TW201033309A - Paste composition for forming heat-resistant conductive patterns on substrate - Google Patents

Abstract

The present invention provides a paste composition for forming heat-resistant and electrically conductive patterns on substrate by direct printing comprising conductive particles, polyamic acid and solvent. The paste composition according to the present invention can form solderable electric circuits or solderable antenna on substrate, especially on flexible sheets by direct printing while to simplify processes, to save time and cost, and to minimize waste.

Description

201033309 VI. Description of the Invention: [Technical Field] The present invention relates to a paste composition for forming a resistance on a substrate, particularly for heat resistance conductive to solderable components by direct printing Patterns to make PCBs or flexible printed circuit boards (FPCB) paste sets φ [Prior Art] A PCB or FPCB is the most basic electronic component with individual functions that are soldered or mounted. PCB or FPCB engraved copper clad laminates (CCL) or flexible copper clad laminates are manufactured to have certain patterns or circuits. It is called "subtractive method" by etching. On the other hand, research and efforts have been made to print a relatively simple pattern in displays (including liquid crystal displays (PDP), touch panels, RFID (without and anti-electromagnetic shielding, etc.). The complexity of the procedure and the reduction of the amount of waste to be treated after the completion of the procedure. In order to expand the scope of the above efforts, the conductive pattern on the board has been printed directly to economically manufacture the complexity of the PCB or the subtractive method and the waste problem. Many components are mounted or soldered on the FPCB, so many problems such as heat resistance, adhesion, and electrical conductivity are still to be overcome by making a PCB or FPCB. The thermal conductive pattern forms a printed circuit board on the substrate. The components are used in a patterning method by etch m (FCCL), respectively, by direct LCD) and plasma line radio frequency identification) instead of causing etching by attempting to avoid PCB or direct printing to system and solderability to -5 - 201033309 [Technical Problem] An object of the present invention is to provide for straight A paste composition for forming a heat-resistant conductive pattern on a substrate is printed. Another object of the present invention is to provide a paste composition for forming a solderable conductive circuit for fabricating an FPCB. A further object of the present invention is to provide A paste composition for forming an antenna that can be combined with an Rfid wafer.Technical Solution According to the present invention, there is provided a paste composition comprising conductive particles, polylysine, and a solvent for forming a conductive pattern by direct printing. The paste composition preferably consists of 导电.〇1% by weight to 96% by weight of conductive particles, 0.5% by weight to 9.6 % by weight of polyamic acid and the remaining solvent. The composition may further comprise a metal precursor. The polyamic acid is preferably as defined in the following formula 1.

R1 and R2 are each a hydrocarbon chain or a hetero atom chain having N, 0 and/or s or a bridge or condensation between benzene rings. For example, r 1 and r 2 are -CO-, _s〇2-, -CH2-, -C2H4:, -C3H6- or -〇-, respectively. The polyamic acid is obtained by addition polymerization of an aromatic dianhydride as defined in the following formula 2 with an aromatic diamine as defined in the following formula 3 of -6-201033309. For example, hydrazine, hydrazine-dimethylformamide ("DMF"), N,N-dimethylacetamide ("DMAc"), N-methylpyrrolidone ("NMP"), four Base urea

"TMU"), dimethyl sulfoxide ("DM SO") or a mixture thereof is used as a solvent to dissolve or disperse the aromatic dianhydride and/or the aromatic diamine. In the present invention, "solvent" is broadly meant to mean a medium including a solvent and a dispersion medium, and a "solution" may be used to include the dispersion as the case may be. The polyamic acid binder is prepared by mixing an aromatic dianhydride solution and an aromatic diamine solution. Preferably, the solvent of the aromatic dianhydride solution is the same as the solvent of the aromatic diamine solution and is introduced as a solvent for the resulting binder without isolation.

R1 and R2 are each a hydrocarbon chain or a hetero atom chain having N, fluorene and/or S, or a bridge or condensation between benzene rings. ® An aromatic dianhydride as defined in the above formula 2 is, for example, 2,4,5-benzenetetracarboxylic acid mono-dry '3,3',4,4'-monophenyl ketone tetracarboxylic dianhydride ("8 butyl 0 八,,), oxydiphthalic anhydride ("ODPA"), 3,3',4,4,-diphenyl maple tetracarboxylic anhydride ("DSDA,"), biphenyltetracarboxylic dianhydride ( "BPDA,,), 3-hydroquinone diacetic anhydride ("HQDA") or 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride ("BPADA") The aromatic diamine as defined in the above formula 3 is, for example, m-phenylenediamine, p-phenylenediamine, monoaminodiphenyl ether, 4,4'-monoaminodiphenylphosphonium or 4,4,-diamine. Diphenyl ketone 201033309 Here, "conductive particles" are particles which direct electrical materials. The material is not limited as long as it has conductivity in a solid state. The material is composed of carbonaceous particles such as carbon black and graphite. a metal or non-metal, an oxide, a carbide, a boride, a nitride or a carbonitride therein. The conductive particles are, for example, gold, aluminum, copper, indium, bismuth, magnesium, chromium, tin, nickel, silver, iron, Titanium and its alloys and their Particles of compounds, carbides, borides, nitrides, and carbonitrides. As carbonaceous particles, there are, for example, natural graphite flakes, expanded graphite, graphene, carbon black, nanocarbon, and carbon nanotubes. The particle shape is not particularly limited and may be, for example, a flat shape, a fibrous shape or a nanometer size. These particles may be used singly or in combination. Here, the metal precursor refers to a metal in which impurities such as P, S, 0, and N are mixed. An organometallic compound in which an atom is bonded to an organic material, and the organometallic compound is metallized at a temperature much lower than the melting point of the corresponding metal. Such an organometallic includes, for example, a ketone, a mercapto group, a carboxyl group, an aniline, an ether or Metals bonded by thiosulfate groups. Direct printing including brushing, spraying, roll coating, screen printing, gravure printing @刷, lithography, offset printing, dispensing, rotary screen printing and inkjet printing In addition to rigid boards, various flexible substrates such as paper, polyester film and polyimide film can also be used in the present invention. The paste of the present invention is printed as a pattern on a substrate and Drying at temperature or ambient temperature, then baking or heat-treating at 15 ° C to 350 ° C to imidize the polyglycolic acid. When a metal precursor is used in the paste, 'at this temperature The heat treatment for metallization and the heat treatment for imidization of 醯-8 - 201033309 are carried out separately or simultaneously in the range. Since the metal precursor is metallized by such heat treatment and the polyglycolic acid binder is closed, the paste is fixed on the substrate. The yttrium imidized adhesive can withstand more than 400 ° C. The paste composition of the present invention can form a conductive pattern on which components can be mounted by soldering. Used as a circuit, but it can also be plated to enhance conductivity, solderability and adhesion. The conductive pattern formed by the paste composition of the present invention includes an electrical circuit, a φ electrode, an Rfid antenna, and a partial coating or a full coating. Advantageous Effects The paste composition of the present invention can form a solderable circuit or a solderable antenna on a substrate, particularly a flexible sheet, by direct printing, while simplifying the procedure, saving time and cost, and reducing waste to least. [Embodiment] φ Embodiment Mode of the Invention Hereinafter, the embodiments will be described in detail, but the scope of the present invention should not be construed as being limited by the embodiments. Various changes or modifications may be made to the invention. These changes or modifications are still within the scope of the invention. Examples 1 to 7 Preparation of Adhesive An OD A solution was prepared by dissolving 19.2 g of 4,4'-diaminodiphenyl ether ("ODA") in 80 g of N-methylpyrrolidone. A PMDA dispersion was prepared by dispersing 20.9 g of pyromellitic dianhydride 201033309 ("PMDA") in 80 g of N-methylpyridinone. The PMDA dispersion was added dropwise to the 〇D A solution over 2 hours. The mixture was subjected to a reaction at room temperature for 24 hours by stirring to prepare a polyglycolic acid binder. The preparation and printing of the paste are 150 g to 2 g of a plate-shaped (50 times the diameter) silver powder having an average particle diameter of 2 μm, 0 to 30 g of fluorene-methylpyrrolidone and 6 g to 150 g of the above-prepared poly The proline adhesives were thoroughly mixed together in the proportions shown in Table 1 to prepare a silver paste. On the polyimine film (1), the silver paste was used as an ink to print a pattern as shown in Fig. 1 by a screen printing machine. The printed matter including the film was baked at 2 °C for about 10 minutes to remove volatile organic compounds. The surface resistance, adhesion, hardness and thermal stability of the formed pattern were measured and shown in Table 2. The surface resistance of each of the embodiments is as shown in the graph of Fig. 4. The surface resistance was measured by a four-probe method, and the adhesion was measured by a tape method (4STM-D3359B), and the hardness was measured by a stray hardness test (ASTM-D3 3 69). The thermal stability of the paste was evaluated by observing the melting and deformation under heating and welding as follows: ◎: Excellent 'contact with the soldering iron heated to 400 ° C for 1 minute without deformation 〇: good 'no soldering after soldering iron Deformation △: Normal, no deformation after 30 minutes in the oven maintained at 2801, but deformation X: after welding with a soldering iron, deformed after 30 minutes in the oven maintained at 2801, 201033309 electroplated on the polyimide film 0.5 Mm χ 1 mm size circuit and baked. The circuit is further electroplated. As shown in Fig. 3, a multilayer ceramic capacitor (1 〇 ) was soldered to the pattern block (2) shown in Fig. 2 by a soldering iron of 40 °C. Adhesion was measured by peel strength using a tensile strength tester. The results are shown in Table 3.

Table 1 Example Paste No. PAA Adhesive (g) NMP (g) Ag Powder (g) 1 AP-A 60 3 0 2 10 2 AP-B 75 15 2 10 3 AP-C 90 _ 2 10 4 AP- D 105 _ 195 5 AP-E 120 1 1 80 6 AP-F 13 5 _ 165 7 AP-G 1 50 - 150

Table 2 Example Paste Number Surface Resistance (X 1 (Γ2 Ω/□) Adhesion Test Hardness Thermal Stability 1 AP-A 4.094 5B 5H 〇2 AP-B 3.428 5B 5H 〇3 AP-C 2.287 5B 5H ◎ 4 AP-D 3.512 5B 5H ◎ 5 AP-E 5.254 5B 5H ◎ 6 AP-F 7.882 5B 5H ◎ 7 AP-G 9.883 5B 5H ◎ ◎ Excellent, good ,, △ normal, X poor -11 - 201033309 Table 3 Example Paste No. Adhesion Test Hardness Peel Strength (gf) 1 AP-A 5B 5H 630 2 AP-B 5B 5H 650 3 AP-C 5B 5H 742 4 AP-D 5B 5H 853 5 AP-E 5B 5H 901 6 AP- F 5B 5H 934 7 AP-G 5B 5H 980 Examples 8 to 1 9 Preparation of binder 7 1 - 75 g of 4,4'-diaminodiphenyl ether ("ODA") was dissolved in 300 g of N-methylpyrrolidone The ODA solution was prepared by dissolving 78.24 g of pyromellitic dianhydride ("PMDA") in 300 g of N-methylpyrrolidone to prepare a PMDA dispersion. The PMDA dispersion was added dropwise over 2 hours. In the ODA solution, the mixture was prepared by stirring at room temperature for 18 hours to prepare a poly-proline ("PAA") binder. The preparation and printing of the paste will have an average particle size of 93.75 g to 112.5 g. 2 μιη plate (50 times the thickness) silver powder, 〇18.75g of Ν-methylpyrrolidone and 37.5g~52.5g of the poly-proline adhesive prepared above according to the ratio shown in Table 4 The silver paste was prepared by mixing together. On the polyimide film, the silver paste was used as an ink to print a pattern by a screen printing machine as shown in Fig. 1. The printed matter including the film was 200. : Baking for about 1 Torr to remove volatile -12-201033309 Sexual organic compound. The surface resistance, adhesion, hardness and thermal stability of the formed pattern were measured and shown in Table 5. Surface of each example The resistance is not shown in the chart in Figure 5. Table 4

EXAMPLES Paste No. PAA Adhesive (g) NMP (g) Ag Powder (g) 8 P AA 1 37.5 18.75 93.75 9 P AB 1 45 11.25 93.75 10 PA-C 1 52.5 3.75 93.75 11 P A-A2 37.5 15 97.5 12 PA-B2 45 7.5 97.5 13 PA-C2 52.5 3 94.5 14 PA-A3 37.5 11.25 101.25 15 P AB 3 45 3.75 101.25 16 PA-C3 52.5 2.25 95.25 17 P A-A4 37.5 _ 112.5 18 P A-B4 45 105 19 P A-C4 52.5 - 97.5 -13- 201033309 Table 5 Example paste number thickness (μιη) Surface resistance (χ10'2Ω/α) Adhesion test hardness Thermal stability 8 PA-A1 7 4.677 5Β 5Η ◎ 9 PA -B1 8 4.129 5Β 5Η ◎ 10 PA-C1 9 4.119 5Β 5Η ◎ 11 PA-A2 12 3.204 5Β 5Η ◎ 12 PA-B2 11 2.798 5Β 5Η ◎ 13 PA-C2 9 4.498 5Β 5Η ◎ 14 PA-A3 13 3.440 5Β 5Η ◎ 15 PA-B3 14 3.083 5Β 5Η ◎ 16 PA-C3 11 2.993 5Β 5Η ◎ 17 PA-A4 17 2.730 5Β 5Η ◎ 18 PA-B4 19 2.381 5Β 5Η ◎ 19 PA-C4 12 3.310 5Β 5Η ◎ ◎ Excellent, Good, △ normal, poor X

Example 2 0 to 3 1 Examples 20 to 3 were carried out in the same manner as in Example 8 except that dimethylacetamide ("DMAc") was used instead of N-methylpyrrolidone as the preparation of PAA. The solvent of the binder. The composition of the prepared silver paste and its ratio are shown in Table 6, for example. The baking method of the printed matter and the method of measuring the surface resistance, the adhesion, the hardness and the thermal stability were the same as in the eighth embodiment. The obtained measurements are shown in Table 7. The surface resistance of each embodiment is not shown in the graph of Fig. 6. -14- 201033309 Table 6

EXAMPLES Paste No. PAA Adhesive (g) DMAc(g) Ag Powder (g) 20 P AJ 1 37.5 18.75 93.75 2 1 P A-K2 45 11.25 93.75 22 P A-L3 52.5 3.75 93.75 23 P A-J2 37.5 15 97.5 24 P A-K2 4 5 7.5 97.5 25 PA-L2 52.5 3 94.5 26 P A-J3 37.5 11.25 101.25 27 P A-K3 45 3.75 101.25 28 P A-L3 52.5 2.25 95.25 29 P A-J4 3 7.5 _ 112.5 3 0 P A-B4 45 • 1 05 31 P A-L4 52.5 - 97.5 Table 7 Example paste number thickness (μπι) Surface resistance (χ10·2Ω/ο) Adhesion test hardness Thermal stability 20 PA-J1 8 4.203 5Β 5Η ◎ 21 PA-K1 8 3.642 5Β 5Η ◎ 22 PA-L1 7 1.832 5Β 5Η ◎ 23 PA-J2 8 4.064 5Β 5Η ◎ 24 PA-K2 10 2.621 5Β 5Η ◎ 25 PA-L2 12 2.025 5Β 5Η ◎ 26 PA-J3 11 3.778 5Β 5Η ◎ 27 PA-K3 14 2.255 5Β 5Η ◎ 28 PA-L3 12 2.320 5Β 5Η ◎ 29 PA-J4 19 2.513 5Β 5Η ◎ 30 PA-K4 13 2.140 5Β 5Η ◎ 31 PA-L4 13 4.368 5Β 5Η ◎

◎Excellent, good ,, △ ordinary, X poor -15-201033309 Example 3 2~3 4 Examples 32 to 34 were carried out in the same manner as in Example 8, except that dimethylformamide was used (" DMF") replaces N-methylpyrrolidone as a solvent for preparing a PAA binder. The composition of the prepared silver paste and its ratio are shown, for example, in Table 8. The method of measuring the baking of the printed matter and the surface resistance, adhesion, hardness and thermal stability was the same as in Example 8. The obtained measurement is shown in Table 9. The surface resistance of each example is shown in the graph of Fig. 7. Table 8 Example paste number Ί PAA binder (g) DMF (g) Ag powder (g) 32 PA-G 37.5 18.75 93.75 33 PA-H 45 11.25 93.75 34 P AI 52.5 3.75 93.75 Table 9 Example paste number Thickness Surface resistance (χ1 (Τ2Ω/mouth) Adhesion test hardness Thermal stability 32 PA-G 8 5.901 5Β 5Η ◎ 33 PA-H 9 4.875 5Β 5Η ◎ 34 PA-I 7 ---- 3.012 5Β 5Η ◎ ◎ excellent, good ,, △ normal, X poor Example 3 5 to 3 7 Examples 35 to 37 were carried out in the same manner as in Example 8, except that the use was carried out. - DM So, ("DM So,") instead of N-methylpyrrolidone as a solvent for the preparation of PAA binder. The composition of the prepared silver paste and its -16-201033309 ratio are shown, for example, in Table 1 。. The baking of the printed matter and the measurement methods of the surface resistance, the adhesive strength, and the thermal stability were the same as in Example 8. The obtained measurement was as shown in Table 11. The surface resistance of each Example is shown in the graph of Fig. 8. Table 10 Example No. PAA Adhesive (g) DMSO (g) Ag Powder (g) 3 5 I —JPA-J 37.5 18.75 93.75 36 45 11.25 93.75 37 —-Pa-l 52.5 3.75 93.75 ❹ Table 1 1 Example paste number thickness (μτη) Surface resistance (χ10-2Ω/port) Adhesion test hardness Thermal stability 35 PA-J 11 5.214 5Β 5Η ◎ 36 PA-K 13 4.504 5Β 5Η ◎ 37 PA-L 12 4.349 5Β 5Η ◎ ◎ excellent, good ,, △ normal, X poorly exemplified Example 3 8~4 1 Example was carried out in the same manner as in Example 8. 3 8 to 4 1, differing in 60.293 g of 4,4'-diaminodiphenyl ether ("ODA") and 59.7 g of pyromellitic dianhydride ("PMDA") (both equivalent ratio) 1 · 1 : 1 ) for the preparation of p AA binder. The composition of the prepared silver paste and its ratio are shown in Table 12. The baking of the printed matter and the surface resistance, adhesion, hardness and thermal stability The measurement method was the same as in Example 8. The obtained measurement was as shown in Table 13. The surface resistance of each example is shown in Fig. 17 - 201033309 in Fig. 9. Table 12 Example No. PAA Adhesive (g) NMP ( g) Ag powder (g) 38 30 26.25 93.75 39 JA-N 37.5 18.75 93.75 40 45 11.25 93.75 41 _P AP 52.5 3.75 93.75

Table 13 Q Example - Paste No. Thickness (μιη) Surface Resistance (=<W2Q/a) Adhesion Test Hardness Thermal Stability 38 pa-m 8 5.193 5Β 5Η ◎ 39 PA-N 8 3.582 5Β 5Η ◎ 40 PA-0 9 2.441 5Β 5Η ◎ 41 PA-P 10 2.232 5Β 5Η ◎ ◎ excellent '〇 good, △ normal, x poor Example 42 to 45 Example 4 2 to 4 5 were carried out in the same manner as in Example 8, The difference is 63.15g of 4,4'-diaminodiphenyl ether ("〇da") and 56.85g of pyromellitic dianhydride ("PMDA") (the equivalent ratio of the two is 1·2· · 1) Used to prepare PAA binders. The composition of the prepared silver paste and its ratio are shown, for example, in Table 14. The baking method of the printed matter and the method of measuring the surface resistance, the adhesion, the hardness and the thermal stability were the same as in the eighth embodiment. The obtained measurements are shown in Table 15. The surface resistance of each of the examples is shown in the graph of Fig. 1A. -18- 201033309 Table 实施 Example No. PAA Adhesive (g) NMP(g) Ag Powder (g) 42 - La-〇30 26.25 93.75 43 3 7.5 18.75 93.75 44 —JA-S 45 11.25 93.75 45 -JA- T 52.5 3.75 93.75 Table 15 Example paste number thickness (μτη) Surface resistance (χ10*2Ω/α) Adhesion test hardness Thermal stability 42 9 5.666 5Β 5Η ◎ 43 pa-r 8 4.129 5Β 5Η ◎ 44 PA-S 9 2.828 5Β 5Η ◎ 45 PA-T 10 2.529 5Β 5Η ◎ ◎ Excellent '〇 is good, △ normal, X is poor [Simplified illustration] Fig. 1 is a view showing a pattern formed and plated in the embodiment. Fig. 2 is a view showing another pattern formed and shovel in the embodiment. Fig. 3 is a view showing soldering on the pattern formed and plated in Example 1. Fig. 4 is a graph showing the surface resistance of the patterns formed in Examples 1 to 7. Fig. 5 is a graph showing the surface resistance of the patterns formed in Examples 8 to 19. Fig. 6 is a graph showing the surface resistance of the pattern formed in Examples 20 to 31. -19- 201033309 Fig. 7 is a graph showing the surface resistance of the pattern formed in Examples 32 to 34. Fig. 8 is a graph showing the surface resistance of the pattern formed in Examples 35 to 37. Fig. 9 is a graph showing the surface resistance of the patterns formed in Examples 38 to 41. Fig. 10 is a graph showing the surface resistance of the patterns formed in Examples 42 to 45. Reference [Main component symbol description] 1 : Polyimide film 2 : Pattern block 10 : Multilayer ceramic capacitor

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Claims (1)

201033309 VII. Patent application: 1 - A paste composition for forming a heat-resistant conductive pattern by direct printing, which comprises conductive particles, polylysine, and a solvent. 2. The paste composition of claim 1, wherein the polyamic acid is as defined in the following formula 1: R1 and R2 are each a hydrocarbon chain or a hetero atom chain having ruthenium, osmium and/or S, or a bridge or condensation between benzene rings. 3. The paste composition of claim 2, wherein the polyamic acid is an addition polymerization of an aromatic dianhydride as defined in the following formula 2 with an aromatic diamine as defined in the following formula 3; Preparation: Equation 2 Equation 3 Ο 0 R1 and R2 are each a hydrocarbon chain or a hetero atom chain having ruthenium, osmium and/or S, or a bridge or condensation between benzene rings. 4. The paste composition of claim 3, wherein the defined aromatic dianhydride is 1,2,4,5-benzenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl Ketotetracarboxylic acid dianhydride ("BTDA"), oxydiphthalic anhydride ("ODPA"), 3,3',4,4'-diphenyltetradecyl anhydride ("〇80八"), Biphenyltetracarboxylic dianhydride ("BPDA"), 3-hydroquinone diacetic anhydride ("HQDA") or 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane di- 21 - 201033309 Anhydride ("BPADA"): and the aromatic diamine is m-phenylenediamine, p-phenylenediamine, diamine 4,4,-diaminodiphenyl maple or 4,4'-diamino Diphenyl ketone. 5. A solvent composition of the bismuth acid, an aromatic dianhydride, and an aromatic diamine of the paste composition of claim 3 or a N,N-dimethylformamide, N,N-dimethyl B a group consisting of decylamine, N-methyl, tetramethylurea, dimethyl hydrazine, and mixtures thereof; 6. The paste composition of claim 3, wherein the electrical particles are selected from the group consisting of metals, non-metals, and oxides. Particles of a group consisting of carbonized, nitrided, carbonitride, and carbonaceous materials. 7. The paste composition sheet of claim 1 is a paper, a polyester film or a polyimide film. 8. The paste composition of claim 1 of the patent application is brushing, spraying, roller coating, screen printing, gravure printing, offset printing, dispensing (disPensing), rotary inkjet printing. 9. The paste composition of claim 1 is an Rfid antenna. A diphenyl ether, wherein the polymer is selected from the group consisting of a pyrrolidone. Wherein the conductor, the conductive material in the boride, wherein the base is in the direct printing, lithographic screen printing or