KR101091231B1 - THERMOSETTING RESIN COMPOSITION CONTAINING CONDUCTIVE Ni PARTICLES AND METHOD THE SAME - Google Patents

Abstract

The present invention is an aqueous polyurethane resin solution; Nickel powder with a surface of 10 to 100 nm with an oleic solution of oleic amine and oleic acid; Polymer dispersants of polyesters or polyamines; It relates to a thermosetting resin composition for steel plate surface treatment comprising a modified crosslinking agent of ethylene glycol or propene diol and a method for producing the composition.

Dispersion stability, nickel powder, surface modification, polyurethane

Description

Heat curable conductive nickel powder-containing ink and its manufacturing method {THERMOSETTING RESIN COMPOSITION CONTAINING CONDUCTIVE Ni PARTICLES AND METHOD THE SAME}

The present invention relates to a nickel nanoparticle dispersion technique, a dispersant selection technique, a surface treatment technique of nickel nanoparticles, and the like, which are excellent in dispersibility for preparing an ink or paste of thermally curable conductive nano nickel particles, which can be utilized in a resin coated steel sheet.

Recently, a method of molding an electric or electronic circuit having a fine size and a fine line width by a printing technique has been actively researched and developed. This is called printable electronics, and is simple, easy to replace, and easy to mass-produce between mass rolls, complex, difficult and expensive processes such as thin film deposition, patterning and lithography. Progressive roll-to-roll (roll to roll) method or inkjet method for discharging the ink solution through the small hole is a major technology development target.

Ink solution containing nano-inorganic particles is the most important parameter for forming a coating film using a roll or inkjet ejection. Therefore, printing or coating ink is required for forming an electronic circuit or a coating film for which a synthetic effect is expected. It is the most important factor in technology.

Inks used for printing or coating on resin coated steel sheets are divided into main materials and media, and main materials are pigments and media, and media are additives added to improve printing (or coating) aptitude, dryness, and color adjustment. .

The host material determines the performance of the ink, and according to the host material, the ink is divided into ink jet ink, offset ink, gravure ink, letterpress ink, silkscreen ink, and the like. Pigments are materials that can be used irrespective of the type of ink, but special pigments can be selected and used when various conditions such as solvent resistance, light resistance, lead resistance, weather resistance, fingerprint resistance, and conductivity are required.

The present invention relates to an optimized coating ink solution that can be used in a resin coated steel sheet using conductive nickel nanoparticles required to prepare a nano nickel ink or paste, and to a method for preparing the same. Its purpose is to provide technology to secure dispersion stability.

The present invention

As a first embodiment, an aqueous polyurethane resin solution; 10 to 100 nm nickel powder surface-modified with an oleic solution of oleic amine and oleic acid; Polymer dispersants of polyesters or polyamines; Thermosetting resin composition for steel plate surface treatment containing a crosslinking agent of ethylene glycol or propene diol,

As a second embodiment, the nickel powder is a thermosetting resin composition for steel sheet surface treatment, characterized in that contained in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the aqueous polyurethane resin solution,

As a third embodiment, the nickel powder and oleic solution is a thermosetting resin composition for steel sheet surface treatment, characterized in that the mixture in a weight ratio of 1: 1 to 10: 1,

As a fourth embodiment, the oleic solution is a thermosetting resin composition for steel sheet surface treatment, characterized in that the oleic amine and oleic acid in a volume ratio of 1: 2 to 2: 1,

As a fifth embodiment, the water-based polyurethane resin solution is a thermosetting resin composition for steel sheet surface treatment, characterized in that the volume ratio of water: polyurethane resin is 1: 4 to 1: 1,

As a sixth embodiment, the crosslinking agent is a thermosetting resin composition for steel sheet surface treatment, characterized in that added in the range of 10 to 30 with respect to the aqueous polyurethane resin solution 100 by volume ratio,

In a seventh embodiment, the polymer dispersant is a dispersant solution obtained by dissolving polyester or polyamine resin particles in methyl ethyl ketone or acetone, characterized in that 0.2 to 1.0 parts by weight based on 100 parts by weight of the surface-modified nickel powder Thermosetting resin composition for steel plate surface treatment,

As an eighth embodiment, the step of surface modification by mixing a nickel powder of 10 to 100nm in a mixed oleic solution of oleic amine and oleic acid; Mixing the surface modified nickel powder with an aqueous polyurethane resin solution; Adding a polymer dispersant of polyester or polyamine to the aqueous polyurethane resin solution; And adding a crosslinking agent of ethylene glycol or propendiol to the aqueous polyurethane resin solution.

As a ninth embodiment, surface modification by mixing a nickel powder of 10 to 100nm to the oleic solution of oleic amine and oleic acid; Adding a crosslinking agent of ethylene glycol or propenediol to the aqueous polyurethane resin solution; Mixing the surface-modified nickel powder with the aqueous polyurethane resin solution; And mixing a polymer dispersing agent of polyester or polyamine with the aqueous polyurethane resin solution.

As a tenth embodiment, the nickel powder is 0.5 ~ 30.0 parts by weight based on 100 parts by weight of the aqueous polyurethane resin solution, the method of producing a thermosetting resin composition for steel sheet surface treatment,

As an eleventh embodiment, the nickel powder and oleic solution is a method for producing a thermosetting resin composition for steel sheet surface treatment, characterized in that the mixture in a weight ratio of 1: 1 to 10: 1,

As a twelfth embodiment, the oleic solution is a method for producing a thermosetting resin composition for steel sheet surface treatment, characterized in that the oleic amine and oleic acid in a volume ratio of 1: 2 to 2: 1,

As a thirteenth embodiment, the water-based polyurethane resin solution is a method of producing a thermosetting resin composition for steel sheet surface treatment, characterized in that the water: polyurethane resin is 1: 4 to 1: 1 in volume ratio,

As a fourteenth embodiment, the cross-linking agent is prepared in the range of 10 to 30 with respect to the aqueous polyurethane resin solution 100 by volume ratio, the method for producing a thermosetting resin composition for steel sheet surface treatment,

In a fifteenth embodiment, the polymer dispersant is a dispersant solution obtained by dissolving polyester or polyamine resin particles in methyl ethyl ketone or acetone, and is 0.2-1.0 parts by weight based on 100 parts by weight of the surface-modified nickel powder. Provided is a method for producing a thermosetting resin composition for steel plate surface treatment.

According to the present invention, it is possible to obtain a thermosetting resin composition for surface treatment of a steel sheet containing a conductive nickel powder having a conductive nickel powder having excellent long-term dispersion stability in a solution.

The present invention provides a thermosetting resin containing a nickel metal or nickel metal alloy powder having a nanoscale particle size, and provides an aqueous polyurethane resin solution ink or paste composition, and furthermore, provides a method of preparing such a composition. Usually, the ink or paste is distinguished according to the viscosity, and in the present invention, the ink includes the paste.

The thermosetting resin composition for steel sheet surface treatment of the present invention includes an aqueous polyurethane resin solution, nano-sized surface-treated nickel powder, a polymer dispersant, and a crosslinking agent.

In the thermosetting resin composition for steel sheet surface treatment of the present invention, an aqueous polyurethane resin solution in which polyurethane resin particles are dispersed in an aqueous solution is used as the thermosetting resin solution. At this time, the aqueous polyurethane resin solution is not particularly limited, but a solution having a ratio of water: polyurethane of 20:80 to 50:50 in volume ratio may be used.

The nickel powder of the present invention includes a nickel metal or nickel metal alloy powder, and the nickel powder uses nano-sized nickel particles. Nickel particles are preferably used as small as possible in order to maintain long-term dispersion stability in the ink or paste. However, when the particle size is too small, it is preferable to use a nickel powder having a particle size of 10 nm or more due to the difficulty of dispersing easily due to the aggregation phenomenon between particles easily generated. On the other hand, it is preferable to use nickel powder within the range which does not exceed 100 nm. Of course, if the surface of the nickel powder is sufficiently modified even if it exceeds 100nm can obtain a good dispersion stability, but there is a problem that the storage life (self storage life) is shortened in the field, having a particle size of less than 100nm Preference is given to using nickel powders.

Such nano nickel particles are preferably contained in the range of 0.5-30 parts by weight based on 100 parts by weight of the polyurethane resin solution. If it is smaller than the above range, the effect of the addition of conductive nickel powder is not obtained, and if it is included in excess of the above range, the viscosity of the coating solution rapidly increases as the weight ratio is increased, which impairs workability. .

Nickel particles used in the present invention is preferably used to modify the surface to improve the bond with the polyurethane resin as the main resin and to increase the dispersibility in the solution. For surface modification of the nickel particles, the nickel particles are subjected to a surface treatment using cationic oleic grease and anionic oleic grease. The greases that may be used at this time include oleic acid and oleic amine, respectively. In this invention, the said oleic amine and oleic acid are mixed and used. In this case, the mixing ratio may be used by mixing in the range of 2: 1 to 1: 2 by volume ratio, and more preferably, the nickel particle surface is known to have half and half of the cationic portion and the lipophilic portion. When the mixing ratio is 1: 1, the most ideal surface modification can be performed. Nano-size nickel particles are added to the mixed oleic solution so that the oleic solution is adsorbed on the surface of the nickel powder to modify the surface of the nickel particles. The oleic solution may be used in excess in order to increase the probability of modification of the surface of the nickel powder, specifically, the nickel powder: oleic solution in a weight ratio of 1: 1 to 10: 1, more preferably 3: 1 to 7 : 1, most preferably 5: 1.

At this time, if the oleic solution is diluted, the surface modification can be more easily performed. The oleic solution can be used by dissolving the oleic solution using ethanol. At this time, the added ethanol content is not particularly limited and may be added in an amount such that the viscosity of the oleic solution has a viscosity similar to that of the aqueous polyurethane solution as the main resin.

After surface modification of the nickel particles, it is preferable to remove the remaining oleic solution and ethanol used for the surface modification in order to improve the subsequent dispersing effect. Removal of the remaining oleic solution and ethanol may be carried out by any method, for example, it is possible to remove the excess oleic mixed solution including ethanol by using centrifugal force.

In this way, the nickel powder whose surface is modified is mixed with the polyurethane resin solution. In this case, a dispersant may be included to allow the nickel powder to be homogeneously dispersed in the resin solution. At this time, the dispersant used is preferably added in the range of 0.2 to 1.0 parts by weight based on 100 parts by weight of nickel powder.

Although it does not specifically limit as such a dispersing agent, The polyester type polymer resin solution or the polyamine type polymer resin solution is mentioned. These polymer resin solutions are obtained by dissolving the resin granules in methyl ethyl ketone or acetone. The polymer resin solution is mixed with the polyurethane solution by arbitrarily adjusting the nickel powder to have a viscosity such that the nickel powder is released, for example, in the range of 10 to 500 cPs.

And the viscosity of a polyurethane resin is adjusted, adding a crosslinking agent to the polyurethane resin solution obtained in this way, and contacting a polyurethane molecular structure. The crosslinking agent is not particularly limited as long as it is generally used as a crosslinking agent for a polyurethane resin, and specific examples thereof include ethylene glycol or propenediol.

The crosslinking agent is added in a range of 10 to 30 with respect to the polyurethane resin solution 100 in volume ratio. If the crosslinking agent is used at less than 10% by volume, it does not exhibit sufficient crosslinking function, and if it exceeds 30% by volume, the viscosity of the solution becomes excessively high and adversely affects the gotting process.

In the present invention, the crosslinking agent may be added after mixing the surface-modified nickel powder in the aqueous polyurethane resin solution and adding a dispersant as described above, and of course, adding the crosslinking agent to the aqueous polyurethane resin solution in advance. After adjusting the viscosity of the aqueous polyurethane resin solution, the surface-modified nickel powder may be mixed, followed by addition of a dispersant.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are examples of the present invention, and the present invention is not limited thereto.

[Example]

[Production Example 1]

Preparation of Nano-size Nickel Powders

A commercial nickel powder having a purity of 99.9% having a particle size of 40 to 50 micrometers was used as a starting material, and nano nickel powder was prepared by using an RF plasma combustion apparatus. At this time, the RF plasma combustion apparatus was adjusted to generate RF power of 30-50 kW, and the supply rate of the starting nickel powder was adjusted to 4-8 gr / min. In addition, the supply gas was a mixture of argon and hydrogen, while the flow rate of argon gas was 120 slpm (standard liter per minute), the flow rate of hydrogen was fixed to 30 slpm.

On the other hand, argon was used as the cooling gas to be sent to the synthesis chamber of the nano-nickel particles, and the particle size of the nanoparticles obtained by changing the flow rate of the argon cooling gas to 150 to 350slpm was controlled.

The nano nickel powder synthesized under these conditions showed a recovery amount of approximately 250 gr / hr, and the purity of the obtained nano nickel powder was also the same as that of the starting nickel powder. The particle diameter of the obtained powder was measured, and the average particle size was 50 nm, and it was confirmed that it had a spherical shape. An SEM photograph of the obtained nickel powder was taken and shown in FIG. 1.

Comparative Example 1

1 part by weight of the nickel powder obtained in Preparation Example 1 was added to 100 parts by weight of a polyurethane resin solution having a ratio of water: polyurethane = 20: 80 by volume and dispersed for 10 minutes using ultrasonic waves. The dispersion state of the powder was observed. As shown in FIG. 2 (a), the observation result confirmed that all nickel particles precipitated after 2 hours.

Example 1

3.0 parts by weight of the nano nickel particles prepared in Preparation Example 1 and an oleic solution (volume ratio of oleic amine: oleic acid = 1: based on 100 parts by weight of a polyurethane resin solution having a ratio of water: polyurethane = 20: 80 by volume ratio. Mixture 1) 0.6 parts by weight was mixed. 0.6 parts by weight of ethanol was added thereto, followed by sonication for 10 minutes to allow the oleic solution to adsorb to the nickel particles, thereby obtaining a nickel powder whose surface was modified with the oleic solution. After the adsorption was completed, the remaining oleic solution and ethanol were removed to recover the surface-modified nickel powder.

3 parts by weight of the surface-modified nickel powder was added to 100 parts by weight of the main polyurethane resin solution mixed in a ratio of water: polyurethane = 20: 80 by volume ratio, and sonicated for 5 minutes to disperse the nickel powder, thereby containing nickel powder. Got.

The dispersion behavior of the nickel powder in the nickel powder containing ink was measured. Dispersion behavior was measured for 7 days using a Turbiscan meter. Measurements were taken every 10 seconds during the first minute of measurement, followed by measurements every minute for one hour thereafter, and at intervals of one hour after one day. As a result, the results of dispersion behavior of the nickel ink are shown in Table 1, and the photograph of the color after 7 days of the nickel powder-containing ink obtained in this example is attached to FIG. 2 (b), and photographs are attached. The curve of dynamic dispersion stability change of the nickel powder-containing ink according to (a) is shown.

Referring to Table 1, it can be seen that it shows an excellent dispersion behavior that is completely different from Comparative Example 1 when the surface treatment agent and the dispersant are not used.

[Example 2]

3.0 parts by weight of the nano nickel particles prepared in Preparation Example 1 and an oleic solution (volume ratio of oleic amine: oleic acid = 1: based on 100 parts by weight of a polyurethane resin solution having a ratio of water: polyurethane = 20: 80 by volume ratio. Mixture 1) 0.6 parts by weight was mixed. 0.6 parts by weight of ethanol was added thereto, followed by sonication for 10 minutes to allow the oleic solution to adsorb to the nickel particles, thereby obtaining a nickel powder whose surface was modified with the oleic solution. After the adsorption was completed, the remaining oleic solution and ethanol were removed to recover the surface-modified nickel powder.

On the other hand, a propenediol crosslinking agent was mixed in a polyurethane resin solution having a ratio of water: polyurethane = 20: 80 in volume ratio such that the polyurethane resin solution: propenediol = 100: 20 in volume ratio. Next, 2 parts by weight of the surface-modified nickel powder was added to 100 parts by weight of the polyurethane resin solution to the polyurethane resin solution containing the crosslinking agent. Thereafter, resin granules of the polyester dispersant were separately dissolved by mixing with methyl ethyl ketone in a weight ratio of 2: 1 to prepare a dispersant solution, and then the nickel powder was added to the mixed polyurethane resin solution. The dispersant solution is added to have a weight ratio of nickel powder: dispersant solution = 100: 0.3. Subsequently, an ultrasonic wave was added and the polyurethane resin solution composition containing the final nickel powder was stirred to obtain a nickel powder-containing ink.

In order to confirm the dispersion behavior of the obtained nickel powder-containing ink was measured for a total of 7 days using a Turby scan meter as in Example 1. The measuring method was performed similarly to Example 1.

As a result, the dispersion behavior of the nickel powder-containing ink is shown in Table 1, and the color after 7 days of the nickel powder-containing ink obtained in this example is shown in FIG. 2 (c), and FIG. The dynamic dispersion stability change curve of the nickel powder-containing ink according to (b) is shown.

Example 3

3.0 parts by weight of the nano-nickel particles prepared in Preparation Example 1 based on 100 parts by weight of a polyurethane resin solution having a ratio of water: polyurethane = 20: 80 by volume ratio of the oleic solution (oleic amine: oleic acid = 1: 1 by volume ratio). Mixture) 0.6 parts by weight of the mixture. 0.6 parts by weight of ethanol was added thereto, followed by sonication for 10 minutes to allow the oleic solution to adsorb to the nickel particles, thereby obtaining a nickel powder whose surface was modified with the oleic solution. After the adsorption was completed, the remaining oleic solution and ethanol were removed to recover the surface-modified nickel powder.

Thereafter, the obtained surface-modified nickel powder was added in an amount of 1 part by weight based on 100 parts by weight of a polyurethane resin solution having a ratio of water: polyurethane = 20: 80 by volume, and dispersed for 10 minutes using ultrasonic waves. Separately, the resin grains of the polyester dispersant were dissolved by mixing with methyl ethyl ketone in a weight ratio of 2: 1 to prepare a dispersant solution, and then the surface-treated nickel particles: dispersant solution was added to the polyurethane resin solution in a weight ratio of 100: 0.3. . As a crosslinking agent, propenediol was added in a volume ratio of polyurethane resin solution: propenediol = 100: 20. Thereafter, the polyurethane resin solution composition containing the final nickel powder was stirred by an ultrasonic process to obtain a nickel powder-containing ink.

In order to confirm the dispersion behavior of the obtained nickel powder-containing ink was measured for a total of 7 days using a Turby scan meter as in Example 1. The measuring method was performed similarly to Example 1.

As a result, Table 1 shows the results of dispersion behavior of the nickel powder-containing ink, and Fig. 2 (d) shows photographs photographing colors after 7 days of the nickel powder-containing ink obtained in this example. The curve of dynamic dispersion stability change of the nickel powder-containing ink with time is shown in (c).

Referring to Table 1, the nickel powder-containing ink obtained according to the present example showed a dispersion change rate of about 1% even after 7 days, which was remarkably superior to the ink according to Comparative Example 1, which did not use the surface treating agent and the dispersing agent of the present invention. It can be seen that the dispersion behavior is shown.

Example No Real-time measurement dynamic dispersion stability change rate (%) Remarks 1 day 2 days 3 days 4 days 5 days 6 days 7 days Example 1 6.2 7.1 7.5 7.75 7.6 7.6 7.8 After day 7
No change Example 2 5.5 5.9 6.2 7.0 7.6 7.6 7.6 After day 7
No change Example 3 0.2 0.2 0.2 0.2 0.3 0.3 0.3 For 7 days
Perfect dispersion behavior

Referring to Table 1, the nickel powder-containing ink obtained according to Examples 1 and 3 exhibited a dispersion change rate of about 7-8% after 7 days, compared to the case where the surface treatment agent and the dispersant of Comparative Example 1 were not used. It shows excellent dispersion stability in solution. Furthermore, when the nickel powder surface-treated in the aqueous polyurethane resin solution, which is the main resin, was carried out in the order of addition-dispersant-crosslinking agent addition as in Example 3, it was confirmed that it showed a remarkably excellent dispersion behavior with a change rate of about 1%. Can be.

1 is an electron micrograph of conductive nano nickel particles.

Figure 2 is a photograph showing the color change of the conductive nano nickel-containing ink prepared according to Comparative Example 1 of the present invention after 3 hours left.

3 is a photograph showing the color change after 7 days of the conductive nano nickel-containing ink prepared according to Example 1 of the present invention.

Figure 4 is a photograph showing the color change after 7 days of the conductive nano nickel-containing ink prepared according to Example 2 of the present invention.

5 is a photograph showing the color change after 7 days of the conductive nano nickel-containing ink prepared according to Example 3 of the present invention.

6 is a graph showing a dynamic dispersion stability change curve measured in real time for the conductive nano nickel-containing ink prepared according to Examples 1 to 3 of the present invention.

Claims (15)

Water based polyurethane resin solution; 10 to 100 nm nickel powder surface-modified with an oleic solution of oleic amine and oleic acid; Polymer dispersants of polyesters or polyamines; Crosslinking agents of ethylene glycol or propene diol and Thermosetting resin composition for steel sheet surface treatment comprising a. The method of claim 1, wherein the nickel powder is a thermosetting resin composition for steel sheet surface treatment, characterized in that contained in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the aqueous polyurethane resin solution. The method of claim 1, wherein the nickel powder and oleic solution is a thermosetting resin composition for steel sheet surface treatment, characterized in that the mixture in a weight ratio of 1: 1 to 10: 1. 4. The thermosetting resin composition for steel sheet surface treatment according to claim 3, wherein the oleic solution comprises oleic amine and oleic acid in a volume ratio of 1: 2 to 2: 1. 2. The thermosetting resin composition according to claim 1, wherein the aqueous polyurethane resin solution is a solution containing water: polyurethane resin in a volume ratio of 1: 4 to 1: 1. 2. The thermosetting resin composition for steel sheet surface treatment according to claim 1, wherein the crosslinking agent is added in a range of 10 to 30 with respect to the aqueous polyurethane resin solution 100 in volume ratio. The method of claim 1, wherein the polymer dispersant is a dispersant solution obtained by dissolving polyester or polyamine resin particles in methyl ethyl ketone or acetone, characterized in that 0.2 to 1.0 parts by weight based on 100 parts by weight of the surface-modified nickel powder. Thermosetting resin composition for steel plate surface treatment. Surface modification by mixing 10-100 nm nickel powder in a mixed oleic solution of oleic amine and oleic acid; Mixing the surface modified nickel powder with an aqueous polyurethane resin solution; Adding a polymer dispersant of polyester or polyamine to the aqueous polyurethane resin solution; And Adding a crosslinking agent of ethylene glycol or propenediol to the aqueous polyurethane resin solution Method for producing a thermosetting resin composition for steel plate surface treatment comprising a. Surface modification by mixing 10-100 nm nickel powder in an oleic solution of oleic amine and oleic acid; Adding a crosslinking agent of ethylene glycol or propenediol to the aqueous polyurethane resin solution; Mixing the surface-modified nickel powder with the aqueous polyurethane resin solution; And Mixing a polymer dispersant of polyester or polyamine to the aqueous polyurethane resin solution Method for producing a thermosetting resin composition for steel plate surface treatment comprising a. The method for producing a thermosetting resin composition for steel sheet surface treatment according to claim 8 or 9, wherein the nickel powder is 0.5 to 30.0 parts by weight based on 100 parts by weight of the aqueous polyurethane resin solution. 10. The method according to claim 8 or 9, wherein the nickel powder and the oleic solution are mixed at a weight ratio of 1: 1 to 10: 1. The method of claim 8 or 9, wherein the oleic solution is a mixture of oleic amine and oleic acid in a volume ratio of 1: 2 to 2: 1. 10. The thermosetting resin composition according to claim 8 or 9, wherein the aqueous polyurethane resin solution is a solution containing water: polyurethane resin in a volume ratio of 1: 4 to 1: 1. Manufacturing method. 10. The method of claim 8 or 9, wherein the crosslinking agent is added in a range of 10 to 30 with respect to the aqueous polyurethane resin solution 100 in volume ratio. The dispersant solution according to claim 8 or 9, wherein the polymer dispersant is a dispersant solution obtained by dissolving polyester or polyamine resin particles in methyl ethyl ketone or acetone, and is 0.2-1.0 parts by weight based on 100 parts by weight of the surface-modified nickel powder. The manufacturing method of the thermosetting resin composition for steel plate surface treatment characterized by the above-mentioned.

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