KR101813752B1

KR101813752B1 - Transparent conductor and optical display apparatus comprising the same

Info

Publication number: KR101813752B1
Application number: KR1020150050475A
Authority: KR
Inventors: 김도영; 심대섭; 강경구; 신동명; 조성흔; 황오현
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-04-09
Filing date: 2015-04-09
Publication date: 2018-01-02
Also published as: KR20160121677A

Abstract

The present invention relates to a composition for matrix comprising a base layer and a conductive layer formed on the base layer and comprising metal nanowires and a matrix, wherein the matrix comprises a siloxane resin comprising units of the formula , The matrix further comprises inorganic particles, and the inorganic particles have an average particle diameter of 50 nm or less.
&Lt; Formula 1 >
R ¹ SiO _3/2
(Wherein R < ¹ > is a reactive functional group)

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent conductor and an optical display device including the transparent conductor.

The present invention relates to a transparent conductor and an optical display device including the transparent conductor.

Transparent conductors used in touch screen panels, flexible displays, and the like included in display devices must have good physical properties such as transparency and sheet resistance. Flexibility characteristics are also required as the area of use is expanded to flexible displays in recent years. Transparent conductors including metal nanowires have a tendency to be used in flexible displays because of their excellent bending properties. The transparent conductor comprising the metal nanowire will include an overcoating layer that prevents oxidation and / or wear of the metal nanowire and enhances adhesion to the substrate layer.

The transparent conductor including the gold nanowire is excellent in the bending property but the transmission b * value of the color difference coefficient is high, so that the transparent conductor may show a color distortion phenomenon and optical characteristics such as transmittance and haze may be deteriorated. Korean Patent Publication No. 2012-0053724 discloses a transparent conductive film and a manufacturing method thereof.

A problem to be solved by the present invention is to provide a transparent conductor capable of solving the problem of pattern visibility during patterning of a conductive layer in a transparent conductor.

Another problem to be solved by the present invention is to provide a transparent conductor capable of solving the phenomenon that the conductive layer is yellow.

Another object to be solved by the present invention is to provide a transparent conductor having low sheet resistance and excellent chemical resistance.

One aspect of the invention is a transparent conductor comprising a substrate layer and a conductive layer formed on the substrate layer and comprising metal nanowires and a matrix, the matrix comprising a siloxane resin comprising units of the formula Wherein the matrix further comprises inorganic particles, and the average particle size of the inorganic particles may be 50 nm or less:

&Lt; Formula 1 >

R ¹ SiO _3/2

(Wherein R < ¹ > is a reactive functional group)

An optical display device according to another aspect of the present invention may include the transparent conductor.

The present invention can provide a transparent conductor capable of solving the problem of pattern visibility during patterning of a conductive layer among transparent conductors.

The present invention can provide a transparent conductor capable of eliminating the phenomenon that the conductive layer appears yellow.

The present invention can provide a transparent conductor having low sheet resistance and excellent chemical resistance.

1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.
2 is a cross-sectional view of another embodiment of a transparent conductor according to an embodiment of the present invention.
3 is a cross-sectional view of still another embodiment of the transparent conductor of the present invention.
4 is a cross-sectional view of still another embodiment of the transparent conductor of the present invention.
5 is a cross-sectional view of another specific example of the transparent conductor of the embodiment of the present invention.
6 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.
7 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. However, the techniques disclosed in this application are not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the widths and thicknesses of components are slightly enlarged in order to clearly illustrate each component. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art can easily grasp the rest of the components. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention.

The terms "upper" and "lower" in this specification are defined with reference to the drawings, wherein "upper" may be changed to "lower", "lower" What is referred to as "on" may include not only superposition, but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly above"

As used herein, "(meth) acrylic" may mean acrylic and / or methacrylic.

In the present specification, the "transmission b * value" means a value obtained by multiplying the transparency obtained by laminating the metal nanowire and the conductive layer (thickness: 10 nm to 1 m) on a polycarbonate base film (thickness: 50 to 125 m) (Konica Minolta) at 400 to 700 nm. However, the material and thickness of the base film, the thickness and wavelength of the conductive layer may be changed, and the present invention can be included in the scope of the present invention.

A transparent conductor according to embodiments of the present invention comprises a substrate layer, a conductive layer formed on the substrate layer and comprising metal nanowires and a matrix, wherein the matrix comprises a siloxane resin comprising a T unit siloxane As shown in FIG. As a result, it is possible to realize a transparent conductor having low transmittance b * and low haze, which does not cause pattern visibility during patterning of the conductive layer, eliminates the visible appearance of the conductive layer, and has low sheet resistance and excellent chemical resistance.

Hereinafter, the transparent conductor according to one embodiment of the present invention will be described with reference to FIGS. 1 to 5. FIG. 1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.

1, the transparent conductor 100 of the present embodiment includes a base layer 110, a conductive layer 120 formed on the base layer 110 and including metal nanowires 121 and a matrix 122, ), And the matrix 122 may be formed of a composition for a matrix containing a siloxane resin including a unit represented by the following formula (1).

&Lt; Formula 1 >

R ¹ SiO _3/2

(Wherein R < ¹ > is a reactive functional group)

The base layer 110 is a film having transparency and can be a film having a transmittance of 85% or more and 100% or less, for example, 90% to 99% at a wavelength of 550 nm. Specifically, the base layer 110 may be formed of a material selected from the group consisting of a polyester including polyethylene terephthalate (PET), polyethylene naphthalate, a cycloolefin polymer, a polycarbonate, a polyolefin May be selected from the group consisting of polysulfone, polysulfone, polyimide, silicone, polystyrene, polyacryl, and polyvinylchloride, or a mixture thereof, But is not limited thereto. The base layer 110 may be a single layer or a laminated type of two or more resin films. The thickness of the base layer 110 may be 10 占 퐉 to 200 占 퐉, specifically, 20 占 퐉 to 150 占 퐉, and 30 占 퐉 to 100 占 퐉. Within this range, it can be used for display.

The conductive layer 120 is formed on the base layer 110 and may include metal nanowires 121 and a matrix 122. The conductive layer 120 may be patterned by a pattern forming method such as etching to form an electrode.

The metal nanowires 121 form a network, and can have conductivity and good flexibility and flexibility. The metal nanowires 121 have better dispersibility than metal nanoparticles due to their nanowire shape. Further, the metal nanowires 121 can provide an effect of significantly lowering the sheet resistance of the transparent conductive film due to the difference in particle shape to nanowire shape. The metal nanowires 121 have a shape of a very fine line having a specific cross section. In an embodiment, the aspect ratio of the nanowire length L to the diameter d of the cross-section of the metal nanowire 121 may be 10 to 2,000. In this range, a high conductivity network can be realized even at a low nanowire density, and the sheet resistance can be lowered. For example, the aspect ratio may be 500 to 1,000, for example, 500 to 700. The diameter d of the cross section of the metal nanowires 121 may be greater than 0 and less than or equal to 100 nm. Within this range, a transparent conductor having high conductivity and low sheet resistance can be realized by securing high L / d. For example, 30 nm to 100 nm, for example, 60 nm to 100 nm. The metal nanowires 121 may have a length L of 20 mu m or more. Within this range, a high L / d can be ensured to realize a conductive film having a low conductivity and a low sheet resistance. For example, 20 占 퐉 to 50 占 퐉. The metal nanowires 121 may comprise nanowires made of any metal. For example, silver, copper, gold nanowires or mixtures thereof. Silver nanowires or mixtures containing them may be preferably used.

The metal nano wire 121 may be manufactured by a conventional method or a commercially available product may be used. For example, it can be synthesized by a reduction reaction of a metal salt (for example, silver nitrate, AgNO 3) in the presence of a polyol and poly (vinylpyrrolidone). Alternatively, a commercially available product of Cambrios (e.g., ClearOhm Ink., A solution containing a metal nanowire) may be used. The metal nanowires 121 may include 13 wt% or more, for example, 13 wt% to 50 wt% of the conductive layer 120. Within this range, sufficient conductivity can be ensured and a conductive network can be formed.

The metal nanowires 121 may be used in a dispersed state in the liquid for easy application to the substrate layer 110 and adhesion to the substrate layer 110. In this specification, a liquid composition in which metal nanowires are dispersed is referred to as "metal nanowire composition ". The metal nanowire composition may include additives and binders for dispersing the metal nanowires. The binder is not particularly limited and includes, for example, carboxy methyl cellulose (CMC), 2-hydroxy ethyl cellulose (HEC), hydroxy propyl methyl cellulose HPMC, methylcellulose (MC), polyvinyl alcohol (PVA), tripropylene glycol (TPG), polyvinylpyrrolidone, xanthan gum (XG), ethoxylates Alkoxylate, ethylene oxide, propylene oxide, or copolymers thereof may be used.

The matrix 122 impregnates the metal nanowires 121. That is, the metal nanowires may be scattered or buried in the matrix 122. Also, some of the metal nanowires 121 may protrude from the surface of the matrix 122 and be exposed. The matrix 122 prevents oxidation and abrasion of the metal nanowires 121 that may be exposed on the top of the conductive layer 120 and provides adhesion between the conductive layer 120 and the substrate layer 110, The optical characteristics, chemical resistance, solvent resistance and the like of the light emitting device 100 may be increased.

The matrix 122 may be formed of a composition for a matrix containing a siloxane resin containing a unit represented by the following formula (1). The pattern may be viewed due to the color difference between the matrix 122 and the substrate layer 110 when patterning the conductive layer 120 to use the transparent conductor 100 as a transparent electrode film. The transparent conductor according to the present embodiment can improve the pattern visibility by lowering the haze of the transparent conductor by forming a matrix by using a composition containing a siloxane resin and can also reduce the transmission b * Can be improved.

&Lt; Formula 1 >

R ¹ SiO _3/2

(Wherein R < ¹ > is a reactive functional group)

In the above formula (1), the reactive functional group may be at least one of a hydroxyl group, an isocyanate group, an oxetane group, a (meth) acrylate group and an epoxy group, and examples thereof include an alkyl group having 1 to 7 carbon atoms .

The siloxane resin may be polysilsesquioxane having a structure in which a T unit including a reactive functional group is connected to the siloxane resin, thereby lowering the haze of the transparent conductor and improving the pattern visibility.

Specifically, the siloxane resin may include the following formula (2).

(2)

(Wherein * is an element connecting part and R1 is the same as in the above formula (1)

The siloxane resin may be prepared by hydrolysis and condensation of a silicone monomer mixture, or a commercially available product may be used.

The silicone monomer mixture may include a monomer represented by the following formula (3). The monomer mixture may be used alone or in combination of two or more kinds of monomers represented by the following formula (3).

(3)

R1, R2, R3 and R4 are each independently a hydroxyl group, an acetoxy group or a C1 to C10 alkoxy group, for example, a methoxy group, an ethoxy group, an isopropoxy group or an aceto Lt; / RTI >

The monomer of Formula 3 may be, for example, a trialkoxysilane, and specifically may be methacryloxypropyltrimethoxysilane.

The hydrolysis and condensation reaction of the monomer mixture can be carried out by a conventional method for producing a siloxane resin. For example, the hydrolysis may comprise reacting the silicone monomer mixture with the monomer in the presence of at least one of water and a predetermined acid or base, and the acid may be a strong acid such as hydrochloric acid, nitric acid, The base may be a strong base such as sodium hydroxide, potassium hydroxide, and the like. For example, the condensation reaction may be carried out at 50 DEG C to 100 DEG C for 10 minutes to 7 hours, but is not limited thereto.

The siloxane resin may have a refractive index of 1.45 to 1.50, specifically 1.47 to 1.49. Within this range, the haze of the transparent conductor is low and the effect of preventing the pattern from being visually recognized can be excellent.

The siloxane resin may have a weight average molecular weight of 1,000 to 10,000, specifically 1,500 to 5,000. And the durability can be excellent within the above range.

Hereinafter, the composition for a matrix will be described. The composition for a matrix may include a siloxane resin containing the unit of the formula (1). The siloxane resin may be contained in the matrix composition in an amount of 10% by weight to 98% by weight, specifically 20% by weight to 95% by weight and 50% by weight to 90% by weight, based on the solid content.

The composition for a matrix may further include an initiator. The initiator may be 1-hydroxycyclohexyl phenyl ketone or a mixture thereof containing alpha-hydroxy ketone series as a conventional photopolymerization initiator. The initiator may be contained in the composition for matrix at a solid content of 0.5 to 15% by weight, specifically 1 to 10% by weight.

The composition for a matrix may further comprise an adhesion promoting agent. The adhesion promoter improves the adhesion of the metal nanowires 121 to the base layer 110 and improves the reliability of the transparent conductive material 100. The adhesion promoter may include a silane coupling agent, at least one of monofunctional to trifunctional monomers Can be used. As the silane coupling agent, a commonly known silane coupling agent can be used. When a silane coupling agent having an amino group or an epoxy group is used, adhesion and chemical resistance may be good. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane ( 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane); A polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and (meth) acryloxypropyltrimethoxysilane; Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-aminopropyltrimethoxysilane) amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; And 3-chloropropyltrimethoxysilane may be used.

The monofunctional or trifunctional monomer may be an acid ester monomer. (Meth) acrylate monomer having a (meth) acrylate group, specifically, a monofunctional or trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms, more specifically a (meth) acrylate (meth) acrylate, isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2) Glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, glycerol tri Meth) acrylate Acrylate such as ethyleneglycol di (meth) acrylate, neopentylglycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclodecanedimethanol di But are not limited to, one or more of cyclodecane dimethanol di (meth) acrylate.

The adhesion promoting agent may be included in the composition for a matrix in an amount of 1 wt% to 15 wt%, specifically 5 wt% to 10 wt%. Adhesiveness can be improved while maintaining the reliability and conductivity of the transparent conductor within the above range.

The composition for a matrix may further comprise an antioxidant. The antioxidant can prevent the oxidation of the metal nanowire network of the conductive layer 120. The antioxidant can be used in combination with an antioxidant such as a triazole antioxidant, a triazine antioxidant, a phosphite- , HALS (Hinder amine light stabilizer) -based antioxidant, and phenol-based antioxidant, for example, by mixing two or more kinds of them, the oxidation of the metal nanowires 121 can be prevented and reliability can be improved. The antioxidant may be contained in the composition for a matrix in an amount of 0.01 wt% to 5 wt%, specifically 0.5 wt% to 2 wt%. Within this range, the antioxidant effect is excellent and the chemical resistance can be excellent.

The composition for a matrix may further include an additive for improving performance, and the additive may include an ultraviolet stabilizer and the like.

The thickness of the conductive layer 120 may be 10 nm to 1 탆, specifically 10 nm to 200 nm, more specifically 20 nm to 150 nm, 50 nm to 130 nm, and 70 nm to 100 nm. In the above range, the transparent conductor 100 can be used as a film for a touch panel. Within this range, there may be an effect that the contact resistance is lowered and the durability and the chemical resistance are improved.

As shown in FIGS. 2 to 4, the functional layer 130 may be further laminated on one side or both sides of the base layer 110. The functional layer 130 may be at least one of a hard coating layer, a corrosion preventing layer, an anti-glare coating layer, an adhesion promoting layer, and an oligomer elution preventing layer, but is not limited thereto.

The transparent conductor 100 can be manufactured by coating the metal nanowire composition on at least one surface of the substrate layer 110, drying the coated composition, coating the composition for a matrix, drying and then curing by irradiating ultraviolet rays. For example, the transparent conductor 100 may be formed by coating a metal nanowire composition on at least one side of the substrate layer 110 and drying in an oven at 50 to 120 DEG C for 30 seconds to 30 minutes, coating the composition for a matrix again, Drying in an oven at 60 to 150 ° C for 30 minutes to 30 minutes, and ultraviolet irradiation at 200 mJ / cm 2 to 1000 mJ / cm 2 for curing, but not limited thereto.

The transparent conductor 100 may have a transmittance b * value at a wavelength of 400 nm to 700 nm of 1 or less, specifically 0.9 or less, 0 to 1, or 0.001 to 0.9. It is possible to prevent the conductive layer from appearing yellow within the above range, and the problem of pattern visibility can be improved.

The transparent conductor 100 may have transparency in a visible light region, for example, a wavelength of 400 nm to 700 nm. In an embodiment, the transparent conductor 100 has a haze of 0 to 1%, such as 0.01% to 0.9%, measured with a haze meter at a wavelength of 400 nm to 700 nm, and a total light transmittance of 90% to 100% 94% to 98%. Within this range, transparency is good and can be used for transparent conductor applications. The transparent conductor 100 may have a sheet resistance of 100 Ω / □ or less, specifically 50-100 Ω / □, or 30-90 Ω / □, as measured with a 4-probe. Within this range, the sheet resistance is low and can be used as an electrode film for a touch panel.

The thickness of the transparent conductor 100 is not limited, but may be 10 탆 to 250 탆, for example, 50 탆 to 200 탆. Within the above range, it can be used as a transparent electrode film including a film for a touch panel, and can be used as a transparent electrode film for a flexible touch panel. The transparent conductor is in the form of a film and is patterned by etching or the like, and can be used as a transparent electrode film of a touch panel, an E-paper, or a solar cell.

1 shows an embodiment in which the conductive layer 120 including the metal nanowires 121 and the matrix 122 is formed on the upper surface of the base layer 110. However, as shown in FIG. 5, the base layer 110 The transparent conductor 150 may further include a conductive layer 120 including a metal nanowire 121 and a matrix 122 on the lower surface of the transparent conductive layer 150.

Hereinafter, the transparent conductor of another embodiment of the present invention will be described.

The transparent conductor of another embodiment of the present invention includes a substrate layer 110, a conductive layer 120 formed on the substrate layer 110 and including metal nanowires 121 and a matrix 122, (122) may be formed of a composition for a matrix containing a siloxane resin including the unit of the formula (1), and the matrix 122 may include inorganic particles (not shown). Is the same as the transparent conductor 100 according to the embodiment of the present invention, except that the matrix 122 further contains inorganic particles.

The transparent conductor of this embodiment may contain inorganic particles in the matrix 122, and thus the pattern visibility improving effect may be excellent.

The inorganic particles may be an oxide such as a metal, a non-metal, or a semi-metal, and may be one or more of, for example, titanium oxide, zirconium oxide, silicon oxide, and aluminum oxide.

The average particle size of the inorganic particles may be 50 nm or less, for example, 10 nm to 40 nm, specifically, 20 nm to 30 nm. Within this range, light scattering may be reduced to reduce the haze.

The inorganic particles may be contained in the matrix 122 in an amount of 5% by weight to 90% by weight, specifically 8% by weight to 60% by weight, based on the solid content of the matrix 122. Within the above range, dispersion stability and pattern visibility improvement effect have.

The weight ratio of the siloxane resin to the inorganic particles in the matrix may be in the range of 1: 1 to 9: 1, the transparency may be high within the range, the problem of pattern visibility may be improved, the sheet resistance may be low, have.

Hereinafter, a transparent conductor according to another embodiment of the present invention will be described with reference to FIG. 6 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.

6, the transparent conductor 200 of another embodiment of the present invention includes a base layer 110, a metal nanowire 121 formed on the upper surface of the base layer 110 and a metal nanowire 121 and a matrix 122 An electrode portion 120a made of a conductive layer containing a metal nanowire 121 and a conductive portion 120b patterned with a pattern portion 120b made of a metal nano- (120 '). Is substantially the same as the transparent conductor 100 of the embodiment of the present invention except that the conductive layer 120 'is patterned.

The conductive layer 120 'may be patterned in a manner that includes etching using a conventional method, for example, a conventional etching solution, which is an acid solution, and the conductive layer 120' is patterned x, and y channels and can be used as a transparent electrode. For example, as shown in Fig. 6, an electrode portion 120a made of a conductive layer containing metal nanowires 121 and a metal nano-wire-free conductive layer made of only the matrix 122 without the metal nanowires 121 And may be patterned including the pattern portion 120b.

Specifically, the patterning can be performed by a photolithography method, but is not limited thereto. For example, a photoresist film is laminated on a conductive layer of a transparent conductor, exposed to ultraviolet rays using a pattern mask, developed, and baked to form a pattern layer on the conductive layer. The transparent conductor including the pattern layer may be dipped in an etchant containing phosphoric acid, nitric acid, and acetic acid at 40 ° C to etch the metal nanowires where no pattern layer is formed to form a pattern.

Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIG. 7 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

The optical display device 300 according to an embodiment of the present invention includes a flexible circuit board 310, a transparent electrode 330 formed on the flexible circuit board 310, a polarizer 340 formed on the transparent electrode 330, And a window film 360 formed on the upper portion of the polarizing plate 340. The transparent electrode body 330 may be formed of a transparent conductor according to embodiments of the present invention.

The transparent electrode member 330 includes a conductive layer 120 'formed on one side or both sides of the base layer 110 base material layer 110. The transparent conductive member of the present invention may be formed by a predetermined method, Etching, etc.). The patterned conductive layer 120 'may include an electrode portion 120a and a pattern portion 120b. The window film 360 performs a screen display function in an optical display device and can be made of a common glass material or a transparent plastic film. The polarizer 340 may be a polarizer or a laminate of a polarizer and a protective film. The polarizer may be a polarizer, and the protective film may be a polarizer, And may include conventional ones known in the art. Adhesive films 320 and 350 are provided between the transparent electrode member 330 and the flexible circuit board 310 and between the window film 360 and the polarizer 340 to form the transparent electrode member 330 and the window film 360 ) And the flexible circuit board 310 can be maintained. The adhesive films 320 and 350 may be ordinary adhesive films, for example, optical clear adhesive films.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to examples, comparative examples and test examples. However, these examples, comparative examples and test examples are provided for illustrative purposes only in order to facilitate understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples, comparative examples and test examples.

Production Example 1: Silicone resin containing T unit

220 g of 3-methacryloxypropyl trimethoxysilane (KBM-503, SHIN-ETSU) and 132.15 g of propylene glycol monoethyl ether (PGME) as a solvent were added and stirred at room temperature for 30 minutes to be mixed , 4.43 g of 0.1N HNO ₃ and 43.41 g of distilled water were slowly added thereto. Methanol (MeOH) as a by-product was removed by decompression to prepare a siloxane resin having a weight average molecular weight of 2,500 including the T unit of Production Example 1

The ingredients used in the following examples and comparative examples are as follows.

(A) siloxane resin: (a1) siloxane resin containing T unit (Production Example 1), (a2) siloxane resin composed of D unit (SIM6485.9, Geles)

(B) Silica sol (SST130U, Rencosa, silica particles 30% by weight, silica particles having an average particle diameter of 20 nm, average particle diameter of 25 nm) (B) Silica sol (SST250U, 55 nm)

(C) acrylate resin: (c1) dipentaerythritol hexaacrylate (DPHA, SK CYTEC), (c2) propoxylated glyceryl triacrylate (SR9020, Sartomer)

(D) Initiator: Irgacure 184 (CIBA)

Example 1

37 weight parts of a solution containing metal nanowires (Clearohm ink, Cambrios, 2.45 weight% of metal nanowire and binder) was added to 63 weight parts of ultrapure distilled water and stirred to prepare a metal nanowire composition.

1.6 parts by weight of a solution prepared by diluting the siloxane resin (Production Example 1) containing T units to methyl isobutyl ketone (MIBK) so that the solid content of the siloxane resin became 60% by weight, 1.3 parts by weight of silica sol (SST250U, 0.03 parts by weight of Irgacure 184 (CIBA) was added to 48.5 parts by weight of methyl isobutyl ketone (MIBK) and 48.5 parts by weight of propylene glycol monoethyl ether (PGME) to prepare a composition for a matrix.

The metal nanowire composition was coated on a polycarbonate base film (Teijin Co., thickness 50 탆) by a spin coater, dried in an oven at 110 캜 for 120 seconds, dried in an oven at 140 캜 for 120 seconds, and then the composition for a matrix was spin- The conductive layer was formed to a thickness of 150 nm, dried in an oven at 80 DEG C for 120 seconds, dried at 110 DEG C for 120 seconds, and then cured by a metal halide lamp (GS YUNA) at 500 mJ / cm2 to prepare a transparent conductor .

Example 2

2.5 parts by weight of a solution prepared by diluting a siloxane resin containing T units (Preparation Example 1) to methyl isobutyl ketone (MIBK) so that the solids content of the siloxane resin became 60% by weight, 0.4 parts by weight of silica sol (SST250U, 0.03 parts by weight of Irgacure 184 (CIBA) was added to 48.5 parts by weight of methyl isobutyl ketone (MIBK) and 48.5 parts by weight of propylene glycol monoethyl ether (PGME) to prepare a composition for a matrix.

The metal nanowire composition was coated on a polycarbonate base film (Teijin Co., thickness 50 탆) by a spin coater, dried in an oven at 110 캜 for 120 seconds, dried in an oven at 140 캜 for 120 seconds, and then the composition for a matrix was spin- The conductive layer was formed to a thickness of 150 nm, dried in an oven at 80 DEG C for 120 seconds, dried at 110 DEG C for 120 seconds, and then cured by a metal halide lamp (GS YUNA) at 500 mJ / cm2 to prepare a transparent conductor.

Comparative Example 1

2.9 parts by weight of a siloxane resin containing T units (Preparation Example 1) diluted with methyl isobutyl ketone (MIBK) to a solids content of the siloxane resin of 60% by weight and 0.03 parts by weight of initiator Irgacure 184 (CIBA) 48.5 parts by weight of ketone (MIBK) 48.5 parts by weight of propylene glycol monoethyl ether (PGME) was added to prepare a composition for a matrix.

Comparative Example 2

1.9 parts by weight of silica sol (SST250U, Lenko Corp.) and 0.03 part by weight of initiator Irgacure 184 (CIBA) were added with 48.5 parts by weight of methyl isobutyl ketone (MIBK) and 48.5 parts by weight of propylene glycol monoethyl ether (PGME) Respectively.

Comparative Example 3

, 1.8 parts by weight of dipentaerythritol hexaacrylate (DPHA, SK CYTEC), 0.1 part by weight of propoxylated glyceryl triacrylate (SR9020, Sartomer) and 0.03 part by weight of initiator Irgacure 184 (CIBA) Ketone (MIBK) in an amount of 98 parts by weight to prepare a composition for a matrix.

Comparative Example 4

2.9 parts by weight of siloxane resin (TIM6485.9, Geles) not including T units but D units and 0.03 parts by weight of initiator Irgacure 184 (CIBA) were mixed with 48.5 parts by weight of methyl isobutyl ketone (MIBK), propylene glycol monoethyl ether PGME) were added to prepare a composition for a matrix.

Comparative Example 5

1.5 parts by weight of a siloxane resin containing T units (Preparation Example 1), 1.5 parts by weight of silica sol (SST130U, Lencosa, 30% by weight of silica particles, 55 nm of average particle diameter of silica particles) and 0.03 parts by weight of Irgacure 184 48.5 parts by weight of methyl isobutyl ketone (MIBK) 48.5 parts by weight of propylene glycol monoethyl ether (PGME) were added to prepare a composition for a matrix.

The following properties of transparent conductors of Examples and Comparative Examples were evaluated, and the results are shown in Tables 1 and 2 below.

(1) Haze and total light transmittance (%): Haze and total light transmittance were measured using a haze meter (NDH-2000, NIPPON DENSHOKU) at a wavelength of 400 to 700 nm with the conductive layer directed toward the light source for the transparent conductor.

(2) Transmission a *, transmission b *: Transparent conductors (polycarbonate film: thickness 50 탆, conductive layer comprising metal nanowire and matrix: thickness 150 nm) in Examples and Comparative Examples were exposed to UV The transmittance color coordinates were measured using a spectrometer (illuminant 65 degrees, observer 2 degrees) and CM6000D (Konica Minolta).

(3) Surface Resistance (Ω / □): The surface resistance of the non-patterned transparent conductor surface was measured using a high frequency non-contact resistance meter EC-80P (NAPSON).

(4) EtOH rubbing: The conductive layer was sprayed with ethanol as an eyedropper, rubbed with a wiper 10 times, and appearance change and resistance change were confirmed. &Quot; Good "when the external appearance by the naked eye was not changed, " Bad" when the resistance change rate was 10% or less, and / or when the resistance change rate exceeded 10%.

(Unit: parts by weight) Example 1 Example 2 (a1) a siloxane resin containing T units 1.6 2.5 (a2) a siloxane resin composed of D units 0 0 (b1) silica sol (average particle diameter of silica: 25 nm) 1.3 0.4 (b2) silica sol (silica average particle diameter: 55 nm) 0 0 Dipentaerythritol hexaacrylate 0 0 Propoxylated glycerol triacrylate 0 0 Initiator 0.03 0.03 menstruum 97 97 Haze (%) 0.71 0.73 Total light transmittance (%) 95.13 95.3 Transmission a * 0.02 0.33 Transmission b * 0.06 0.48 Sheet resistance (Ω / □) 50 to 55 50 to 55 EtOH rubbing Good Good

(Unit: parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (a1) a siloxane resin containing T units 2.9 0 0 0 1.5 (a2) a siloxane resin composed of D units 0 0 0 2.9 0 (b1) silica sol (average particle diameter of silica: 25 nm) 0 1.9 0 0 0 (b2) silica sol (silica average particle diameter: 55 nm) 0 0 0 0 1.5 Dipentaerythritol hexaacrylate 0 0 1.8 0 0 Propoxylated glycerol triacrylate 0 0 0.1 0 0 Initiator 0.03 0.03 0.03 0.03 0.03 menstruum 97 97 98 97 97 Haze (%) 0.86 1.02 1.25 0.76 12.25 Total light transmittance (%) 95.21 95.49 96.49 95.08 95.22 Transmission a * 0.05 -0.35 -0.64 0.11 -0.22 Transmission b * 0.54 1.25 1.45 0.51 1.02 Sheet resistance (Ω / □) 50 to 55 50 to 55 50 to 55 50 to 55 50 to 55 EtOH rubbing Bad Bad Good Bad Bad

From the results shown in Tables 1 and 2, the transparent conductor of Examples has low haze, high total light transmittance, transparency b * value of 1 or less, high transparency, And is excellent in chemical resistance. On the other hand, in Comparative Example 1 which did not contain inorganic particles, EtOH rubbing was poor, and when a silicone resin other than a siloxane resin containing T units was used (Comparative Examples 2 and 4), transparency and pattern visibility were poor, (Comparative Example 3), the transparency and the pattern visibility were not good because of high haze and high transmission b * value when an acrylic resin was used instead of the silicone resin (Comparative Example 3). In the case of Comparative Example 5 in which the particle size of the inorganic particles was out of the range of the present invention, external haze was generated and the surface of the film became puffy, and the curing reaction was insufficient, and EtOH rubbing was poor.

Claims

A base layer, and a conductive layer formed on the base layer and including metal nanowires and a matrix,
Wherein the matrix is formed of a composition for a matrix comprising a siloxane resin comprising units of the following formula (1)
Wherein the matrix further comprises inorganic particles,
Wherein the inorganic particles have a mean particle size of 50 nm or less,
&Lt; Formula 1 >
R ¹ SiO _3/2
(Wherein, in the formula (1), R ¹ is a (meth) acrylate group-containing group)
The siloxane resin has a refractive index of 1.47 to 1.49,
The transparent conductor has a transmittance b * value of not more than 1 at a wavelength of 400 nm to 700 nm,
Wherein the transparent conductor has a haze value of 1% or less.

delete

The method according to claim 1,
Wherein the siloxane resin has a weight average molecular weight of 1,000 to 10,000.

The method according to claim 1,
Wherein the composition for a matrix further comprises at least one of an initiator, an adhesion promoter and an antioxidant.

The method according to claim 1,
Wherein the inorganic particles are at least one of titanium oxide, zirconium oxide, silicon oxide, and aluminum oxide.

The method according to claim 1,
Wherein the inorganic particles have an average particle diameter of 20 nm to 30 nm.

The method according to claim 1,
Wherein the metal nanowire comprises silver nanowires.

delete

The method according to claim 1,
Wherein at least one of a hard coating layer, a corrosion preventing layer, an anti-glare coating layer, an adhesion promoting layer, and an oligomer elution preventing layer is further formed on an upper surface or a lower surface of the substrate layer.

An optical display device comprising the transparent conductor according to any one of claims 1, 4 to 8 and 11.