TWI554345B - Fabricating method of noble catalyst ink for inkjet printing and noble catalyst ink thereof - Google Patents

Description

Manufacturing method of precious metal catalyst ink for printing and precious metal catalyst ink thereof

The invention relates to a method for manufacturing a noble metal catalyst ink for printing and a noble metal catalyst ink thereof, in particular, the first aqueous solution of the precious metal catalyst is firstly reduced to reduce the corrosion harmful factor, and then the viscosity control agent or the viscosity stabilizer is used to control the viscosity thereof. The surface tension is used to produce a noble metal catalyst ink for printing with catalytic activity.

In recent years, the printing technology has developed rapidly. Because printing has the advantages of simple plate making work, low cost, accurate position, easy copying of printing plates, etc., it can undertake a large number of productions; the main principle of printing is to use pre-conditioned ink to The set pattern is printed on the object; among the various printing methods, the most common and flexible advantages are inkjet printing techniques using a printer, and patterning by printing has many process and cost advantages. The advantages can be roughly divided into six items: (1) no contact process, direct printing of the required pattern on the desired substrate; (2) solution process, dispersing the material in one In the solvent, and by inkjet printing and printing, the choice of materials is diverse; (3) large area process, which can be quickly completed by printing technology; (4) low cost (low cost) Compared with the yellow lithography technology, the inkjet printing device has no complicated and expensive vacuum equipment and developing equipment, so the cost is extremely low; (5) medium resolution, as long as the material is accurately printed at the desired printing position On the top, the resolution can be up to about 20μm, the speed is fast, and the waste of materials can be reduced. (6) Digital data transmission, this technology can be quickly completed and designed and printed by software design, not only Can save more processing time and cost, and it is easier to achieve customized demand, so in recent years A lot of research scholars have tried to apply it to the production of electronic components.

Due to the fast and low cost advantages of the printer output pattern, the metallized metal pattern technology formed by printing is very suitable for the metallization process. This technology can not only print the pattern quickly by digital printing, but also can be large. The metal wires required for mass production have considerable development potential.

Conventionally, in the apparatus of the printing machine, the ink for printing is used to disperse the ink through the inkjet head (printing head) to be printed on the surface of the object, in order to control the droplet size and the printing speed, it is required Adjust the viscosity and surface tension of the ink to the desired range. For example, Taiwan patent TWI320797 uses guanamines, ethers, glycols, and lower alkyl ethers to participate in the ink synthesis reaction to adjust the viscosity and surface tension. Or, as the Taiwan patent TWI259843, a water-soluble resin, a phosphate ester surfactant, or the like is used. These inks are generally used for inkjet or printing. In the industrial metallization process, the metallized ink materials used can be roughly classified into three types, and the first type is mainly metal particle ink (nano metal paste), such as The inkjet printing of nano gold and silver particles, the second type is mainly conductive polymers, such as conductive polymers, colloidal suspended particles, etc., and the third type is mainly composed of metal catalyst activation liquid for printing patterns. A metallized pattern (such as a circuit, etc.) is formed, such as the Taiwan patents TWI433957, TWI361208, or as in US Pat. No. 8,029,276, US Pat.

Wherein, the metal particle ink has a high concentration of precious metal particles (such as nano gold, silver particles) in the ink to be printed, and the precious metal particles are reduced or pyrolyzed by heating to precipitate precious metal particles, and the structure thereof is The precursor of the noble metal is mixed into the polymer, such as the Taiwan patents TWI324954 or TWI324954, the US patent US8440263, the US Patent Publication No. US20110226511, US20090274833 and the like. The noble metal catalyst ink of this kind of precious metal precursor has high viscosity during synthesis, which is not suitable for painting or printing, and it is often necessary to add a solvent to reduce the viscosity. US Patent Publication No. US 20040107869 discloses that a platinum catalyst ink uses a polar aprotic organic solvent to adjust the viscosity to about 1 CP, or US Patent Publication No. US 20110226511 to use 1 to 20 wt% of BYK-323 or F-781F, adjust the viscosity to 7~12mP. s surface tension is 27~30mN/m. Or, as disclosed in WIPO Publication No. WO2014021941, a precious metal ink containing an electroplating catalyst such as palladium acetate, palladium 2,4-pentanedionate, silver (Ag), platinum (Pt), gold (Au), or lanthanum (Er), Using bisphenol A diacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate monomer, and neopentyl tetraacrylate to adjust the viscosity at 50 cps to Between 10,000 cps.

Among them, the second type of conductive polymer has limitations due to the stability or conductivity of the polymer, and it is difficult to perform electroless plating on the ink that has been printed to form a metal layer, which has limitations for application of circuit lines and the like. .

Another type of catalyst ink, such as the aforementioned noble metal catalyst ink (or metal catalyst activation liquid), is disclosed in the following paper: "Ink-Jet Printing, Self-Assembled Polyelectrolytes, and Electroless Plating: Low Cost Fabrication of "Electronics.", Macro. U.S. Patent No. 7,662,434 is, for example, a noble metal catalyst of poly(styrene-co-N-isopropylacrylamide) having a structure in which a noble metal is attached to a polymer. In application, as shown in the first figure, the first figure is a schematic diagram of printing a pattern by using a precious metal catalyst ink to print a pattern, and then metallizing; in the figure, the patterned metal is coated on the substrate 921. The pattern layer 94, or further, the conductive layer 95 is further formed on the metal pattern layer 94; first, a noble metal catalyst ink 931 is prepared, and the noble metal catalyst ink 931 is a solution of the noble metal catalyst 32, which is sprayed by the printer 935. The ink head 936 sprays the noble metal catalyst ink 931 on the substrate 921 in a patterned manner to form a noble metal catalyst layer 937, and is immersed in the electroless metal plating solution 941 to form a metal pattern layer 94 having a metallization pattern; The metallization pattern is formed on the patterning of the circuit or on the casing of the 3C electronic device.

However, the metal catalyst ink of this type is a low concentration aqueous solution (or solvent solution), which has a low viscosity and a small surface tension, and is easy to splash when printing, which is not conducive to the printing of fine patterns, and thus has an adjusted viscosity. Necessary. Moreover, such metal catalyst inks are acidic, and acidic inks may cause corrosion to various parts of the printer and the ink jet head, and also have the necessity of adjusting the pH. Since the activity of the noble metal catalyst ink is one of the most important characteristics, how to maintain the activity of the noble metal catalyst ink is a major problem in selecting the added substance or process when adjusting the viscosity, surface tension, and pH.

In view of the above problems of the prior art and the motive of the present invention, one of the main objects of the present invention is to provide a method for manufacturing a precious metal catalyst ink for printing, comprising the following steps:

S1: first taking a precious metal catalyst initial aqueous solution, the initial aqueous solution of the noble metal catalyst is an aqueous solution or an organic solvent solution of a precious metal catalyst; wherein the noble metal catalyst is a temperature sensitive polymer attached to one of the catalytic metal particles; Chloride ion, at least to a chloride ion concentration of less than 50 ppm; removal of chloride ions can be used without limitation, in the embodiments of the present invention, a dialysis method is used to remove chloride ions, but not limited thereto; wherein the catalytic metal particles It is gold (Au), silver (Ag), palladium (Pd), platinum (Pt) or ruthenium (Ru); wherein the temperature sensitive polymer is: A (styrene monomer and N-isopropyl acrylamide) Copolymer (Poly (Styrene-Co-NIPAAmb)), B (copolymer of styrene monomer and hydroxypropylcellulose), C (styrene monomer and polyvinyl caprolactam ( Poly(vinylcaprolactame)), one of D (a copolymer of styrene monomer and poly(vinyl methyl ether)) or a combination thereof; S2: complete removal of chloride ions (eg dialysis) Completed) the initial aqueous solution of the precious metal catalyst under agitation Slowly adding an aqueous solution of a metal salt having a hydroxide, or an aqueous ammonia or a combination thereof, adjusting the pH to near neutral, and making the pH between 6.5 and 8.0; wherein the pH is dependent on the addition of hydrogen and oxygen The concentration and volume of the metal salt or aqueous ammonia solution of the root vary.

S3: preparing a viscosity control solution, wherein the viscosity control agent is formed by dissolving a viscosity control agent in a solvent of water or an alcohol or a combination thereof, the viscosity control agent is hydrophilic; and the precious metal after adjusting the pH The initial aqueous solution of the catalyst is placed in a mixing environment, and the quantitative viscosity control solution is slowly added to form a precious metal catalyst ink for printing; the mixing environment is: the temperature is controlled between 18 and 42 ° C, and the temperature changes. Within ±5 ° C; the stirring rate is 300~600 r. pm; the viscosity of the precious metal catalyst ink for printing is between 2 and 40 cps (mg.s ^-1 .cm ^-1 ), and the surface tension is 20 to 45 dyne. Between /cm; when adding the viscosity control solution, at the same time continue to control its pH, so that the pH of the noble metal catalyst ink for printing is between 6.5 and 8.0; wherein, the printing of precious metal catalyst ink Viscosity and surface tension are varied depending on the concentration and volume of the viscosity control solution.

Wherein, the viscosity control agent is selected from one or a combination of the following groups: the first group is a high molecular polymer, which is one of waterborne polyurethane, polyvinylpyrrolidone (PVP) or Combination; the second group is a hydroxyl-rich organic solvent, which is 3-methoxy-3-methylbutanol (3-Methoxy-3-Methyl-1-Butanol, MMB), glycerol (glycerol) , inositol (D-Mannitol), 2,2,6,6- tetramethyl-pyridine (2,2,6,6-tetramethylpiperidine, TMP), ethylene glycol monobutyl ether (Butyl Cellosolve ^TM), or one a combination thereof, which, Butyl Cellosolve ^TM is a trademark of Dow Chemical Company's name.

S4: filtering the printing ink with precious metal catalyst ink to filter out the solid matter; forming a precious metal catalyst ink which can be used for the ink jet head of the printer.

Further, in order to make the noble metal catalyst ink for printing have better viscosity stability, in S3, the viscosity control agent is added to control the viscosity of the noble metal catalyst ink for printing to satisfy 1.1 ≦ (20 ° C and The ink viscosity measured at a shear rate of 0.5 sec ^-1 ) / (ink viscosity measured at 20 ° C and shear rate of 100 sec ^-1 ) ≦ 2.0. The viscosity at the shear rate of the noble metal catalyst ink for printing varies depending on the concentration and volume of the viscosity control solution.

For the requirements of different inkjet heads of the printer, the viscosity of the precious metal catalyst ink for printing can be adjusted to be between 2 and 25 cps (mg.s ^-1 .cm ^-1 ), and the precious metal catalyst for printing can be adjusted. The surface tension of the ink is between 25 and 40 dyne/cm; in step S3, a viscosity stabilizer may be added to the viscosity control solution, the viscosity stabilizer being selected from one or a combination of the following groups: polyether One or a combination of a modified polydimethoxide (Polyether Modified polydi Methy siloxane), a polyether modified polydimethoxide (acrylate), or an acrylate copolymer.

In order to achieve better stability of the viscosity of the precious metal catalyst ink for printing, when the viscosity control agent is one of water urethane, polyvinylpyrrolidone (PVP) or a combination thereof (for In the case of a group of high molecular polymers, the viscosity stabilizer is selected from the group consisting of polyether modified polydimethoxide (Polyether Modified polydi Methy siloxane) and polyether modified polydimethoxide (Polyether Modified polydi Methy siloxane). One or a combination thereof.

Same as above, when the viscosity control agent is 3-methoxy-3-methylbutanol (3-Methoxy-3-Methyl-1-Butanol, MMB), glycerol, hexamethylene alcohol (D- Mannitol), 2,2,6,6- tetramethyl-pyridine (2,2,6,6-tetramethylpiperidine, TMP), BC solvent (Butyl Cellosolve ^TM), one or a combination of (a second group enriched When the organic solvent of the hydroxyl group is selected, the viscosity stabilizer is selected from one or a combination of acrylate copolymers; wherein the viscosity and surface tension of the noble metal catalyst ink for printing are added The viscosity control solution changes with the concentration, ratio and volume of the viscosity stabilizer.

Another main object of the present invention is to provide a noble metal catalyst ink for printing, which is used for an ink jet head of a printing machine, the precious metal catalyst ink for printing is composed of a noble metal catalyst and a hydrophilic viscosity control agent. The aqueous solution or the organic solvent solution formed; wherein the noble metal catalyst is a temperature sensitive polymer to which one catalytic metal particle is attached; the catalytic metal particle is gold (Au), silver (Ag), palladium (Pd), Platinum (Pt) or ruthenium (Ru); wherein the temperature sensitive polymer is: A (Poly(Styrene-Co-NIPAAmb), styrene monomer and N-isopropyl acrylamide monomer), B (copolymer of styrene monomer and hydroxypropylcellulose), C (copolymer of styrene monomer and polyvinylcaprolactame), D (styrene monomer) One or a combination thereof with a copolymer of polyvinyl (vinyl methyl ether); wherein the viscosity control agent is selected from one or a combination of the following groups: the first group is a polymer The polymer is made of waterborne polyurethane (polyurethane), polyvinylpyrrolidone (polyvinylpyrrolidone, PVP). One or a combination thereof; the second group is a hydroxyl-rich organic solvent, which is 3-methoxy-3-methylbutanol (3-Methoxy-3-Methyl-1-Butanol, MMB), C Glycerol, D-Mannitol, 2,2,6,6-tetramethylpyridine (2,2,6,6-Tetramethylpiperidine, TMP), ethylene glycol monobutyl ether (Butyl Cellosolve) One or a combination of ^TM ; by the action of the viscosity control agent, the viscosity of the noble metal catalyst ink for printing is between 2 and 40 cps (mg.s ^-1 .cm ^-1 ) and the surface tension is 25 Between ~45dyne/cm and the pH of the pH is between 6.5 and 8.0; wherein the viscosity and surface tension of the noble metal catalyst ink for printing are changed according to the concentration and volume of the viscosity control solution.

Furthermore, the aforementioned precious metal catalyst ink for printing can be loaded into the ink cartridge of a printer, and the ink cartridge can be inserted and detachably mounted on the printer, and one or more nozzle holes of the ink cartridge are used for spraying. The control of the printing machine ejects the ink droplets from the ejection holes by the precious metal catalyst ink for printing. For different applications, the ink cartridge can be used in a cylindrical or bottle shape, and is drawn to the inkjet head of the printer by the ink tube, and the ink droplets are ejected from the nozzle holes of the inkjet head, which is not limited.

For the needs of different inkjet heads of the printer, the present invention provides a noble metal catalyst ink for printing, which is formed by a noble metal catalyst, a viscosity control agent and a viscosity stabilizer. The viscosity of the noble metal catalyst ink for printing is between 2 and 25 cps (mg.s ^-1 .cm ^-1 ), and the surface tension of the noble metal catalyst ink for printing is between 25 and 40 dyne/cm.

Wherein the noble metal catalyst is a temperature sensitive polymer to which a catalytic metal particle is attached; the catalytic metal particle is gold (Au), silver (Ag), palladium (Pd), platinum (Pt) or bismuth ( Ru); wherein the temperature sensitive polymer is: A (Poly(Styrene-Co-NIPAAmb) of styrene monomer and N-isopropyl acrylamide monomer, B (styrene monomer and hydroxyl Copolymer of hydroxypropylcellulose, C (copolymer of styrene monomer and polyvinylcaprolactame), D (styrene monomer and polyvinyl methyl ether ( One or a combination of poly(vinyl methyl ether) copolymers; wherein the viscosity control agent is selected from one or a combination of the following groups: the first group is a high molecular polymer, which is an aqueous polyurethane (Polyurethane), one of polyvinylpyrrolidone (PVP) or a combination thereof; the second group is a hydroxyl-rich organic solvent, which is 3-methoxy-3-methylbutanol (3-Methoxy- 3-Methyl-1-Butanol, MMB), glycerol, D-Mannitol, 2,2,6,6-tetramethylpyridine (2,2,6,6-Tetramethylpiperidine , TMP), one or a combination of ethylene glycol monobutyl ether (Butyl Cellosolve ^TM ); wherein the viscosity stabilizer is selected from one or a combination of the following groups: polyether modified polydimethyl oxime One or a combination of polyether modified polydiMethy siloxane, polyether modified polydimethoxide, or acrylate copolymer; wherein the viscosity and surface tension of the noble metal catalyst ink for printing The viscosity is controlled by adding the viscosity control solution to the concentration, ratio and volume of the viscosity stabilizer.

According to the present invention, a method of manufacturing a noble metal catalyst ink for printing and a noble metal catalyst ink thereof can have one or more of the following advantages:

(1) The method for producing a noble metal catalyst ink for printing according to the present invention, which can reduce the chloride ion concentration of the noble metal catalyst ink for printing by removing chlorine ions (such as dialysis) to reduce the corrosion factor and pH The value is adjusted to neutral, improving the shortcomings of the conventional precious metal catalyst ink which easily corrodes the ink jet head of the printer.

(2) The range and table of the viscosity used to match the inkjet head of a general printer In the range of surface tension, the present invention adjusts the viscosity and surface tension of the noble metal catalyst ink by adding a viscosity control agent or a viscosity stabilizer further; the inkjet head of the printer can be easily agglomerated and easily formed into a uniform shape. The droplets make the pattern fine and easy to handle.

(3) In order to maintain the neutral pH value of the precious metal catalyst ink for printing, in the selection of the viscosity control agent and the viscosity stabilizer, a polymer or a hydroxyl-rich organic solvent which cannot be destroyed by the pH balance is used. Produces stable viscosity and surface tension.

(4) Furthermore, in order to avoid the corrosion factor, the noble metal catalyst ink for printing according to the present invention is dialyzed to reduce the chloride ion content, however, the chlorine ion is reduced, but the dispersibility of the noble metal catalyst is liable to be poor, and the present invention By using the viscosity control agent and viscosity stabilizer, that is, controlling the viscosity and surface tension range, the precious metal catalyst can be completely dispersed in the aqueous solution without reducing the activity of the noble metal catalyst.

(5) The noble metal catalyst ink for printing of the present invention can be used to print a 2D pattern on the surface of the workpiece in combination with a flat ink jet head of the printer, and electrolessly plated or further electroplated into a metallized pattern. Layer, 2D circuit for 2D circuit, RFID antenna line, mobile phone RF antenna line or automotive electronic components, or metallized decorations; if combined with 3D inkjet head of the printer, it can be used in the workpiece The 3D pattern is printed on the electroless plating or further electroplated into a metallized pattern conductive layer for use in 3D circuits, RFID antenna lines, cell phone antenna lines or 3D circuits of automotive electronic components.

For a better understanding of the features and technical aspects of the present invention, reference should be made to the accompanying drawings.

1‧‧‧Precious metal catalyst ink for printing

11‧‧‧Viscosity Control Solution

111‧‧‧Viscosity Control Agent

112‧‧‧Viscosity stabilizer

2‧‧‧ precious metal catalyst

21‧‧‧ Temperature sensitive polymer

22‧‧‧ Catalytic metal particles

31‧‧‧Reaction tank

32‧‧‧water bath

33‧‧‧Agitator

34‧‧‧ thermometer

35‧‧‧Viscometer

4‧‧‧Ink 匣

41‧‧ ‧ room

42‧‧‧ orifice

921‧‧‧Substrate

93‧‧‧

931‧‧‧ precious metal catalyst ink

932‧‧‧ precious metal catalyst

935‧‧‧Printing machine

936‧‧‧Inkjet head

937‧‧‧ precious metal catalyst layer

94‧‧‧metal pattern layer

941‧‧‧Electroless plating bath

M ⁺ ‧‧‧catalytic metal particles

S1~S4, S3’‧‧‧ method steps

1 is a schematic view showing a conventional method for forming a metallization pattern using a noble metal catalyst ink; and FIG. 2 is a step view showing a method for manufacturing a noble metal catalyst ink for printing according to a first embodiment of the present invention; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 4 is a schematic view showing a manufacturing method of a noble metal catalyst ink for printing according to a second embodiment of the present invention; and FIG. 5 is a printing method of the present invention. A schematic diagram of filling the ink cartridge with a noble metal catalyst ink.

The above and other technical contents, features and advantages of the present invention will be apparent from the following description of the drawings and the appended claims.

<First Group of Embodiments>

Please refer to FIG. 2 and FIG. 3, FIG. 2 is a diagram showing a method for manufacturing a noble metal catalyst ink for printing according to a first embodiment of the present invention, and FIG. 3 is a noble metal catalyst ink for printing according to an embodiment of the present invention. Schematic diagram of the manufacturing method;

S1: First, an initial aqueous solution of a precious metal catalyst is used, wherein the noble metal catalyst 2 is a temperature-sensitive polymer 21 to which catalytic metal particles 22 are attached; the catalytic metal particles 22 are gold (Au), silver (Ag), and palladium ( Pd), platinum (Pt) or ruthenium (Ru), palladium (Pd) is used in the present embodiment; the temperature sensitive polymer 21 is: A (styrene monomer and N-isopropyl acrylamide monomer) Copolymer (Poly (Styrene-Co-NIPAAmb)), B (copolymer of styrene monomer and hydroxypropylcellulose), C (styrene monomer and polyvinyl caprolactam (Poly) (copolymer of vinylcaprolactame)), one of D (a copolymer of styrene monomer and poly(vinyl methyl ether)) or a combination thereof; in this group of examples, A (styrene) is used. Copolymer of monomer and N-isopropylacrylamide monomer (Poly (Styrene-Co-NIPAAmb)).

The initial aqueous solution of the noble metal catalyst in the present embodiment is a copolymer of palladium styrene monomer and N-isopropyl acrylamide monomer (Pd-Poly (Styrene-Co-NIPAAmb)), and its preparation and For the properties, see "Wen-Ding Chen et. al., The preparation of thermo-responsive palladium catalyst with high activity for electroless nickel deposition, Surface and Coating Technology 204 (2010) P. 2130-2135".

The initial aqueous solution of the noble metal catalyst is dialyzed to remove chloride ions; in this embodiment, the precise ion exchange membrane is used for electrodialysis, and the yin and yang electrodes are placed in the initial aqueous solution of the precious metal catalyst, and the electrodes are alternately inserted between the yin and yang electrodes. The cation exchange membrane and the anion exchange membrane are arranged, the cation exchange membrane can only be selected to pass through the cation, and the anion exchange membrane can only be selected to pass the anion; when the two electrodes are connected to the direct current, the anion is moved by the traction of the cathode, and the chloride ion is subjected to the anode The traction movement, under the characteristic of selective exchange of the exchange membrane, produces concentration and dilution, and removes the high concentration chloride ion solution to remove the chloride ion of the initial aqueous solution of the precious metal catalyst.

Among them, the anion and cation exchange membrane are polymerized from a polymer resin, and have a pore diameter of about 0.5 nm, which can block the noble metal catalyst (Pd-styrene monomer and N-isopropyl acrylamide monomer). The copolymer Pd-(Poly(Styrene-Co-NIPAAmb)) is passed through to pass chloride ions, whereby the noble metal catalyst can be separated from the chloride ions.

In the examples of this group, the dialysis to a chloride ion concentration of less than 50 ppm, and the dialysis time should be properly controlled, and the phenomenon that the chloride ion is reduced but the dispersion of the noble metal catalyst is not good can not be caused.

S2: slowly adding a metal salt or an aqueous ammonia solution having hydroxide to the dialysis aqueous solution of the noble metal catalyst under stirring to adjust the pH to near neutral; in the present embodiment, sodium hydroxide and ammonia are respectively added. The aqueous solution is adjusted to be nearly neutral. For the non-limiting embodiment, other metal salts containing hydroxide, such as potassium hydroxide, may be used, and are not limited thereto.

S3: the viscosity control agent 111 is dissolved in pure water to prepare a viscosity control solution 11, and the initial aqueous solution of the noble metal catalyst is placed in the reaction tank 31 in the water bath 32, and the stirring rate is controlled to be 300 to 600 rpm. The temperature is between 18~42 °C, and the temperature changes within ±5 °C; when the viscosity control solution 11 is slowly added to the desired viscosity and surface tension, the addition is stopped to form a printing precious metal catalyst ink 1; The temperature is controlled by the thermometer 34, and the stirring rate is controlled by the agitator 33, and the viscosity is controlled by the viscosity meter 35.

S4: The printing precious metal catalyst ink 1 is filtered, and the solid matter is filtered to obtain a noble metal catalyst ink 1 for printing. The operating conditions and results of the examples of the examples of the examples are shown in Table 1.

In the present embodiment, the noble metal catalyst ink 1 for printing according to the present invention is formed on the plastic sheet of PC-ABS material by printing and electroless plating (see the printer of FIG. 1). A WWAN antenna line is formed inside the back cover of the plastic material, and a metal layer is formed by electroless plating of nickel-phosphorus (NiP). The mobile phone case of the WWAN antenna application is functionally up to the specification of the adhesion of 4B or more in accordance with the BaGe test, and meets the requirements of the receiving band area corresponding to the return loss (RL) of less than -10 dB, thereby demonstrating the addition. The noble metal catalyst ink 1 for printing of the viscosity control agent 111 still has good catalytic activity.

Please refer to FIG. 5, which is a schematic diagram of loading the noble metal catalyst ink 1 for printing on the ink cartridge in the embodiment of the present invention. Further, the precious metal catalyst ink 1 for printing can be loaded in a printer. In the ink cartridge 4, the ink cartridge 4 has a chamber 41 for accommodating the noble metal catalyst ink 1 for printing, and an array of orifices 42 are arranged at the upper end of the ink cartridge 4, and the ink cartridge 4 is detachably mounted on the ink cartridge 4. In the printing machine, the printing precious metal catalyst ink 1 is ejected from the orifices arranged in the array by the control of the printer.

In the present embodiment, the precious metal catalyst ink 1 for printing of each embodiment was filled in the ink cartridge 4, and after 48 hours, the nozzle hole 42 was observed to be free from clogging, and after 200 hours, the nozzle hole 42 and each were observed. The portion of the precious metal catalyst ink 1 that is in contact with the printing is non-corrosive.

For different applications, the ink cartridge 4 is a cylindrical or bottle-shaped container, which is installed in the printer or outside the printer, and uses the ink tube to extract the ink for printing the precious metal catalyst ink 1 to the inkjet of the printer. In the head, ink droplets are ejected from the nozzle holes of the ink jet head, which are not limited.

<Second Group of Embodiments>

In this embodiment, which is the same as the first group of examples, the noble metal catalyst 2 also uses A (a copolymer of styrene monomer and N-isopropylacrylamide monomer (Poly (Styrene-Co-NIPAAmb)). The precious metal catalyst initial aqueous solution is dialyzed to remove chloride ions to make the chloride ion concentration less than 50 ppm; then slowly add 0.1 N sodium hydroxide solution or 0.1 N ammonia water to adjust the pH to near neutral.

In the same manner as in step S3, the viscosity control agent 111 is dissolved in pure water to prepare a viscosity control solution 11, and the initial aqueous solution of the precious metal catalyst is placed in the reaction tank 31 in the water bath 32 to control the stirring rate to 300 to 600 r. .pm, temperature between 18~42 °C, and the temperature change is within ±5 °C; slowly add the viscosity control solution 11 to the desired viscosity and surface tension, stop adding to form a printing precious metal catalyst ink 1; However, the viscosity control solution 11 added in the examples of the present group has a higher concentration, and the total number of moles added is larger. Finally, the printing precious metal catalyst ink 1 is still filtered, and the solid matter is filtered off. The operating conditions and results of the examples of the examples of the examples are shown in Table 2.

In the embodiment of the present invention, the precious metal catalyst ink 1 for printing according to the present invention is also used on a plastic sheet of PC-ABS material, and is formed by a method of printing and electroless plating to form a WWAN inside a back cover of a plastic material. The antenna line is electrolessly plated with nickel-phosphorus (NiP) to form a metal layer. The mobile phone case of the WWAN antenna application is functionally up to the specification of the adhesion of 4B or more in accordance with the BaGe test, and meets the requirements of the receiving band area corresponding to the return loss (RL) of less than -10 dB, thereby demonstrating the addition. The noble metal catalyst ink 1 for printing of the viscosity control agent 111 still has good catalytic activity.

<Third Group Embodiment>

Please refer to FIG. 3 and FIG. 4, FIG. 3 is a schematic view showing a manufacturing method of a noble metal catalyst ink for printing, and FIG. 4 is a step view showing a manufacturing method of a noble metal catalyst ink for printing according to a second embodiment of the present invention;

The steps S1, S2, and S4 of the method for manufacturing the noble metal catalyst ink for printing of the present embodiment are the same as those of the first group of embodiments, and are not described herein again.

S3': the viscosity control agent 111 is dissolved in pure water, and the viscosity stabilizer 112 is slowly added to prepare the viscosity control solution 11, and the initial aqueous solution of the precious metal catalyst is placed in the reaction tank 31 in the water bath 32 to control the stirring. The rate is 300~600r.pm, the temperature is between 18~42°C, and The temperature change is within ±5 °C; when the viscosity control solution 11 is slowly added to the desired viscosity and surface tension, the addition is stopped to form a printing precious metal catalyst ink 1; as shown in Fig. 3, wherein the temperature is displayed by the thermometer 34. Further, the stirring rate is controlled by the agitator 33, and the viscosity is controlled by the viscosity meter 35.

S4: The printing precious metal catalyst ink 1 is filtered to filter out the solid matter. The operating conditions and results of the examples of the examples in the examples are shown in Table 3.

In the present embodiment, the noble metal catalyst ink 1 for printing using the present invention is also formed on the plastic sheet of PC-ABS material by printing and electroless plating (see the printer of FIG. 1). The mobile phone case for RFID application is functionally up to the specification of the universal ISM band and the reading range of 4.5m, and conforms to the specification of the adhesion of 4B or more of the BaGe test, thereby demonstrating the addition of the viscosity control agent 111 and the viscosity stabilizer. The noble metal catalyst ink 1 for printing on 112 still has good catalytic activity.

Similarly, in the first and second embodiments of the present embodiment, the noble metal catalyst ink 1 for printing is filled in the ink cartridge 4, and the nozzle hole 42 is observed to be non-clogging after 48 hours, except by the printing operation. After 200 hours, the nozzle holes 42 and the portions of the noble metal catalyst ink 1 that were in contact with the printing were observed to be non-corrosive.

In the third and fourth embodiments of the present embodiment, the precious metal catalyst ink 1 for printing is filled in a bottle-shaped ink cartridge 4, and the ink cartridge 4 is installed in the printer or outside the printer, and the catheter is used first. It is connected to the ink pump, and then connected to the ink jet head of the printer, and is ejected from the ink ejection orifice 42 of the ink jet head. In the third embodiment and the fourth embodiment, the precious metal catalyst ink for printing 1 was observed to have no clogging, such as the outlet of the ink cartridge 4, the catheter, the ink pump, the ink jet head, and the injection hole 42 after 48 hours, except for the printing operation. After 200 hours, the portion of the ink cartridge 4 outlet, the catheter, the ink pump, the ink jet head, the orifice 42 and the like which were in contact with the noble metal catalyst ink 1 for printing were observed to be non-corrosive.

<Fourth Group of Embodiments>

The steps of the manufacturing method of the noble metal catalyst ink for printing of the present embodiment are the same as those of the third group of embodiments, and the noble metal catalyst ink for printing prepared by the embodiments of the present embodiments will not be described again. 1 Operating conditions and results are shown in Table 4.

In the embodiment of the present invention, the mobile phone casing made of RFID application by the method of printing and electroless plating has the function of conforming to the specification of the universal ISM frequency band and the reading range of 4.5 m, and conforms to the adhesion of 4B or more of the hundred-dimensional test. The specification of the force can prove that the noble metal catalyst ink 1 for printing with the viscosity control agent 111 and the viscosity stabilizer 112 still has good catalytic activity. And after 48 hours It was observed that the nozzle holes 42 were not clogged, and the nozzle holes 42 and the portions of the noble metal catalyst ink 1 that came into contact with the printing were not corroded after 200 hours.

The invention discloses a method for manufacturing a noble metal catalyst ink for printing and a noble metal catalyst ink for printing, and the noble metal catalyst ink is an inkjet head of a jet printer as an embodiment, but can be easily converted and applied. In various other printing processes, the pH stability of the printing precious metal catalyst ink, the stability of viscosity, or the stability of surface tension are exhibited.

The specific examples and embodiments provided herein are merely exemplary and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Therefore, the scope of protection is not limited by the description of the above, but is only limited by the scope of the following claims.

S1~S4‧‧‧ method steps

Claims (10)

A method for manufacturing a noble metal catalyst ink for printing comprises the following steps: S1: removing a chloride ion from an initial aqueous solution of a precious metal catalyst to at least a chlorine ion concentration of less than 50 ppm; wherein the initial aqueous solution of the noble metal catalyst is a precious metal catalyst An aqueous solution or an organic solvent solution; wherein the noble metal catalyst is a temperature sensitive polymer to which a catalytic metal particle is attached; the catalytic metal particle is gold (Au), silver (Ag), palladium (Pd), platinum ( Pt) or ruthenium (Ru); wherein the temperature sensitive polymer is: A (Poly(Styrene-Co-NIPAAmb)), B (benzene) of styrene monomer and N-isopropyl acrylamide monomer a copolymer of ethylene monomer and hydroxypropylcellulose), C (copolymer of styrene monomer and polyvinylcaprolactame), D (styrene monomer and poly One or a combination of a copolymer of poly(vinyl methyl ether); S2: adjusting the pH of the initial aqueous solution of the noble metal catalyst to remove neutral chloride to neutrality, wherein the adjustment of the pH is performed with hydrogen and oxygen Root metal salt or ammonia water The combined aqueous solution; S3: formulating a viscosity control solution, placing the initial aqueous solution of the precious metal catalyst adjusted to pH in a compounding environment, slowly adding the quantitative viscosity control solution to form a printing precious metal catalyst ink; Wherein, the viscosity of the noble metal catalyst ink for printing is between 2 and 40 cps (mg.s ^-1 .cm ^-1 ), and the surface tension of the noble metal catalyst ink for printing is between 20 and 45 dyne/cm. The pH of the noble metal catalyst ink for printing is between 6.5 and 8.0; wherein the viscosity control solution is formed by dissolving a viscosity control agent in a solvent of water or an alcohol or a combination thereof, and the viscosity is formed. The control agent is hydrophilic; wherein the mixing environment is: the temperature is controlled between 18 and 42 ° C, and the temperature changes within ± 5 ° C; the stirring rate is 300 to 600 r. pm; S4: the printing is used Precious metal catalyst ink is filtered to remove solids. For example, the manufacturing method of the noble metal catalyst ink for printing of the first application patent range, wherein the viscosity of the noble metal catalyst ink for printing further satisfies the ink viscosity measured at 1.1 ° C (20 ° C and shear rate 0.5 sec ^{-1 )} . ) / (20 ℃ and shear rate of 100 sec ^-1 measured ink viscosity) ≦ 2.0. For example, in the manufacturing method of the noble metal catalyst ink for printing of the first application, the viscosity control agent is selected from one or a combination of the following groups: the first group is a high molecular polymer, which is an aqueous polyurethane ( Polyurethane, one or a combination of polyvinylpyrrolidone (PVP); the second group is a hydroxyl-rich organic solvent, 3-methoxy-3-methylbutanol (3-Methoxy-3) -Methyl-1-Butanol, MMB), glycerol, D-Mannitol, 2,2,6,6-tetramethylpyridine (2,2,6,6-Tetramethylpiperidine, TMP ), ethylene glycol monobutyl ether (Butyl Cellosolve ^TM), or one of the combinations. The method for manufacturing a noble metal catalyst ink for printing according to claim 3, wherein the viscosity control solution further comprises a viscosity stabilizer selected from one or a combination of the following groups: polyether modification One or a combination of polyether modified polydiMethy siloxane, polyether modified polydimethoxide, acrylate copolymer. For example, in the fourth section of the patent application, a method for manufacturing a noble metal catalyst ink for printing, wherein When the viscosity control agent is selected from the first group, the viscosity stabilizer is selected from the group consisting of polyether modified polydimethoxide (Polyether Modified polydiMethy siloxane) and polyether modified polyoxyalkylene oxide (Polyether). One or a combination of modified polydiMethy siloxanes; wherein, when the viscosity control agent is selected from the second group, the viscosity stabilizer is selected from one or a combination of acrylate copolymers. For example, in the fourth aspect of the patent application, a method for producing a noble metal catalyst ink for printing, wherein the viscosity of the noble metal catalyst ink for printing is between 2 and 25 cps (mg.s ^-1 .cm ^-1 ), the printing The surface tension of the precious metal catalyst ink is between 25 and 40 dyne/cm. A noble metal catalyst ink for printing is an aqueous solution or an organic solvent solution formed by a precious metal catalyst and a viscosity controlling agent; wherein the noble metal catalyst is a temperature sensitive polymer to which a catalytic metal particle is attached; The catalytic metal particles are gold (Au), silver (Ag), palladium (Pd), platinum (Pt) or ruthenium (Ru); wherein the temperature sensitive polymer is: A (styrene monomer and N-isopropyl group) Copolymer of acrylamide monomer (Poly (Styrene-Co-NIPAAmb)), B (copolymer of styrene monomer and hydroxypropyl cellulose), C (styrene monomer and polyethylene base) One or a combination of a copolymer of poly(vinylcaprolactame), D (a copolymer of a styrene monomer and a polyvinyl methyl ether); wherein the viscosity control agent Is selected from one or a combination of the following groups: the first group is a high molecular polymer, one of water polyurethane (polyvinylpyrrolidone, PVP) or a combination thereof; the second group Is a hydroxyl-rich organic solvent, 3-methoxy-3-methylbutanol (3-Methoxy-3-Methy) l-1-Butanol, MMB), glycerol, D-Mannitol, 2,2,6,6-Tetramethylpiperidine, TMP Or one or a combination of ethylene glycol monobutyl ether (Butyl Cellosolve ^TM ); wherein the viscosity of the noble metal catalyst ink for printing is between 2 and 40 cps (mg.s ^-1 .cm ^-1 ); The surface tension of the noble metal catalyst ink for printing is between 25 and 45 dyne/cm; wherein the pH of the noble metal catalyst ink for printing is between 6.5 and 8.0, wherein the precious metal catalyst ink for printing The chloride ion concentration is less than 50 ppm. The noble metal catalyst ink for printing according to claim 7 , further comprising a viscosity stabilizer selected from one or a combination of the following groups: polyether modified polydimethyl One or a combination of a polyether modified polydiMethy siloxane, a polyether modified polydimethoxide, an acrylate copolymer, or a combination thereof. For example, the noble metal catalyst ink for printing according to the eighth aspect of the patent application, wherein the viscosity of the noble metal catalyst ink for printing is between 2 and 25 cps (mg.s ^-1 .cm ^-1 ), the printing is used for printing The surface tension of the precious metal catalyst ink is between 25 and 40 dyne/cm. The precious metal catalyst ink for printing according to the seventh aspect of the patent application, the precious metal catalyst ink for printing is disposed in an ink cartridge, and the ink cartridge is detachably mounted on a printer; The ink cartridge has one or a plurality of orifices, and the inkjet ink for printing is controlled to eject ink droplets from the orifices.