WO2016006840A1

WO2016006840A1 - Transparent electrode assembly

Info

Publication number: WO2016006840A1
Application number: PCT/KR2015/006308
Authority: WO
Inventors: 이정열; 배민영; 이승준; 변자훈; 안민석; 차영철; 홍우성; 박성연; 정재훈; 김동민
Original assignee: 주식회사 동진쎄미켐
Priority date: 2014-07-08
Filing date: 2015-06-22
Publication date: 2016-01-14
Also published as: CN106489182A; KR20160005960A; KR102287289B1; TWI679165B; CN106489182B; TW201609523A

Abstract

The present invention relates to a transparent electrode assembly comprising: a transparent electrode layer; a polysiloxane-based polymer layer formed on the transparent electrode layer and having a contact angle of 60° or greater with respect to water; and a photosensitive resin layer formed on the polysiloxane-based polymer layer.

Description

【Specification】

[Name of invention]

Transparent electrode composite

[Cross Citation with Related Application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2014-0085142 of 2014-07-08, and all contents disclosed in the literature of that Korean patent application are incorporated as part of this specification.

Technical Field

The present invention relates to a transparent electrode composite.

[Technique to become background of invention]

The transparent electrode film is defined as a thin film which is transparent to visible light and is electrically conductive, and is used in various fields such as a plasma display panel, a liquid crystal display device, a light emitting diode device, an organic light emitting device, a touch panel, and a solar cell. .

In the production of such a transparent electrode film, a method of manufacturing an electrode having a crystal pattern formed by covering a dry film solder resist on a substrate such as a PET film, and proceeding in the order of exposure, development, and etching is widely used. However, in the case of using dry film solder resist, there was a limit that it is difficult to realize a line width of less than 40um. Accordingly, in order to remove the limitation on the implementation of the line width, a photoresist is applied on the conductive substrate, and the transparent electrode film is exposed and developed. The method of preparation was also used.

The transparent electrode film manufactured as described above forms a predetermined protective layer between the conductive substrate and the photoresist layer, and has a low resistance value while having a high bonding strength that the previously known protective layer has on the conductive substrate and the porter resist layer. It should also have low interfacial resistance between neighboring layers.

[Content of invention]

Problem to be solved

The present invention has a high bonding force between the layers, but also has a low sheet resistance and interfacial resistance, and has a high degree of integration through a simplified step, or It is to provide a transparent electrode composite that can form an ultra-fine pattern. [Measures of problem]

In the present specification, one kind selected from the group consisting of a conductive polymer, carbon nanotubes, graphene, silver nanowires (AgNw), copper nanoparticles, indium tin oxide, and antimony tin oxide Transparent electrode layer containing the above compound; A polysiloxane-based polymer layer formed on the transparent electrode layer and having a contact angle with respect to water of 60 ^° or more; And a photosensitive resin layer formed on the polysiloxane-based polymer layer. A transparent electrode composite may be provided. Hereinafter, a transparent electrode composite according to a specific embodiment of the present invention will be described in detail. The present inventors experimented through the sol-gel reaction that the polysiloxane-based polymer layer formed on the transparent electrode layer has high hydrophobicity and can secure high coating property and adhesion even to the photosensitive resin layer without a separate post-treatment process. Confirmed through and completed the invention.

Specifically, by applying a sol-gel reaction solution containing a siloxane monomer on the transparent electrode and reacting or drying at a temperature of 50 ^° C or more, or 1 CX C or more, it is possible to form a polysiloxane polymer with a hydrophobic surface, Such a polysiloxane-based polymer layer may have a high coating property and adhesion to the photosensitive polymer resin composition. Accordingly, a finer pattern can be easily formed in the process of exposing and developing the photosensitive resin layer formed from the photosensitive polymer resin composition.

Specifically, the polysiloxane-based polymer layer may have a contact angle with respect to water of 60 ^° or more, or 65 ^° to 90 ^° .

In addition, as described above, the polysiloxane-based polymer layer is coated with a sol-gel reaction solution containing a siloxane monomer on the transparent electrode and 50 ^° C or more, or ioo ° c or more, 5 (rc to 2 (xrc The polysiloxane-based polymer layer may be formed by reacting or drying at a temperature of the alkyloxy silane monomer, the amino silane monomer, the vinyl silane monomer, the epoxy silane monomer, the methacryloxy silane monomer, the isocyanate silane monomer, and the like. Consisting of fluorine silane monomer It may comprise one polymer or two or more copolymers selected from the group.

Specifically, the polysiloxane-based polymer layer may be tetraethyloxysilane, vinyltrieoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, methacryloxypropyltrimethoxysilane, β− (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, Υ-aminopropyltriethoxysilane, Ν-β-(aminoethyl)- _γ -aminopropyltrimethoxysilane, _γ -euraidpropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide modified silane monomer, polymethylethoxysiloxane and nucleus yarn It may include one polymer or two or more copolymers selected from the group consisting of methyldisirazine.

In order to secure a low sheet resistance while the polysiloxane-based polymer layer has a higher bonding strength or adhesion to other neighboring layers, the polysiloxane-based polymer layer is 60 to 90 weight of tetraethyloxysilane and vinyl trieoxysilane, vinyl Trimethoxysilane, Vinyltris (β-Methoxyethoxy) silane, _Υ -methacryloxypropyltrimethicsilane, β- (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane, VII-glycidoxy Propyl trimethoxysilane, mercaptopropyl trimethoxysilane, aminopropyl triethoxysilane, Ν-β-

(Aminoethyl) Aminopropyltrimethoxysilane, Euraid Propylene Trisilane, Phenyltriethoxysilane, Methyltriethoxysilane, Methyltrimethoxysilane Polyethyleneoxide Modified Silane Monomer, Polymethylethoxysiloxane and Nuclear Yarn 10 to 1 or more compounds selected from the group consisting of methyldisirazine

40 weight%; And hepatic copolymers.

If the content of the tetraethyloxysilane in the monomer used in the synthesis of the copolymer included in the polysiloxane-based polymer layer is less than 60% by weight, the sheet resistance of the polysiloxane-based polymer layer may increase significantly. In addition, the content of tetraethyloxysilane in the monomer used in the synthesis of the copolymer contained in the polysiloxane-based polymer layer

If it exceeds 90% by weight, the density of the polysiloxane-based polymer layer may be excessively high or surface cracking may occur, and moisture resistance may be greatly reduced.

Wherein the transparent electrode composite includes the above-mentioned polysiloxane-based polymer layer Therefore, high coating property and adhesion can be maintained without additional hydrophobic fixation before forming the photosensitive resin layer, and thus a finer pattern can be formed on the photosensitive resin layer.

The polysiloxane-based polymer layer may have a thickness of 0.050 to 0.300 zm, or 0.1 to 0.200. In addition, the polysiloxane-based polymer layer may have a sheet resistance of 80 Ω / sq to 400 Ω / sq, or 150 Ω / sq to 280 Ω / sq.

Meanwhile, the transparent electrode layer may include various materials known to be used for the transparent electrode, specifically, a conductive polymer, carbon nanotubes, graphene, silver nanowires (AgNw), copper nanoparticles, and indium tin oxide (Indium) Tin Oxide) and antimony tin oxide may include one or more compounds selected from the group consisting of.

The conductive polymer may be a polymer known to be used for a transparent electrode. Specifically, the conductive polymer may be a polyaniline-based polymer, a polypyrrole-based polymer, a polythiophene-based polymer, and derivatives thereof. It may include, and may specifically use PED0T: PSS [Poly (3, 4- et hy 1 ened i oxy thi ophene): Polystyrene sul fonate].

The transparent electrode layer may have a thickness of 0.20 // m to 3.00, or 0.30 μs to 1.0. If the thickness of the transparent electrode layer is too thin, the effective sheet resistance may also be greatly reduced, and the sheet resistance may be uneven. If the thickness of the transparent electrode layer is too thick, transparency or optical characteristics may be degraded.

In addition, the transparent electrode layer may have a sheet resistance of 80 Ω / sq to 400 Ω / sq, or 150 Ω / sq to 280 Ω / sq.

As described above, according to the inherent characteristics of the polysiloxane-based polymer layer, the photosensitive resin layer may be uniformly and firmly bonded on the polysiloxane-based polymer layer, thereby providing a finer pattern on the photosensitive resin layer. Can be formed.

Formation of the photosensitive resin layer may be used a photosensitive resin composition or photoresist composition commonly known, specifically, the photosensitive resin layer is a positive photoresist composition containing an alkali-soluble resin; Or including monomers or multimers and photoinitiators comprising one or more semi-active functional groups Negative photoresist composition; and preferably from positive photoresist composition.

The photosensitive resin layer may have a thickness of 1 to zm, or 2 // m to 4 / zm. If the thickness of the photosensitive resin layer is too thin, staining or appearance damage may occur on the photosensitive resin layer and / or the polysilonic acid polymer layer during exposure, development, and etching, thereby causing a cloudy appearance. If the thickness of the photosensitive resin layer is too thick, exposure may not be easy and development may not occur sufficiently or mismatch of line width may occur.

On the other hand, the electrode film may further include a release film layer formed on the photosensitive resin layer. The release film layer may be a polymer film or the like, which is commonly used in the transparent electrode film, and specifically, a silicone adhesive film, an acrylic adhesive film, a PE protective film, or the like may be used.

On the other hand, the electrode film may further include a base film layer formed on one surface of the transparent electrode layer to face the polysiloxane-based polymer layer.

That is, after the transparent electrode layer is formed on the base film layer, the transparent electrode layer, the polysiloxane-based polymer layer, and the photosensitive resin layer may be sequentially formed to form the transparent electrode composite. In addition, after the polysiloxane-based polymer layer and the photosensitive resin layer are sequentially formed on the transparent electrode layer, the base film layer may be formed on the other surface of the transparent electrode layer to form the transparent electrode composite.

In the manufacturing process of the transparent electrode composite, a conventionally known coating method or coating method may be used, and also commonly known pressing methods may be used. As the coating method, a conventional coating method used in the art, such as spray method, bar coating method, doctor blade method, coating method, dipping method may be applied. 【Effects of the Invention】

According to the present invention, a transparent electrode composite having high bonding force and low sheet resistance and interfacial resistance between each layer, and having a high integration degree or a micronized pattern can be formed through a simplified step can be provided. .

The transparent electrode composite provides a transparent electrode structure including a photosensitive resin layer which is a photoactive layer, and serves as a buffer of the transparent electrode and the photosensitive resin layer. Including a polysiloxane-based polymer layer can be exhibited its unique properties. In particular, high coating properties and adhesion can be maintained without additional hydrophobic fixation prior to coating of the photosensitive resin layer, thereby forming a finer pattern on the photosensitive resin layer.

[Brief Description of Drawings]

1 illustrates contact angles of water of the polysiloxane-based polymer layers obtained in Examples 1 and 2 and Comparative Example 1. FIG.

Figure 2 shows the appearance of the pattern of Example 1 and Comparative Example 1 observed in Experimental Example 2.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. Production Example 1: Preparation of Electrode Layer

PED0T ： PSS [Po 1 y (3, 4-et hy 1 ened i oxy thi ophene) Polystyrene sul fonate, solids wt%], IPA (isopropylene alcohol), MeOH (methane) and DMS0 (dimethylsulfoxide) Was mixed at a weight ratio of 75: 15: 5: 5, and 500 parts of Dynol 607, a surface regulator, was added to the mixture and stirred.

After the stirring was completed, the mixture was coated on a PET substrate using a bar coater, followed by hot air drying (110 ^° C./60 seconds) to prepare an electrode layer having a thickness of 0.096. The sheet resistance of the finally prepared electrode layer was 240Q / sq.

Production Example 2: Preparation of Electrode Layer

PED0T ： PSS [Po 1 (3, 4-et hy 1 ened i oxy thi ophene) Polystyrene sul fonate, solid content 0.35wt%], silver nanowire dispersion (lwt%, water), IPA (isopropylene alcohol) ， DI water And EG (ethylene glycol) was mixed in a weight ratio of 28.5: 10: 10: 41.5: 10, and the surface control agent 3M FC-4330 was added to 500ppmw compared to the mixture and stirred.

After the stirring is completed, the mixture using a bar coater on the PET substrate After coating, hot air drying (1 C / 60 seconds) was performed to prepare an electrode layer having a thickness of 0.055. The sheet resistance of the finally prepared electrode layer was 60Q / sq.

[Examples and Comparative Examples: Preparation of the electrode film]

Example 1

(1) Formation of Polysiloxane-based Polymer Layer

16.08 g of TE0S (tetraethyloxysilane), 4.02 g of PTMS (phenyltrimethoxysilane), 23.55 g of water, 54.95 g of IPA (isopropylene alcohol) and 1.4 g of acetic acid were mixed and reacted for 3 hours at 70 ^° C. 100 g of the gel reaction solution (solid content 7.8wt) was prepared and 500 g of the sol-gel reaction solution (solid content 1.56 wt¾) was prepared by diluting the prepared sol-gel reaction solution and isopropylene alcohol at a weight ratio of 1: 4.

The sol-gel reaction solution (solid content 1.56 ^%) was coated on the electrode layer obtained in Preparation Example 1 with a thickness of 11.4 kPa using a bar coater, and then dried for 10 minutes at 20 ^° C. A polysiloxane polymer layer (surface resistance: 260 ^Q / sq) having a thickness of mi was formed.

(2) Formation of Photosensitive Resin Layer

Dongjin Semicam photoresist (Posi tive Type) SJ-631 (10cP, solid content 23 ^%) was applied to the polysiloxane-based polymer layer formed by using a bar coating, and dried at 120T for 1 minute to be about 2.62 thick The photosensitive resin layer was produced. Example 2

(1) Formation of Polysiloxane-based Polymer Layer

16.08 g of TE0S (tetraethyloxysilane), 4.02 g of VTMS (vinyltrimethoxysilane), 23.55 g of water, 54.95 g of IPA (isopropylene alcohol) and 1.4 g of acetic acid were mixed and reacted for 3 hours at 70 ^° C. 100 g of a gel reaction solution (solid content 7.2%) was prepared, and 500 g (solid content of 1.44%) of a sol-gel reaction solution was prepared by diluting the prepared sol-gel reaction solution with isopropylene alcohol at a weight ratio of 1: 4. .

The sol-gel reaction solution (solid content 1.44 ^%) was coated on the electrode layer obtained in Preparation Example 1 with a thickness of 11.43 using a bar coater, and then hot air. After drying at 20 ^° C. for 10 minutes under conditions, a polysiloxane-based polymer layer (surface resistance: 265Q / sq) having a thickness of 0.165 was formed.

(2) Formation of Photosensitive Resin Layer

Dongjin Semichem photoresist (Positive Type) SJ-631 (10cP, solid content 23 \ ^%) was applied to the polysiloxane-based polymer layer formed by using a bar coating, and dried at a temperature of 12 (C temperature for 1 minute to about 2.62 thick A photosensitive resin layer was prepared.

(1) Formation of Polysiloxane-based Polymer Layer

The polysiloxane sol-gel reaction solution (solid content 1.44 ^%) prepared in Example 2 was coated on the electrode layer obtained in Preparation Example 2 to a thickness of 11.43 kPa using a bar coater, and then subjected to hot air conditions at 20 ^° C. It dried for 10 minutes at and formed the polysiloxane-type polymer layer (surface resistance: 80Q / sq) of 0.165 thickness.

(2) Formation of Photosensitive Resin Layer

Dongjin Semichem photoresist (Positive Type) SJ-631 (10cP, solid content 23wt¾) was applied to the polysiloxane-based polymer layer formed by using a bar coating, dried at 120 ^° C for 1 minute to a thickness of about 2.62 / / Π1 The photosensitive resin layer was produced. Examples 4-6

The pressure-sensitive adhesive PET film (25 thickness) on the composite of the electrode layer-polysiloxane-based polymer layer-photosensitive resin layer formed in Examples 1, 2, and 3, respectively, was applied at a temperature of 0.45 Mp to the outside of the photosensitive resin layer. It was laminated to cotton. Comparative Example 1

(1) Formation of Polysiloxane-based Polymer Layer

20 g of TE0S (tetraethyloxysilane), 23.55 g of water, 54.95 g of IPA (isopropylene alcohol) and 1.4 g of acetic acid were mixed and reacted at 70 ^° C for 3 hours to give 100 g of the sol-gel reaction solution (solid content 7 ^%) To prepare the prepared sol-gel reaction solution Isopropylene alcohol was diluted to a weight ratio of 1: 4 to prepare 500 g of a sol-gel reaction solution (solid content 1.4 wt «).

The sol-gel reaction solution (solid content 1.4wt%) was coated on the electrode layer obtained in the preparation example using a bar coater at a thickness of 11.4 im, and then dried at a temperature of 20 ^° C. for 10 minutes under hot air conditions. A polysiloxane polymer layer (surface resistance: 256 Q / sq) having a thickness of 160 was formed.

(2) Formation of Photosensitive Resin Layer

Dongjin Semichem Photoresist (Posi tive Type) SJ-631 (10cP, solid content 23wt%) was applied to the polysiloxane-based polymer layer formed by using a bar coating, dried at 120 ^° C for 1 minute to about 2.62 / zm The photosensitive resin layer of thickness was produced.

Experimental Example: Evaluation of Physical Properties of Electrode Film

Experimental Example 1 Contact Angle Measurement

The contact angle with respect to the water of the polysiloxane-based polymer layer obtained in Examples 1 to 3 and Comparative Example 1 was measured using the image digital contact angle analyzer (phoenix-10, SE0). Experimental Example 2: Evaluation of Coating and Adhesion

50 mJ ultraviolet rays were applied to the photosensitive resin layers obtained in Examples 1 to 3 and Comparative Example 1 using an exposure apparatus (MA-6), and developed at room temperature for 35 seconds using a developer DPD-200 (Dongjin Semichem). Then, using strip liquid ST-09 Dongjin Semichem), the strip (removal) was performed for 50 seconds at room temperature.

At this time, the coating property and adhesion on the basis of whether or not the line width of the pattern is removed in the pattern formation process is represented by 0 when the pattern is maintained and X when removing the pattern shown in Table 1 below, It is described in Figure 2 below.

Table 11

As shown in Table 1, the electrode films of Examples 1 to 3 can be more easily and firmly combined with the photosensitive resin layer, including a polysiloxane-based polymer layer having a contact angle of 60 degrees or more, thereby improving coating properties and adhesion. The castle can be secured. On the contrary, it was confirmed that the bonding force between the polysiloxane-based polymer layer and the photosensitive resin layer of the electrode film of Comparative Example 1 was not sufficient, so that the formed pattern did not adhere well or part of the shape was not maintained.

Claims

[Patent Claims]

[Claim 1]

Contains at least one compound selected from the group consisting of conductive polymers, carbon nanotubes, graphene, silver nanowires (AgNW), copper nanoparticles, indium tin oxide and antimony tin oxide Transparent electrode layer;

A polysiloxane-based polymer layer formed on the transparent electrode layer and having a contact angle with respect to water of 60 ^° or more; And

A photosensitive resin layer formed on said polysiloxane-based polymer layer; Transparent electrode composite.

[Claim 2]

The method of claim 1,

The polysiloxane-based polymer layer is 60 to 90 weight of tetraethyloxysilane and vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β_methoxyethoxy) silane, methacryloxypropyltrimethicsilane, β- (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, Υ-aminopropyltrieoxysilane, Ν-β-(aminoethyl) _Υ -aminopropyltrimethoxysilane, γ-urethane propyltriethylsilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide modified silane monomer, polymethylethoxysiloxane and nucleus yarn 10 to 1 or more compounds selected from the group consisting of methyldisirazine

40 weight%; A transparent electrode composite, comprising a copolymer of the liver. [Claim 3]

The method of claim 1,

The contact angle with respect to the water of the polysiloxane-based polymer layer is 65 ^° to 90 ^° , transparent electrode composite. [Claim 4] The method of claim 1,

The polysiloxane-based polymer layer has a thickness of 0.050 to 0.300 卿 and a sheet resistance of 80 Ω / sq to 400 Ω / sq. [Claim 5]

The method of claim 1,

Wherein the transparent electrode layer has a thickness of 0.20 to 3.00 and a sheet resistance of 80 Ω / sq to 400 Ω / sq. [Claim 6]

The method of claim 1,

The conductive polymer comprises at least one selected from the group consisting of polyaniline-based polymers, polypyrrole-based polymers, polythiophene-based polymers and derivatives thereof, transparent electrode composite.

[Claim 7]

In U,

The photosensitive resin layer has a thickness of 1 / m to 5, transparent electrode composite. [Claim 8]

The method of claim 1, wherein.

The photosensitive resin layer is a positive photoresist composition containing an alkali-soluble resin; Or a negative photoresist composition comprising a monomer or multimer comprising at least one semi-active functional group and a photoinitiator;

[Claim 9]

According to claim 1,

The polysiloxane-based polymer layer is formed by applying a sol-gel reaction solution containing a siloxane monomer on the transparent electrode and dried at a temperature of 5 (C or more, Transparent electrode composite

[Claim 9]

The method of claim 1,

An electrode film, further comprising a release film layer formed on the photosensitive resin layer.

[Claim 10]

The method of claim 1,

The transparent electrode composite further comprises a base film layer formed on one surface of the transparent electrode layer to face the polysiloxane-based polymer layer.