TW201609523A - Transparent electrode complex - Google Patents

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 DEG or greater with respect to water; and a photosensitive resin layer formed on the polysiloxane-based polymer layer.

Description

Transparent electrode composite

The present invention relates to a transparent electrode composite.

The transparent electrode film is defined as a film that is transparent to visible light and has conductivity, and is used in various fields such as a plasma display panel, a liquid crystal display element, a light emitting diode element, an organic electronic light emitting element, a touch panel, and a solar cell.

The method for producing such a transparent electrode film is widely used by placing a dry film solder resist on a substrate such as a PET film, and manufacturing an electrode having a predetermined pattern in the order of exposure, development, and etching. However, when a dry film solder resist is used, it is difficult to achieve a line width of 40 μm or less. To eliminate this limitation, a photoresist is coated on a conductive substrate, and exposure and development are performed to manufacture a transparent electrode. Membrane method.

The transparent electrode film thus produced forms a predetermined protective layer between the conductive substrate and the photoresist layer, and it is known that the protective layer has a large bonding force to the conductive substrate and the photoresist layer, and has low resistance. Value, and the interface resistance between adjacent layers should also reach a lower level.

[Questions to be solved]

It is an object of the present invention to provide a transparent electrode composite which has high bonding force between layers and has low sheet resistance and interface resistance, and can also have high integration or ultrafine formation through a simplified step. Pattern.

[Technical means to solve the problem]

The invention can provide a transparent electrode composite comprising: a transparent electrode layer comprising a material selected from the group consisting of a conductive polymer, a carbon nanotube (CNT), a graphene, a nano silver wire (AgNw), and a nano copper particle. And one or more compounds of indium tin oxide (Indium Tin Oxide) and antimony tin oxide; a polyoxyalkylene polymer layer formed on the transparent electrode layer and having a contact angle with water of 60° And a photosensitive resin layer formed on the polyoxyalkylene polymer layer.

Hereinafter, the transparent electrode composite according to the specific embodiment will be described in further detail.

The inventors of the present invention have experimentally observed that a polyoxyalkylene polymer layer formed on a transparent electrode layer by a sol-gel reaction has high hydrophobicity even without other subsequent treatment, and can also be used for a photosensitive resin layer. The present invention has been completed by ensuring high coatability and adhesion.

Specifically, a sol-gel reaction solution containing a siloxane-based monomer is applied onto the transparent electrode layer, and the reaction or drying is carried out at a temperature of 50 ° C or more or 100 ° C or more to form a hydrophobic surface. The polyoxyalkylene polymer layer which has high coatability and adhesion to the photosensitive polymer resin composition. Therefore, in the process of exposing and developing the photosensitive resin layer formed of the photosensitive polymer resin composition, a finer pattern can be easily formed.

Specifically, the contact angle of the polyoxyalkylene polymer layer to water may be 65° or more or 65° to 90°.

Further, as described above, the polyoxyalkylene polymer layer can be coated with a sol-gel reaction solution containing a siloxane-based monomer on the transparent electrode layer, and is 50 ° C or higher or 100 ° C or higher. It is reacted or dried at a temperature of 50 ° C to 200 ° C.

The polyoxyalkylene polymer layer may comprise an alkoxydecane monomer, an aminodecane monomer, a vinyl decane monomer, an epoxy decane monomer, and a methacryloxy decane. One of a methacryloxy silane monomer, an isocyanate silane monomer, and a fluorononane monomer or a copolymer of two or more.

Specifically, the polyoxyalkylene polymer layer may comprise a group selected from the group consisting of tetraethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, and vinyl tris (β-methoxy ethoxy).矽, γ-methacryloxypropyltrimethoxydecane, β-(3,4-epoxycyclohexane)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, Γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxy Decane, phenyltriethoxydecane, methyltriethoxydecane, methyltrimethoxydecane, polyethylene oxide modified decane monomer, polymethylethoxysiloxane and six A polymer or two or more copolymers of Hexamethyldisilazane.

In order to ensure that the polyoxyalkylene polymer layer has a higher bonding force or adhesion to another layer and has a low sheet resistance, the polyoxyalkylene polymer layer may contain 60 to 90% by weight. Tetraethoxy decane; and 10 to 40% by weight selected from the group consisting of vinyl triethoxy decane, vinyl trimethoxy decane, vinyl tris (β-methoxyethoxy) decane, γ-methyl propylene醯-methoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexane)ethyltrimethoxydecane, γ-glycidyloxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxy Baseline, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, phenyltriethoxylate More than one of decane, methyltriethoxy decane, methyltrimethoxy decane, polyethylene oxide modified decane monomer, polymethylethoxy siloxane, hexamethyldioxane a compound; a copolymer of these compounds.

In the monomer for synthesizing the copolymer of the polyoxyalkylene polymer layer, if the content of the tetraethoxysilane is less than 60% by weight, the sheet resistance of the polyoxyalkylene polymer layer may be Will increase significantly. Further, in the monomer for synthesizing the copolymer of the polyoxyalkylene polymer layer, if the content of the tetraethoxysilane is more than 90% by weight, the density of the polyoxyalkylene polymer layer will be It becomes too high or may cause surface fragmentation, and water resistance is significantly reduced.

The transparent electrode composite including the polyoxyalkylene polymer layer can maintain high coatability and adhesion without further imparting hydrophobicity before forming the photosensitive resin layer. The photosensitive resin layer forms a finer pattern.

The polyoxyalkylene polymer layer may have a thickness of from 0.050 μm to 0.300 μm, or from 0.120 μm to 0.200 μm. Moreover, the sheet resistance of the polyoxyalkylene polymer layer may be from 80 Ω/sq to 400 Ω/sq, or from 150 Ω/sq to 280 Ω/sq.

In addition, the transparent electrode layer may include various materials known to be used for the transparent electrode, and specifically may include a material selected from the group consisting of a conductive polymer, a carbon nanotube, a graphene, a nano silver wire (AgNw), and a nano copper particle. One or more compounds of indium tin oxide (Indium Tin Oxide) and antimony tin oxide.

As the conductive polymer, a polymer known to be used for a transparent electrode may be used, and the conductive polymer may specifically include a polyaniline-based polymer, a polypyrrole polymer, a polythiophene polymer, and a derivative thereof. For one or more of them, poly 3,4-dioxyethyl thiophene: polystyrene sulfonate (PEDOT: PSS, Poly(3,4-ethylenedioxythiophene): Polystyrene sulfonate) can also be specifically 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 becomes too thin, the effective sheet resistance is also greatly reduced, which may cause unevenness of the sheet resistance, and when the thickness of the transparent electrode layer becomes too thick, transparency or optical characteristics may reduce.

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

As described above, due to the intrinsic properties of the polyoxyalkylene polymer layer, the photosensitive resin layer can be uniformly and firmly bonded to the polyoxyalkylene polymer layer, and thus, in the photosensitive A finer pattern can be formed on the resin layer.

In order to form the photosensitive resin layer, a known photosensitive resin composition or a photoresist composition may be used, and the photosensitive resin layer may specifically be composed of a positive type resist composition containing an alkali-soluble resin, or may include one The monomer or oligomer of the above reactive functional group and the negative photoresist composition of the photoinitiator are preferably formed of a positive photoresist composition.

The photosensitive resin layer may have a thickness of 1 μm to 5 μm or 2 μm to 4 μm. The thickness of the photosensitive resin layer is too thin, and spots or shape damage may occur on the photosensitive resin layer and/or the polyoxyalkylene polymer layer during exposure, development, and etching, thereby causing white turbidity. If the thickness of the photosensitive resin layer is too thick, development is insufficient or the line width is inconsistent due to difficulty in exposure.

In addition, the electrode film may further include a release film layer. As the release film layer, a polymer film or the like which is usually used for a transparent electrode film can be used, and specifically, a silicone adhesive film, an acrylic adhesive film, a PE protective film, or the like can be used.

Further, the electrode film may further include a base film layer formed on one surface of the transparent electrode layer and opposed to the polyoxyalkylene polymer layer.

That is, after the transparent electrode layer is formed on the base film layer, the transparent electrode layer, the polyoxyalkylene polymer layer, and the photosensitive resin layer are sequentially formed to form the transparent electrode composite. Further, after the polyoxyalkylene 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 conventional coating method or coating method can be used, and a conventional crimping method or the like can be used. The coating method may be a conventional coating method suitable for use in the art, and includes a spray coating method, a bar coating method, a doctor blade method, a roll coating method, a dipping method, and the like.

[efficacy]

According to the present invention, it is possible to provide a transparent electrode composite which has high bonding strength between layers and has low sheet resistance and interface resistance, and which can have a high degree of integration or an ultra-fine refinement pattern through a simplified procedure.

The transparent electrode composite provides a transparent electrode structure including a photoactive layer, that is, a photosensitive resin layer, and is provided by including the polyoxyalkylene polymer layer capable of buffering the transparent electrode and the photosensitive resin layer. Inherent characteristics. In particular, before the application of the photosensitive resin layer, high coatability and adhesion can be maintained without further imparting hydrophobicity, whereby a finer pattern can be formed on the photosensitive resin layer.

The invention is illustrated in more detail in the following examples. However, the following examples are merely illustrative of the invention, and the contents of the invention are not limited to the following examples.

[Manufacturing Example 1: Manufacturing an electrode layer]

PEDOT: PSS [Poly (3,4-ethylenedioxythiophene) Polystyrene sulfonate, solids 1 wt%], IPA (isopropanol), MeOH (methanol) and DMSO (dimethyl hydrazine) at 75:15:5: After mixing the weight ratio of 5, 500 ppmw of a surface conditioner, Dynol 607, was added to the mixture for stirring.

After the completion of the stirring, the mixture was applied onto a PET substrate by a bar coater, followed by hot air drying (110 ° C / 60 seconds) to prepare an electrode layer having a thickness of 0.096 μm. The resulting electrode layer sheet resistance was 240 Ω/sq.

[ First 2 Manufacturing example: manufacture of electrode layers ]

PEDOT: PSS [Poly (3,4-ethylenedioxythiophene) Polystyrene sulfonate, solid content 0.35 wt%], nano silver wire dispersion (1 wt%, water), IPA (isopropanol), DI water ( After mixing with deionized water and EG (ethylene glycol) in a weight ratio of 28.5:10:10:41.5:10, 500 ppmw of a surface conditioner, i.e., 3M FC-4330, was added to the mixture for stirring.

After the completion of the stirring, the mixture was applied onto a PET substrate by a bar coater, and then hot air dried (110 ° C / 60 seconds) to prepare an electrode layer having a thickness of 0.055 μm. The resulting electrode layer sheet resistance was 60 Ω/sq.

[ Examples and Comparative Examples: Fabrication of Electrode Films ]

Example 1

(1) Formation of a polyoxyalkylene polymer layer

After mixing TEOS (tetraethoxydecane) 16.08 g, PTMS (phenyltrimethoxydecane) 4.02 g, water 23.55 g, IPA (isopropanol) 54.95 g, 1.4 g acetic acid, the reaction was carried out at 70 ° C. 100 g of a sol-gel reaction solution was prepared in 3 hours (solid content: 7.8 wt%), and the prepared sol-gel reaction solution and isopropyl alcohol were diluted in a weight ratio of 1:4 to prepare a sol-gel reaction solution. 500 g (solids 1.56 wt%).

The sol-gel reaction solution (solid content: 1.56 wt%) was applied to the electrode layer obtained in the first production example by a bar coater at a thickness of 11.43 μm, and then dried at a temperature of 120 ° C under hot air conditions. After 10 minutes, a polysiloxane polymer layer (sheet resistance: 260 Ω/sq) having a thickness of 0.178 μm was formed.

(2) Formation of photosensitive resin layer

The photosensitive type sold by Dongjin Shimeiken, Model SJ-631 (10 cP, solid content 23 wt%) was applied to the formed polyoxyalkylene polymer layer by a bar coater. Then, it was dried at a temperature of 120 ° C for 1 minute to prepare a photosensitive resin layer having a thickness of about 2.62 μm.

Example 2

(1) Formation of a polyoxyalkylene polymer layer

After mixing TEOS (tetraethoxydecane) 16.08 g, VTMS (vinyl trimethoxydecane) 4.02 g, water 23.55 g, IPA (isopropanol) 54.95 g and 1.4 g acetic acid, the reaction was carried out at 70 ° C. 100 g of a sol-gel reaction solution (7.2 wt% solids) was prepared in 3 hours, and the prepared sol-gel reaction solution and isopropyl alcohol were diluted in a weight ratio of 1:4 to prepare a sol-gel reaction. Solution 500 g (solids 1.44 wt%).

The sol-gel reaction solution (solid content 1.44 wt%) was applied to the electrode layer obtained in the first production example by a bar coater at a thickness of 11.43 μm, and then dried at a temperature of 120 ° C under hot air conditions. After 10 minutes, a polysiloxane polymer layer (sheet resistance: 265 Ω/sq) having a thickness of 0.165 μm was formed.

(2) Formation of photosensitive resin layer

The photosensitive type sold by Dongjin Shimeiken, Model SJ-631 (10 cP, solid content 23 wt%) was applied to the formed polyoxyalkylene polymer layer by a bar coater. Then, it was dried at a temperature of 120 ° C for 1 minute to prepare a photosensitive resin layer having a thickness of about 2.62 μm.

Example 3

(1) Formation of a polyoxyalkylene polymer layer

The polysiloxane oxide sol-gel reaction solution (solid content 1.44 wt%) prepared in Example 2 was applied to the electrode layer obtained in the second production example by a bar coater at a thickness of 11.43 μm, and then It was dried at a temperature of 120 ° C for 10 minutes under hot air conditions to form a polyoxyalkylene polymer layer (sheet resistance: 80 Ω/sq) having a thickness of 0.165 μm.

(2) Formation of photosensitive resin layer

The photosensitive type sold by Dongjin Shimeiken, Model SJ-631 (10 cP, solid content 23 wt%) was applied to the formed polyoxyalkylene polymer layer by a bar coater. Then, it was dried at a temperature of 120 ° C for 1 minute to prepare a photosensitive resin layer having a thickness of about 2.62 μm.

Example 4 To the embodiment 6

A PET film (25 μm thickness) coated with a binder was placed in the electrode layer-polysiloxane polymer layer-photosensitive resin layer formed in the first embodiment, the second embodiment, and the third embodiment. The pressure was applied to the outer surface of the photosensitive resin layer by applying a pressure of 0.45 Mp at room temperature.

Comparative example 1

(1) Formation of a polyoxyalkylene polymer layer

After mixing TEOS (tetraethoxynonane) 20.01 g, water 23.55 g, IPA (isopropanol) 54.95 g, and 1.4 g acetic acid, the reaction was carried out at 70 ° C for 3 hours to prepare a sol-gel reaction solution 100 g. (solid content: 7 wt%), the prepared sol-gel reaction solution and isopropyl alcohol were diluted in a weight ratio of 1:4 to prepare a sol-gel reaction solution of 500 g (solid content: 1.4 wt%).

The sol-gel reaction solution (solid content 1.4 wt%) was applied to the electrode layer obtained from this production example by a bar coater at a thickness of 11.43 μm, and then dried at a temperature of 120 ° C under hot air conditions. In a minute, a polysiloxane polymer layer (sheet resistance: 256 Ω/sq) having a thickness of 0.160 μm was formed.

(2) Formation of photosensitive resin layer

The photosensitive type sold by Dongjin Shimeiken, Model SJ-631 (10 cP, solid content 23 wt%) was applied to the formed polyoxyalkylene polymer layer by a bar coater. Then, it was dried at a temperature of 120 ° C for 1 minute to prepare a photosensitive resin layer having a thickness of about 2.62 μm.

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

Experimental example 1 : Measuring contact angle

With respect to the contact angle of the polyoxyalkylene polymer layer obtained in Examples 1 to 3 and Comparative Example 1, the static contact was measured by a digital video contact angle analyzer (SEO Corporation, model phoenix-10). Angle (static contact angle method).

Experimental example 2 : Evaluation of coating properties and adhesion

The photosensitive resin layers obtained in Examples 1 to 3 and Comparative Example 1 were irradiated with ultraviolet rays of 50 mJ by an exposure apparatus (MA-6), and then used in a developing solution DPD-200 (sold by Dongjin Shimeiken). The film was developed under temperature for 35 seconds, and then subjected to a peeling (removal) process at room temperature for 50 seconds using a stripping solution ST-09 (available from Tojin Seike).

At this time, in the pattern formation process, the coatability and the adhesion were evaluated based on whether or not the line width of the pattern was removed. In the following Table 1, the symbol ○ indicates pattern maintenance, the symbol × indicates that the pattern was removed, and the actually formed pattern shape Shown in Figure 2.

【Table 1】

As shown in Table 1, the electrode films of Examples 1 to 3 are more strongly and easily bonded to the photosensitive resin layer because they contain a polyoxyalkylene polymer layer having a contact angle of 60 or more, thereby ensuring improvement. Coating and adhesion. On the contrary, the bonding force between the polyoxyalkylene-based polymer layer of the electrode film of Comparative Example 1 and the photosensitive resin layer was insufficient, resulting in difficulty in adhesion of the formed pattern or partial shape unsustainability.

Fig. 1 shows the contact angle of the polyoxyalkylene polymer layer obtained in Example 1 and Example 2 and Comparative Example 1 with respect to water. FIG. 2 shows the outer shape of the patterns of Example 1 and Comparative Example 1 observed in Experimental Example 2.

Claims (10)

A transparent electrode composite comprising: a transparent electrode layer comprising at least one selected from the group consisting of a conductive polymer, a carbon nanotube, a graphene, a nano silver wire, a nano copper particle, an indium tin oxide, and a tin oxide A polyoxyalkylene polymer layer formed on the transparent electrode layer having a contact angle with water of 60 or more; and a photosensitive resin layer formed on the polyoxyalkylene polymer layer. The transparent electrode composite according to claim 1, wherein the polyoxyalkylene polymer layer contains 60 to 90% by weight of tetraethoxydecane; and 10 to 40% by weight of the selected one is vinyl Ethoxy decane, vinyl trimethoxy decane, vinyl tris (β-methoxyethoxy) decane, γ-methyl propylene methoxy propyl trimethoxy decane, β-(3,4-ring Oxycyclohexane) ethyltrimethoxydecane, γ-glycidyloxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β- (Amineethyl)-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxydecane, phenyltriethoxydecane, methyltriethoxydecane, methyltrimethoxydecane, A compound of one or more of polyethylene oxide modified decane monomer, polymethylethoxy siloxane, hexamethyldioxane; copolymer of these compounds. The transparent electrode composite according to claim 1, wherein the polyoxyalkylene polymer layer has a contact angle with water of from 65 to 90. The transparent electrode composite according to claim 1, wherein the polyoxyalkylene polymer layer has a thickness of from 0.050 μm to 0.300 μm and a sheet resistance of from 80 Ω/sq to 400 Ω/sq. The transparent electrode composite according to claim 1, wherein 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. The transparent electrode composite according to the first aspect of the invention, wherein the conductive polymer comprises one or more selected from the group consisting of a polyaniline polymer, a polypyrrole polymer, a polythiophene polymer, and a derivative thereof. The transparent electrode composite according to claim 1, wherein the photosensitive resin layer has a thickness of from 1 μm to 5 μm. The transparent electrode composite according to claim 1, wherein the photosensitive resin layer is composed of a positive photoresist composition containing an alkali-soluble resin; or a monomer or oligomer containing one or more reactive functional groups. A negative photoresist composition of a polymer and a photoinitiator is formed. The transparent electrode composite according to claim 1, wherein the polyoxyalkylene polymer layer is coated with a sol-gel reaction solution containing a siloxane-based monomer on the transparent electrode layer. It is formed by drying at a temperature of 50 ° C or higher. [Equation 9] The electrode film according to Item 1, wherein the electrode film further comprises a release film layer formed on the photosensitive resin layer. The transparent electrode assembly according to claim 1, further comprising a base film layer formed on one surface of the transparent electrode layer and facing the polyoxyalkylene polymer layer.