KR102287289B1 - TRANSPARENT ElECTROD COMPLEX - Google Patents

Abstract

The present invention is a 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 the polysiloxane-based polymer layer.

Description

Transparent electrode composite {TRANSPARENT ElECTROD COMPLEX}

The present invention relates to a transparent electrode composite.

Transparent electrode film is defined as a thin film that is transparent to visible light and has electrical conductivity, and is used in various fields such as plasma display panel, liquid crystal display device, light emitting diode device, organic light emitting device, touch panel, solar cell, etc. .

In the manufacture of such a transparent electrode film, a method of manufacturing an electrode having a crystal pattern formed by placing a dry film solder resist on a substrate such as a PET film and proceeding in the order of exposure, development and etching was widely used. However, in the case of using a dry film solder resist, there was a limitation in that it was difficult to implement a line width of 40 μm or less. Accordingly, in order to solve the limitation in line width implementation, a photoresist was applied on a conductive substrate, exposed and developed to form a transparent electrode film. The manufacturing method was also used.

The transparent electrode film produced in this way forms a predetermined protective layer between the conductive substrate and the photoresist layer, and the previously known protective layer has a high bonding strength with respect to the conductive substrate and the photoresist layer, but has a low resistance value. It should also have a low level of interfacial resistance between neighboring layers.

An object of the present invention is to provide a transparent electrode composite that has low sheet resistance and interfacial resistance while having high bonding strength between each layer, and can have a high degree of integration or form an ultra-fine pattern through a simplified step.

In the present specification, at least one selected from the group consisting of conductive polymers, carbon nanotubes, graphene, silver nanowires (AgNw), copper nanoparticles, indium tin oxide, and antimony tin oxide a transparent electrode layer comprising a 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; including, 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 more detail.

The present inventors have tested that the polysiloxane-based polymer layer formed on the transparent electrode layer through the sol-gel reaction has high hydrophobicity without a separate post-treatment process and can secure high coating properties and adhesion to the photosensitive resin layer. Confirmed through and completed the invention.

Specifically, a polysiloxane-based polymer layer having a hydrophobic surface can be formed by coating a sol-gel reaction solution containing a siloxane-based monomer on the transparent electrode and reacting or drying at a temperature of 50°C or higher, or 100°C or higher, The polysiloxane-based polymer layer may have high coating properties 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 water contact angle of 60° or more, or 65° to 90°.

The polysiloxane-based polymer layer is one selected from the group consisting of an alkyloxy silane-based monomer, an amino silane-based monomer, a vinyl silane-based monomer, an epoxy silane-based monomer, a methacryloxy silane-based monomer, an isocyanate silane-based monomer, and a fluorosilane-based monomer. of a polymer or two or more copolymers.

Specifically, the polysiloxane-based polymer layer is tetraethyloxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidepropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide-modified silane monomer, polymethyl It may include one type of polymer or two or more types of copolymers selected from the group consisting of ethoxysiloxane and hexamethyldisirazine.

In order to secure a low sheet resistance while the polysiloxane-based polymer layer has a higher bonding strength or adhesion to other adjacent layers, the polysiloxane-based polymer layer may contain 60 to 90% by weight of tetraethyloxysilane; and vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethyl Toxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane , γ-ureidepropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide-modified silane monomer, polymethylethoxysiloxane and hexamethyldisirazine selected from the group consisting of 10 to 40% by weight of one or more compounds; It may contain a copolymer of liver.

If the content of tetraethyloxysilane among the monomers used for synthesizing 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 be greatly increased. In addition, if the content of tetraethyloxysilane among the monomers used for synthesizing the copolymer included in the polysiloxane-based polymer layer exceeds 90% by weight, the density of the polysiloxane-based polymer layer is excessively increased or the surface is cracked. and moisture resistance may be greatly reduced.

As the transparent electrode composite includes the above-described polysiloxane-based polymer layer, high coatability and adhesion can be maintained without additional hydrophobicity imparted and fixed before the photosensitive resin layer is formed, and thus the photosensitive resin layer is further refined pattern can be formed.

The polysiloxane-based polymer layer may have a thickness of 0.050 μm to 0.300 μm, or 0.120 μm to 0.200 μm. 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.

On the other hand, the transparent electrode layer may include a variety of materials known to be used in the transparent electrode, specifically, conductive polymer, carbon nanotubes, graphene, silver nanowires (AgNw), copper nanoparticles, indium tin oxide (Indium) It may include one or more compounds selected from the group consisting of tin oxide) and antimony tin oxide.

As the conductive polymer, a polymer known to be used in a transparent electrode may be used, and specifically, the conductive polymer is at least one selected from the group consisting of polyaniline-based polymers, polypyrrole-based polymers, polythiophene-based polymers, and derivatives thereof. It may include, specifically, PEDOT: PSS [Poly (3,4-ethylenedioxythiophene): Polystyrene sulfonate] may be used.

The transparent electrode layer may have a thickness of 0.20 μm to 3.00 μm, or 0.30 μm to 1.0 μm. When the thickness of the transparent electrode layer is too thin, the effective sheet resistance is also greatly reduced, so that the sheet resistance may be non-uniform, and if the thickness of the transparent electrode layer is too thick, transparency or optical properties may be deteriorated.

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, depending on the intrinsic properties of the polysiloxane-based polymer layer, the photosensitive resin layer may be uniformly and firmly bonded to the polysiloxane-based polymer layer, and thus a finer pattern is formed on the photosensitive resin layer. can be formed

A commonly known photosensitive resin composition or photoresist composition may be used to form the photosensitive resin layer, and specifically, the photosensitive resin layer may include a positive photoresist composition including an alkali-soluble resin; or a negative photoresist composition comprising a monomer or multimer comprising at least one reactive functional group and a photoinitiator, preferably from a positive photoresist composition.

The photosensitive resin layer may have a thickness of 1 μm to 5 μm, or 2 μm to 4 μm. If the thickness of the photosensitive resin layer is too thin, stains or appearance damage may occur in the photosensitive resin layer and/or the polysilonic acid-based polymer layer during exposure, development, and etching, resulting in cloudiness. When the thickness of the photosensitive resin layer is too thick, exposure may not be easy, so that development may not occur sufficiently or a line width mismatch may occur.

Meanwhile, the electrode film may further include a release film layer formed on the photosensitive resin layer. As the release film layer, a polymer film known to be commonly used in a transparent electrode film may be used, and specifically, a silicone adhesive film, an acrylic adhesive film, and a PE protective film may be used.

Meanwhile, 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 are sequentially formed to form the transparent electrode composite. In addition, after sequentially forming the polysiloxane-based polymer layer and the photosensitive resin layer 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 commonly known coating method or coating method may be used, and a commonly known compression method may be used. As the coating method, a conventional coating method used in the art such as a spray method, a bar coating method, a doctor blade method, a roll coating method, a dipping method, etc. may be applied.

According to the present invention, a transparent electrode composite that has a high bonding force between each layer and low sheet resistance and interfacial resistance, has a high degree of integration or can form an ultra-fine pattern 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 includes the polysiloxane-based polymer layer serving as a buffer for the transparent electrode and the photosensitive resin layer to exhibit its unique properties. . In particular, high coatability and adhesion may be maintained without additional hydrophobicity imparted and fixed prior to coating of the photosensitive resin layer, and thus a finer pattern may be formed on the photosensitive resin layer.

1 shows the contact angle of the polysiloxane-based polymer layer obtained in Examples 1 and 2 and Comparative Example 1 with respect to water.
Figure 2 shows the appearance of the pattern of Example 1 and Comparative Example 1 observed in Experimental Example 2.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

[ Preparation Example 1 : of the electrode layer manufacturing]

PEDOT:PSS [Poly(3,4-ethylenedioxythiophene) Polystyrene sulfonate, solid content 1 wt%], IPA (isopropylene alcohol), MeOH (methanol) and DMSO (dimethylsulfoxide) in a weight ratio of 75:15:5:5 After mixing, 500 ppmw of Dynol 607, a surface control agent, was added to the mixture and stirred.

After the stirring was completed, the mixture was coated on a PET substrate using a bar coater, and then hot air drying (110° C./60 seconds) was performed to prepare an electrode layer having a thickness of 0.096 μm. The final prepared electrode layer had a sheet resistance of 240 Ω/sq.

[ Preparation Example 2 : of the electrode layer manufacturing]

PEDOT:PSS [Poly(3,4-ethylenedioxythiophene) Polystyrene sulfonate, solids 0.35 wt%], silver nanowire dispersion (1 wt%, water), IPA (isopropylene alcohol), DI water and EG (ethylene glycol) 28.5: It was mixed in a weight ratio of 10:10:41.5:10, and 500ppmw of 3M FC-4330 as a surface control agent was added to the mixture and stirred.

After the stirring was completed, the mixture was coated on a PET substrate using a bar coater, and then hot air drying (110° C./60 seconds) was performed to prepare an electrode layer having a thickness of 0.055 μm. The final prepared electrode layer had a sheet resistance of 60 Ω/sq.

[ Example and comparative example : Preparation of electrode film]

Example One

(1) Formation of polysiloxane-based polymer layer

16.08 g of TEOS (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 are mixed and reacted at 70° C. for 3 hours to form a sol-gel 100 g (solid content: 7.8 wt%) of the reaction solution was prepared, and the prepared sol-gel reaction solution and isopropylene alcohol were diluted in a weight ratio of 1:4 to prepare 500 g (solid content: 1.56 wt%) of the sol-gel reaction solution .

The sol-gel reaction solution (solid content: 1.56 wt%) was coated on the electrode layer obtained in Preparation Example 1 to a thickness of 11.43 μm using a bar coater, and then dried at 120° C. under hot air conditions for 10 minutes to obtain a thickness of 0.178 μm. A thick polysiloxane-based polymer layer (sheet resistance: 260Ω/sq) was formed.

(2) Formation of photosensitive resin layer

Dongjin Semichem Photoresist (Positive Type) SJ-631 (10cP, solid content 23wt%) was applied on the formed polysiloxane-based polymer layer using a bar coating, and dried at 120°C for 1 minute to have a thickness of about 2.62㎛ photosensitive water. A layer was prepared.

Example 2

(1) Formation of polysiloxane-based polymer layer

16.08 g of TEOS (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 at 70° C. for 3 hours to form a sol-gel 100 g (solid content: 7.2 wt%) of the reaction solution was prepared, and the prepared sol-gel reaction solution and isopropylene alcohol were diluted in a weight ratio of 1:4 to prepare 500 g (solid content: 1.44 wt%) of the sol-gel reaction solution .

The sol-gel reaction solution (solids content of 1.44 wt%) was coated on the electrode layer obtained in Preparation Example 1 to a thickness of 11.43 μm using a bar coater, and then dried at 120° C. under hot air conditions for 10 minutes to obtain a thickness of 0.165 μm. A thick polysiloxane-based polymer layer (sheet resistance: 265Ω/sq) was formed.

(2) Formation of photosensitive resin layer

Dongjin Semichem Photoresist (Positive Type) SJ-631 (10cP, solid content 23wt%) was applied on the formed polysiloxane-based polymer layer using a bar coating, and dried at 120°C for 1 minute to have a thickness of about 2.62㎛ photosensitive water. A layer was prepared.

Example 3

(1) Formation of polysiloxane-based polymer layer

The polysiloxane-based sol-gel reaction solution (solids content 1.44 wt%) prepared in Example 2 was coated on the electrode layer obtained in Preparation Example 2 to a thickness of 11.43 μm using a bar coater, and then 10 at 120° C. under hot air conditions. After drying for minutes, a polysiloxane-based polymer layer (sheet resistance: 80 Ω/sq) having a thickness of 0.165 μm was formed.

(2) Formation of photosensitive resin layer

Dongjin Semichem Photoresist (Positive Type) SJ-631 (10cP, solid content 23wt%) was applied on the formed polysiloxane-based polymer layer using a bar coating, and dried at 120°C for 1 minute to have a thickness of about 2.62㎛ photosensitive water. A layer was prepared.

Example 4 to 6

On the composite of the electrode layer-polysiloxane-based polymer layer-photosensitive resin layer formed in Examples 1, 2 and 3, respectively, a PET fabric film (25 μm thick) coated with an adhesive was applied at room temperature to a pressure of 0.45 Mp to form the photosensitive resin layer. laminated to the outside

Comparative Example 1

(1) Formation of polysiloxane-based polymer layer

20.01 g of TEOS (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 prepare 100 g (solid content of 7 wt%) of a sol-gel reaction solution. and diluting the prepared sol-gel reaction solution and isopropylene alcohol in a weight ratio of 1:4 to prepare 500 g (solid content: 1.4 wt%) of the sol-gel reaction solution.

The sol-gel reaction solution (solid content: 1.4 wt%) was coated on the electrode layer obtained in Preparation Example to a thickness of 11.43 μm using a bar coater, and then dried at 120° C. under hot air conditions for 10 minutes to a thickness of 0.160 μm. of a polysiloxane-based polymer layer (sheet resistance: 256Ω/sq) was formed.

(2) Formation of photosensitive resin layer

Dongjin Semichem Photoresist (Positive Type) SJ-631 (10cP, solid content 23wt%) was applied on the formed polysiloxane-based polymer layer using a bar coating, and dried at 120°C for 1 minute to have a thickness of about 2.62㎛ photosensitive water. A layer was prepared.

[ Experimental example : Evaluation of the physical properties of the electrode film]

Experimental Example 1 : contact angle measurement

The contact angle of the polysiloxane-based polymer layer obtained in Examples 1 to 3 and Comparative Example 1 with respect to water was measured by using an image digital contact angle analyzer (Phoenix-10 by SEO Corporation) to measure the static contact angle method.

Experimental Example 2 : coatability and adherence evaluation

50 mJ of ultraviolet light was 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, the strip (removal) process was performed at room temperature for 50 seconds using a strip solution ST-09 (Dongjin Semichem).

At this time, the coating properties and adhesion properties are evaluated based on whether the line width of the pattern is removed during the pattern formation process, and expressed as O when the pattern is maintained and X when the pattern is removed, described in Table 1 below, and the appearance of the actually formed pattern is It is described in Figure 2 below.

electrode layer 80Ω/sq (0.055㎛) 240Ω/sq (0.096㎛) Polysiloxane-based polymer layer Example 3 Example 1 Example 2 Comparative Example 1 80Ω/sq (0.165㎛) 260Ω/sq
(0.178㎛) 265Ω/sq
(0.165㎛) 256Ω/sq
(0.160㎛) Contact angle of polysiloxane-based polymer layer 65.8 67.8 65.8 49 photosensitive resin layer 2.65㎛ Coating and adhesion of photosensitive resin layer ○ ○ ○ ×

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 the polysiloxane-based polymer layer having a contact angle of 60 degrees or more, and thus improved coating properties and adhesion castle can be obtained. On the other hand, 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 was not well attached or a part of the shape was not maintained.

Claims (10)

a transparent electrode layer comprising a conductive polymer;
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
Including; a photosensitive resin layer formed on the polysiloxane-based polymer layer;
The polysiloxane-based polymer layer is tetraethyloxysilane 60 to 90% by weight; and vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethyl Toxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane , γ-ureidepropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide-modified silane monomer, polymethylethoxysiloxane and hexamethyldish 10 to 40% by weight of at least one compound selected from the group consisting of razine; comprising a copolymer of the liver,
The polysiloxane-based polymer layer has a thickness of 0.050 μm to 0.300 μm and a sheet resistance of 80 Ω/sq to 400 Ω/sq, a transparent electrode composite.
delete According to claim 1,
A contact angle of the polysiloxane-based polymer layer with respect to water is 65° to 90°, a transparent electrode composite.
delete According to claim 1,
The transparent electrode layer has a thickness of 0.20 μm to 3.00 μm and a sheet resistance of 80 Ω/sq to 400 Ω/sq, a transparent electrode composite.
According to 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, a transparent electrode composite.
According to claim 1,
The photosensitive resin layer has a thickness of 1 μm to 5 μm, a transparent electrode composite.
According to claim 1,
The photosensitive resin layer may include a positive photoresist composition including an alkali-soluble resin; or a negative photoresist composition comprising a monomer or multimer comprising at least one reactive functional group and a photoinitiator;
According to claim 1,
The transparent electrode composite further comprising a release film layer formed on the photosensitive resin layer.
According to claim 1,
The transparent electrode composite, further comprising a base film layer formed on one surface of the transparent electrode layer to face the polysiloxane-based polymer layer.

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