KR101051650B1 - Ion complex type conductive material and manufacturing method thereof - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive material added to a curable coating agent, and more particularly, to an ion complex conductive material prepared by the reaction of an organic compound containing a primary or secondary amide with a metal salt, such as an LCD, LED, plastic compound, or the like. The present invention relates to a conductive material applied to a component material to which the charging performance of.

Metal Ion Complex, Metal Salt, Amide, Antistatic, Conductive Material

Description

ION COMPLEX CONDUCTIVE MATERIAL AND METHODS OF MANUFACTURING THEREOF

The present invention relates to an ion complex conductive material which can be added to a curable coating material and is produced by the reaction of an organic compound containing a primary or secondary amide and a metal salt such that migration does not occur and surface resistance is antistatic. .

In general, conductive materials are mainly made of ionic liquids and polymers, which are prepared by metathesis of anionic and cationic materials, and an ionic conductive agent that gives conductivity by adding metal salts to surfactants and nonionic surfactants. It is classified as a conductive polymer.

Surfactants utilize the hydrophilicity of surfactants as the oldest conductive material. In other words, the surfactant uses hydrogen bonds or surface charges with water, and the migration to the surface of the coating material is very short (less than 3 months) and causes secondary surface contamination due to migration. The development here is an ion conductive agent that dissolves metal salts that can impart conductivity to nonionic surfactants, which can significantly reduce the migration phenomenon of surfactants and improve secondary surface contamination, but the surface resistance of the coating surface is rather high. There were disadvantages that appeared.

In order to solve the problems of the two materials, an ionic liquid having good solubility in organic solvents has been developed and used, but the price is very high compared to the two materials, and since many materials are not developed, accessibility is low in the variety of products. In addition, the conductive polymer has a monopoly position in the world, and it is widely used because it has excellent conductivity, does not exhibit migration performance, and is competitive in price compared to the ion conductive agent. There is a problem that requires a separate process because it is not mixed with the solvent-type coating material. In addition, the four kinds of conductive materials have respective characteristics, but there is a problem that it is difficult to use them.

Therefore, in the present invention, in order to solve the problem of the conductive material, it is intended to develop a conductive material that can play a role as a conductive material with a cost competitiveness through an easily accessible material.

In order to solve the disadvantages of the conventional conductive materials described above, in the present invention, by melting the metal salt consisting of an organic compound having a primary or secondary amide and an alkaline earth metal at high temperature, a solid at room temperature and a liquid at high temperature, an ionic complex type As a conductive material, it is dissolved in a general solvent, and when measuring surface resistance alone, it shows 10 4 ~ 5 cm ^-1 and it shows that antistatic performance can be suppressed when it is added to the coating material. In addition, it is dissolved in an organic solvent and dissolved in a coating material to ensure transparency even when an excessive amount is added and to minimize the change in physical properties of the surface of the present invention was able to solve the problems of the conductive materials.

In order to achieve the above object, the present invention relates to a conductive material added to the curable coating agent, the present invention relates to an ion complex conductive material of the formula (3) composed of a mixture of the amide compound of formula (1) and the alkaline earth metal of formula (2) Main technical configuration.

In Formula 1, R1 and R2 are any one selected from the group containing hydrogen, saturated hydrocarbons containing 1 to 22 carbon atoms, double bonds, unsaturated hydrocarbons including benzene groups, fluorine or silicon.

(Sulfonate trifluoromethyl), OTs ^{- -} M 2 in the formula is any one selected from alkali metals of lithium, sodium, potassium, X is OTf an anionic substance (toluene-4-sulfonate), OMs ^{- (sulfonate), Cl -, Br -,} I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 _{^{COO -, CH 3 SO 3 -}} , CF 3 SO 3 -, (CF 3 SO 2) 2N -, (CF 3 SO 2) 3C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F ^{(HF) n -, (CN} ) 2N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2N -, C 3 F 7 COO - or _{(CF 3 SO 2) (CF} 3 CO) N ^-Any one selected.

Hereinafter, the technical configuration will be described in detail.

The present invention relates to a metal which is solid at room temperature and liquid at high temperature as a conductive material, and that the conductive material is liquid at room temperature may cause a migration phenomenon when added to the coating material. When coated on a film or the like, its own surface resistance is less than the ionic liquid and solubility in organic solvents.

The conductive material of the present invention, which is solid at room temperature and liquid at high temperature, is composed of a mixture of the amide compound of Formula 1 and the alkaline earth metal of Formula 2, wherein R1 of Formula 1 is specifically alkyl having 1 to 22 carbon atoms. Methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, cetyl, stearyl, oleyl, bihenyl groups, acrylic, benzyl, phenyl and the like as unsaturated hydrocarbons, alkyl As silane and perfluoro alkyl, it is any 1 type chosen from said C1-C22 alkyl or unsaturated hydrocarbon. And, R2 includes all corresponding to hydrogen or R1.

In addition, the alkaline earth metal of Formula 2 corresponds to any one selected from LiClO ₄ , LiPF ₆ , LiBF ₄ , NaClO ₄ , NaPF ₆ , NaBF ₄ , KClO ₄ , KPF ₆ , KBF ₄ , and others specified above. Anything consisting of anionic moieties may correspond to this. And it is not limited to the specified compounds, and alkaline earth metal materials separated by cations and anions are also equivalents.

Next, look at with respect to the formula (3) prepared by the reaction of the amide compound of Formula 1 and the alkaline earth metal of the formula (2).

To prepare the compound corresponding to Formula 3, 0.8 to 1.2 parts by weight of the amide compound of Formula 1 is heated to an amide melting point to completely dissolve the amide compound of Formula 1, and then 0.8 to 1.2 weight of the alkaline earth metal of Formula 2 The part is prepared by stirring for 1-6 hours.

Herein, the compounds corresponding to Formula 1 and Formula 2 are each used 0.8 to 1.2 parts by weight, which is to be added in an equivalent ratio of 1 to 0.9 to 1.2, preferably 1 to 1.2, the equivalent ratio of Formula 1 When the amide compound of less than 1 is added, the unreacted amide compound acts as a deterrent to the conduction performance. When the alkaline earth metal of Formula 2 is added in an amount of more than 1.2 equivalents, the amide compound does not act as an obstacle to the electrostatic performance. Meltability is lowered and the price is increased as a factor determining the economic part.

And the reaction temperature is not significantly affected if the melting point of the amide compound or more, but lower than the amide compound is very slow reaction rate, it is preferable to maintain the melting point or more.

The ion complex type charging material thus prepared is applied by inducing solidification or liquefaction at room temperature, and the ion complex composed of acetamide and alkali metal salts has excellent antistatic performance and scratch resistance, such as ITO or ATO. Compared with the metal oxide, since it is not a dispersion but a dissolved state, there is no dispersion problem in the coating liquid and instability of the coating liquid, and there is a characteristic that the haze is low and the contrast is not lowered.

In addition, the ion complex conductive material thus prepared may be a film material of a prism film, a diffusion film, a reflective sheet, a light guide plate or an optical film, a touch panel, an organic EL, an LCD, a PDP, an EL keypad, and a flexible display PET, PC, and Acryl. It can be applied to the transparent room materials of film or shield room, partition, flooring, wall material, spacer tape, major forming tray, carrier tape for IC chip, clean room material of LCD module tray, or packaging material for electronic products including LCD module tray. have.

As described above, the conductive material according to the present invention is provided by a new type of conductive material manufacturing method using an organic compound and an alkaline earth metal compound containing primary or secondary amides, and has high advantages in terms of conductivity as well as processability. Antistatic materials, EMI shielding (electromagnetic interference shielding, electrostatic control, radio wave shielding), chemical sensors, actuators, secondary batteries, electrical paints, functional catalysts, PDP (Plasma Display Panel) optical filters, OLED (Organic Light Emitting Diode) ) And LCD (Liquid Crystal Display), touch screen, EL for mobile phones, TFT (Thin Film Transistor) terminal electrode and RFID (Radio Frequency Identification) antenna, antistatic film, transparent conductive electrode, inorganic EL material, electrolyte for capacitor It can be applied to various applications such as materials.

Hereinafter, specific embodiments will be described with reference to the above technical configuration. However, these do not limit the technical scope of the present invention.

Example 1

277.45 g of acetamide was added to a 1 L reactor equipped with a temperature controller and a heater to control the temperature, and the reaction temperature was raised to 60 ° C. to completely melt the acetamide. Then, 500 g of LiClO ₄ was slowly added while stirring. Input.

After all of the LiClO ₄ was added, the mixture was stirred for 2 hours, and cooled at room temperature to obtain 776.2 g of an acetamide ion complex compound (yield 99.8%).

Example 2

After adding 334.05 g of acrylamide to the same apparatus as in Example 1, the reaction product was heated to 60 ° C. to completely melt the acrylamide, and then slowly added 500 g of LiClO ₄ while stirring.

After all of the LiClO ₄ was added, the mixture was stirred for 2 hours, and cooled at room temperature to obtain 831.5 g (yield 99.7%) of an acrylamide ion complex compound.

Example 3

799.6 g (yield 99.6%) were obtained by reacting 590 g of CME (nonionic surfactant, manufactured by Miwon Corporation) with 212.8 g of LiClO ₄ under the same apparatus and the same conditions as in Example 1.

Example 4

795.7 g (yield 94.3%) were obtained by reacting 236.28 g of acetamide and 607.6 g of LiPF ₆ under the same apparatus and the same conditions as in Example 1.

Example 5

598 g (yield 97.8%) were obtained by reacting 236.28 g of acrylamide and 375 g of LiBF ₄ under the same apparatus and the same conditions as in Example 1.

Example 6

813.4 g (yield 91.2%) was obtained by reacting 284.32 g of acrylamide instead of acetamide under the same apparatus and the same conditions as in Example 4.

Example 7

757 g (98.1%) was obtained by reacting 236.3 g of acetamide and 535.4 g of LiI under the same apparatus and the same conditions as in Example 1.

Example 8

690 g (yield 99.7%) were obtained by reacting 118.1 g of acetamide and 574.2 g of LiTfSI (3M HQ-115) under the same apparatus and the same conditions as in Example 1.

Some of the compounds prepared in Examples 1 to 8 were subjected to performance evaluation using a curable coating material provided by Dongwoo Fine Chem, an application company, and the conditions and results according to the evaluation are as follows.

Test Example 1

2.8 parts of trimethylolpropane triacrylate, 3.8 parts of bisphenol A-ethylene glycol diacrylate, 13.4 parts of polyethylene glycol diacrylate, reactive silica particles (content of hydrolyzable silane having a hydroxyl group is about 80%, average particle size 0.005 μm) 13 parts, 64 parts of an organic solvent in which isopropanol and methyl cellosolve are mixed at a ratio of 1: 1, 1 part of 1-hydroxysimolonucleosil phenyl ketone, and B-1 of Example 1 as an antistatic agent. 1 part was mixed. A small amount of propylene wax and an ultraviolet absorber, which are light stabilizers, were added thereto to prepare a hard coating composition.

Applying the hard coating composition prepared on the transparent substrate film (40㎛, TAC) to the moisture film thickness of 14㎛ by a meyer bar and dried at 70 ℃ for 1 minute, and then cured at 720mJ / ㎠ to laminate a film with a hard coating layer Prepared.

Test Example 2

It carried out similarly to Example 1 except using 5 parts of preparations of Example 1 as an antistatic agent.

Test Example 3

It carried out similarly to Example 1 except using 10 parts of preparations of Example 1 as an antistatic agent.

Test Example 4

It carried out similarly to Example 1 except using 15 parts of preparations of Example 1 as an antistatic agent.

Test Example 5

It carried out similarly to Example 1 except using 20 parts of preparations of Example 1 as an antistatic agent.

Test Example 6

It carried out similarly to Example 1 except using 30 parts of preparations of Example 1 as an antistatic agent.

Test Example 7

It carried out similarly to Example 1 except using 10 parts of preparations of Example 7 as an antistatic agent.

Test Example 8

It carried out similarly to Example 1 except using 10 parts of preparations of the said Example 8 as an antistatic agent.

Comparative Example 1

As antistatic agents except that 10 parts of LiClO ₄ was conducted in the same manner as in Example 1.

Comparative Example 2

The same procedure as in Example 1 was carried out except that 10 parts of 4-methyl-1hexylpyridinium hexafluorophosphate as a liquid at room temperature were used as an antistatic agent.

The components and compositions of the hard coat agent compositions of Test Examples 1 to 8 and Comparative Examples 1 and 2 are shown in Table 1 below. At this time, the content of each component represents parts by weight.

division Acrylic system
Monomer Responsive
Silica

abandonment
menstruum Lightness
Initiator
Antistatic agent A-1 A-2 A-3 B-1 B-1 B-1 B-1 B-1
Test Example 1 2.8 3.8 13.4 13 64 3 One Test Example 2 2.8 3.8 13.4 13 64 3 5 Test Example 3 2.8 3.8 13.4 13 64 3 10 Test Example 4 2.8 3.8 13.4 13 64 3 15 Test Example 5 2.8 3.8 13.4 13 64 3 20 Test Example 6 2.8 3.8 13.4 13 64 3 30 Test Example 7 2.8 3.8 13.4 13 64 3 10 Test Example 8 2.8 3.8 13.4 13 64 3 10 Comparative Example 1 2.8 3.8 13.4 13 64 3 10 Comparative Example 2 2.8 3.8 13.4 13 64 3 10

In Table 1, the components of the acrylic monomer and the antistatic agent are as follows.

A-1: trimethylol propane triacrylate

A-2: Bisphenol A-ethylene glycol diacrylate

A-3: polyethylene glycol diacrylate

B-1: antistatic agent of Example 1

B-2: Antistatic Agent of Example 7

B-3: Antistatic Agent of Example 8

B-4: LiCLO ₄

B-5: 4-methyl-1hexylpyridinium hexafluorophosphate (liquid at room temperature)

Property evaluation

(1) transmittance and haze

Total light transmittance and total haze were measured using a spectrophotometer (HZ-1, manufactured by Suga Japan).

(2) pencil hardness

Pencil hardness was measured using a pencil hardness tester (PHT, manufactured by Seokbo Science, Inc.) under a 500g load. The pencil was made 5 times per pencil hardness using Mitsubishi products. If there were two or more gases, it was determined to be defective.

Kiss: 0 OK

Kiss: 1 OK

Ges: 2 or more NG

(3) scratch resistance

The scratch resistance was tested by using a steel wool tester (WT-LCM100, manufactured by Protec Co., Ltd.) for 10 reciprocations at 1 kg / (2 cm × 2 cm).

Steel wool used # 0000.

A: 0 scratches

A ': 1 to 10 scratches

B: 11-20 scratches

C: 21-30 scratches

D: 31 or more scratches

(4) adhesion

Eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm each to form 100 squares, and then three peel tests were conducted using a tape (CT-24, Nichi Nippon Corp.). Three 100 squares were tested and averaged.

The adhesion was recorded as follows.

Adhesion = n / 100

n: number of rectangles that do not peel out of the entire rectangle

100: total number of squares

Therefore, when none of the peeling was recorded as 100/100.

(5) surface resistivity

Using a surface resistance measuring instrument (MCP-HT450, manufactured by Mitsubishi Chemical Co., Ltd.), the surface resistance of each of three points was measured 10 times with the hard coating layer laminated on the transparent protective film layer as a surface, and the average value was represented.

division Transmittance / haze (%) Pencil hardness Scratch resistance Adhesion Surface resistivity (Ω / □) Test Example 1 92.3 / 0.3 2H A ' 100/100 3 x ^{10 11} Test Example 2 91.8 / 0.4 2H A ' 100/100 1 x ^{10 11} Test Example 3 91.5 / 0.4 2H A ' 100/100 5 x ^{10 10} Test Example 4 90.9 / 0.5 2H B 100/100 1 x ^{10 10} Test Example 5 90.7 / 0.6 2H B 100/100 8 x 10 ⁹ Test Example 6 90.4 / 0.9 2H B 100/100 5 x 10 ⁹ Test Example 7 90.1 / 1.1 2H A ' 100/100 2 x 10 ¹⁰ Test Example 8 91.2 / 0.4 2H A ' 100/100 3 x 10 ¹⁰ Comparative Example 1 91.3 / 0.4 2H C 98/100 7 x ^{10 13} Comparative Example 2 91.6 / 0.3 2H D 100/100 2 x 10 ¹²

Claims (2)

delete In preparing the conductive material of the formula (3) by stirring the amide compound of the formula (1) and the alkaline earth metal of the formula (2), The conductive material of Chemical Formula 3 is used in a curable coating agent, and then 0.8 to 1.2 parts by weight of an amide compound represented by Chemical Formula 1 is heated to 60 ° C., completely dissolved therein, and 0.8 to 1.2 parts by weight of alkaline earth metal of Chemical Formula 2 is added thereto. Method for producing an ion complex conductive material, characterized in that it is prepared by stirring for 1 to 6 hours [Formula 1]

R1 of Formula 1 is an alkyl having 1 to 22 carbon atoms, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, cetyl, stearyl, oleyl, bihenyl group, unsaturated The hydrocarbon is any one selected from acryl, benzyl, phenyl, alkylsilane and perfluoro alkyl, and R2 is any one selected from hydrogen or all of R1. [Formula 2]

(Sulfonate trifluoromethyl), OTs ^{- -} M of Formula 2 is any one selected from alkali metals of lithium, sodium, potassium, X is OTf an anionic substance (toluene-4-sulfonate), OMs ^- (methane ^{sulfonate), Cl -, Br -,} I -, AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO _{^{-, CH 3 SO 3 -,}} CF 3 SO 3 -, (CF 3 SO 2) 2N -, (CF 3 SO 2) 3C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F ( ^{HF) n -, (CN)} 2N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2N -, C 3 F 7 COO - or _{(CF 3 SO 2) (CF} 3 CO) N - It is any one selected. (3)