KR20130000466A - Photocurable resin composition with organic-solvent base dispersed conductive polymer and film or sheet coated with the composition - Google Patents

Abstract

PURPOSE: A photo-curable resin composition is provided to have stable physical properties for a coated specimen by placing poly(3,4-dioxythiophene) which can be dispersed in an organic solvent into an oil UV curable resin. CONSTITUTION: A photo-curable resin composition comprises 10-50 wt% of a photo-curable resin and 10-30 wt% of poly(3,4-dioxythiophene) which can be dispersed in an organic solvent. The photocurable resin is a silicon-based resin in which silicon and colloid silica are mixed to an acrylic monomer. The poly(3,4-dioxythiophene) is dispersed in an alcohol with the carbon number 3 or higher, N-methy-2-pyrrolidone, dimethylformamide, diethylene glycol, or dimethylsulfoxide.

Description

Photocurable resin composition with organic-solvent base dispersed conductive polymer and film or sheet coated with the composition

The present invention relates to a photocurable resin composition comprising a conductive polymer organic solvent dispersion, and more specifically, to a poly (3,4-ethylenedioxythiophene) (poly (3,4-dioxythiophene: PEDOT) powder is an organic solvent). It relates to a photocurable resin composition contained in a dispersed form.

Semiconductors, liquid crystal displays or various electronic products are transported using antistatic film or in an antistatic container to prevent electrostatic damage that may occur in various stages of manufacturing, transportation, and handling. Should be.

There are several kinds of antistatic agents used for antistatic purposes, and typically include conductive carbon black, surfactant type antistatic agent, ionic liquids, inherently conductive polymers (ICP), and metal salt compounds. There are several types of antistatic agents (inherently dissipative polymers, IDP).

In particular, in the case of using the conductive polymer of the various types of antistatic agents, many of the shortcomings of the conventional photocurable resins prepared using other types of antistatic agents. The conductive polymer as an antistatic agent is an organic polymer whose material itself has electrical conductivity. A representative conductive polymer currently commercialized is poly (3,4-ethylenedioxythiophene, a conductive polymer of HC Starck, Clevious P). ) (the poly (3,4-dioxythiophene: PEDOT). The conductive polymer is in a water-dispersible form and mixed with a water-soluble organic binder to form an antistatic coating solution, and then coated on the surface of the coating material to form an antistatic layer to form an electrostatic charge. In addition, PEDOT may be used as an antistatic agent component of a photocurable resin composition, and there are a number of conventional technologies for manufacturing methods using the same, for example, Korean Patent Application No. 10-2004-0097669. An example of a conductive polymer in the arc is Bayer PEDOT (trade name: Baitron PH), which exhibits thermal and atmospheric safety in the form of water dispersion. The PEDOT can be easily coated by diluting with such a solvent because it is well mixed with water or alcohol or a solvent having a high dielectric constant, and is superior to other conductive polymers such as polyaniline and polypyrrole when forming a coating film. On the other hand, according to Korean Patent Application No. 10-2000-0059432, a photocurable transparent conductive material is used by using an aqueous solution containing 1.3 wt% of polyethylene dioxythiophene polystyrene sulfonate (PEDT / PSS) as a conductive polymer. Prepare a coating.

In the case of the antistatic agent coating layer formed of the photocurable composition using the water-dispersible PEDOT mentioned in the prior art, it has a permanent antistatic property of 10e6-9, there is no humidity dependence, and does not have a problem of transition to the surface over time Do not. As such, even in the application of the water-dispersible PEDOT having excellent properties as an antistatic agent, the photo-curable antistatic coating solution in which the water-dispersible PEDOT is applied to the water-based photocurable resin has a disadvantage of being difficult to apply because it does not fit with many manufacturers' coating systems. Thus, applying a water dispersion type PEDOT dispersion in the charging of the oil type photocurable resin causes a serious problem in the liquid phase stability.

An object of the present invention is to provide a photocurable antistatic coating composition containing an organic solvent dispersion form using an organic solvent dispersed PEDOT powder in order to solve the above problems and to implement a solution stability and stable physical properties of the coating specimen. It is. That is, the present invention is characterized in that the organic solvent dispersion form is included in the coating composition, not the aqueous dispersion form.

According to an aspect of the present invention, there is provided a photocurable antistatic coating composition employing an organic solvent dispersed PEDOT in the form of dispersion in an organic solvent as an antistatic agent. The coating composition according to the present invention comprises a UV curable resin and an organic solvent dispersed PEDOT. UV-curable resin according to the present invention is preferably a silicone-based resin in which silicon and colloidal silica are mixed with an acrylic monomer, the organic polymer dispersed PEDOT is employed as the conductive polymer according to the present invention, the conductive polymer is Agfa (Agfa) of Belgium It is an organic dry powder under the trade name developed by). The organic solvent-dispersed PEDOT may be obtained in powder form from the supplier, but may also be prepared by freeze-drying the water-dispersible PEDOT.

The coating composition according to the present invention may include 10 to 50 parts by weight of UV-curable silicone resin, 10 to 30 parts by weight of organic solvent-dispersed PEDOT, and other solvents and additives. When the UV-curable silicone resin is less than 10%, the physical properties such as solvent resistance, antifouling properties, hardness, etc., as well as substrate adhesion is insufficient, on the contrary, when used more than 50% has an excessive antistatic properties of 10e11 or more. In addition, if the PEDOT content is less than 10%, it is difficult to implement the desired antistatic properties, and when added in excess of 30%, the transmittance is less than 70%, resulting in a decrease in optical properties and other physical properties (solvent resistance, hardness, etc.). In the present invention, the solvent for dispersing the antistatic agent PEDOT is N-methyl-2-pyrrolidone, 2-pyrrolidone, dimethylformamide, diethylene glycol, Dimethyl sulfoxide and the like can be used. Preferred contents of PEDOT in powder form include 1 to 5 parts by weight. Other additives may further include surface modifiers to assist in forming polyethylene, PTFE and Carnauba based waxes and / or coated surface appearances as surface blocking agents.

The coating composition according to the present invention is polymethyl methacrylate, polycarbonate, polyethylene terephthalate, amorphous polyethylene terephthalate, polyether sulfone, polyvinyl chloride, MS resin (copolymer of MMA and SM), triacetate, which requires transparency It is coated and used on a transparent film or sheet made of plastic such as cellulose, and generally a flow coating method and the like can be applied together with a gravure coating method.

Still another object of the present invention is to provide an antistatic film or sheet molding prepared using the photocurable coating composition.

By adding the organic solvent dispersion type PEDOT to the oil type UV curable resin, the UV curable hard coating composition having the antistatic performance can be applied to the coated specimen as well as the solution stability compared to the composition using the antistatic agent impregnated with the conventional water dispersion type PEDOT. There is an advantage that can implement stable physical properties.

Example  One

      Organic Solvent Base PEDOT Dispersion Preparation

1.5 g of poly (3,4-ethylenedioxythiophene) powder (Orgacon Dry) obtained from Agfa, Belgium was added to 98.5 g of each solvent of Table 1 and 10,000 using a Hi-speed homogenizer. The organic solvent base PEDOT dispersion was prepared by dispersing at rpm for 30 minutes. The organic solvent here is ethanol, dimethyl sulfoxide, ethylene glycol, formamide. Examples 2 to 4 selected dimethyl sulfoxide having excellent liquid stability and surface resistance among selected organic solvents.

 Example 1-1 Examples 1-2 Example 1-3 Example 1-4 combination Orgacon dry 1.5 1.5 1.5 1.5 EtOH 98.5 DMSO 98.5 EG 98.5 FA 98.5 gun 100.0 100.0 100.0 100.0 Properties Surface resistance ^* 1,000-3,000 500-800 700 to 900 800 Solution Stability ^** Layer separation stability stability stability

^* Surface resistance: Measurement of surface resistance after coating / drying on polyester film base with Meyer Bar # 12, Ω

^** Solution stability: Liquid stability after 3 days at 40 ℃

Example  2 to 4

Coating composition manufacturing

The PEDOT dispersion dispersed in dimethyl sulfoxide prepared above was mixed with an oil type UV curable resin (Dow Corning, trade name AY-42-150), followed by adding CeraFlour 981 (surface slip agent) for 20 minutes at 500 rpm. Mixing to complete the coating composition. These component mixing ratios are shown in Table 2 below.

Example 2 Example 3 Example 4 AY42-150 ^* 15.0 30.0 45.0 PEDOT ^** Dimethyl Sulfoxide Dispersion 20.0 20.0 20.0 EtOH 62.5 47.5 32.5 CeraFlour 981 ^*** 0.5 0.5 0.5 sum 100.0 100.0 100.0

^* AY42-150: UV curable resin obtained from Dow Corning;

^** PEDOT: poly (3,4-ethylenedioxythiophene) powder obtained from Agfa Belgium (AGFA);

^*** CeraFlour 981: surface slip agent obtained from BYK, Germany

Comparative example

A composition obtained by mixing Cleviou P of H.C Starck, Germany, a water-dispersible conductive polymer, with UV curable resin was adopted as a comparative coating composition, and compared with the physical properties of Examples 2 to 4. Comparative Coating Compositions The component mixing ratios are shown in Table 3 below.

Comparative example AY42-150 30.0 Clevious P Water Dispersion 20.0 EtOH 47.5 CeraFlour 981 0.5 sum 100.0

Experimental Example

The coating compositions prepared in Examples and Comparative Examples were coated with a Meyer Bar # 5 on a 38 micron polyester film, dried at 100 ° C. for 1 minute, and then irradiated with a mercury lamp to a light amount of 400 mJ / cm ² , followed by coating appearance. Surface resistance, hardness, transmittance, solvent resistance, in particular, solvent resistance to methylethylketone and toluene were measured. The measuring method is briefly described.

(1) surface resistance

-Measuring equipment: CMT-SR1000N (4-Point probe method)

-Method of measurement: Measure the surface resistance by measuring the voltage between the two points inside the 4-point probe and the current between the two outside points;

(2) pencil hardness

Measurement using a Mitsubishi pencil hardness tester;

(3) solvent resistance

-Appearance change (results-no abnormality or peeling of coating) when rubbing the two chemicals of toluene and MEK to give 250g / cm ² and 500g / cm ² loads;

(4) transmittance

-Measuring equipment: Nippon Denohoku, NDH-5000 / Measuring wavelength range: 380 ~ 780 nm

The measurement results are summarized in Tables 4 and 5 below.

Example 1 Example 2 Example 3 Coating appearance Good Good Good Surface resistance 10e5 10e6 10e6 ~ 7 Hardness 3H 3 ~ 4H 4H Transmittance 80% 89% 91% Solvent Resistant MEK
Toluene Little peeling Good Good Little peeling Good Good Solution stability stability stability stability

Comparative example Coating appearance Good Surface resistance 10e10 Hardness 2H Transmittance 87% Solvent Resistant MEK
Toluene Good Good Solution stability Instability

As can be seen from the above experimental results, the coating composition according to the present invention shows improved coating film properties compared to the photocurable coating composition containing a water-dispersible conductive polymer. Therefore, the photocurable coating composition having an antistatic performance according to the present invention prepared by adding an organic solvent dispersed PEDOT to an oil type UV curable resin has a solution stability as compared to a composition using an antistatic agent impregnated with a water-dispersible PEDOT. Stable physical properties of the coated specimens can also be achieved.

Claims (5)

A photocurable antistatic coating composition, comprising a photocurable resin and an organic solvent dispersion type PEDOT (poly (3,4-ethylenedioxythiophene)), wherein the photocurable antistatic coating composition. The photocurable antistatic coating composition according to claim 1, wherein the photocurable resin is a silicone resin in which silicone and colloidal silica are mixed with an acrylic monomer. The method according to claim 1, wherein the photocurable resin is a photocurable resin obtained under the trade name AY42-150 from Dow Corning, and the conductive polymer is a poly (3,4) obtained under the trade name Organo Dry from Agfa, Belgium. -Ethylenedioxythiophene), photocurable antistatic coating composition. The alcohol according to any one of claims 1 to 3, wherein the photocurable resin is 10 to 50 parts by weight based on the total weight of the photocurable antistatic coating composition and the organic solvent dispersion type PEDOT has 3 or more carbon atoms. Dispersed in N-methyl-2-pyrrolidone, 2-pyrrolidone, dimethylformamide, diethylene glycol or dimethyl sulfoxide to enhance the electrical conductivity, characterized in that it contains 10 to 30 parts by weight, Photocurable antistatic coating composition. An antistatic film or sheet molding prepared by coating the photocurable antistatic coating composition according to claim 4.