KR101440859B1 - Conductivity reducing agent for conductive polymer film and patterning process using same - Google Patents

Abstract

The present invention relates to a conductivity reducing agent for a conductive polymer film and a method of forming a pattern using the same, the conductivity reducing agent including a solvent having a sodium chloride based compound, an acidic compound, and a metal based catalyst. The conductivity reducing agent reduces variation in optical characteristics such as a color difference before and after etching with respect to a polymer film so a shape of an etched pattern is rarely viewed. The method of forming a pattern on a conductive polymer film can form fine patterns, and reduce environmental pollution and process cost and time by using an aqueous solvent. Therefore, the method can be used for manufacturing upper and lower electrode films for touch panels, an inorganic electroluminescent device (EL) for mobile phones, a transparent electrode film for displays, an electromagnetic wave blocking layer of a screen for cathode-ray tube TVs and computer monitors, etc.

Description

TECHNICAL FIELD [0001] The present invention relates to a conductive reducing agent for a conductive polymer film and a pattern forming method using the conductive reducing agent. [0002]

The present invention relates to a conductive reducing agent for use in a conductive polymer film and a method for forming a pattern on the conductive polymer film using the same.

BACKGROUND ART Conductive polymers such as polyaniline (PAN), polypyrrole (PPy) and polythiophene (PT) which are widely used at present are easy to polymerize and have excellent conductivity, thermal stability and oxidation stability. In particular, polyethylene dioxythiophene (PEDOT), which is a polythiophene conductive polymer, exhibits excellent transparency in comparison with polyaniline-based and polypyrrole-based polymers as well as other polythiophene-based conductive polymers. The polythiophene conductive polymer may be PEDOT or PEDOT doped with polystyrene sulfonate. An example of such a water-dispersed PEDOT is Clevios ^TM P commercially available from Heraeus Co., Ltd. .

These conductive polymeric compounds can be used as an electrode of a secondary battery or an electrode for shielding electromagnetic waves by substituting indium tin oxide (ITO), silver nanowire, carbon nanotube, There have been proposed applications for various applications such as materials, flexible electrodes, antistatic materials, and corrosion inhibiting coating materials. Particularly, these conductive materials are attracting attention as they are actively used as electrodes in a touch panel applied to liquid crystal display (LCD), plasma display (PDP), organic light emitting display (OLED) .

In order to apply these conductive materials to a touch panel of a display, an electrode patterning process is necessarily required. In the patterning of the conductive polymer, it is necessary to impart appropriate processability to the conductive polymer, and it is required that the electrical or electro-optical properties of the polymer are changed little after the patterning, and the convenience of the process and low cost are considered for industrial application It is an important point to be made.

However, a conventional method of forming an etching-type pattern using a photoresist, dry film resist (DFR), or the like (refer to Korean Patent Laid-Open Publication No. 2011-86707 and the like), an optical characteristic before and after etching There is a problem that the shape of the pattern is well visible. In addition, it is difficult to form a fine pattern due to a small contact angle with the substrate, a large amount of process cost is required due to the exposure equipment, and organic solvents used during the process contaminate the environment.

Korean Patent Laid-Open Publication No. 2011-86707 (2011.07.29.) Toagosei Co., Ltd., etc.

Accordingly, it is an object of the present invention to provide a conductive reducing agent which reduces variations in optical characteristics such as color difference before and after etching of a conductive polymer film, and the shape of the pattern is not easily seen.

Another object of the present invention is to provide a method of forming a pattern on a conductive polymer film using the conductive reducing agent.

According to the above object, the present invention provides a conductive reducing agent for a conductive polymer film, comprising 0.5 to 10% by weight of a sodium chloride-based compound, 0.1 to 2% by weight of an acid compound, and 0.1 to 2% by weight of a metal-based catalyst in a solvent.

According to another aspect of the present invention, there is provided a method of forming a pattern on a conductive polymer film by reducing the conductivity of a part of the conductive polymer film using the conductive reducing agent for the conductive polymer film.

The present invention also provides a re-doping solution of a conductive polymer film comprising an acid compound and an aqueous solvent.

The conductive reducing agent according to the present invention reduces the change in optical characteristics such as color difference before and after etching of the polymer film, and the shape of the etched pattern is hardly visible. In addition, the method of forming a pattern on the conductive polymer film using the conductive reducing agent can form a fine pattern and reduce environmental pollution by using an aqueous solvent, and can save the processing cost and time. Accordingly, the present invention can be advantageously used for manufacturing upper and lower electrode films for touch panels, inorganic EL (electroluminescence) electrode films for mobile phones, transparent electrode films for displays, TV cathode-ray tubes, and electromagnetic wave shielding layers on a computer monitor screen.

1 shows an example of a method of forming a pattern on a conductive film using a conductive reducing agent according to the present invention.

Hereinafter, the present invention will be described more specifically.

Conducting Reducing Agent for Conductive Polymer Film

The conductive reducing agent of the present invention includes a sodium chloride-based compound. As used herein, the sodium chloride compound means a compound containing chlorine (Cl) and sodium (Na). For example, the sodium chloride-based compound may be a salt compound in which anion containing sodium chloride and sodium ion are bonded. In addition, the sodium chloride-based compound may be an oxidizing agent. As a specific example, the sodium chloride-based compound may be selected from the group consisting of sodium hypochloride (NaOCl), sodium dichloroisocyanurate (C ₃ Cl ₂ N ₃ NaO ₃ ), sodium chlorite (NaClO ₂ ) ≪ / RTI > and mixtures thereof.

The sodium chloride-based compound is contained in an amount of 0.5 to 10 wt%, more preferably 3 to 7 wt%, based on the total weight of the conductive reducing agent. The stability of the conductive reducing agent may be better in the above range of the preferable content.

In addition, the conductive reducing agent composition includes an acid compound. Specific examples of the acid include hydrochloric acid (HCl), acetic acid (CH ₃ COOH), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), and mixtures thereof. Preferably the acid is hydrochloric acid (HCl), it may be an acid (CH ₃ COOH), or a mixture thereof. The content of the acid may be 0.1 to 2% by weight, more preferably 0.5 to 2% by weight based on the total weight of the conductive reducing agent. If the content of the acid is more than 2% by weight, the inactivating performance may be deteriorated, and the optical characteristics such as color difference before and after deactivation may increase, and the pattern shape may be clearly visible.

In addition, the conductive reducing agent includes a metal catalyst. The metal catalyst may be a metal phthalocyanine catalyst, for example, Zn phthalocyanine, Cu phthalocyanine, Ni phthalocyanine, or a mixture thereof. The content of the metal catalyst is 0.1 to 0.2% by weight, more preferably 0.5 to 2% by weight based on the total weight of the conductive reducing agent. When the content of the metal catalyst is more than 2% by weight, the deactivation performance may be drastically reduced due to deterioration with time.

In addition, the conductive reducing agent includes a solvent. The solvent is not particularly limited, but an aqueous solvent can be preferably used, and more preferably, distilled water is used, since the angle of contact with the substrate surface is large without causing environmental problems due to the use of an organic solvent, . The content of the solvent may be any amount except for the sodium chloride based compound, acid and metal catalyst in the conductive reducing agent, and may be, for example, 89 to 96% by weight based on the total weight of the conductive reducing agent.

The conductive reducing agent according to the present invention can be applied to a conductive polymer film. The conductive reducing agent of the present invention not only has excellent reactivity to the conductive polymer film, but also reduces the change of optical characteristics such as color difference before and after the reaction, and is excellent in non-visibility of the pattern shape. In addition, by using an aqueous solvent instead of an organic solvent, it is possible to form a fine pattern with less environmental pollution.

The conductive polymer film may be a polythiophene-based, polyaniline-based or polypyrrole-based conductive polymer film. Preferably, the conductive polymer film may be a polythiophene conductive polymer, and more preferably a polyethylene dioxythiophene (PEDOT) conductive polymer film, more preferably a polystyrene sulfonate-doped PEDOT film.

The conductive polymer film may be a conductive polymer film formed on a substrate. Examples of the substrate include an insulating substrate made of a transparent material and may be selected from the group consisting of glass, casting polypropylene (CPP), polyethylene terephthalate (PET), polycarbonate, and acrylic resin Or the like.

Pattern formation method of conductive polymer film

The present invention also provides a method of forming a pattern on a conductive polymer film by reducing the conductivity of a part of the conductive polymer film using the conductive reducing agent.

The method of the present invention more specifically includes: (a) forming a mask pattern on a conductive polymer film; (b) reducing the conductivity of the conductive polymer film by reacting the exposed portion of the conductive polymer film with the conductive reducing agent; And (c) removing the mask pattern using a peeling liquid to obtain a conductive polymer film having a conductive pattern formed thereon.

Further, the method of the present invention may further include a step of re-doping the pattern using a re-doping solution after forming a pattern on the conductive polymer film. The re-doping process may be performed after the step (c).

One embodiment of the method of the present invention will now be described with reference to Figure 1,

(i) forming a conductive polymer film 200 on a substrate 100,

(ii) forming a mask pattern 300 on the conductive polymer film 200,

(iii) forming a conductive pattern 210 and a nonconductive pattern 220 by reacting a portion of the conductive polymer film 200 exposed from the mask pattern 300 with a conductive reducing agent;

(iv) removing the mask pattern 300 from the conductive polymer film 200 using a peeling solution; And

(v) re-doping the reduced conductive pattern 211 due to the stripping liquid to complete the conductive pattern 210.

Hereinafter, the method according to the present invention will be described in detail for each step.

Preparation of conductive polymer film

The conductive polymer film 200 to be used in the method of the present invention may be any of various conductive polymer films exemplified above.

The conductive polymer film 200 may be prepared by applying a conductive polymer solution to the substrate 100 and then drying the conductive polymer solution. The conductive polymer solution may include a conductive polymer and an organic solvent. The organic solvent may include an alcohol-based organic solvent, an amide-based organic solvent, or a mixed solvent thereof. The alcohol-based organic solvent may be methanol, ethanol, propanol, isopropanol, butanol, or a mixed solvent thereof. As the amide organic solvent, there may be used formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N-methylpyrrolidone or a mixed solvent thereof. The conductive polymer solution may include a binder selected from the group consisting of polyester, polyurethane, acrylic resin, alkoxysilane, and mixtures thereof. The polyesters and polyurethanes used as the binder may be any of those conventionally used in the art, and the alkoxysilanes are preferably trifunctional or tetrafunctional alkoxysilane compounds, more preferably trimethoxysilane And / or tetraethoxysilane.

The method of applying the conductive polymer solution may be performed by a method known in the art. For example, bar coating, roll coating, flow coating, dip coating, spin coating and the like can be used. The subsequent drying step may be carried out at a temperature of 100 DEG C to 145 DEG C for 1 minute to 10 minutes. The thickness of the conductive polymer film prepared by the application and drying may be about 1 탆 to 5 탆. According to one example, the conductive polymer solution (for example, a polythiophene conductive polymer solution) is coated on a transparent substrate (for example, a PET film) by a bar coating method and then heated in an oven at about 125 ° C And then dried for about 5 minutes to prepare a polythiophene-based conductive polymer film having a thickness of 5 탆 or less.

Formation of mask pattern

The process of forming the mask pattern 300 on the conductive polymer film 200 can be suitably performed using various methods.

Preferably, a resist mask pattern can be formed on the conductive polymer film by screen printing.

At this time, as the resist mask to be used, a peelable mask or the like can be used by using a physically peelable mask or a chemical stripper solution, and the type and application method of the resist mask are well known in the technical field related to the present invention And is not particularly limited.

In addition, the thickness of the resist mask pattern may be 10 to 20 占 퐉, and may be dried in a convection drying oven at about 80 to 120 占 폚 for about 5 minutes to about 20 minutes after the mask pattern is formed.

Formation of conductive pattern using conductive reducer

In this step, a pattern is formed on the conductive polymer film 200 by using the conductive reducing agent of the present invention described above.

As an example of a method for reacting the conductive polymer film with the conductive reducing agent, the conductive polymer film 200 having the mask pattern 300 may be dipped in the conductive reducing agent.

The reaction with the conductive reducing agent in this step can be performed at room temperature, and the time required may be 0.1 minute to 10 minutes, more preferably 0.5 minutes to 5 minutes.

As a result, the exposed portion of the conductive polymer film 200 from the mask pattern 300 reacts with the conductive reducing agent to lose conductivity. Specifically, the reaction between the conductive polymer film and the conductive reducing agent may be an oxidation reaction, and as a result, a part of the conductive polymer film may be oxidized to lose conductivity. More specifically, the structure of the conjugated double bond in the portion of the conductive polymer film reacted with the conductive reducing agent may be chemically modified to lose the conductivity. As a result, the portion of the conductive polymer film 200 exposed from the mask pattern 300 forms a nonconductive pattern 220. Therefore, the nonconductive pattern 220 may be formed by oxidizing a part of the conductive polymer film 200. On the other hand, the portion of the conductive polymer film 200 that is not exposed from the mask pattern 300 maintains the conductivity, thereby forming the conductive pattern 210.

The electrical conductivities of the conductive pattern 210 and the nonconductive pattern 220 are significantly different. For example, the conductivity of the conductive pattern may be at least about 10 times the conductivity of the non-conductive pattern. More specifically, the conductivity of the conductive pattern may be at least about 100 times the conductivity of the non-conductive pattern. More specifically, the conductivity of the conductive pattern may be at least about 1000 times the conductivity of the non-conductive pattern. More specifically, the conductivity of the conductive pattern may be at least about 10 ⁶ times the conductivity of the non-conductive pattern. More specifically, the conductivity of the conductive pattern may be at least about 10 ¹⁰ times the conductivity of the non-conductive pattern. In this case, the conductivity of the conductive pattern may be about 10 ²⁰ times or less the conductivity of the non-conductive pattern. As such, the conductive pattern may be a conductor, and the non-conductive pattern may be an insulator.

Also, the electrical conductivity of the conductive pattern 210 may be about 100 to 10000 S / cm. More specifically, the conductivity of the conductive pattern may be about 500 to 3000 S / cm. In addition, the surface resistivity of the conductive pattern may be about 10-5000 [Omega] / sq. More specifically, the surface resistivity of the conductive pattern may be about 50 to 1000 ohms / sq. More specifically, the surface resistivity of the conductive pattern may be about 100 to 500 [Omega] / sq.

In addition, the electrical conductivity of the non-conductive pattern 220 may be about 10 ^-5 to 10 ^-15 S / cm. More specifically, the conductivity of the nonconductive pattern can be about 10 ^-7 to 10 ^-9 S / cm. The surface resistivity of the nonconductive pattern may be greater than or equal to about 10 ¹² Ω / sq. More specifically, the surface resistivity of the nonconductive pattern may be about 10 ¹² to 10 ²⁰ Ω / sq. More specifically, the surface resistivity of the nonconductive pattern may be between about 10 < ¹³ > and 10 < ²⁰ >

The conductive reducing agent only changes electrical characteristics of a part of the conductive polymer film 200 and does not substantially etch the conductive polymer film. Therefore, there is almost no difference in height between the conductive pattern 210 and the nonconductive pattern 220. That is, the conductive pattern 210 and the nonconductive pattern 220 may be integrally formed on the same plane. In addition, only the electrical interface exists between the conductive pattern 210 and the nonconductive pattern 220, but the mechanical interface may not exist.

In addition, there may be little optical difference between the conductive pattern 210 and the nonconductive pattern 220. That is, the conductive pattern 210 and the nonconductive pattern 220 may have little difference in terms of chromaticity, light transmittance, and refractive index. For example, the difference in light transmittance between the conductive pattern 210 and the non-conductive pattern 220 may be about 0.0001% to 0.1%. The difference in refractive index between the conductive pattern 210 and the nonconductive pattern 220 may be about 0.0001 to 0.01. Accordingly, the conductive pattern 210 may be visually hardly recognized.

Removal of mask using exfoliating liquid

In this step, the mask pattern 300 is removed from the conductive polymer film 200 by using the exfoliation liquid.

The peeling process may be performed by reacting and removing the mask pattern 300 with the peeling liquid. For example, the conductive polymer film 200 may be formed by immersing the conductive polymer film 200 having the mask pattern 300 in a peeling liquid or spraying a peeling liquid onto the conductive polymer film 200.

The peeling liquid may include an alkali compound and a solvent. At this time, as the alkali compounds include sodium hydroxide (NaOH), ammonium hydroxide (NH ₄ OH) or mixtures thereof. The content of the alkali compound may be 0.5 to 10% by weight, more preferably 3 to 7% by weight based on the total weight of the exfoliant. As the solvent, an aqueous solvent may be used, and distilled water may preferably be used.

The temperature of the peeling liquid may be 10 ° C to 60 ° C, preferably 30 ° C to 40 ° C. The reaction time with the peeling solution may be 0.5 minutes to 10 minutes, preferably 1.5 minutes to 5 minutes.

Re-doping process

By the above stripping process, the conductive pattern 210 can be reduced in doping, and such a doped reduced conductive pattern 211 can be re-doped using a redo doping liquid.

The re-doping process may be performed by reacting the re-doping solution with the conductive polymer film 200.

For example, by immersing the conductive polymer film 200 in a re-doping solution or spraying a re-doping solution onto the conductive polymer film 200.

The re-doping solution will be separately described later.

In the re-doping step, the time required for the peeling step at room temperature may be 0.1 minute to 5 minutes, preferably 0.5 minutes to 3 minutes.

Through the re-doping process of this step, the conductive pattern 210 can be obtained in which the doping level reduced due to the peeling liquid is restored to the level before the peeling liquid is used, thereby improving the electrical / optical characteristics of the conductive polymer .

Thereafter, the conductive polymer film may further be rinsed with distilled water or the like.

The pattern forming method according to the present invention can be applied to an electrode film, an electromagnetic wave shielding layer or a conductive film for a touch panel, specifically, an upper or lower electrode film for a touch panel, an inorganic electroluminescent (EL) electrode film for a mobile phone, An electrode film, a TV cathode ray tube, an electromagnetic wave shielding layer on a computer monitor screen, a conductive film for a touch panel for use in electric and electronic devices, and the like.

The re-doping solution of the conductive polymer film

In addition, the present invention provides a re-doping solution, in particular, a re-doping solution of a conductive polymer film.

The re-doping solution includes an acid compound and a solvent.

Examples of the acid compound include hydrochloric acid (HCl) and the like. The content of the acid compound may be 0.5 to 5 wt% based on the total weight of the redoing solution.

As the solvent, an aqueous solvent may be used, and distilled water may be preferably used.

Such a re-doping solution can increase the doping level of the conductive polymer, and in particular, the reduced doping level can be restored to the level before use of the dissolution solution due to the exfoliation solution (alkaline compound, etc.).

Concrete Example: Preparation of conductive reducer for conductive polymer and pattern formation using the same

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

Preparation of Conducting Reducing Agent for Conductive Polymer Film

Sodium chloride-based compounds, acid compounds and metal-based catalysts were mixed with distilled water to prepare respective conductive reducing agents having the preferred composition of the present invention as in the conductive reducing agents A1 to A6 shown in Table 1 below.

As a comparative example, each of the conductive reducing agents deviating from the preferred composition of the present invention was prepared as in the conductive reducing agents B1 to B12 of Table 1 below.

conductivity
Abatement agent Sodium chloride compound Acid compound Metal catalyst ingredient weight% ingredient weight% ingredient weight% A1 NaOCl 4 HCl One Cu-Pc One A2 NaOCl 4 CH ₃ COOH One Cu-Pc One A3 C ₃ Cl ₂ N ₃ NaO ₃ 5 HCl One Cu-Pc One A4 C ₃ Cl ₂ N ₃ NaO ₃ 5 CH ₃ COOH One Cu-Pc One A5 NaClO ₂ 6 HCl One Cu-Pc One A6 NaClO ₂ 6 CH ₃ COOH One Cu-Pc One B1 NaOCl 4 HCl One radish - B2 NaOCl 4 CH ₃ COOH One radish - B3 C ₃ Cl ₂ N ₃ NaO ₃ 5 HCl One radish - B4 C ₃ Cl ₂ N ₃ NaO ₃ 5 CH ₃ COOH One radish - B5 NaClO ₂ 6 HCl One radish - B6 NaClO ₂ 6 CH ₃ COOH One radish - B7 NaOCl 4 radish - Cu-Pc One B8 NaOCl 4 radish - radish - B9 C ₃ Cl ₂ N ₃ NaO ₃ 5 radish - Cu-Pc One B10 C ₃ Cl ₂ N ₃ NaO ₃ 5 radish - radish - B11 NaClO ₂ 6 radish - Cu-Pc One B12 NaClO ₂ 6 radish - radish - NaOCl: Sodium hypochlorite (Aldrich)
C ₃ Cl ₂ N ₃ NaO ₃ : Sodium dichloroisocyanate sodium (Aldrich)
NaClO ₂ : Sodium chlorite (Aldrich)
Cu-Pc: Cu phthalocyanine

Examples and Comparative Examples: Pattern Formation of Conductive Polymer Film

Step (1): Formation of a conductive polymer film

A conductive polymer solution containing polystyrene sulfonate-doped PEDOT, methanol, propanol, N-methylacetamide and trimethoxysilane was prepared. The prepared conductive polymer solution was applied to a PET film and then dried in an oven at about 125 캜 for about 5 minutes to form a conductive polymer film. The thickness of the formed conductive polymer film was about 5 탆 or less.

Step (2): Formation of pattern

A resist mask was coated on the conductive polymer film prepared above by a screen printing method and dried in a convection drying oven at 100 캜 for 10 minutes to form a resist mask having a thickness of 10 to 20 탆. The conductive polymer film on which the resist mask is formed is immersed in any one of the conductive reducing agents A1 to A6 and the conductive reducing agents B1 to B12 prepared as described above and allowed to react so that the portion of the conductive polymer film exposed without being masked by the mask pattern Thereby reducing the conductivity. As a result, a conductive pattern and a non-conductive pattern were formed on the conductive polymer film.

Step (3): removal of the resist mask

The patterned conductive polymer film was immersed in an alkaline removing solution (containing 0.5 to 10% by weight of NaOH, NH ₄ OH, etc.) to remove the resist mask, followed by washing with distilled water.

Step (4): The re-doping process

The conductive polymer film from which the resist mask had been removed was immersed in a re-doping solution (containing 0.5 to 5 wt% of hydrochloric acid) to perform a re-doping process.

At this time, the present re-doping process step was not performed in some embodiments and comparative examples.

The conductive reducing agents and process conditions used in the respective Examples and Comparative Examples are summarized in Table 2 below.

Test Example

Test (1) Evaluation of the reactivity of the conductive reducing agent

The reactivity of the conductive reducers A1 to A6 and B1 to B12 used in the above Examples and Comparative Examples was evaluated.

Specifically, the Examples and Comparative Examples phase and the surface of the electrode substrate to react with the reduced conductivity claim (2) resistance meter as measured by (Trustat worksurface tester ST-3, SIMCO, Inc.), a surface resistance of 10 ¹³ Ω / sq or more, it is classified into the following categories:

○: less than 20 minutes △: less than 20 minutes and less than 30 minutes X: more than 30 minutes

Test (2) Evaluation of the stability of the conductive reducing agent

Each of the conductive reducing agents used in the step (1) of the Examples and Comparative Examples was allowed to stand at room temperature for 5 days, and the stability was evaluated according to the degree of agglomeration.

That is, when the coagulation did not occur, the evaluation was evaluated as good, and when the coagulation occurred, the evaluation was made as poor.

Test (3) Non-visibility evaluation of pattern

The non-visibility of the pattern formed on the electrode substrate finally manufactured in the above Examples and Comparative Examples was evaluated by the change ( ? ) Of color coordinates.

That is, L *, a * and b * values were measured in a transmission mode and a reflection mode at a wavelength of 550 nm for a non-conductive pattern exposed to a conductive reducing agent and for an unexposed conductive pattern using a UV spectrometer (CM-3500d, measured using a Minolta Co.), Δ E * value ^{(Δ E * 2 = Δ L} * 2 + Δ a * 2 + Δ b *) to obtain classified into the following categories: to evaluate the non-visibility of the pattern:

a. Transmission mode

? E *? 0.5: Good (no pattern is seen)

0.5 < Δ E * ≤ 1: Normal (the pattern is visible to some extent)

1 < Δ E *: bad (pattern looks very good)

b. Reflection mode

Δ E * ≤ 2: Good (pattern not visible)

2 < Δ E * ≤ 3: Normal (pattern is visible to some extent)

3 < Δ E *: Bad (pattern is visible)

The results of the evaluation of the reactivity and stability of the conductive reducer thus tested and the non-visibility of the pattern are summarized in Table 2 below.

division Process conditions Conductive reducer evaluation Pattern non-visibility conductivity
Abatement agent Redonding
fair Reactivity stability Permeation
mode reflect
mode Example 1 A1 practice ○ Good Good Good Example 2 A2 practice ○ Good Good Good Example 3 A3 practice ○ Good Good Good Example 4 A4 practice ○ Good Good Good Example 5 A5 practice ○ Good Good Good Example 6 A6 practice ○ Good Good Good Example 7 A1 Absenteeism ○ Good Good usually Example 8 A2 Absenteeism ○ Good Good Good Example 9 A3 Absenteeism ○ Good usually Good Example 10 A4 Absenteeism ○ Good Good Good Example 11 A5 Absenteeism ○ Good usually Good Example 12 A6 Absenteeism ○ Good Good Good Comparative Example 1 B1 practice ○ Good usually Good Comparative Example 2 B2 practice ○ Good usually Good Comparative Example 3 B3 practice ○ Good usually Good Comparative Example 4 B4 practice ○ Good usually Good Comparative Example 5 B5 practice △ Good usually Good Comparative Example 6 B6 practice △ Good usually Good Comparative Example 7 B7 practice ○ Bad usually usually Comparative Example 8 B8 practice ○ Good usually usually Comparative Example 9 B9 practice ○ Bad usually usually Comparative Example 10 B10 practice ○ Good usually usually Comparative Example 11 B11 practice △ Bad usually usually Comparative Example 12 B12 practice △ Good usually usually Comparative Example 13 B1 Absenteeism ○ Good Bad Bad Comparative Example 14 B2 Absenteeism ○ Good Bad Bad Comparative Example 15 B3 Absenteeism ○ Good Bad Bad Comparative Example 16 B4 Absenteeism ○ Good Bad Bad Comparative Example 17 B5 Absenteeism △ Good Bad Bad Comparative Example 18 B6 Absenteeism △ Good Bad Bad Comparative Example 19 B7 Absenteeism ○ Bad Bad Bad Comparative Example 20 B8 Absenteeism ○ Good Bad Bad Comparative Example 21 B9 Absenteeism ○ Bad Bad Bad Comparative Example 22 B10 Absenteeism ○ Good Bad Bad Comparative Example 23 B11 Absenteeism △ Bad Bad Bad Comparative Example 24 B12 Absenteeism △ Good Bad Bad

As shown in Table 1, when the conductive reducing agents (conductive reducing agents A1 to A6) according to the present invention are used as in Examples 1 to 12, the conductivity and the stability of the conductive reducing agent are excellent and the non- I was able to see that it was excellent. In particular, when the re-doping process was performed after the peeling process as in Examples 6 to 12, pattern non-visibility was excellent.

On the other hand, when the conductive reducing agents (conductive reducing agents B1 to B6) without addition of the metal catalyst were used as in Comparative Examples 1 to 6, non-visibility in the transmission mode was lowered. As described above, when non-visibility is deteriorated in the transmissive mode, a problem of visible pattern may occur when the light emitted from the backlight unit of the display panel passes through the conductive film.

In addition, when the conductive reducing agent (conductive reducing agent B7 to B12) containing no acid compound as in Comparative Examples 7 to 12 was used, the non-visibility was poor in the transmission and reflection modes. Particularly, it is found out that the stability of the conductive reducing agent is lowered when the conductive reducing agents (conductive reducing agents 7, 9 and 11) containing the metal-based catalyst and containing no acid compound as in Comparative Examples 7, 9 and 11 are used there was.

In addition, when the re-doping process is not performed as in Comparative Examples 13 to 18, the non-visibility of the pattern becomes very poor.

100: substrate 200: conductive polymer film
210: conductive pattern 211: reduced doped conductive pattern
220: nonconductive pattern 300: mask pattern

Claims (26)

A conductive reducing agent for a conductive polymer film comprising 0.5 to 10% by weight of a sodium chloride compound, 0.1 to 2% by weight of an acid compound and 0.1 to 2% by weight of a metal catalyst in a solvent, wherein the solvent comprises an aqueous solvent.
The method according to claim 1,
Wherein the sodium chloride compound is selected from the group consisting of sodium hypochlorite (NaOCl), sodium dicarboxylate sodium (C ₃ Cl ₂ N ₃ NaO ₃ ), sodium chlorite (NaClO ₂ ), and mixtures thereof. Conductive reducer.
The method according to claim 1,
Wherein the sodium chloride-based compound is contained in an amount of 3 to 7% by weight based on the weight of the conductive reducing agent.
delete The method according to claim 1,
The acid compound is hydrochloric acid (HCl), acetic acid (CH ₃ COOH) or conductivity for reducing a mixture thereof, a conductive polymer film.
The method according to claim 1,
Wherein the acid compound is contained in an amount of 0.5 to 2% by weight based on the weight of the conductive reducing agent.
The method according to claim 1,
Wherein the metal-based catalyst is a metal phthalocyanine-based catalyst.
The method according to claim 1,
Wherein the metal catalyst is contained in an amount of 0.5 to 2% by weight based on the weight of the conductive reducing agent.
The method according to claim 1,
Wherein the conductive polymer film is a conductive polymer film formed on a substrate.
The method according to claim 1,
Wherein the conductive polymer film is a polythiophene-based, polyaniline-based, or polypyrrole-based conductive polymer film.
11. The method of claim 10,
Wherein the conductive polymer film is a polythiophene-based polymer film.
12. The method of claim 11,
Wherein the conductive polymer film is a polymer film doped with polyethylene dioxythiophene (PEDOT) and polystyrene sulfonate.
The method according to claim 1,
Wherein the conductive polymer film is used for an electrode film, an electromagnetic wave shielding layer, or a conductive film for a touch panel.
A conductive reducing agent for a conductive polymer film according to any one of claims 1 to 3 and 5 to 13 is used to reduce the conductivity of a part of the conductive polymer film to form a pattern on the conductive polymer film How to.
15. The method of claim 14,
Wherein the conductive polymer film is formed by applying a conductive polymer solution to a substrate and then drying the conductive polymer film.
15. The method of claim 14,
Wherein the conductive polymer film has a thickness of 1 占 퐉 to 5 占 퐉.
15. The method of claim 14,
Wherein the method further comprises the step of re-doping the pattern using a re-doping solution after forming a pattern in the conductive polymer film.
15. The method of claim 14,
The method comprises:
(a) forming a mask pattern on a conductive polymer film; And
(b) reducing the conductivity by reacting the conductive reducing agent with a portion of the conductive polymer film exposed from the mask pattern; And
(c) removing the mask pattern from the conductive polymer film using a peeling liquid.
19. The method of claim 18,
A method for forming a pattern on a conductive polymer film, wherein the mask pattern is formed in a resist mask pattern using a screen printing method in step (a).
20. The method of claim 19,
Wherein the resist mask pattern has a thickness of 10 占 퐉 to 20 占 퐉.
19. The method of claim 18,
In the step (b), the reaction between the conductive polymer film and the conductive reducing agent is performed for 0.1 to 10 minutes, thereby forming a pattern on the conductive polymer film.
19. The method of claim 18,
Wherein in step (c), the stripping liquid contains an alkaline compound and an aqueous solvent.
23. The method of claim 22,
Wherein the peeling liquid contains the alkali compound in an amount of 0.5 to 10% by weight.
19. The method of claim 18,
In the step (c), the mask pattern is reacted with the exfoliation liquid at 10 ° C to 60 ° C for 0.5 minutes to 10 minutes to remove the mask pattern, thereby forming a pattern on the conductive polymer film.
18. The method of claim 17,
Wherein the re-doping liquid comprises an acid compound and an aqueous solvent.
26. The method of claim 25,
Wherein the acid compound is contained in an amount of 0.5 to 5 wt% based on the weight of the re-doping solution.

Images