KR102566130B1 - Method for manufacturing conductive resin nano-material uniformly dispersed - Google Patents

Abstract

Method for manufacturing uniformly dispersed resin of conductive nanomaterial according to the present invention A method for manufacturing a dispersed resin of conductive nanomaterial applied to the manufacture of bakelite manufactured in the form of a plate by impregnating/curing a phenolic resin into a reinforcing material such as paper, as a conductive nanomaterial Preparing a first dispersion by using carbon nanotubes and mixing 1.0 to 2.0 wt% of the carbon nanotubes and a dispersion stabilizer in a dispersing solvent, wherein the carbon nanotube content is 0.2 to 0.5 wt% before impregnation of the reinforcing material. It is composed of a step of diluting to prepare a secondary dispersion so that it is composed of a resin for impregnating reinforcing materials in which nanomaterials are uniformly dispersed as a previous step for manufacturing plate materials and panel products having excellent conductivity and excellent heat resistance and other mechanical durability. can provide

Description

Conductive nanomaterial uniformly dispersed resin manufacturing method {Method for manufacturing conductive resin nano-material uniformly dispersed}

The present invention relates to a method for manufacturing a resin product in which conductive nanomaterials are uniformly dispersed, and more particularly, to a method for manufacturing a conductive nanomaterial uniformly dispersed resin prepared by impregnating and curing a phenolic resin into a reinforcing material.

ESD (Electrostatic Discharge) phenomenon is used in various fields such as copiers and powder coatings, but it is an important cause of serious damage in the production process of semiconductor, display, and electronic parts industries. We are trying to minimize this through investment.

Micro-miniature high-speed integrated circuits used throughout the industry are constantly increasing circuit damage caused by a small amount of ESD during the production process due to the minimization of driving power. Impurity contamination of the panel caused by static electricity during the deposition process is a serious cause of defects.

There are dozens of domestically produced static electricity related products to solve these problems, such as ionizer, tray, antistatic film, and wrist strap, but mainly low-cost products are formed, and the business area is formed around small and medium-sized enterprises.

On the other hand, in the electronic parts production process, Test Fixture (Jig) and Carrier are important sub-materials for the transfer of electronic parts between production processes and the performance test of parts. As the working conditions of the production process become harsh, the need for functional elements such as heat resistance, chemical resistance, and mechanical properties is increasing.

In other words, a lot of research is being done to give ESD performance to plastic materials that can make test fixtures (jigs) and carriers, and carbon, metal, TCOs, and polymers are applied as materials to be used, but when thermoplastics are applied Since most of them are surface treatment methods, it is difficult to effectively respond to additional harsh conditions (heat resistance, mechanical properties) required by customers.

The existing product is a plate type product ^manufactured by compounding POM with CNT, carbon black, etc. and injection or extrusion processing ^. Jig) and carrier materials, but recently, due to the introduction of high-temperature processes for high integration, precision, and productivity improvement of IT products, when using existing POM products, warpage of test fixtures (jigs) and carriers occurs during the process or external deformation due to thermal expansion. This causes problems that cannot function as a Test Fixture (Jig) and Carrier. It is a situation that cannot be solved without change.

KR 10-1838848 B1

The present invention impregnates/cures a phenolic resin into a reinforcing material such as paper in order to replace the POM material and to manufacture a plate product having sufficient ESD performance and high heat resistance and other durability even when applied to a test fixture (jig) and a carrier. It is an object of the present invention to provide a method for preparing a dispersed resin of a conductive nanomaterial applied to the manufacture of bakelite manufactured in the form of a plate.

In order to achieve the above object, the conductive nanomaterial uniformly dispersed resin manufacturing method according to the present invention is a conductive nanomaterial applied to the manufacture of bakelite manufactured in the form of a plate by impregnating / curing a phenolic resin into a reinforcing material such as paper. A dispersion resin manufacturing method, using carbon nanotubes as a conductive nanomaterial, mixing 1.0 to 2.0 wt% of the carbon nanotubes and a dispersion stabilizer in a dispersion solvent to prepare a first dispersion, prior to the impregnation of the reinforcing material; and preparing a secondary dispersion by diluting the carbon nanotube content to 0.2 to 0.5 wt%.

At this time, it is preferable that the length of the carbon nanotube is 0.5 to 3.0 μm.

At this time, the dispersion solvent is preferably methanol.

At this time, the dispersion stabilizer is preferably one or more components selected from sodium dodecylsulfonate (SDS) and polyvinyl pyrrolidone (PVP),

Moreover, it is more preferably polyvinylpyrrolidone.

Moreover, the dispersion stabilizer polyvinylpyrrolidone is preferably PVP K-30 having a molecular weight of 40,000.

Meanwhile, the dispersion for the first dispersion preparation step or the second dispersion preparation step is preferably performed by a rotary mill.

Moreover, the operating conditions of the rotor mill are characterized in that the following, conductive nano-material uniformly dispersed resin manufacturing method.

- Vessel 100~200 rpm

- Rotor 1,200~1,600 rpm

- Bead size 0.8~1.5 mm

- Vessel temperature less than 45℃

- Operating time 2-4 hours

Meanwhile, the viscosity of the primary dispersion is preferably 450 or less.

Meanwhile, the viscosity of the secondary dispersion is preferably 50 to 150.

By the conductive nanomaterial uniformly dispersed resin manufacturing method having the configuration described above, as a previous step for manufacturing plate materials and panel products having excellent conductivity and excellent heat resistance and other mechanical durability, a resin for impregnating reinforcing materials in which nanomaterials are uniformly dispersed is prepared. can provide

1 is a graph showing the change in viscosity of a phenolic resin according to nanomaterial dispersion.
Figure 2 is a graph showing the viscosity change of the dispersion according to the solvent dispersion of the nanomaterial.

Hereinafter, the configuration of the conductive nano-material uniformly dispersed resin manufacturing method according to the present invention described above will be described in more detail with reference to the drawings and embodiments showing an embodiment of the present invention.

Bakelite is a thermosetting composite material manufactured in the form of a plate by impregnating/curing a reinforcing material composed of impregnated paper such as paper. In particular, it is widely used as a product for intermediate processing such as jigs and mockups due to its excellent processability.

Therefore, making sheet products using Bakelite is a product that can be used for test fixtures (jigs) and carriers, which are important subsidiary materials in the transfer of electronic parts and part performance tests in the electronic parts production process, as well as ESD performance. It enables the manufacture of products with heat resistance, chemical resistance, and mechanical properties that can withstand conditions without deformation, which starts with resin synthesis, a process of impregnating the synthesized resin into a reinforcing material, ) Manufacturing process, heat press process for laminating/curing prepreg, and post-processing to be manufactured in the form of a plate. In particular, the impregnation process to adjust the resin content by completely immersing the reinforcing material in resin so that the resin permeates the entire reinforcing material to remove air bubbles. This is the core process.

At this time, it is a key factor for the ESD performance to ensure that the conductive nanomaterial is uniformly dispersed in the resin immediately before the impregnation process, and thus the basic physical properties of the product may be influenced.

In the present invention, in the case of an aqueous dispersion of conductive nanomaterials, damage to the reinforcing material may occur during impregnation, and in the case of nanomaterial dispersion solutions, the solvent dispersion form is more difficult in terms of stability than the aqueous dispersion form, so the solvent ( methanol, propanol, acetone, etc.), and it is characterized in that the dispersion solution is prepared in the form of dispersion, and the dispersion degree and concentration control of the dispersion solution so that the particles such as nanomaterials can be uniformly distributed between the reinforcing material structures, as well as impregnation using the same It is characterized by developing technology and implementing it to enable constant antistatic performance.

As the conductive nanomaterial, it is necessary to select an optimal conductive nanomaterial capable of uniform distribution of the nanomaterial within the structure of the reinforcing material (Paper) as well as conductivity, and carbon nanotubes (CNT) suitable for such criteria were selected.

In addition, for dispersion stability in a dispersed state, the dispersion stabilizer should be selected in consideration of the physical properties of the dispersion solvent, and sodium dodecylsulfonate (SDS) and polyvinyl pyrrolidone (PVP) are used. can be chosen

The molecular weight of thermosetting phenolic resin was designed and applied in consideration of the mechanical correlation with the nanomaterial dispersion using the dispersing solvent as the resin for manufacturing the Bakelite panel of the electric discharge line.

Hereinafter, the optimal configuration of the present invention will be described in more detail through experimental examples.

[Experimental Example 1] Selection of nanomaterials

For the conductive nanomaterial (CNT, Carbon nanotube), based on the physical properties and characteristics of each manufacturer, the optimal conductive nanomaterial was selected by figuring out whether the nanomaterial could be uniformly distributed within the structure of the reinforcing material (Paper).

When dispersing nanomaterials (CNT) in phenolic resin for antistatic bakelite, the viscosity of the dispersion resin is a very important quality factor in the production of prepreg. This is because it is difficult to penetrate the material, and if it is too low, the desired resin content (R/C) cannot be buried in the reinforcing material.

<Characteristics of conductive nanomaterials by manufacturer>

[Experimental Example 2] Direct dispersion experiment of nanomaterials in resin

The viscosity level of the dispersion resin was confirmed according to the input amount of nanomaterials by manufacturer, and in the lab scale experiment, it was confirmed that the minimum viscosity should be less than 100cps and the solid content should be more than 55% in order to impregnate the reinforcing material (basis weight 100 ~ 150g / m ² ). As in 1, it was confirmed that the optimal conditions for resin impregnation could not be satisfied when the nanomaterial (CNT 0.2~0.5wt.% relative to the amount of phenolic resin) was directly dispersed in the phenolic resin using the Rotate Mill owned by Yuwon Co., Ltd. Therefore, it is difficult to disperse and uniformly impregnate due to the increase in the viscosity of the phenolic resin due to the dispersion of the nanomaterial, and when the phenolic resin is impregnated into the reinforcing material, local deviation of the nanomaterial occurs due to the filtration effect of the reinforcing material, thereby obtaining a uniform intermediate material. came to a difficult conclusion.

[Experimental Example 3] Nanomaterial dispersion experiment using a solvent

In order to solve the problem of local deviation of nanomaterials due to the filtration effect of the viscosity, solid content and reinforcing material (Paper) of the dispersion resin that occurs when the conductive nanomaterial (CNT) is directly dispersed in the resin, the intermediate material (Prepreg ) was to be prepared.

Therefore, as the first process, the nanomaterial (CNT) was first dispersed in a solvent (methanol) that is easy to impregnate, and the reinforcement was first impregnated to try to solve the problem of viscosity. Then, a certain amount of nanomaterial (compared to methanol) was added to the solvent (methanol). CNT 0.2 ~ 2.0wt.%) was added and then dispersed using a rotate mill in possession. At this time, the operating conditions of the rotate mill are as follows.

- Vessel 100~200 rpm

- Rotor 1,200~1,600 rpm

- Bead size 0.8~1.5 mm

- Vessel temperature less than 45℃

- Operating time 2~4 hours

Nanomaterial (CNT) manufacturers Company N Company C Company O Length of nanomaterial (CNT) (um) 1.5 5 50 Dispersion Final Viscosity (cps, 25°C, Brookfield)* 430 1,220 2,950 dispersion stability Good Very Good Very Good

<Evaluation of dispersion of conductive nanomaterials by manufacturer>

As shown in Table 2, the shorter the length of the nanomaterial, the lower the viscosity of the dispersion, which is advantageous for impregnation. It was judged that it was dangerous for work (explosion, fire) and ineffective compared to N company's products due to the increase in .

The dispersion of nanomaterials (Company N, CNT) was considered whether the viscosity and storage stability suitable for uniformly impregnating the reinforcing material were secured. The following dispersion was advantageous.

Therefore, considering production conditions, it was determined that it was most appropriate to first prepare a dispersion with 1.0 wt.% and then dilute it again with 0.2 to 0.5 wt.% before impregnation.

On the other hand, the nanomaterial dispersion of 2.0 wt.% or more was determined to be dangerous (explosion, fire) in field conditions because the vessel temperature of the rotor mill rose to 45 ° C. or more during the manufacturing process and the viscosity became too high.

In addition, the results of evaluating the dispersion for each nanomaterial ratio in terms of final viscosity and stability are shown in Table 3 below.

Nanomaterial (CNTwt.% in MeOH) content 0.2 0.5 1.0 2.0 Dispersion Final Viscosity (cps, 25°C, Brookfield) 50 150 430 1,900 dispersion stability Bad Poor Good Very Good

<Evaluation of dispersion of conductive nanomaterials by nanomaterial ratio>

[Experimental Example 4] Dispersion stabilizer selection experiment

As a dispersion stabilizer for dispersing and stabilizing nanomaterials (CNT) in a solvent (methanol), sodium dodecylsulfonate (SDS, Sodium dodecylsulfonate) and polyvinylpyrrolidone (PVP, Polyvinyl pyrrolidone) are used at a certain ratio (0 ~ 250wt.%) were added separately to examine the dispersion stability of the dispersion.

In the case of applying SDS, SDS was not sufficiently dissolved in methanol, so the nanomaterial was successfully dispersed by mixing some water. (Curl) occurred and it was confirmed that it was a problem in the secondary impregnation work.

Since PVP is very soluble in methanol and does not cause curling of the reinforcing material due to water, the dispersion stability of the dispersion was verified by preparing the dispersion at various ratios compared to the nanomaterial when preparing the dispersion.

The optimal product and ratio were selected by measuring the methanol solubility, dispersion rate, and dispersion stability for each molecular weight of PVP (Duksan Chemical, k30 ~ k90).

[Experimental Example 5] Dispersion stability test according to nanomaterial dispersion technology development and optimization

- Development of solvent dispersion technology for conductive nanomaterials (CNT)

The dispersion stability evaluation of the nanomaterial dispersion using PVP was carried out as shown in Table 4. In the case of PVP (k-90) with a molecular weight of 90,000, the viscosity and temperature rise during rotation mill dispersion were higher than that of PVP (k-30) with a molecular weight of 40,000. It was excluded from the experiment by application rate.

A B C D Nano materials (CNT, N company, NC-7000) One One One Dispersion stabilizer (PVP k-30) Methanol 100 100 100 100 Dispersion Stability of Dispersion Solution Good Very Good Very Good Very Good Dilution ratio (Methanol/dispersion stock solution) 5/1 5/1 5/1 5/1 Dispersion stability of 5/1 diluted dispersion diluent - Poor Poor Good

As above, specific parts of the present invention have been described in detail through preferred embodiments, etc., to those skilled in the art, these specific descriptions are only preferred embodiments, thereby limiting the scope of the present invention. It will be clear that it is not. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

In the method for producing a dispersed resin of a conductive nanomaterial applied to the production of bakelite prepared in the form of a plate by impregnating / curing a phenolic resin into a reinforcing material such as paper,
Carbon nanotubes are used as conductive nanomaterials,
Preparing a primary dispersion having a viscosity of 450 or less by mixing 1.0 to 2.0 wt% of the carbon nanotubes and a polyvinylpyrrolidone dispersion stabilizer having a molecular weight of 40,000 in any one of dispersing solvents composed of methanol, propanol, and acetone;
Preparing a secondary dispersion having a viscosity of 50 to 150 by diluting the carbon nanotube content to 0.2 to 0.5 wt% before impregnation of the reinforcing material;
According to claim 1,
Characterized in that the length of the carbon nanotubes is 0.5 to 3.0 μm, conductive nanomaterial uniformly dispersed resin manufacturing method.
delete delete delete delete The method of claim 1, wherein the dispersion for the first dispersion preparation step or the second dispersion preparation step is performed by a rotor mill.
The method of claim 7, wherein the operating conditions of the rotary mill are as follows.
- Vessel 100~200 rpm
- Rotor 1,200~1,600 rpm
- Bead size 0.8~1.5 mm
- Vessel temperature less than 45℃
- Operating time 2-4 hours
delete delete