composite comprising a layer of a polyimide and a substrate wherein the process comprises at least: step i. 101 providing a first composition comprising an acid compound and a first organic carrier, and a second composition comprising a diamine compound and a second organic carrier;

[0166] step ii. 102 forming a first layer on the substrate, wherein the first or the second composition can be applied; step iii. 103 forming a second layer on the substrate. If the first layer is formed by applying the first composition, then the second layer is formed by applying the second composition. However, if the first layer is formed using the second composition, the second layer is formed by applying the first composition. The first and the second layer overlap at least in part thereby forming a pattern on the substrate; step iv. 104 conducting a thermal treatment on the pattern wherein the polyimide layer is formed.

[0167] FIG. 2 shows a kit 201 comprising a first 202 and a second 203 composition.

[0168] FIG. 3 shows a composite comprising a substrate 302 and a layer of polyimide 301.

[0169] FIG. 4 shows an example of a first layer 401.

[0170] FIG. 5 shows an example of a first layer 501 and a second layer 502, which overlap in part.

[0171] Only the overlapping regions can polymerize to provide the precursor polymer of the polyimide layer.

[0172] FIG. 6 shows another example of a first layer 601 and a second layer 602, which overlap in part. Only the overlapping regions can polymerize to provide the precursor polymer of the polyimide layer.

Test Methods

[0173] The following test methods were used for the purposes of the invention. Unless otherwise stated the measurements were made at ambient temperature 23° C., ambient air pressure 100 kPa (0.986 atm) and relative humidity 50%.

a. Viscosity [0174] The viscosity was measured using a Brookfield DX3TLVKJ0 viscometer. 20 ml of a probe composition were poured into a 75 ml ULA-31EY sample chamber using a YULA-15E spindle (all measurement equipment available from Brookfield Engineering Labs, Inc.). The measurements were conducted at a speed of 50 rpm, a shear rate of 61.15/s and a measurement time of 60 seconds. The temperature of (either 20° C. or 50° C., as indicated) was controlled using an external thermostat. Calibration of the viscosimeter was done using calibration standards for Newtonian liquids from “Zentrum für Messen and Kalibrieren & Analtytik GmbH, DAkks-registration no. D-K-15186-01-00. (DAkks is the national accreditation body for Germany.)
b. Water [0175] The content of water in a composition was determined using a Deutsche METROHM KF Coulometer 899 titration system and according to ASTM E1064-08.
c. Thickness [0176] Thickness of a polyimide layer was determined be analyzing the difference in height in a direction perpendicular to a substrate on which a layer of polyimide is positioned. For this purpose, a cut is made through the layer of polyimide and the layer is removed from the substrate on one side of the cut. A Dektak XT-E with a cutting tip of 12.5 μm was used to determine the difference in thickness.
d. Molecular Weight [0177] Average weight number molecular weight (M.sub.w) of polyimide was determined by GPC using a PSS SECcurity.sup.2 GPC System equipped with one PSS GRAM 10 μm 30 Å 8×300 mm and two PSS GRAM 10 μm 1000 Å 8×300 mm GPC columns with a PSS GRAM 10 μm 8×50 mm precolumn. DMSO with 5 g/L LiCl was used as GPC eluent with a flow of 1 ml/min. GPC samples were prepared by dissolving 40 mg of the corresponding polyamic acid substrates in 1.5 ml of DMSO with 5 g/L LiCl and filtering them with 0.45 μm PTFE syringe filter. External calibration was performed with PSS PMMA standards. The elugrams were interpreted utilizing the detector response of the RI detector.
e. Ultimate Tensile Strength [0178] The ultimate tensile strength was measured according to ASTM D-882-91.

EXAMPLES

[0179] The invention is now further described with the aid of examples. These examples are for illustrative purposes and are not to be considered as limiting the scope of the invention.

[0180] 10 mmol of 3,3′-4,4′-(Benzophenone)tetracarboxylic anhydride (BTDA) was dissolved in DMSO to generate a first 10 wt % ink solution. Further, 4,4′-(9-Fluorenylidene)dianiline (FDA) was dissolved in DMSO to generate a second ink solution of equal concentration. Each ink solution had a viscosity of 3 mPas at 20° C. and a water content of less than 0.05 wt. %. The first ink solution was printed using a Fuji Dimatix printer with 1270 dpi on a glass substrate at room temperature forming a first layer. Subsequently, the second ink solution was printed forming a second layer on top of the first layer. Upon completion of the printing, the layer was cured at 230° C. for 30 minutes to form polyimide. A cut was made through the foil using a cutter knife. The thickness of the polyimide layer was then analyzed using the profilometer, as described in the test method. The thickness of the polyimide layer was 5 μm.

[0181] The polyimide layer had an ultimate tensile strength of 13 MPa, measured according to ASTM D-882-91.

REFERENCE NUMERALS

[0182]

TABLE-US-00001 101 Step i. 102 Step ii. 103 Step iii. 104 Step iv. 201 Kit 202 Composition 1 203 Composition 2 301 Polyimide layer 302 Substrate 401 First layer 501 First layer 502 Second layer 601 First layer 602 Second layer